DE2820860A1 - CATALYST CARRIER - Google Patents

Description

The invention relates to the production of special polyolefin resins, particularly of single reactor blow molding resins. The invention particularly relates to a catalytic one Process for the selective production of polyethylene resins with controlled properties, e.g. certain melt rheological Properties.

Moldings and especially blown articles such as bottles are usually made from polymers of 1-olefins, e.g. Polyethylene. It is important to the commercial use of a given polymer system that the converted Product, e.g. the bottle, an optimal balance of properties, e.g. an acceptable durability against stress cracking and flexural rigidity. Furthermore, it is necessary that the poly

809848/0727

TEiLZ = F-ON

TEU ^ JC OH-Q t: \ HCt

mere has a suitable workability, ie a satisfactory Theological Behavior _: when flowing and a satisfactory deformation during manufacture. Although the viscoelastic behavior of polymer melts has been the subject of extensive studies, it has not been possible to establish a relationship between the behavior during manufacture and the end use of the articles in such a way that the polymerization and especially the catalyst requirements can be selectively established . In addition, the behavior of the catalyst must also be measured with regard to the effectiveness or the productivity and the stability over an appreciable service life.

The use of chromium compounds in polymerization of olefins is well known. In U.S. Patents 2,825,721 and

2 951 816 states the use of CrO ^ based on inorganic Materials such as silica, alumina or combinations of silica with alumina are deposited and activated by heating to elevated temperatures, described for the polymerization of lefins. Although these catalyst systems for various polymerization processes, for example for the known particle-forming Processes that are used are the resins made with them, although they are suitable for many uses, Cannot be used for other purposes because they have certain properties, such as the melt index, Show deficiency.

Improved supported chromium-based catalysts are also known and are used in particular in the US patents

3,984,351 and 3,985,676. Such catalysts allow the production of resins with improved flow properties and shear response properties. It has

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however, these products proved difficult to use technically, without product segregation or resin mixing occurring, which is due to variations in theological properties of the polymer produced is due. This applies in particular to the manufacture and in particular to the Blow molding, for example for collectors or collector-ramming devices.

An investigation of this phenomenon using the now classic measurement methods of the Harz shear response (HLMI / MI values, determined according to ASTM-D-1238, conditions F / E) give no obvious reason for the different behavior of these resins in manufacturing facilities. Empirical Research has suggested that a more precise viscosity analysis is required in order to select resins that will do this are suitable to result in shortened cycle times or in some other way in selected blow molding devices to have improved behavior. It has been found that such determinations can be made using the viscosity ratio Eta ^ / Eta ^ QQQ can be made with the included Area is expanded. The range from 1 to 1000 reciprocal seconds is expressly included. These values result a correlative measure of the critical end-use behavior, as described in more detail below will. Furthermore, the selection of resins is permitted which are suitable for such blow molding devices, such as collectors or collector-ramming devices, are suitable.

Further investigations into the variability of certain chromium-catalyzed Resins in terms of viscosity ratio allow the identification of factors of production that are critical for the controlled production of resins with the desired properties.

809848/0727

In US Patents 3,231,550 and 3,242,099 poly (hydrocarbyl aluminum oxides) which have been prepared by reacting water with an organohydrocarbyl aluminum compound are. These are reacted with transition metal compounds, e.g. chromium compounds, and used as olefin polymerization catalysts used.

US Pat. No. 3,882,096 describes ethylene catalysts which consist of a support containing chromium oxide and the reaction product of water impregnated with an alkyl ester of titanium and heat activated.

In US Pat. No. 3,152,105, an alpha-olefin catalyst is composed from a carboxylic acid salt of chromium, water and an organoaluminum compound, described.

Modifications of silica gel for catalytic activity by Burwell in "Chemtech.", Pp. 370-377 (1974) and by Peri in »J. Cat. " 41, pages 227-239 (1976). In none of these publications, however, is the control of the Theological resin properties in the process for the polymerization of 1-olefins described, with a heat-activated Supported chromium catalyst is used.

It has now been found that the amount and type of aluminum values deposited on a supported catalyst critically control the properties. They can be used in a chromium catalyst system as a direct measure to obtain selective resin production in a controlled 1-olefin polymerization. The same effects can be can be obtained indirectly by having a fixed ratio of water to the aluminum compound during catalyst preparation trains and maintains.

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The invention is based on the discovery that variations in resin properties can be attributed to system water or moisture present in the course of catalyst preparation. Silica gel and other inorganic catalyst supports are known to be active adsorbents and they will rapidly take up significant amounts of water (dried silica gel with less than 0.5% water poured through 30.5 cm of water at 50-6 relative humidity and at 27 ° C , reaches a moisture content of 2%). Accordingly, the exposure to a humid atmosphere is conventionally controlled in the handling and the content of adsorbed water is usually within low limits such as a few% by weight so that the water does not constitute an appreciable element of the system. However, such handling measures have so far allowed considerable variation within this range.

In the manufacture of general-purpose resins, there is a moisture variation in the catalyst manufacturing system no noteworthy differentiation of the resin properties. However, it has now been found not to date contemplated differences in theological properties in certain critical applications, for example in bottle blow molding, using collector rams. Surprisingly it has been found that such resin variations have an effect on the moisture content of the catalyst preparation system can be traced back.

The selective behavior of the novel catalyst systems according to the invention can presumably have an effect on the morphology or stereoconfiguration the activated catalyst surface area relative to the aluminum species obtained in situ by controlled hydrolysis are formed, are returned. Presumably results

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AO

a number of compositional modifications from the hydrolysis reactions with residual moisture in the system. These modifications extend through varying steric configurations of the groups containing aluminum and they appear individually to permanent. You control selectively the polymerisation behavior after heat activation. It can thus selectively and a range of resin properties can be produced in a controllable manner, which is based on the control of water and aluminum contents in the catalyst preparation is due.

According to the invention, a catalyst is now made available, containing an inorganic oxide support maintained under controlled humidity conditions will. The aluminum treated carrier can be activated by being in a non-reducing atmosphere, for example an oxygen-containing atmosphere, to a temperature is heated above about 93.3 ° C to the decomposition temperature of the support material. It can be used directly as a hydrogenation or cracking catalyst, e.g. for the isomerization of hexane, with excellent activity, selectivity, stability and abrasion resistance can be used. Such materials can therefore be used as supports with other catalyst promoters can be used in a variety of catalyzed reactions. You can also directly for the isomerization, Reforming, cracking, polymerization, alkylation, dealkylation, hydrogenation, dehydrogenation or hydrocracking are used will.

Preferably, the support is coated with an aluminum compound and also with a catalytic element, viz a compound of a metal from the group of chromium, cobalt, nickel, vanadium, molybdenum and tungsten, and mixtures thereof, which are usually present as oxides, treated. Will be best

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a chromium-containing compound, in particular a chromium oxide or the organophosphorylchromium reaction product according to the US-PS 3,985,676 used.

In the most preferred embodiment of the invention, an organophosphoryl chromium reaction product is deposited on a silica gel with a high specific surface and with a controlled water content with a water-reactive aluminum compound deposited and the intermediate catalyst product so formed is heat activated for use.

The inorganic support materials suitable for the invention include those normally used in supported chromium catalysts for olefin polymerization and as described, for example, in US Pat. No. 2,825. Such carrier materials are, for example inorganic oxides of silicon dioxide, aluminum oxide, silicon dioxide-aluminum oxide mixtures, thorium dioxide, zirconium dioxide and comparable oxides. They are porous, have a medium specific surface area and they have surface hydroxyl groups. Preferred carrier materials are silica xerogels or xerogels, the silicon dioxide or silicic acid as Main ingredient included. Particularly preferred are the silica xerogels as described in US Patents 3,652,214, 3,652,215 and 3,652,216. These silica xerogels have a specific surface area in the range from 200 to 500 m / g and a pore volume of more than about 2.0 cm / g. A major part of the pore volume is provided by pores with diameters in the range from 300 to 600 S .

Such carriers are made with a regulated water content van up to 15 to 25% by weight, based on the carrier, preferably 0.25 to 6.0% by weight, provided. The carrier material

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Rial can be dried or humidified, for example by equilibrating with an atmosphere, until a selected water content is obtained. In general, water contents of considerably more than 3.5% by weight have little additional effect on the results obtained with low aluminum contents, for example 3.7%. Accordingly, lower levels are preferred for best system control. Higher water contents may be necessary with higher aluminum contents, for example 10%. Optimal results, ie an increased sensitivity of the resin differentiation, are ensured if the water content is regulated within the range of 0.25 to 6.0 ί 0.15% by weight for the preferred silica gel.

The aluminum-containing compound used herein is opposite Water reactive, i.e. it is subject to controlled hydrolysis through stages of partial hydrolysis (depending on the content of available moisture in the system versus that added Aluminum compound), which are related to the selected aluminum types and mixtures thereof can be. The aluminum compounds are also associated with the surface hydroxyl groups of the inorganic support material as the reaction products are reactive with water.

Preferred aluminum compounds can be given by the formula:

Al (X) a (Y) b (Z) c

in which X stands for R, Y stands for OR and Z represents H or a halogen, a has the value 0 to 3, b has the value 0 to 3, c has the value 0 to 3 and a + b + c is the same 3, and in which R is an alkyl or aryl group having 1 to 8 carbon atoms.

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Examples of such aluminum compounds are aluminum alkoxides, such as aluminum sec.-butoxide, aluminum ethoxide, aluminum isopropoxide, Alkyl aluminum alkoxides, such as ethyl aluminum ethoxide, methyl aluminum propoxide, diethyl aluminum ethoxide, Diisobutyl aluminum ethoxide etc., alkyl aluminum compounds, such as triethyl aluminum, triisobutyl aluminum etc., alkyl or Aryl aluminum halides, such as diethyl aluminum chloride, aryl aluminum compounds, such as triphenyl aluminum, aryloxy aluminum compounds ,. such as aluminum phenoxide, and mixed aryl, alkyl and aryloxy-alkyl aluminum compounds.

To prepare the preferred polymerization catalysts, the support is pre-treated with a chromium-containing compound the heat activation treated.

The chromium containing compounds useful in the invention include any chromium containing compound capable of reacting with the surface hydroxyl groups of an inorganic support. Examples of such compounds include chromium trioxide, chromate, such as the disabled di-tert-polyalicyclic chromate, Silylchromatester and phosphorus-containing chromate according to the US-PS ¹ en 3642749 and 3704287 and Organophosphorylchromverbindungen, for example according to US-PS 3 985 676. This is the reaction product of chromium trioxide with an organophosphorus compound of the formula:

0 OH

RO-p-OR or RO-P-OR OR

where R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, but at least one R has a meaning other than hydrogen Has. The preferred organophosphorus compounds are Trialkyl phosphates such as triethyl phosphate.

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The new catalyst according to the invention can in the manner be prepared that the chromium-containing compound and the aluminum compound on the inorganic support in in any suitable manner, for example by vapor coating or by impregnation of the support with solutions of the chromium-containing compound and the aluminum compound in a suitable inert solvent, the is usually an anhydrous organic solvent. Examples of such organic solvents are cycloalkyl and alkylaryl aliphatic hydrocarbons and their halogen derivatives. A particularly preferred organic The solvent is dichloromethane. The chrome and aluminum compounds can be applied together or individually.

In the usual way of preparing the catalyst, the carrier is first with the chromium-containing compound and then impregnated with the aluminum compound. For an optimal reproducibility, the application is the most important an anhydrous organic solvent preferably by impregnation, with about 1 to 2 pore volumes of a solvent, such as methylene chloride can be used.

When an organophosphoryl chromium compound is disclosed in U.S. Pat 3,985,676 is used, then it is preferred to use the special catalyst preparation techniques described there. In such a case, the Organoaluminum compound can be applied to the catalyst support under conditions similar to those used for the deposition the organophosphoryl chromium compound applied.

It has been found that the most effective catalysts are those which contain the chromium compound in such an amount that the amount by weight of chromium based on weight

809848/0727 ORiGjNAL inspected

of the carrier, about 0.25 to 2.5%, preferably about 0.5 to 1.25%, although amounts outside of these ranges are also possible still give suitable catalysts. The aluminum compound should be added in sufficient amounts that about 0.1 to 10% by weight of aluminum, based on the weight of the carrier, preferably about 0.5 to 5.5%, although Catalysts which can also be used in amounts outside of these ranges can be obtained.

After the chromium-containing compound and the aluminum compound have been deposited on the inorganic carrier, the carrier is heated in a non-reducing atmosphere, preferably in an oxygen-containing atmosphere, to a temperature above about 93.3 ° C. to the decomposition temperature of the carrier. Typically, the Trägerzusainmens et tongues are at a temperature from 427 to 1093 ⁰ C heated. The heating time can vary, for example, from 1/2 hour or less to 50 hours or more, depending on the temperatures used. Typically, the heating is carried out 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 should preferably have been dehumidified to a few parts per million (ppm) water in order to obtain maximum catalyst activity. Typically the air used is dried down to less than 2 to 3 ppm water.

Although anhydrous solvents are used in the deposition and dehumidified air for drying or for heat activation in practice, a control of the moisture on the carrier has proven to be sufficient to prevent the To achieve objects of the invention. With a constant carrier water content it is of course also possible to adjust the moisture content in the solution

809848/0727

treatment systems are in place. The time of reaction or alternation reaction of the aluminum compound appears not to be critical. The deposition is normally carried out under ambient conditions, for example in a conventional Mix Coater, performed.

The 'catalyst can also be prepared in such a way that the catalyst is separated after each separate component has been added activated.

The absolute content of the aluminum compound and the ratio of water to aluminum compound is controlled for Polymerization according to the invention is considered important. In general, the proportion of the aluminum compound can be about 0.1 to 10% by weight, based on the support, preferably 0.35 to 5.5%. It shows up at a constant moisture content in the preparation when used by the reduced molecular weight of the aluminum content and by an increased Molecular weight distribution as measured by melt index values of the resin produced. The molar ratio of water to aluminum can vary from a substantially anhydrous system to about 4.0, preferably 0.5 to 2.0, where lower values with a lower molecular weight and an intermediate shear response or molecular weight distribution in association with.

The proportions of water and the aluminum compound are herein expressed as percent by weight based on the aluminum containing carrier, and expressed as the molar ratio of water on the aluminum containing carrier to aluminum. These Values can be easily calculated, however, for the sake of simplicity, reference is made to the following table.

809848/0727

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2820360

- 1th -

The control of these respective variables under otherwise equivalent operating conditions results in a response selection of the resin properties. However, as mentioned above, the differentiation of the resin properties - albeit for the manufacturer critical - can only be traced back to the use of specialized melt viscometry measurements. Certain Manufacturing facilities, for example a collector-ram-flow device, are responsive to a melt rheology which has higher shear rates and different Shear rate responses are related as they are using conventional melt index measurements can be set.

For the purposes of the invention, the melt viscosity is measured directly as "Eta" at shear rates of 1 and 1000 reciprocal. The shear response is expressed as the viscosity ratio Eta ^ / Et expressed. This measurement provides a reliable tool to reproducibly determine the rheological properties of the Bring resin with the requirements for production in relation. Show lower ratios of water to aluminum as lower Eta values (molecular weight) and as intermediate viscosity ratios (broadest shear response or the molecular weight distribution is shown with an intermediate ratio of water to aluminum). Lower absolute aluminum contents show up as increased Eta values and lower viscosity ratios at constant values Ratios of water to aluminum.

Specific resins can therefore be used for the respective application, for example with regard to the shear value and the response, can be tailor-made by the ratios from water to aluminum and the content of the aluminum coating can be controlled.

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2820360

Best results have been obtained with the organophosphorylchromium reaction product on Polypor silica gel for a collector ram blow molder at an absolute aluminum value of 0.596 and a molar ratio of water to aluminum of 0.5. The resins thus prepared showed a viscosity ratio of about 37 to 43 under standard conditions (1 ppm TEB, about 1 wt% Cr and H ₂ 0.3 to 0.7 mol%). It is apparent that the shape of the molecular weight distribution curve and therefore the shear response for a given average molecular weight can be easily controlled by those skilled in the art according to the invention.

The heat-treated, carrier-deposited chromium and aluminum compounds of the invention can be used in combination with metallic and / or non-metallic reducing agents are used to create new catalyst systems for polymerization of olefins. Examples of suitable metallic reducing agents are trialkylaluminum compounds such as Triethyl aluminum, triisobutyl aluminum, alkyl aluminum halides, Alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium and metal borohydrides, for example those of the alkali metals, especially of sodium, lithium and potassium, and those of magnesium, beryllium and aluminum. The non-metal 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.

For example, for a catalyst composition containing about 1 wt% Cr based on the weight of the support, the preferred amount of an organometallic reducing agent such as triisobutyl aluminum (TIBAL) is about 11.4 wt% and an Al / Cr -Atom ratio of about 3: 1 equivalent. The preferred range of atomic ratios of Al to Cr is about 0.5: 1 to about 8: 1 or about 1.9 to about 30

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TIBAL. The total practical limits of TIBAL, expressed as the Al / Cr atomic ratio, are about 0.1: 1 to 20: 1. In In terms of weight, they are about 0.4 to about 75 wt .- ^.

The heat-treated chromium-containing compound deposited on a carrier and aluminum compound can be mixed with metallic or non-metallic reducing agents are combined before going into an olefin polymerization reactor or these two components can be fed separately into an olefin polymerization reactor.

A fairly wide latitude is available in proportioning the amount of metallic or non-metallic reducing agent to the amount of chromium compound used in the catalyst system of the invention. However, certain guidelines have emerged which are consistent with good yield, favorable polymer properties and economical use of the materials. When using metallic and / or non-metallic reducing agents with an amount of the chromium compound which is sufficient to give about 1 % by weight of Cr of the support, the parameters given below are representative, for example. The atomic ratios are based on a calculation of the metal in the metallic reducing agent and / or the non-metal in the non-metallic reducing agent versus the chromium content present in the chromium compound on the carrier.

Another example of an organometallic reducing agent for use in connection with the invention The catalyst composition is triethylaluminum. If, in turn, a catalyst composition with about 1 wt .-% Cr, based on the weight of the support, then the preferred amount of triethylaluminum (TEA) is about 6.6 Gev /, -%,

809848/0727

based on the weight of the support, giving an Al / Cr atomic ratio of about 3 t 1 is obtained. The preferred range of atomic ratios of Al to Cr is about 0.5: 1 to about 8: 1 or about 1.1 to about 18 weight percent TEA. The total practical limits of TEA, expressed as the Al / Cr ratio, are about 0.1: 1 to 20: 1 and, in terms of weight, about 0.22 to about 44 weight percent.

Triethylboron (TEB) can be taken as a preferred example of the preparation of a non-metallic reducing agent for use with the catalyst composition of the present invention. Again, based on a catalyst composition containing about 1 wt% Cr based on the weight of the support, the preferred amount of TEB is about 5 wt .-% 6 based on the weight of the support, creating a B / Cr Atomic ratio of about 2.7: 1 is obtained. The preferred range of atomic ratios of B to Cr is about 0.1: 1 to 10: 1 or about 0.19 to about 19% TEB. The overall practicable limits, expressed as B / Cr ratio, are from about 0.01: 1 to about 20: 1 and in terms of weight, about 0.02 to 38 wt -%, based on the weight of the carrier..

As stated above, the preferred catalyst compositions according to the invention in conventional polymerization processes for olefins, especially 1-olefins having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, either alone or can be present as a mixture, and used in their copolymerization with ethylenically unsaturated monomers, such as vinyl acetate, acrylonitrile or methyl methacrylate, with or without modifying agents, chain transfer agents or terminating agents and the like. Such a polymerization can be carried out under customary temperature and pressure conditions, for example at temperatures from about 40 to about 200 ^° C., before

809848/0727

atm to 70.3 preferably from about 70 to 11O ⁰ C, and pressures of about 14.1, preferably from 21.1 to 56.2 atm, as are commonly used in slurry or Teilchenbildungspolymerisationen.

The catalysts of the invention act in a unique way in the polymerization of 1-olefins, and in particular in particular when hydrogen is used in the polymerization zone. This establishes the relationship between the molecular weight and the molecular weight distribution modified in response to the hydrogen demand compared to catalysts, bsi where the water content is not controlled. The excellent hydrogen response, which turns out to be a low molar ratio from water to aluminum allows for a wider range of hydrogen contents while maintaining acceptable productivity. In addition, the shape of the molecular weight distribution curves with respect to the The shear response and the nozzle threshold properties are differentiated can be.

These properties are expressed in the behavior of the resins the end. So far it has been common practice and an industrial necessity to have the necessary Theological Properties for certain extrusion and deformation processes, in particular for blow molding, in such a way as to obtain resin products from more than one reactor as a combination of solution and particulate molding resins. According to the invention, a single resin, i.e. the product, gives one "single reactor" directly the necessary theological properties.

In the examples, preferred ways of carrying out the preparation of the new catalysts according to the invention and the Use of such catalysts for the production of poly-

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Ethylenes with modified and controlled theological Properties described.

The indicated melt viscosities are measured using an Instron capillary rheometer determined at 190 ° C and shear rates of 1 to 1000 reciprocal see. The viscosity ratio given is the ratio of Eta./Eta^QQQ, based on the 1 and 1000 reciprocal Second value. The absolute values are given as poise.

The melt indexes were determined according to ASTM-D-123S, conditions E (MI) and F (HLMI) are determined and the HLMI / MI ratios are determined measured over a 1OX shear rate range only.

Water determinations were made in a standard manner using a titration technique in pyridine with Karl Fisher reagent. The values are calculated on the basis of the weight based on the aluminum-containing carrier.

The "single reactor" resin according to the invention has a melt index of up to about 0.4, a viscosity ratio of 35 to 45 and values relating to melt strength, nozzle swell and the extrusion time, which are equivalent to otherwise comparable resin blends. This makes them special well suited for use in molding operations, for example for use as the sole resin in blow molding using a collector or collector rammer. These facilities are critical for theirs Behavior towards the cycle time and the wall distribution as well as the trimming characteristics, the peak load values and the Surface properties of the manufactured article known.

For blow molding, a resin can be made which has a density of 0.953 to 0.955, a melt index of 0.25 to 0.40,

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a melt viscosity of 3.65 to 3.85 χ 1θ 'poise 1000 see ", a viscosity ratio of 35 to 45 and e nozzle swelling at 1000 see of 170 to 185%.

The following methods can be used to prepare the catalysts used in the present invention. as Examples are given of certain preferred embodiments:

The inorganic oxide support, for example a silica xerogel, having a pore volume of about 2.5 cm / g, prepared in accordance with US Pat. No. 3,652,215, is as described herein to a selected moisture content, usually at least 0.25 and 6.0% by weight - 0.15% by weight, adjusted by drying in nitrogen at an elevated temperature under vacuum or by humidifying in contact with a humid atmosphere. Then it is coated with the aluminum and the chromium compound or another catalytic material.

In the case of spray coating, the aluminum compound is, for example Aluminum sec.-butoxide, with a pore volume (relative to the silica gel) diluted by methylene chloride and added to a clean or chromium-coated support 32.2 ° C sprayed on over a period of 1 h (during this time three bed rotations are accomplished). The coated one The catalyst is dried for 2 to 6 hours at 112.8 ° C. in a vacuum of 25.4 to 38.1 cm Hg to remove volatiles to remove. In a preferred embodiment of this procedure, the aluminum compound has 2 pore volumes slurried by anhydrous methylene chloride and the solvent is removed by drying as described above, removed.

In a similar manner, vapor deposition can be carried out

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are held by the carrier is that "at a temperature of 204.4 ⁰ C, sprayed with the aluminum compound at 79.4 ⁰ C over a period of 1.5 hours and then the temperature for drying at 260 ° C increased, and holds there for 1 hour at a maximum vacuum.

The gel with regulated moisture content can also be used in simpler Manner in a suitable anhydrous solvent such as methylene chloride with the aluminum compound and the chromium compound Can be slurried and then dried to remove volatiles. The dried catalyst may be with untreated silica gel, silica gel coated with the chromium compound, or another Support material are mixed if a further adjustment of the ratio of water to aluminum is desired, and in particular to calculated values of water, based on the aluminum-containing carrier, of less than 0.4% by weight 6.

For heat activation of the catalyst, the catalyst deposited on a support is whirled up with dry air at a linear speed of 0.06 m / min and ^{heated to a temperature of 900 °} C. in the process. This temperature is maintained for 6 hours. The activated catalyst deposited on a support is obtained as a powder.

example 1

Silica gel having a pore volume of about 2.5 cm / g, made in accordance with US Pat. No. 3,652,215, is placed in a 2000 ml three-necked flask given, equipped with a stirrer, a nitrogen outlet and a y-tube with a water condenser is. A nitrogen atmosphere is created during the coating process maintain. Dichloromethane is then added to the flask containing the silica gel and

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it is stirred, doing so to ensure a uniformly moistened gel. A dichloromethane solution of the reaction product of CrO with 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 weight percent of Cr. The supernatant liquid is filtered off and the coated gel is dried in a rotary evaporator at 6O ⁰ C and a vacuum of 73.7 cm of Hg.

Dichloromethane is added to a similar flask as prepared above and stirring is started while maintaining a nitrogen atmosphere. The chromium composition deposited on a carrier prepared in the above manner is then placed in the flask. A solution of dichloromethane and aluminum sec-butoxide is made up in a pressure equalizing addition funnel and the funnel is attached to the stirring flask. The aluminum sec-butoxide solution is gradually added to the flask at a rate of 10 g of solution per minute. When the addition of the solution is complete, the slurry in the flask is stirred for about 1 hour. The supernatant liquid is filtered off and the coated gel is dried up in a rotary evaporator at a temperature of from about 6O ⁰ C and a vacuum of 73.7 cm of Hg.

The deposited on a supported catalyst is placed in a cylindrical container and with dry air at a linear velocity of 0.06 m / sec swirled with heating at a temperature of 900 ⁰ C. It is held at this temperature for 6 hours. The activated catalyst deposited on a support is obtained as a powder.

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A series of polymerizations is carried out to obtain the To illustrate results obtained using a varying amount of the aluminum compound in the manufacture the catalyst content of 1% Cr at a constant water content in the carrier. The results obtained are compiled in Table II.

Unless otherwise stated, the polymerizations are carried out at 93.5 ° C. and with hydrogen (2.11 kg / cm) been. Triethylborane (2.7 B / Cr atomic ratio) was entered into the polymerization reactor.

Table II

Al, wt. # / SiO ₂ ( ¹ ) Productivity MI HIMI

(g polymers / g cat./h)

558 low 7.0

0.1 1328 0.04 9.1

0.2 717 0.05 11.4

1.0 780 0.36 67.5

2.4 926 1.10 116.5

3.7 886 2.68 340

5.5 ^ 616 4.90 390

(1) g Al per 100 g SiO ₂ carrier

(2) polymerization temperature 99 ° C; B / Cr atomic ratio 2.9.

Example 2

A chromium catalyst deposited on a support (1 wt .-? O Cr), prepared according to Example 1, the 1.85% Al as Aluminum sec.-butoxide (with 2 pore volumes of methyl chloride solvent-coated) on silica gel with varying water contents, as indicated, is added to the

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- 2h ~ -

Ethylene polymerization at 1 ppm TEB and varying hydrogen kept used to make an MI resin. the The results obtained are summarized in Table III:

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O - 25 -

^ Table III

N wt .-% water MI HLMI HLMI / MI viscosity ratio, hydrogen response nozzles%-V (HPO / Al molar) eta ₁ / eta ₁₀₀₀ Η _2/0? Ηλ molar ratio swelling

1000 see 0.1

0.5 (0.45) 0.20 28 146 55.4

0.6 (0.50) 0.17 29 151 56.1

1.3 (1.1) 0.16 24 142 60.6

2.5 (2.1) 0.21 27 129 53.8

0.07 172.5 0 176 0.033 165 0.35 162

Example 3

Further polymerization of ethylene is carried out at a temperature of 104.4 ⁰ C, a hydrogen content of 0.5 to 0.8 mol% (Ethylene = 6 to 8 mol #) to an MI resin having 0.30 Receive £ 0.5. 1 ppm of triethylborane is used. A heat activated catalyst composed of the organophosphorylchromium reaction product ( 3/4% Cr) and polypore silica xerogel (manufactured by National Petro Chemicals Corp.) having a water content of 0.5 to 0.6 is used. It is coated (2 pore volumes, methylene chloride) with 1.85 % by weight of aluminum as aluminum sec-butoxide and in a weight ratio of about 4: 1 with the same chromium-containing catalyst without added aluminum compound (nominal water content 0.5 to 0 , 6 wt. SS) in order to obtain a molar ratio of water (based on the aluminum-containing carrier) to aluminum of 0.5 and an aluminum content (calculated on the total carrier) of 0.5 wt.%.

The resin produced has a density of 0.953, a melt index of 0.3, a melt viscosity of 3.75 x 10 poise 1000 see "and a viscosity ratio of about 40. The resin shows a nozzle swell of 171% at 1000 see "* and it can can be used successfully without mixing in an accumulator-ram blow molding device, for example a Manufacture detergent bottle with 624 g, with comparable There are extrusion and cycle times to blended resins.

Example 4

A catalyst is made from the reaction product of CrO, and Triethy! Phosphate (manufactured according to US Pat. No. 3,935,676), from

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divorced with about 1 wt % Cr on silica xerogel

with a specific surface of about 300 m / g and a pore volume of about 2.5 cnrVg, which contains 7.4% water, and coated with 10 Gevr .-% aluminum as aluminum sea-butoxide (coatings with 2 pore volumes of methylene chloride ). It is dried and heat activated.

Ethylene is polymerized with this catalyst and triethyl boron at 99 ° C., 2.1 kg / cm H ₂ and a B / Cr ratio of 3.7, whereby a polymer with MI 8.2 is produced.

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Claims (17)

P 12,693 claims 1. Catalyst support, characterized in that it contains or consists of a silicon dioxide xerogel with a specific surface area in the range from 200 to 500 m / g and a pore volume of more than about 2.0 cm / g, a major part of the pore volume of pores are formed with diameters in the range of 300 to 600 2, wherein said xerogel contains 0.25 to 6.0 wt .- $ £ water and wherein the water content within - has been regulated 0.15 wt .-%. 2. ' Catalyst, characterized in that that it contains the catalyst support according to claim 1, which is reactive with a water-reactive aluminum compound has been coated and that it is in a non-reducing atmosphere at a temperature of about 93.3 ° C has been heat activated to the decomposition temperature of the support. 3. Catalyst according to claim 2, characterized that he stacked a compound of a metal from the group of chromium, cobalt, nickel, vanadium, Contains molybdenum, tungsten and mixtures thereof and that the coated catalyst is in a non-reducing atmosphere has been heat-activated at a temperature of 93.3 to 1093 ° C and for a period of 2 to 12 hours. 4. 'Catalyst according to claim 2 or 3, characterized in that it is stacked thereon the reaction product of CrO, which contains triathy! phosphate. 5. Process for the preparation of catalysts for polymerization of oc-olefins, the catalyst having a heat 809848/0727 ORIGINAL INSPECTED 2820060 contains activated porous inorganic support which has been coated with a chromium-containing compound and an aluminum-containing compound which is reactive towards water, characterized in that the compounds are deposited on the support prior to heat activation and that the total water content of the system is prior the heat activation within the range from 0.25 to 6.0 ί 0.15% by weight , based on the carrier. 6. The method according to claim 5, characterized in that that an organophosphoryl chromium reaction product is used as the chromium-containing compound. 7. The method according to claim 6, characterized in that that the reaction product is the product of CrO and triethyl phosphate. 8. The method according to any one of claims 5 to 7, characterized in that there is used as a carrier a silica xerogel with a specific surface area in the range from 200 to 500 m / g and a pore volume greater than about 2.0 cm / g is used, with the majority of the pore volume being pores with diameters in the range of 300 to 600 S. is formed. 9. Process for the production of polyolefin resins by Polymerization of at least one 1-olefin at an elevated temperature and pressure in a polymerization zone which is a catalytic amount of a polymerization catalyst for the 1-olefin contains, characterized in that the catalyst used is a porous inorganic oxide support used which has been coated with a chromium-containing reaction product and an aluminum compound, and that that by reaction with a controlled amount of water 8098A8 / 0727 hydrolyzed aluminum compound has been heat-activated. 10. The method according to claim 9, characterized in that that a silica xerogel with a specific surface area in the range of 200 to 500 m / g and a pore volume of more than about 2.00 cm / g is used, with a major part of the pore volume being through Pores with diameters in the range of 300 to 600 S is formed. 11. The method according to claim 9 or 10, characterized in that the heat activation in a non-reducing atmosphere at a temperature of 93.3 ° C to the decomposition temperature of the support. 12. The method according to any one of claims 9 to 11, characterized in that there is used as chromium reaction product containing an organophosphoryl chromium-containing compound is used. 13. The method according to any one of claims 9 to 12, characterized in that the amount of water present within the range from 0.25 to 6.0 wt ί 0.15 - regulated.%. 14. One reactor blow molding polyethylene resin with a Density from 0.953 to 0.955, a melt index from 0.25 to 0.40, a melt viscosity from 3.65 to 3.85 χ 10 ^ poise at 1000 sec, a viscosity ratio of 35 to 45 and a nozzle swell at 1000 see "" ¹ of 170 to 185? $. 15. Resin according to claim 14, characterized in that it is polymerized by catalytic ^ of ethylene in the presence of a chromium-containing catalyst 809848/0727 -Ot This catalyst contains an aluminum compound which is reactive towards water on a porous inorganic oxide support, the aluminum content being 0.1 to 0.5% by weight , based on the support, the water content of the support being 0.5 to 0.8 moles of water per mole of aluminum and wherein the catalyst has been heat-activated in a non-reducing atmosphere at a temperature of 93.3 ° C to the decomposition temperature of the support. 16. Resin according to claim 15, characterized in that the chromium catalyst is an organophosphorylchromium reaction product and that the carrier is a silica xerogel with a specific surface area of 200 to 500 m / g, a pore volume greater than about 2.0 cm / g, with a major portion of the pore volume being provided by pores with diameters is formed in the range of 300 to 600 S. 17. Method of making blow molded containers in collector ram blow molding equipment in conventional Polyethylene resin conditions characterized in that the single reactor blow molding resin is used as the only resin according to claim 14 used. 809848/0727