Process for the preparation of a catalyst component and components therefrom obtained

Process for the Preparation of a Catalyst Component and Components Therefrom Obtained

Background of the invention

This present invention relates to a process for preparing a component in a catalyst for the polymerization of olefin compounds CH2=CHR, where R is a hydrogen or hydrocarbon moiety having from 1 to 12 carbon atoms. In particular, the present invention relates to a process for preparing catalyst components loaded on Mg dichloride further comprising a compound containing Ti and an electron donor, as well as to certain catalyst components obtained therefrom. These catalyst components, when converted into a catalyst, are particularly suitable for the preparation of copolymers of ethylene with alpha-olefins due to their ability to uniformly distribute the alpha-olefins along the polymer chain and between different polymer chains.

Catalysts containing titanium compounds loaded with magnesium halides are well known in this field. For example, catalysts of this type are described in US Patent No. 4,298,718. These catalysts include titanium tetrahalides loaded on magnesium halides. Although the catalysts have great activity in the alpha-olefin polymerization of alpha olefins such as propylene, they do not have great stereospecificity. Fundamental improvements in stereospecificity have been achieved by adding certain electron donor compounds to the solid component of the catalyst.

Modern methods used in preparing these catalysts include starting by making contact between MgCl2, or the material that produces it, with an electron donor compound and a compound containing titanium (usually TiCl4), and then performing one or more treatments of the solid material obtained in this way using a liquid. Hot from TiCl4. Examples of this process are disclosed, among others, in European Patent No. 491566. These processes provide catalyst components that are highly active and stereospecific for propylene polymerization in general, but have some drawbacks. For example, with this type of process, it is difficult to achieve precise control of the final amount of donor material since successive treatments using hot TiCl4 waste a large part of it. Furthermore, certain types of electron donor materials are not stable during hot treatments with TiCl4. These disadvantages are particularly relevant to certain types of propylene catalysts that require a large amount of donor material to function efficiently.

Among the types of catalyst preparation processes capable of immobilizing large amounts of the donor material on a catalyst component, one can mention, for example, those processes described in US Patent No. 4,521,573, which include the use of a large increase of the electron donor compound that acts as a solvent for MgCl2 and the titanium compound. . The catalyst component can then be separated from the solution by precipitation or crystallization. This process suffers from many shortcomings. The first is that some donor materials cannot be used because, in light of their chemical composition, they are not able to act as solvents, and the second is that a high-porosity catalyst component cannot be prepared unless a large amount of the donor material is removed from the aforementioned catalyst component or the catalyst in turn is deposited on it. Porous inert carrier material. However, in the latter case, an additional step and the use of additional materials are required, resulting in process complexity and increased costs. Another drawback is that the polymerization activity exhibited by these catalysts is generally relatively low.

In European Application No. 156 452, a catalyst prepared in accordance with the procedure comprising one or more pretreatments with an excess amount of hot TiCl4 after the addition of the donor material is further treated, using an additional electron donor compound in the presence of a high molar amount of AlEt3. However, this method would not be viable due to the mainly increased content of electron donor material in the catalyst component, since it would bring the catalyst component itself into contact with very large amounts of a highly active compound (AlEt3), which would significantly alter , of the properties of the pre-formed catalyst component.

Therefore, it will be important to find a suitable process for preparing a donor containing a catalyst component in which the donor content can be easily modified and where the catalyst component can also exhibit additional properties or retain those acquired from its basic components.

General description of the invention

Therefore, one feature of the present invention is a process for preparing a component of a MgCl2-loaded catalyst comprising the use of a compound containing Ti, an electron donor (ED) compound selected from alcohols, glycol compounds, esters, ketones, amines, amide compounds, nitrites, and alkoxysilanes, and aliphatic ethers as basic compounds, and this process includes two or more reaction steps that include the use of at least one of those basic compounds as a new reactant alone or in a mixture in which this reactant is the component This process is characterized by the fact that at the end of the one or more reaction steps mentioned above, the basic compound used as a new reactant is an electron donor compound (ED).

Another feature of the present invention is the catalyst components that can be obtained by the required process.

In the present invention, the expression “new reactant” means a quantity of a basic compound that comes into contact - for the first time - with the reaction mixture.

The expression “a mixture in which it is the main component” means that the basic compound must be the main component in terms of molar quantity, with respect to other possible compounds, excluding inert solvents or diluents used in handling that mixture.

Electron donor (ED) compounds can be used alone or in mixtures. The preferred esters are alkyl esters of C1-C20 aliphatic carboxylic acids, especially alkyl esters C1-C8 for aliphatic mono carboxylic acids, such as:

ethylacetate, methyl formiate, ethylformiate, methylacetate, propylacetate, i-propylacetate, n-butylacetate, i-butylacetate.

The preferred alkoxysilanes are those with the formula Ra5Rb6Si(OR7)C, where a and b are integers from 0 to 2 and c is an integer from 1 to 4 so that the sum of (c+b+a) equals 4, and R5, R6 and R7 are alkyl radicals. Cycloalkyl, or aryl, has from 1 to 18 carbon atoms and can contain chirality atoms. Among the particularly preferred compounds are silicon compounds, in which a is a 0 or 1, 2 is a 2 or 3, R6 is an alkyl or cycloalkyl group, and may contain heterogeneous atoms, and R7 is a methyl. Examples of these preferred silicon compounds include:

methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and t-butyltrimethoxysilane. The preferred alcohols are those with the formula R3OH, where the R3 group is a hydrocarbon group C1-C2O. Preferably, R3 is the alkyl group C1-C1O. Specific examples are methanol, ethanol, isopropanol, and butanol.

The preferred amines are those with the formula NR43, where the R4 group, each separately, is a hydrogen, or the C1-C20 hydrocarbon group, provided that they are not all hydrogen at the same time. Preferably, R4 is an alkyl group Cl-Cl0. Specific examples are dietilamine, diisopropylamine and triethylamine.

The preferred amides are those with the formula R5CONR62 in which R5 and R6, each individually, represent a hydrogen or hydrocarbon group C1-C2O. Specific examples are formamide and acetamide.

The preferred nitrite compounds are those that have the formula R3CN, where R3 has the same meanings mentioned above, and the specific example is acetonitrile.

The preferred glycol compounds are those with a total number of carbon atoms of less than 50. Among them, A,2 or 1,3 glycol, which has a total number of carbon atoms of less than 25, is particularly preferred. Specific examples are ethylenglycol, 1,2- propylenglycol and 1,3-propylenglycol. .

The preferred ED compound is chosen from among amide compounds and alkoxysilanes.

Among the suitable titanium compounds, we can mention tetrahalides or compounds with the formula TiXn(OR`)4-N, where 3 ≤ n ≤ zero, x is a halogen, preferably chlorine, and R` is a C1-C10 hydrocarbon group. Titanium tetrachloride is the preferred compound.

In the catalyst components obtained from the process of the invention, MgCl2 is the primary carrier even though small amounts of other carriers are present. MgCl2 can be used by reacting with halogenated compounds. It is particularly preferable to use MgCl2 as it is, or to obtain it from Mg compounds used as its producing materials that can be converted into MgCl2 in a widely known active form published in previous patents as a carrier material for Ziegler-Natta catalysts. US Patents Nos. 4,298,718 and 4,495,338 were the first patents to describe the use of a Ziegler-Natta catalyst. It is known from these patents that magnesium dihalides in the active form used as a carrier or auxiliary carrier in the components of polymerization olefins catalysts are characterized by an And it expands. In the X-ray spectrum of magnesium dihalides detailed in an active form, those lines with maximum intensity disappear and are replaced by a halide compound, with a shift of its maximum intensity towards smaller angles relative to those of the lines with maximum intensity.

In this basic form, the process of the present invention is simple to implement. In fact, it involves firstly making contact of the titanium compound and a Mg compound, preferably magnesium halides, optionally in the presence of an inert medium, so that an intermediate product can be prepared, containing the titanium compound loaded with Mg dichloride, which can be isolated if desired.

After that, the ED compound can be brought into contact with this intermediate product so that it is added to the reaction mixture alone or in a mixture with other compounds in which it represents the main component in terms of molecular quantity. The processed ED product can then be subjected to a washing process using appropriate solvents so that the final product can be recovered. If desired, treatment with the desired ED compound can be repeated one or more times. If preformed MgCl2 is used as a starting compound, it should preferably be in the active form. US patents 4,298,718 and 4,495,338 describe how MgCl2 can be obtained in active form. The titanium compound is preferably titanium tetrachloride.

In this basic process, many changes can be made whose purpose is to impart specific properties to the catalyst or to the process itself. Therefore, as previously mentioned, the Mg dihalide can be used as the base Mg compound. It can be chosen, for example, from among the Mg compounds with the formula MgR`2. Where R` groups can be C1-C2O hydrocarbon groups and can have optional substitution, OR groups, OCOR groups, or halogen groups, where R` are C1-C2O hydrocarbon groups with optional substitution, provided that they are not R` groups They are all halogen at the same time, which is an obvious condition, of course. Suitable compounds as production materials include Lewis addition compounds between Mg dihalide and Lewis bases. A special and preferred group has been formed by the addition compounds MgX2(R``OH)m in which the R`` groups are hydrocarbon groups C1-C2O, preferably alkyl groups C1-C2O, x is halogen, preferably chlorine, and m is a number ranging between 0.1. 6, preferably between 0.5 and 3, and preferably between 0.5 and 2. In general, addition compounds of this type can be obtained by mixing alcohol with magnesium chloride in the presence of an inert hydrocarbon that does not mix with the addition compound, and stirring at the melting temperature of the addition compound (100-130 °C). The emulsion is then quickly quenched, and the additive compound solidifies into small particles. There are examples of the methods used to prepare these spherical addition compounds, for example, in US patents 4,469,648 and 4,399,054 and international patent 44009/98. Another useful method for vulcanization is spray cooling, which is described, for example, in US Patents Nos. 5,100,849 and 4,829,034.

Particularly interesting are the addition compounds MgCl2.(EtOH)m, with m between 0.15 and 1.7, which are obtained by subjecting addition compounds with a high alcohol content to a thermal dealcoholization process carried out in a stream of nitrogen at temperatures ranging Between 50 and 150 °C until the alcohol content is reduced to the value mentioned above. There is an explanation of a process of this type in European Patent No. 395083.

The process of removing alcohol can also be carried out chemically by contacting the addition compound with compounds capable of reacting with alcohol groups.

These dealcoholic additive compounds are generally characterized by porosity (measured by the mercury method) due to the presence of pores with a radius of up to 0.1 µm, ranging from 0.15 to 2.5 cm3/g, preferably between 0.25 and 1.5 cm3/g.

In general, MgX2(R``OH)m addition compounds are converted to the corresponding halide by a chemical with functional groups capable of reacting with OH groups. Among the special groups of substances that remove alcohol, aluminum compounds can be mentioned. Suitable alkyl aluminum compounds are trialkyl aluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tris(2,4,4-trimethyl-pentyl)aluminum. Mixtures of trialkyl aluminum compounds can also be used with:

alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3.

It is known that alkyl aluminum compounds can have reductive activity for Ti compounds. Accordingly, if this activity is not required, an activity reducing agent, such as O2, can be added before performing step (b), thus avoiding the reduction of the titanium compound.

There is another group of substances that remove alcohol, which are silicon compounds containing halogen. Specific examples of silicon compounds include silicon halides with the formula SiX4-nUn, where X and U represent halogen atoms, such as Cl and Br, and n is a number between 0 and 3. It is particularly preferable to use SiCl4.

In one particular embodiment of the present invention, it is preferable to carry out the alcohol removal reaction at the same time as the reaction step involving the use of the titanium compound. Accordingly, these addition compounds react with the previously mentioned TiXn(OR`)4-n compound (or potentially with mixtures thereof), which is preferably titanium tetrachloride. The reaction with a titanium compound can be carried out by suspending the addition compound in TiCl4 (which is generally cold), heating the mixture to temperatures ranging between 80 and 130 °C, and keeping it at that temperature for a period ranging between 0.5 and 2 hours. Titanium treatment can be performed one or more times. It is preferable to repeat it twice. It can also be implemented in the presence of electron donor compounds such as those mentioned above. At the end of the process, the solid is recovered by separating the suspension by conventional methods (such as agitation, deliquidation, filtration, and centrifugation) and can be subjected to washing with solvents. Although washing operations are typically carried out using inert hydrocarbon liquids, polar solvents (e.g. with a high dielectric constant) such as halogenated hydrocarbons can also be used.

The intermediate solid compound obtained in this way can be subjected to subsequent treatment using special compounds suitable to give it certain characteristics. For example, it can be subjected to treatment with a reducing compound such as an Al-alkyl compound, to reduce the oxidation state of the titanium compound present in the solid material.

Another example of the treatments that can be performed on the intermediate compound is the polymerization step. The pre-polymerization step can be carried out using any olefin compound CH2 = CHR, where R is H or the hydrocarbon group Cl-Cl0. In particular, it is preferable to prepolymerize ethylene, propylene, or mixtures thereof using one or more alpha-olefins. These mixtures contain up to 20% moles of alpha-olefin, forming amounts of polymer from about 0.1 g to about 1000 g per gram. Of the intermediate solid compound, preferably from about 0.5 to about 500 grams per gram of intermediate solid compound. The prepolymerization step can be carried out at temperatures ranging between 0 and 80°C, and preferably between 5 and 70°C, in the liquid or gas phase. It is particularly preferable to pre-polymerize the intermediate compound using ethylene and propylene so that an amount of polymer ranging between 0.5 and 20 grams per gram of intermediate compound can be produced. Prepolymerization is performed using a suitable catalyst such as organolithium compounds which can also be used in combination with one or more external donor materials which will be discussed later in detail.

As previously mentioned, the intermediate compound is then brought into contact with the electron donor compound under conditions that make it possible to fix a sufficient amount of the donor material on the solid. Due to the great versatility of this method, the amount of donor material used can vary greatly. As an example, they can be used with a molar ratio relative to the Ti content in the intermediate compound between 0.5 and 20, preferably between 1 and 10. Although it is not inevitable, the contact is carried out in a liquid medium such as a liquid hydrocarbon. The temperature at which contact occurs can vary according to the nature of the materials. In general, it falls in the range from 10°C to 150°C, preferably between 0 and 120°C. It is known that temperatures that cause decomposition or breakdown of any specific reactant must be avoided, even if they fall within the generally appropriate range.

The processing time may also vary according to other conditions such as the nature of the reactants, temperature, concentration, etc. In general, this contact step can last between 10 minutes and 10 hours, and most commonly between 0.5 and 5 hours. If desired, and in order to obtain a greater increase in the final content of the donor material, this step can be repeated once or several times. At the end of this step, the solid is recovered by separating the suspension by traditional methods (such as agitation, deliquidation, filtration, and centrifugation) and can be subjected to solvent washing. Although washing operations are typically carried out using inert hydrocarbon liquids, more polar solvents (e.g. having a higher dielectric constant) such as halogenated or oxygenated hydrocarbons can also be used.

In this case, the solid material obtained in this way can also be subjected to subsequent treatment with suitable compounds to give it certain characteristics. For example, it can be subjected to treatment with a reducing compound, such as alkyl aluminum compounds, in order to reduce the oxidation state of the titanium compound present in the solid material.

It has already been shown that various donor materials in large quantities relative to the titanium content can be used in the process of the invention. In general, all the catalysts obtained showed a good level of performance, especially in the autopolymerization of ethylene, and in its copolymerization with alpha-olefin C3-C10 to produce alpha olefin copolymers of ethylene containing up to 20 pmol% of alpha. olefin. Particularly interesting catalyst components include a Ti complex and an electron donor ED selected from:

alcohol, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers, and esters of aliphatic carboxylic acids

Loaded on MgCl2, where the molar ratio between ED and Ti ranges between 1.5 and 3.5, and where the molar ratio between Mg and Ti is greater than 5.5. It is preferable that the molar ratio between ED and Ti range between 3.4 and preferably between 2.2 and 3.3. It is preferable that the molar ratio between Mg and Ti range between 7 and 110, and it is preferable that it range between 8 and 80, and in particular it is preferable that it range between 8 and 50.

The preferred donor materials are those mentioned above. Moreover, aliphatic ethers are also preferred, especially C2-C2O aliphatic ethers. Preferably in cyclic ethers of 3-5 carbon atoms such as tetrahydrofurane (THF) or dioxane are particularly preferred.

Excellent results have been obtained using esters such as ethylacetate as an electron donor compound. Compounds with a dark composition that are also pre-polymerized are also preferred.

According to the present invention, the components of the solid catalyst are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum compounds according to known methods.

In particular, one of the objects of the present invention is to achieve a catalyst for the polymerization of olefins CH2=CHR, where R is a hydrogen or hydrocarbyl moiety having from 1 to 12 carbon atoms, and comprising the reaction product between:

(a) Solid catalyst component as previously explained,

(b) solid catalyst compound as previously explained,

(h) An external electron-donating compound.

It is preferable to choose an alkyl aluminum compound from trialkyl aluminum compounds, such as:

trimethylaluminum (TMA), triethylaluminum (TEAL), triisobutylaluminum (TIBA), tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum.

Alkylaluminum halides, especially alkylaluminum chlorides, can also be used, such as:

diethylaluminum chloride (DEAC), diisobutylalumunum chloride, Al-sesquichloride and dimethylaluminum chloride (DMAC)

It is also possible, in specific preferable cases, to use mixtures of trialkyl aluminum compounds with alkylaluminum halides. Among them, TEAL mixtures with DEAC and TIBA mixtures with DEAC are preferred.

The exogenous electron donor compound may be equal to or different from the electron donor compound used in the solid catalyst component. It is preferable to choose it from the group consisting of ethers, esters, amines, ketones, nitriles, silanes, and mixtures of the above. In particular, it can be advantageously selected from aliphatic ethers C2-C2O, especially from cyclic ethers, which preferably have from 3 to 5 carbon atoms, such as tetrahydrofurane and dioxane.

In addition, it is also possible, in a useful way, to choose the electron-donating compound from silicon compounds with the formula Ra5Rb6Si(OR7)C, where a and b are integers whose value ranges between 0 and 2, and c is an integer whose value ranges between 1 and 3, and where the sum of ( a+ b+ c) equals 4. R5, R6, and R7 are alkyl, cycloalkyl, or aryl radicals with 1 to 18 carbon atoms and may contain chirality atoms. Among the particularly preferred compounds are silicon compounds, in which a is a 0 or 1, 2 is a 2 or 3, R6 is an alkyl or cycloalkyl group, and may contain heterogeneous atoms, and R7 is a methyl. Examples of these preferred silicon compounds include cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane. The previous components from (a) to (c) can be fed separately into the reactor, where, under polymerization conditions, their activity can be exploited. However, it is a particularly useful model to pre-contact the aforementioned components, optionally in the presence of small amounts of olefins, for a period of between 0.1 and 120 minutes and preferably between 1 and 60 minutes. Precontacting can be carried out in a liquid diluent at a temperature between 0 and 90°C, preferably between 20 and 70°C.

The catalyst system formed in this way can be used directly in the main polymerization process, or alternatively it can be prepolymerized, especially if the intermediate solid has not been prepolymerized. The prepolymerization step is usually preferred when the main polymerization process is carried out in the gas phase. The prepolymerization step can be carried out using any olefin compound CH2 = CHR, where R is H or the hydrocarbon group Cl-Cl0. In particular, it is preferable to prepolymerize ethylene, propylene, or mixtures thereof using one or more alpha-olefins. These mixtures contain up to 20% moles of alpha-olefin, forming amounts of polymer from about 0.1 g to about 1000 g per gram. m of the intermediate solid compound, preferably from about 0.5 to about 500 grams per gram of the intermediate solid compound. The prepolymerization step can be carried out at temperatures ranging between 0 and 80°C, and preferably between 5 and 70°C, in the liquid or gas phase. The prepolymerization step can be carried out on-site as part of a continuous polymerization process, or separately in an independent batch production process. Batch prepolymerization of the catalyst of the invention using ethylene or propylene is preferred to produce an amount of polymer between 0.5 and 20 g per gram of catalyst component.

The pre-polymerized catalyst component can also be subjected to post-treatment with a titanium compound before use in the main polymerization step. In this case, the use of TiCl4 is particularly preferable. The reaction with a Ti compound can be carried out by suspending the prepolymerized catalyst component in a liquid Ti compound and optionally in a mixture with a liquid diluent, heating the mixture to a temperature of between 60 and 120°C and maintaining it at that temperature for a period of between 0.5 and 2 hours.

Examples of gas-phase processes, when it is possible to use the catalysts of the invention, are International Patent No. 21706/92 and US Patent 5,733987. These processes include a pre-contact step of catalyst components, a pre-polymerization step, and a gas-phase polymerization step in a reactor. One or more connected in series in a fluidized or mechanically stirred bed. In a special embodiment, the gas phase process can be carried out, in an appropriate manner, according to the following steps:

(1) Contact the catalyst components (a), (b), and optionally (c) for a period of time ranging from 0.1 to 120 minutes, and at temperatures ranging from 0 to 90 degrees Celsius, optionally.

(2) prepolymerizing with one or more olefins of the formula CH2=CHR, where R is H or a C1-C10 hydrocarbon group, up to the formation of amounts of polymer ranging from 0.1 to 1000 g per g of solid catalyst (a); And

(3) Performing gas-phase polymerization of gas-phase ethylene, or mixtures thereof with alpha olefin s CH2=CHR, in which R is a hydrocarbon moiety with 1 to 10 carbon atoms, in one or more fluidized or stirred bed reactors. Mechanically, in the presence of the product resulting from step (1) or (2).

As previously mentioned, the catalyst of the present invention is particularly suitable for the preparation of linear low-density polyethylene (LLDPE, which has a density of less than 0.94 g/cm3) consisting of copolymers of ethylene with one or more polyolefin having from 3 to 12 atoms. Carbon, which has a mole content of ethylene-derived units greater than 80%. However, they can also be used to prepare a wide range of polyolefin products including, for example, polymers of high-density ethylene (HDPE, which has a density greater than 0.94 g/cm3), including homopolymers and copolymers of ethylene with its alpha-olefin 3 to 12 carbon atoms, elastomeric copolymers of ethylene for ethylene and propylene and elastomeric terpolymers of ethylene for ethylene and propylene with small amounts of diene containing a small weight percentage of ethylene-derived units ranging between 30 and 70%, and compounds Regular repeating polypropylenes and crystalline copolymers of propylene, ethylene and/or other alpha-olefin with propylene-derived units having a content exceeding 85% by weight, and impact-resistant polymers made of propylene obtained by sequential polymerization of propylene and mixtures of propylene with ethylene, which Containing up to 30% by weight of ethylene, copolymers of propylene 1-butene have a number of 1-butene derived units between 10 and 40% by weight.

The following examples are given to further explain the present invention in a way that is not limited to its scope.

Determine properties

Properties are determined according to the following methods:

Melting coefficient: Measured at 190°C according to ASTM-D 1238 - Condition E (load 2.16 kg), Condition F (load 21.6 kg).

The part that dissolves in xylene

The solubility of xylene was determined at 25 °C according to the following method: About 2.5 g of the polymer and 250 ml of xylene were placed in a round-bottomed flask equipped with a cooler and a reflector condenser and maintained in an atmosphere of nitrogen. The resulting mixture was heated to 135°C and continued stirring for approximately 60 minutes. The final solution was left to cool to 25°C with constant stirring, and the filtrate was then evaporated in a stream of nitrogen at 140°C to reach a constant weight. The content of that soluble fraction in xylene is expressed as a percentage of the original 2.5 grams.

Co-monomer content

1-butene was determined by infrared spectrophotometry.

Alpha-olefins higher than 1-butene were identified by infrared analysis.

Effective density: ASTM-D 1505

Thermal analysis: Thermal measurements were carried out using a differential scanning calorimeter. Perkin-Elmer DSC.

The device was calibrated with standard indium and tin samples. The weighed samples (5-10 mg), which were obtained from determining the "melting coefficient", were inserted into aluminum basins and closed tightly, their temperature was set at 5 °C for 3 minutes, and heated to 200 °C at a rate of 20 °C/min and maintained at This temperature is maintained for a sufficient period of time (5 minutes) to allow complete melting of all crystalline grains. Sequentially, after cooling at a rate of 20°C/min until 20°C. The maximum temperature was assumed to be the temperature of fusion (Tm) and the area was taken to be the total enthalpy of fusion (DH).

Determination of Mg and Ti: carried out by inductively coupled plasma emission spectrometry. (ICP).

Determination of Cl: carried out by potentiometric titration.

Determination of ED: by gas chromatography.

Detailed description

Examples:

The general procedure for preparing MgCl2 (EtOH) addition compounds in spherical form:

An additive compound of magnesium chloride and an alcohol containing moles of alcohol was prepared by following the method described in Example 2 of US Patent 4,399,054, but operating at 2,000 rpm instead of 10,000 rpm.

Addition compounds containing smaller amounts of alcohol (47 wt%, 35 wt%, 25 wt%, and 15 wt%) were prepared by heat treatment with a stream of nitrogen, at temperatures between 50 and 150 °C.

General procedure for preparing the intermediate compound of the solid catalyst component:

Into a 500 ml round flask with four holes, washed with nitrogen, 250 ml of TiCl4 at zero were introduced. At the same temperature, 17.5 g of the additive compound MgCl2/EtOH, which is in the form of pellets and contains 25% by weight of ethanol, was added and etched in the previously described manner, with stirring. The temperature was raised to 130°C within an hour and maintained for 60 minutes. Stirring was then stopped, the solid product was allowed to settle and the supernatant was centrifuged.

The solid was washed six times with anhydrous hexane (6100 ml) at 60°C and once at 25°C. Finally, the solid was dried under low pressure and analyzed (Ti=4.9 wt%, and Mg=19.4 wt%).

General procedure for preparing the final solid catalyst composition (contacting the intermediate compound with the electron donor compound):

In a 500 ml four-hole round flask equipped with a mechanical stirrer and washed with nitrogen, 200 ml of anhydrous hexane and 10 g of the solid intermediate component obtained by the method previously disclosed were introduced at room temperature. At the same temperature, and with stirring, an amount of the required electron donor material was added drop by drop to reach a molar ratio between the electron donor material and titanium. The temperature was raised to 50°C and the mixture was stirred for 3 hours. Stirring was then stopped, the solid product was allowed to settle and the supernatant was centrifuged.

The solid was washed 3 times with anhydrous hexane (3100 ml) at 25 °C, extracted, dried under low pressure, and then analyzed.

Copolymerization of ethylene/alpha-olefin: general procedure

A 4.5 liter sterilizer made of stainless steel and equipped with a magnetic flap, temperature and pressure indicators, and a feeding line for:

ethylene, propane, 1-butene, hydrogen, and a steel bottle for injecting the catalyst, by passing pure nitrogen at 70°C for 60 minutes. It was then washed with propane, heated to 75 °C, and finally charged with 800 g of propane, 1-butene (in the amount shown in Table 4), ethylene (partial pressure 7 bar), and hydrogen (as in Table 2 and Table 4).

In a 100 cc three-hole glass vial, then insert the following in the same order: 50 cc of anhydrous hexane, 9.6 cc of a 10% w/v TEA/hexane solution (or the equivalent amount of the catalyst declared in Table 2 and Table 4), and optionally the external compound. The electron donor (Table 2 and Table 4) and the solid catalyst used in the example (in the amount mentioned in Table 2 and Table 4). These quantities were mixed together and stirred at room temperature for 5 minutes, then introduced into the reactor through a steel bottle using increased pressure of nitrogen. With continuous stirring, the total pressure was maintained constant at 75 °C for 60 minutes by feeding with ethylene. Finally, the pressure in the reactor was reduced and the temperature was reduced to 30°C. The extracted polymers were dried at 70°C in a nitrogen atmosphere and then weighed.

Examples 1 through 12

A series of catalyst components were prepared using different electron donor (ED) compounds. The catalysts were prepared using addition compounds (EtOH), which we treated first with TiCl4 to prepare an intermediate compound according to the procedure previously disclosed, and then it was brought into contact, according to the general procedure, with the specific electron-donating compound used at the feed ratio mentioned in Table 1.

The catalysts obtained in this way were then used in the polymerization of ethylene, carried out according to the general procedure mentioned above and under the specific conditions mentioned in Table 2, which also contains data related to determining the properties of the polymer.

Examples 13 and 14

The catalyst was prepared according to the same procedure previously disclosed in Examples 1 to 12 using AcOEt as the electron donor compound, but the molar feed ratio between the electron donor and Ti was 8, 4, and 1, respectively. The catalysts thus obtained were then used in the copolymerization of ethylene. It was carried out in accordance with the general procedure mentioned above and in the specific conditions mentioned in Table 4, which also contains data related to the determination of polymer properties.

Example 15

A solid medium prepared according to the general procedure was injected into an autoclave and maintained at 30°C with stirring in anhydrous hexane (solid concentration was 40 g/L) in an atmosphere of nitrogen. The suspension was treated with a solution of triethylaluminum TEA, 10 wt%, in hexane to reach a ratio between TEA and solid equal to 0.5 wt/wt. An amount of propylene equal to 0.7 times the original amount of solid was then slowly added at an appropriate rate to keep the temperature constant at 30°C. After 30 minutes, the polymerization was stopped. The solid was washed 3 times with anhydrous hexane at 250 °C, suspended again in hexane, and treated with AcOEt as the electron-donating compound according to the general procedure, but making the feed molar ratio between AcOEt and Ti equal to 8. The properties of the catalyst component are listed in Table 3 and the results are included. Copolymerization in Table 4.

Example 16

The catalyst is prepared according to the same procedure as previously disclosed in Examples 1 through 12, using AcOEt as the electron donor but setting the temperature at which the contact occurs to be zero. The properties of the catalyst component are listed in Table 3 and the results of the copolymerization in Table 4.

Example 17

The catalyst was prepared according to the same procedure previously disclosed in Examples 1 through 12 using AcOEt as the electron donor but the contact was carried out at 100°C in heptane instead of hexane. The properties of the catalyst component are listed in Table 3 and the results of the copolymerization in Table 4.

Example 18

The catalyst was prepared according to the same procedure previously disclosed in Examples 1 through 12 using AcOEt as the electron donor but the contact was carried out in toluene rather than hexane. The properties of the catalyst component are listed in Table 3 and the results of the copolymerization in Table 4.

Example 19

The catalyst was prepared according to the same procedure as previously disclosed in Examples 1 through 12 using AcOEt as the electron donor compound but with the contact carried out twice.

The first of them was carried out with a molar feed ratio between AcOEt and Ti of 1 for 30 minutes. The second was carried out after washing the solid material with hexane. The molar feed ratio between AcOEt and Ti was 4 and the contact continued for 2.5 hours. The properties of the catalyst component were listed in Table 3. List the copolymerization results in Table 4.

Example 20

The catalyst was prepared according to the procedure previously disclosed in Examples 1 through 12 using AcOEt as the electron donor compound but carrying out the contact step with the electron donor compound for one hour. The properties of the catalyst component are listed in Table 3 and the polymerization results are listed in Table 4.

Example 21

The catalyst was prepared according to the procedure previously disclosed in Examples 1 through 12 using AcOEt as the electron donor compound but carrying out the contact step with the electron donor compound for two hours. The properties of the catalyst component are listed in Table 3 and the polymerization results are listed in Table 4.

Example 22

The catalyst was prepared according to the procedure previously disclosed in Examples 1 through 12 using AcOEt as the electron donor compound but carrying out the contact step with the electron donor compound for 3 hours. The properties of the catalyst component are listed in Table 3 and the polymerization results are listed in Table 4.

Example 23

The catalyst intermediate solid was stirred according to the general procedure in anhydrous heptane at 90 °C (solid concentration was 40 g/L) with aluminum diethyl monochloride (DEAC), and in a nitrogen atmosphere using DEAC with a molar ratio between AL and Ti of 10.

After one hour, stirring was stopped, the solid product was allowed to settle, and the supernatant was centrifuged. A DEAC treatment process was carried out under the same conditions as before.

The solid was washed once with anhydrous heptane at 90°C and twice with anhydrous hexane at room temperature. The solid was dried under low pressure and analyzed (TiTotal = 4.6 wt%, Ti3+ = 2.9 wt%, and Mg = 20 wt%). Then the contact step with the electron-donating compound was carried out, as previously explained in the general procedure, using AcOEt as the electron-donating compound, but with the reaction time being two hours. The properties of the catalyst component are listed in Table 3 and the copolymerization results are listed in Table 4.

Example 24

The prepolymerized intermediate obtained in Example 15 was suspended in hexane and cured, with stirring, at 50°C for 1 hour with TiCL4 (ratio of prepolymer to TiCL4 equal to 24 w/w). The solid was washed three times with anhydrous hexane at 25°C, and resuspended in hexane again. The next treatment was carried out with AcOEt as previously explained in the general procedure, but with the feed molar ratio between the electron donor compound and titanium equal to 8. The properties of the catalyst component are listed in Table 3 and the results of the copolymerization in Table 4.

Example 25

The catalyst was prepared according to the same procedure previously disclosed in Examples 1 to 12, using AcOEt as the electron donor compound, but with the process of preparing the intermediate solid compound being carried out. TiCl4 was treated at 100°C instead of 130°C, and a second treatment of TiCl was introduced (30 minutes). Before washing steps. (Ti=1.9 wt%, Mg=19.4 wt%). The properties of the catalyst component are listed in Table 3 and the copolymerization results are listed in Table 4.

Example 26

The catalyst was prepared by the same procedure as previously disclosed in Examples 1 through 12, but in the electron donor compound contact step, the electron donor compound was formed from a mixture of AcOEt and THF (1/1 mol/mol).

The total molar ratio between ED and Ti was 4. The catalyst properties are listed in Table 3 and the copolymerization results are listed in Table 4.

Example 27

A substance producing MgCl4 was prepared following the previous procedure described in Example (a) in US Patent No. 4,220,554. The solid thus obtained was then treated with TiCl4 until the intermediate solid compound could be prepared, according to the general procedure, but with the TiCl4 treatment being carried out. At 120 °C instead of 130 °C, two more treatments were introduced for TiCl4 at 120 °C (30 minutes) before the washing steps. The solid was washed twice with anhydrous hexane (2 100 ml) at 60°C and then twice at 25°C.

Finally, the solid was dried under low pressure and analyzed (Ti = 5.8 wt%, Mg = 18.8 wt%). The contact step with AcOEt was performed according to the general procedure. The properties of the catalyst component are listed in Table 3 and the polymerization results are listed in Table 4.

Examples 28 to 30

The catalyst components were prepared according to the same procedure previously disclosed in Examples 1 to 13 with AcOEt as the electron donor compound but in the spherical MgCl2(EtOH) starting addition compounds having alcohol contents of 47.3%, 35% and 14.3% by weight, respectively. The properties of the catalyst components are listed in Table 3 and the copolymerization results are listed in Table 4.

Table 1

Catalyst installation

Catalyst preparation

Example

MG/Ti

ED/Ti

EO/Ti

In nutrition

electron donor compound (ED)

Molecular ratio

Molecular ratio

Molecular ratio

8.7

2.8

Ethyl acetate

7.6

Diethyl malonate

7.3

2.4

Diethyl succinate

8.3

THF

4

8.1

2.4

Dimethylformamide

9.8

3.6

Diethylamine

7.7

2.8

di-i-propylamine

7.7

3.4

Triethylamine

8.5

Tetrahydrofurfuryl Acetate

8.6

2.7

Ehtylen-Glycol

7.7

1.6

DimethyldimethoxySilane

8.2

1.8

MethyltrimethoxySilane

Table 2

Polymer properties

Polymerization conditions

Example

a olefin

Common catalyst

XS

Medium temperature

Density

MIE

C`4

The resulting

H2

C`4

Al/ED

Type

Type

Catalyst

% by weight

M

g/cm3

g/10

% by weight

kg/g* hour

bar

Jim

mall

mg

2.3

122.3

0.905

0.6

4.9

11.8

1.8

150

THF

TMA

10.2

122.1

0.916

2.2

19.3

4.4

1.5

180

THF

TMA/DEAC2-1

20.5

14.6

122.7

0.9179

1.26

9.8

3.2

1.5

180

THF

TMA/DEAC2-1

2.08

12.8

121.5

0.9161

8.1

13.4

150

---

TMA

13.7

12.1

123.2

0.9175

0.7

7.9

2.7

150

---

TMA

20.7

16.5

122.9

0.9195

3.5

10.6

2.2

150

---

TMA

22

25.8

118.9

0.9113

2.1

14.8

19.3

150

---

TMA

5.3

18.8

121.2

0.9115

2.5

9.8

7.7

150

---

TMA

21.4

19

121.5

0.9124

0.8

8.6

7.7

180

---

TMA

24.8

15.7

121.5

0.9168

0.8

9.7

3.5

1.5

200

THF

TMA/DEAC2-1

41.1

10.1

122.7

0.9234

2.2

6.5

8.5

150

---

TMA

20.5

6.7

0.1223

0.9227

0.3

7.4

150

---

TMA

21

Table 3

Catalyst installation

Example

MG/Ti

ED/Ti

E.D

Cl

Ti

MG

9.6

6.6

36.5

48.7

3

14.6

13

8.3

4.1

27

52

3.6

15.2

14

8.6

5.7

24

do not apply

2.3

10.1

15

7.8

1.4

12.6

62.6

4.8

19

16

7.9

3.4

26

49.4

4.1

16.5

17

13.1

4.2

21.7

60.4

2.8

18.6

18

9.5

6.0

31.9

47

2.9

14

19

8.7

4.4

25.9

47.7

3.2

14.2

20

8.1

3.8

25.9

51.7

3.7

15.2

21

8.7

4.3

26.7

50.6

3.4

15.1

22

8.8

3

20.7

54.9

3.7

16.5

23

6.3

6.4

23.5

do not apply

2

6.4

24

41.8

6.5

10.7

59.4

0.9

19.1

25

8.4

2/2.5

13.5/141

53.9

3.7

15.7

26

8

4.2

28.3

51.1

3.6

14.7

27

6.5

4.2

33.5

do not apply

4.3

14.1

28

6.6

3.9

29.2

do not apply

4.2

14.1

29

17.9

4.6

17.6

do not apply

2.1

19.1

30

Table 4

Polymer properties

Polymerization conditions

Example

Catalyst

XS

Medium temperature

Density

MIE

C4

H2

C`4

Type

Catalyst

% by weight

M

g/cm3

g/10

% by weight

kg/g*

hour

bar

Jim

Mg

2.2

120.7

0.92.6

0.5

6.4

2.6

1.5

150

TMA

13

8.5

121.7

0.9211

1.4

8.6

10

1.5

180

TMA/DEAC2-1

14

4.8

121.7

0.9189

0.43

6.1

13

1.5

150

TMA

15

4.7

121.2

0.921

0.5

6.5

3.4

1.5

150

TMA

16

2.8

122.3

0.9165

0.3

5.1

5.1

1.5

150

TMA

17

11.7

118.1

0.9161

0.76

10.5

2.5

1.5

200

TMA/DEAC4-1

18

6.7

120.6

0.921

0.7

8.5

2.3

1.5

180

TMA/DEAC2-1

19

6.8

121.7

0.9255

1.6

8.1

12.5

1.5

180

TMA/DEAC2-1

20

11.9

121.1

0.9201

2.7

9

11.2

1.5

180

TMA/DEAC2-1

21

12.3

120

0.9174

8.3

11.3

1.5

180

TMA/DEAC2-1

22

2.3

121.6

0.9238

0.3

4.1

9.8

1.8

150

TMA

23

12.9

121.6

0.9168

1.1

9.4

2.42

1.5

200

TMA

24

3.7

122

0.9239

0.9

6.8

7.7

1.5

180

TMA/DEAC2-1

25

11.06

121.5

0.9188

2.2

9.7

4.6

1.5

150

TMA/DEAC2-1

26

4.8

123.5

0.9260

1.1

6

8.8

1.5

150

TMA

27

11.7

120.8

0.918

3.3

8.4

6.3

1.8

150

TMA

28

5.7

122.2

0.921

0.96

7.2

15.8

1.8

200

TMA

29

8.8

122.1

0.921

2

6.9

4.2

1.8

150

TMA

30

- THF was used as an external donor (except Example 33).

The ratio between A1 and THF is 5.