NL7905294A - OLEFINE POLYMERIZATION CATALYST, METHOD FOR THE PREPARATION THEREOF, AND METHOD FOR POLYMERIZING OLEFINS. - Google Patents

Description

*. .

NATIONAL PETRO CHEMICALS CORPORATION, of New York, New York, Ver. St. V. America.

Olefin polymerization catalyst, process for its preparation and process for polymerizing olefins.

The invention relates to olefin polymerization catalysts and to methods of polymerizing olefins in the presence of chromium-supported supported catalysts.

The use of chromium compounds in the polymerization of olefins is well known. U.S. Pat. Nos. 2,825,721 and 2,951,816 describe the use of chromium trioxide supported on an inorganic material, such as silica, alumina or combinations of silica and alumina, and activated by heating in reducing atmospheres to polymerize olefins. However, when a catalyst system of this type is used in techniques such as the well-known particulate process, the resins produced, although useful for many applications, are unsatisfactory for others, due to a lack of certain properties, such as the melt index.

Attempts to test the properties of polyolefins produced using supported heat-activated chromium oxide catalysts have been made by adding various compounds to the supported chromium oxide prior to its heat activation. For example, U.S. Patent 3,622,522 shows that an alkoxide of gallium or tin can be added to supported chromium oxide prior to heat activation (and that the addition of aluminum isopropoxide is comparatively unfavorable). US Patent 3,715,321 proposes adding a Group IIA or Group IIIB metal compound to supported chromium oxide prior to heat treatment, while US Patent 3,780,011 describes the addition of alkyl esters of titanium, vanadium or boron and U.S. Pat. No. 3, 8,... 28 describes the addition of alkyl boranes to such a catalyst.

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It is also known to use other chromium compounds in the preparation of olefin polymerization catalysts. Such compounds include various silyl chromate and polyalicyclic chromate esters as described, for example, in U.S. Pat. Nos. 3,332,095, 3,324,101, 3,642,749 and 3,704,287. Other such catalysts are described in U.S. Pat. Nos. 3,474,080, 3,985,676 and 4,100,104. These catalysts can be used with organometallic reducing agents such as, for example, trialkyl aluminum compounds.

US patents 3,984,351 and 4,049,986 disclose that the properties of olefin polymers, for example, melt indices, can be significantly improved by using a catalyst obtained by depositing an organophosphoryl chromium compound and an aluminum compound such as aluminum sec-butoxide. on an inorganic support material and heat-activating the supported material in a non-reducing, preferably oxygen-containing atmosphere, at a temperature of about 300 ° C up to the decomposition temperature of the support. The resulting material, which is preferably combined with a metallic and / or non-metallic reducing agent, provides a catalyst system capable of producing polymers with improved flow properties and shear responses in addition to increased melt indices.

Among the objects of the present invention is to provide a further improved technique for the preparation of olefin polymerization catalysts and a polymerization process using them which results in the formation of polymers with high melt indexes and other desirable properties, such as variations in the molecular weight distribution.

According to the invention, it has been found that an effective olefin polymerization catalyst can be prepared by depositing an organophosphoryl chromium product and a non-volatile aluminum-containing product obtained from the reaction of an aluminum alkoxide and an aluminum salt of a lower aliphatic monocarboxylic acid on an inorganic support material and heating of the support material in a non-reducing atmosphere at a temperature above about 300 ° C up to the decomposition temperature of the support material.

790 5 2 94 3

The procedure described in U.S. Patent 3,905,676 can be followed in the preparation of the organophosphoryl chromium compound deposited on an inorganic support material of the present invention.

It is also within the scope of the invention to deposit the non-volatile aluminum-containing reaction product on the support followed by a first heat activation step and then depositing the chromium compound on the support followed by a second heat activation step. as in the double activation procedure, described in the above-mentioned U.S. Patent U.100.10U. Double activation of the catalysts, as observed by the Applicant, provides an even further increase in the polymer melt indices.

If desired, the heat activated catalysts can be treated with a metallic and / or non-metallic reducing agent, such as described in U.S. Pat. No. 3,998,351.

The catalysts of the invention are suitable for use in conventional polymerization processes and are suitable for polymerization conducted under temperature and pressure conditions commonly used in the art, for example temperatures from about 30 to about 250 ° C, and preferably about J0 to about 110 ° C, and pressures from about 1380 to about 6900 kPa, and preferably from about 2070 to about 5520 kPa, as used in slurry polymerizations.

The organophosphoryl compounds deposited on the inorganic support material are prepared by reacting an organophosphorus compound with chromium trioxide in an inert solvent, for example cyclohexane, n-hexane, methylene chloride, carbon tetrachloride, etc. In this step of the preparation from the catalyst system, the solid CrO2 is suspended in the solvent and the organophosphorus compound is added. After some time, for example about 1 hour, the reaction between the compounds is completed and the chromium trioxide disappears. During this time, the solution turns reddish-brown in color. It is usually filtered in a simple manner to ensure that no unreacted solid CrO2 is present. This solution is then applied to the support material in such a way that the catalyst solution is deposited thereon, suitably by any wet coating technique, for example spraying. Usually the solution is added to a dispersion of <fe carrier.

The solvent is removed from the base by drying, for example, using heat, inert gas stripping or reduced pressure, alone or in combination. In this way, the reaction product is applied to the support material. It is considered significant that the organophosphoryl-chromium reaction product is preformed, that is, the reacting dependencies are combined prior to introduction onto the support. The active catalyst is therefore considered not to be derived from chromium trioxide but from the organophosphoryl chromium reaction product as described.

Among the organic phosphorus compounds which can be used in the preparation of the organophosphorryl chromium compounds are the triorganophosphates and diorganophosphates, including such compounds as triphenyl phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, trimethyl phosphate, etc. Also suitable are the mono ( phosphate or phosphite and di (hydrogen) phosphate derivatives (which include, for example, monobutyl phosphate, dibutyl phosphate and monoethyl phosphite) and these materials may, of course, comprise mixtures. Organophosphoryl chromium reaction products are also formed with such phosphorus based compounds as phenyl phosphoric acid, diethyl phosphonate and trialkyl phosphine oxide. Preferred compounds are those of formulas 1 and 2, wherein R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, but wherein at least one group R differs from hydrogen and when R is a hydrocarbon group it may contain up to 18 carbon atoms. For ease of description, the useful materials in the description and claims are collectively and comprehensively referred to as "organophosphoryl chromium" reaction products.

The non-volatile aluminum-containing product which is also deposited on the inorganic support according to the invention is prepared by an aluminum alkoxide of formula 3, wherein η is 1, 2 or 3 and R and R 'are each alkyl and at most 8 carbon atoms with an aluminum carboxylic acid salt of formula H, wherein RH is alkyl having at most about 8 carbon atoms. Among the aluminum alkoxides which can be used are aluminum sec-butoxide, aluminum ethoxide, aluminum propoxide, aluminum isopropoxide, aluminum n-butoxide, 790 5 2 94 * 5 methyl aluminum propoxide, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide and the like. In the preferred aluminum alkoxides, η will be 3 and of these alkoxides, aluminum sec-butoxide is most preferred. Examples of aluminum carboxylic acid salts which can be reacted with the aforementioned aluminum alkoxides according to the invention are aluminum acetate, aluminum formate, aluminum propionate, aluminum butyrate, aluminum isobutyrate, etc. Aluminum acetate, AlCoOCCH 2) is preferred. The reaction of the aluminum alkoxide and the aluminum carboxylic acid salt can be conveniently carried out by heating the reactants under reflux in a suitable inert solvent which is normally an anhydrous organic solvent. Such organic solvents include aliphatic, cycloalkyl and alkylayl hydrocarbons and their halogenated derivatives, for example, toluene, xylene and decalin. The molar ratios of the reagents can vary over 15 broad ranges, with ratios of aluminum alkoxide to aluminum carboxylic acid salt ranging from 1:10 to 10: 1 being particularly preferred, with ratios of these reagents ranging from 1: 3 to 3: 1. Likewise, the reflux temperatures and reaction periods can extend over a wide range. For example, the aluminum alkoxide and the aluminum carboxylic acid salt can be heated under reflux at a temperature of about 50 to about 250 ° C for about 15 minutes to about 2 hours. Excellent results have been obtained at reflux temperatures of about 120 to 200 ° C and reaction periods of about 3 to 22 hours. During the reaction, the initially insoluble aluminum alkoxide slowly dissolves in the solvent and in some cases the solvent develops an easily distinguishable color change. In addition to the desired non-volatile aluminum-containing product, the reaction also yields a volatile product of no use in the present invention. Currently, the exact nature of the non-volatile aluminum-containing reaction product is not known, although it is believed likely to actually form a mixture of compounds. Without wishing to be bound in any way by the following possible explanation, the applicant has speculated that the reaction of aluminum alkoxide and aluminum carboxylic acid salt takes place in two steps, in the first step forming a complex of the two reagents and in the second step yu-oxo -aluminium compound- 79052 94 «6 things and volatiles.

The inorganic support materials useful in the present invention include those commonly used in supported chromium catalysts for use in olefin polymerizations, such as those discussed in U.S. Pat. No. 2,825,721. Typically, these support materials are inorganic oxides, such as silica, alumina, silica-alumina mixtures, thoria, zirconia, and similar oxides, which are porous, have a moderately specific surface, and have surface hydroxyl groups. Preferred carrier materials are silica-xero gels or xero gels containing silica as the major constituent. Particular preference is given to the silica xerogels described in U.S. Pat. Nos. 3,652,211, 3,652,215 and 3,652,216, which have a specific surface area of from about 200 to about 500 m / g and a pore volume greater than about 2.0 ml / g, with most of the pore volume being provided by pores with diameters from about 300 to 600 angstroms.

The catalysts of the invention can be prepared by depositing the organophosphoryl chromium compound and the non-volatile aluminum-containing reaction product as described above on the inorganic support in any suitable manner. The organophosphoryl chromium compound can be deposited by vapor coating or in a suitable inert solvent. The aluminum-containing product can be deposited in a suitable inert solvent, such as those which can be used as the reaction medium in which the aluminum-containing product is prepared.

Dichloromethane is a preferred solvent for this purpose,

The organophosphoryl chromium compound may be applied to the support first, or the aluminum-containing product may be applied first, or the chromium and aluminum products may be applied together.

In the usual manner of catalyst preparation, the support is first impregnated with the organophosphoryl chromium compound and then with the aluminum-containing product.

According to the alternative double activation treatment of the present catalysts, the non-volatile aluminum-containing reaction product is first deposited on the support as in the single activation procedure described above and the coated support is initially heat activated in a non- reducing atmosphere, preferably in a dry oxygen-containing atmosphere, temperatures of at least about 130 ° C up to the decomposition temperature of the support. Typically, the support with the aluminum-containing reaction product deposited thereon is heated to a temperature of from about 130 to about 1100 ° C, and preferably from about 260 to about 020 ° C. The period required for the initial activation step varies, depending on the temperatures used, from an hour or less to about 50 hours or more, and normally takes place from about 2 to about 12 hours. Partial activation 10 is completed by then depositing the organophosphozyl chromium compound on the aluminum-containing support in the manner described above for the single activation step procedure and heating the thus-treated support in a preferably dry oxygen-containing atmosphere, at temperatures above about ^ 30 ° C, up to the decomposition temperature of the support. Activation is suitably performed at temperatures from about U30 to 1100 ° C, the best results being obtained by activation at temperatures from about 8HO to about 990 ° C. Activation can be performed in this last heating step for periods of about one hour or less to 50 hours or more and usually for periods of about 2 to about 12 hours.

The most effective catalysts have been found to be those containing the organophosphoyl chromium compound in an amount such that the amount by weight of chromium, based on the weight of the support, is about 0.25 to 2.5%, and preferably about 0.5 to Is 1.25%, although amounts outside these ranges still yield useful catalysts. The aluminum-containing product should be added in sufficient amounts to provide about 0.1 to 10 weight percent aluminum, based on the weight of the support, and preferably about 0.5 to 5.5 weight percent, although amounts outside these ranges can be used to obtain useful catalysts.

After the organophosphozyl chromium compound and the aluminum-containing product have been deposited on the inorganic support, the support is heated in a non-reducing atmosphere, preferably in

an oxygen-containing atmosphere, at a temperature above about 300 ° C

790 52 94 8 up to the decomposition temperature of the support. Usually, the supported materials are heated at a temperature of 500 to 1000 ° C. The heating time may vary, for example, depending on the temperatures used, from one hour or less to 50 hours or more. Normally the heating takes place over a period of 2 to 12 hours. The non-reducing atmosphere, which is preferably air or other oxygen-containing gas, should be dry and preferably should be dehumidified to a few parts per million (ppm) of water to obtain maximum catalyst activity. Typically, air used in the procedure of the present application is dried to less than 2 to 3 ppm water.

The heat-treated supported chromium-containing and aluminum-containing catalyst according to the invention can, if desired, be used in combination with metallic and / or non-metallic reducing agents. Examples of metallic reducing agents include tri-15 alkyl aluminum, such as triethyl aluminum, triisobutyl aluminum, alkyl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium and metal borohydrides, including those of the alkali metals, especially sodium, lithium and potassium, and of magnesium, beryllium and aluminium. The non-metallic reducing agents include alkyl boranes, such as triethyl borane, triisobutyl borane, and trimethyl borane, and hydrides of boron, such as diborane, pentaborane, hexaborane, and decaborane.

The present heat-treated catalysts can be combined with the metallic or non-metallic reducing agent before being fed to an olefin polymerization reactor or these two forms can be fed separately to an olefin polymerization reactor.

A fairly large clearance is available in proportioning the amount of metallic or non-metallic reducing agent to the amount of chromium compound used in the catalyst systems of the invention, but some guidelines have been established which are related with good yield, favorable polymer properties and economical use of materials. For example, when using metallic and / or non-metallic reducing agents with an amount of chromium compound sufficient to provide about 1 percent by weight chromium of the support, the parameters listed below are representative. The atomic ratios are based on a calculation 790 52 94 9 * of the metal in the metallic reducing agent and / or of the non-metal in the non-metallic reducing agent to the chromium content contained in the chromium compound on the support.

For example, based on a catalyst material containing about 1% by weight of chromium, based on the weight of the support, the preferred amount of an organometallic reducing agent for use therein, for example trixsobutylaluminum (Tibal) is about 11% by weight and equivalent to an aluminum to chlorine atomic ratio of about 3: 1. The preferred range of atomic-10 ratios of aluminum to chlorine is from about 0.5: 1 to about 8: 1 or from about 1.9 to about 30 percent by weight Tibal. Overall, Tibal's useful limits in terms of the aluminum to chromium atomic ratio are from about 0.1: 1 to 20: 1, and in terms of weight from about 0.5 to about 75 percent by weight.

Another example of an organometallic reducing agent for use in conjunction with the catalyst material of the invention is triethyl aluminum. Again based on a catalyst material containing about 1% by weight Cr, based on the weight of the support, the preferred amount of triethyl aluminum (TEA) is about 6.6 weight percent based on the weight of the carrier, giving an aluminum to chromium atomic ratio of about 3: 1. The preferred range of aluminum to chromium atomic ratios is from about 0.5: 1 to about 8: 1, or from about 1.1 to about 18% by weight TEA. The overall useful limits of TEA, in terms of the aluminum to chromium ratio, are from about 0.1: 1 to 20: 1, and in terms of weight from about 0.22 to about kk percent by weight. .

Triethyl boron (TEE) can be taken as a preferred example of the non-metallic reducing agent ratios for use in conjunction with the catalyst material of the invention. Based again on a catalyst material containing about 1 weight percent chromium, based on the weight of the support, the preferred amount of TEB is about 5 percent by weight based on the weight of the support, giving an atomic ratio of boron to chromium of about 2.7: 1. The preferred range of boron to chromium atomic ratios is from about 0.1: 1 to 10: 1 or from about 0.19 to about 19% TEB, The general useful limits, in terms of 790 5 2 94 10 of the ratio of boron to chromium are from about 0.01: 1 to about 20: 1, and in terms of weight from about 0.02 to about 38 percent, based on the weight of the support.

The preparation of catalysts according to the invention is described in the procedures given below.

(1) Preparation of non-volatile aluminum-containing reaction products of aluminum sec-butoxide and aluminum acetate.

Preparation example A

10 1 +, 1 + 3 g of aluminum acetate, 21.7 mmol, were placed in a flask together with 65.5 g of CHgClg. 5 * 3 µg aluminum sec-butoxide, 21.7 mmol, was added and the contents were heated under reflux under nitrogen. After heating under reflux for 3 hours, the clear gray solution was stirred at room temperature overnight. The volatiles were removed in vacuo to provide 9.30g of a clear viscous residue (0.00g weight loss based on non-volatile starting materials). When it is ascertained that there is no loss in the aluminum content, the residue contains the original 1 * 3 .3 mmol aluminum.

20 1 * 3.1 * mmol Al x 27 x 10 ~ 3 g Al% Al = -——- x 100% = 12.6% 9 »30 g residue * ^

Preparation example B

1.06 g (19.9 mmol) aluminum acetate, 5.15 g (20.9 25 mmol) aluminum sec-butoxide and 52.1 g toluene were combined as above. Within 15 minutes of the start of reflux, the acetate was dissolved to provide a pale yellow viscous solution. As the reflux heating progressed, the color became more intense, while the viscosity decreased. After heating under reflux for 6 hours, the volatiles were removed in vacuo to provide 7.78 g of a gray viscous residue (1.1 * 3 g weight loss) containing 11.1% aluminum.

Preparation example C

6.1 + 9g (31.8mmol) aluminum acetate, 7.92g (31.8mmol) aluminum sec-butoxide and 157.1 * g xylene were used. The acetate dissolved easily as reflux heating took place. The temperature of the refluxing volatile materials (head temperature) dropped to 130 ° C during reflux heating for 5 hours. Distillation of 108 g of volatile material raised the reflux temperature to 138.5 ° C. 76.7 g of fresh xylene was added and the refluxing continued. After refluxing for 22 hours, 95.3 g of distillate was collected and after cooling, the remaining volatiles were removed in vacuo. The viscous gray residue weighed 9.13 g (5.28 g weight loss) and contained 18.8% aluminum.

10 Preparation example D

1.7 * g (23.2 mmol) aluminum acetate, 11.1 * 5 g (1 * 6, U mmol) aluminum sec-butoxide and 85.25 g xylene were used. As the cloudy mixture was heated, a yellow coloring developed.

At the boiling point, the cloudiness quickly disappeared to give a clear yellow solution. After refluxing for 5 hours, 26.7 g of distillate was removed (the head temperature rose from 135 to 138 ° C). No fresh xylene was added. After 22 hours of reflux, a gray color was evident and another 31.2 g of distillate was collected (the head temperature rose from 136.5 to 138 ° C). After cooling, the remaining volatiles were removed under vacuum.

The viscous gray-green residue weighed 12.17 g (1.02 g weight loss) and contained 15.1% aluminum.

Preparation example E

6.23 g (30.9 mmole) aluminum acetate, 15.22 g (61.8 mmole) aluminum sec-butoxide and 95.1 * g decalin were heated to reflux. A clear yellow solution was obtained at reflux (cup temperature 153 ° C). After heating under reflux for 2 hours, the yellow color had disappeared and an aqueous white solution was obtained (cup temperature 150 ° C). After heating under reflux for 5.5 hours, 37.8 g of distillate was collected (head temperature increased from 150 to 189 ° C).

After heating under reflux for 22 hours, a gray solution was obtained. 51.5 dest distillate was collected (cup temperature increased from 159 to 189 ° C). The remaining volatiles were removed in vacuo to give a white solid weighing 10.32 g (11.22 g weight loss) containing 2 * 1.2% aluminum.

The data for the reaction products of Preparation 79052 94 12 Examples A to E are listed in Table A below.

Table A

Reaction Mole Ratio Solvent, b.p. Ratio% Al in product (alkoxide / ° C (g volatile residue 5 acetate) constituents / g (theory acetate) tisch) a 1.0 ch 2 Cl 2 HO 0.2 12.6 B 1.0 toluene 110 0, 35 1Π, 2 C 1.0 xylene 1H0 0.81 18.8 10 D 2.0 xylene 1H0 0.85 15, 2,0 E 2.0 decalin 195 1.78 2Π, 2 * Starting mixtures contain 12.0% Al ( A, B and C) and 11.6 $ Al (D and E).

(2) Preparation of Heat Activated Catalyst A 15 A silica gel with a pore volume of about 2.5 ml per gram prepared according to U.S. Pat. No. 3,652,215 is added to a 200 ml three neck round bottom flask equipped with a stirrer, nitrogen inlet and y tube with water cooler. A nitrogen atmosphere is maintained during coating. Dichloromethane is then added to the flask containing the silica gel and stirring is started to ensure uniform wetting of the gel. A dichloromethane solution of the reaction product of CrO2 and triethyl phosphate, prepared according to US Pat. No. 3,985,676, is then added to the flask in an amount sufficient to provide a dry coated catalyst containing about 1% by weight of chromium. . The supernatant is removed by filtration, and the coated gel is dried in a rotary evaporator at about H0 ° C and a pressure of 20 td Ho mm Hg column.

Then, dichloromethane is added to the flask containing the supported chromium material prepared in the above step (about 8 g of dichloromethane per gram of silica gel) and stirring is started to ensure even wetting of the gel. A solution of dichloromethane and the non-volatile reaction product of the above Preparation Example A is prepared in a pressure equalizing dropping funnel and the funnel is attached to the stirred flask. The aluminum-containing solution is gradually added to the flask at a rate of about 10 g of solution per minute. After the addition of the solution 790 52 94 13 is complete, the suspension is stirred in the flask for about an hour. The supernatant is removed by filtration and the coated gel is dried in a rotary evaporator at temperatures up to about 10 ° C and a pressure of 20 to 10 mm mercury-5 column. The amount of aluminum compound added depends on the percentage of aluminum desired for the production of olefin polymers with specific properties necessary for certain end uses.

To heat-activate the catalyst material, the supported catalyst is placed in a cylindrical container and fluidized with dry air at a linear rate of 30 to 10 meters per hour under heating to a temperature of 900 ° C and held at this temperature for 6 hours. After cooling under nitrogen, the activated supported catalyst is recovered as a powder.

In the same manner as described above, the heat-activated catalysts (2) B to (2) E were prepared with each of the non-volatile aluminum-containing reaction products of Preparation Examples B to E.

In Table B, the catalysts (2) A to (2) E 20 were used in the polymerization of ethylene, with the following results: 79052 94 iu

Table B

Powder resin properties

Example Catalyst% Al-Hg MIa HLMI ^ HLMI / MI _ _ touring (Ufa) _ _ 5 I {2) A 3.7 207 2.0 160 80 II (2) A 3.7 828 k, 9 ^ 36 89 III (2) B 3.7 207 2.1 163 76 IV (2) B 3.7 828 3.5 260 7 ^ V (2) C 1.85 207 3.1 162 53 10 VI (2) C 1 , 85 828 3.7 211 57 VII (2) C 3.7 207 M 268 65 VIII (2) C 3.7 828 U, 3 389 91 IX (2) D 1.85 207 7.5 512 68 X ( 2) D 1.85 82 813.9 15 XI (2) D 3.7 207 30 XII (2) D 3.7 828 60 - - mi (2) e 1.85 207 1.0 96 96 XIV (2) E - 1.85 828 1.0 77 77 XV (2) E 3.7 207 1.3 122 92 20 XVI (2) E 3.7 828 1.0 76 75

a - Melt index, ASTM-D-1238, Condition E b - High load melt index, ASTM-D-1238, Condition P Reactor conditions 25 TE temperature - 100 ° C

Diluent - iso-butane

Reducer - 0.5 ml of triethyl borane in hexane / g catalyst (B / Cr f »3 to 1)

Ethefen - 10 mol% 30 Productivity - 300-600 g polyethylene / g catalyst.

The polyethylene resins obtained from the polymerizations listed in Table B were analyzed by gel permeation chromatography. The results are shown in Table C.

790 5 2 94 15

TABLE C

Polyethylene-MI M xlCf1 * 2) M 3) Μ / M

, 17 n w wa hars_ _ ____________ _________ ___

Example I 2.0 0. 3 3.80 8.8¾ Example III 2.1 0.93 6.35 6.83

Example VII U, 1 0.83 U, 6o 5.5¾

Example IX 7.5 0.62 6.0¾ 9.7¾

Example XI 30 0 9 2.89 5.90

Example XV 1.3 0.82 6.1¾ 7 ^ 9 10 Comparison1} 13 0.37 3.05 8.2¾ 1) Heat-activated reaction product of chromium oxide and triethyl phosphate and aluminum sec-butoxide modifier deposited on silica gel up to an aluminum content of 3.7% was used as a catalyst.

2) Mq is the number average molecular weight.

3) Mw is the weight-average molecular weight.

As can be seen from the above data, the polyethylenes produced with the catalysts of the invention generally have narrow molecular equilibrium distributions compared to the polyethylene produced with the comparison catalyst, as shown by the values for the ratio Μ / M in Table C. In addition, vn each of the polyethylenes prepared with the catalysts of the invention have a significantly different set of properties compared to those prepared with the comparative catalyst, as study of the demonstrated properties in Table C clearly shows. To substantiate the observed MI and the narrow molecular profile distribution, as well as the reproducibility of the present catalyst systems, reaction product D was resynthesized and used to prepare an identical catalyst system.

Slightly larger scale polymerizations were carried out.

The polyethylene resins obtained using catalysts of the invention were compared to polyethylenes prepared with catalysts heretofore used in the polymerization of olefins. The properties of the polyethylenes are shown in Table D.

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Claims (13)

Process for the preparation of an olefin polymerization catalyst system, characterized in that a) an organophosphoryl chromium reaction product of chromium trioxide and an organophosphorus compound is deposited on a solid inorganic support material; b) a non-volatile aluminum-containing product obtained from the reaction of an aluminum alkoxide and an aluminum carboxylic acid salt deposition on said carrier material; and c) activates the supported organophosphoryl chromium reaction product and non-volatile aluminum-containing reaction product in a non-reducing atmosphere at a temperature above about 300 ° C up to the decomposition temperature of the support material. Method according to claim 1, characterized in. That the organophosphorus compound is a compound of formula 1 or 2, wherein R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, but wherein at least one group R is different from hydrogen. 3. Process according to claim 1 or 2, characterized in that the non-volatile aluminum-containing reaction product is first deposited on the support material and the support thus treated is activated by heat in a non-reducing atmosphere at a temperature of at least about 130 ° C up to the decomposition temperature of the support and then the organophosphoryl chromium reaction product is deposited on the support and the thus treated support is reactivated by heat but at a temperature above about 300 ° C up to the decomposition temperature of the support. k. Method according to one of the preceding claims, characterized in that the carrier material contains silica gel. A method according to claim 4, characterized in that the silica gel is a silica xerogel having a specific surface area of 7905294 2 about 200 to about 500 m / g and a pore volume greater than about 2.0 ml / g, wherein the most of the pore volume is provided by pores with diameters from about 30 to about 60 nm. 6. Process according to any one of the preceding claims, characterized in that the organophosphoryl chromium reaction product is derived from the reaction of chromium trioxide and triethyl phosphate. 7. A process according to any one of the preceding claims, characterized in that the carboxylic acid is a lower aliphatic monocarboxylic acid, a process according to any one of the preceding claims, characterized in that the non-volatile aluminum-containing product is obtained from the reaction of aluminum sec-butoxide and aluminum acetate. 9. A method according to any one of the preceding claims, characterized in that a metallic and / or non-metallic reducing agent is added to the heat-activated catalyst, 10. Process according to claim 9, characterized in that the reducing agent is a metallic reducing agent selected from triethylamine, triisobutyl aluminum, alkyl aluminum halide, alkyl aluminum alkoxide, dialkyl zinc, dialkyl magnesium and metal borohydride. A method according to claim 9, characterized in that the reducing agent is a non-metallic reducing agent selected from alkyl boranes and boron hydrides. A method according to claim 11, characterized in that the alkyl borane is triethyl borane. Process according to any of the preceding claims, characterized in that the organophosphoryl chromium reaction product is present in an amount sufficient to provide from about 0.25 to about 2.5% by weight of chromium, based on the weight of the support material and the deposited non-volatile aluminum-containing compound is present in an amount sufficient to provide about 0.10 to about 10 weight percent aluminum, based on the weight of the support material. 1U. Olefin polymerization catalyst system obtained by the method of any of the preceding claims. A process for polymerizing an olefin, characterized in that the olefin is contacted with a catalytic converter system obtained according to the process of any one of claims 1 to 13. Process according to claim 15, characterized in that hydrogen gas is present in the reaction medium. A method according to any one of the preceding claims, characterized in that the olefin is ethylene. 18. Methods and articles essentially as described in the description and / or the examples. , 79052 94 O OH II I RO — P — OR RO — P - OR OR Γ '^ / RM “Al_ ^ 3 ai (ooor") 3 4 7905294 NATIONAL PET EO CHEMICALS CORPORATION, New York, New York, Ver. St.v.America. V \