KR19980020194A - Catalyst systems for making highly crystalline polypropylene - Google Patents

Abstract

The present invention provides a catalyst system for controlling desirable properties in polymer products. The catalyst system comprises a conventional Ziegler-Natta catalyst and an electron donor compound of formula SiR _m (OR ') _4-m wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, M is 0 to 3, and when R is an alkyl group, R is the same as R ', and when m is 0, 1 or 2, R' are the same or different and m is 1, 2 or 3 And the R groups are the same or different. The system easily obtains efficiencies over 30 kg / g-cat · h. The system also exhibits better control of the xylene solubles of the polymer product and produces a highly crystalline polymer product. The electron donor is preferably represented by the formula (1).

In the above formula, R ₁ is an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom bonded to a silicon atom, R ₂ and R ₃ are alkyl or aryl groups, R ₄ is a bond to a silicon atom Or an alkyl or cycloalkyl group having a secondary or tertiary carbon atom.

More preferably, R ₁ and R ₄ are both cycloalkyl groups and are the same. Most preferably, R ₁ and R ₄ are both cyclopentyl groups and R ₂ and R ₃ are both methoxy groups. In particular, the electron donor may be dicyclopentyldimethoxysilane.

Description

[Title of the Invention]

Catalyst systems for making highly crystalline polypropylene

DETAILED DESCRIPTION OF THE INVENTION [

[Object of the invention]

It is an object of the present invention to provide an electron donor compound of the formula SiR _m (OR) _4-m , wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, with a conventional supported Ziegler- , R 'is an alkyl group, m is 0 to 3, R is the same as R' when R is an alkyl group, R 'is the same or different when m is 0, 1 or 2, m is 1, 2 > or R < 3 > groups are the same or different). The electron donor preferably has the following formula (1).

[Chemical Formula 1]

In the above formula, R ₁ is an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom bonded to a silicon atom, R ₂ and R ₃ are alkyl or aryl groups, R ₄ is a bond to a silicon atom Wherein R ₁ and R ₄ are the same or different and R ₂ and R ₃ are the same or different.

[TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]

Catalyst systems for the polymerization of olefins are well known in the art. Typically, these systems comprise a Ziegler-Natta type polymerization catalyst; Cocatalyst, generally an organoaluminum compound; And electron donors, typically organosilicon compounds. Examples of such catalyst systems are shown in U.S. Patent Nos. 4,107,413, 4,294,721, 4,439,540, 4,115,319, 4,220,554, 4,460,701 and 4,562,173, the disclosures of which are incorporated herein by reference . These are only a few of the dozens of granted patents relating to catalysts and catalyst systems mainly for the polymerization of propylene and ethylene.

Conventional supported Ziegler-Natta catalysts generally include complexes of a halide of a transition metal (e.g., titanium, chromium, or vanadium) with a metal hydroxide and / or a metal alkyl (typically, an organoaluminum compound). The catalyst generally consists of a titanium halide supported on a magnesium compound that is complexed with alkyl aluminum. A more crystalline polymer can be prepared by adding to improve the stereoregularity of the external electron donor or selectivity modifier (SCA) catalyst.

The development of such polymerization catalysts improves catalyst and polymer properties. In addition to the improved catalyst, the improved activation method also increases the catalyst efficiency. One of the improved activation methods involves pre-polymerizing the catalyst just prior to introducing the catalyst into the reaction zone. Such a prepolymerization process is described in U.S. Patent No. 4,767,735, which is incorporated herein by reference.

In addition to the development of new catalysts and new reaction processes, the discovery of suitable electron donors in combination with supported Ziegler-Natta catalysts in forming the overall catalyst system is of great benefit to the polymerization art in dramatically improving catalyst and polymer properties . In such a catalyst system, it is believed that the cocatalyst activates the catalyst and initiates the polymer chain. The cocatalyst that works well with the supported Ziegler-Natta catalyst component is an organoaluminum compound, typically an alkylaluminum and most typically a trialkylaluminum such as triethylaluminum (TEAI) or triisobutylaluminum (TIBAI). Examples of organoaluminum compounds useful as cocatalysts for the supported Ziegler-Natta catalyst component of the catalyst include alkylaluminum dihalides and dialkylaluminum halides.

Electron donating compounds are used in polymerization reactions to modulate and increase the production of stereoregular or crystalline polymers by reducing the polymer in the form of an atactic. Although a wide variety of compounds are generally known as electron donors, certain catalysts may have certain compounds or particularly group of compounds that are miscible. It would be highly advantageous to find an appropriate type of electron donor that not only improves the isotactic index of the desired polymer product and other properties of the product but also provides excellent catalytic efficiency. One such group of electron donors is described in U.S. Patent No. 4,927,797.

[Technical Problem]

The present invention includes other such findings. Surprisingly, electron donors in combination with certain types of catalysts have been found to produce polymers with significantly increased crystallinity compared to previously known crystallinity of certain known types of catalyst systems as well as certain types of catalysts.

[Structure and operation of the invention]

The present invention provides a catalyst system for the polymerization of propylene comprising a combination of a specific group of electron donating compounds with a specific type of catalyst that greatly increases the crystallinity of the polymer product. The catalyst comprises a conventional supported Ziegler-Natta catalyst component, an organoaluminum cocatalyst and an organosilicon electron donor. Such a combination provides a catalyst system that produces a polymer product (having low xylene solubles) that is significantly higher than that provided by prior catalyst systems as described by the comparative examples described below. In addition, the catalyst systems of the present invention using certain existing supported Ziegler-Natta catalyst components better control the xylene solubles of the polymer product than other forms of catalyst components. In addition, the catalyst systems of the present invention using certain electron donors provide better control of the xylene solubles of the polymer product than other forms of electron donors. These and other advantageous advantages will become more apparent from the following detailed description of the invention and the accompanying examples.

The above described catalyst significantly increases the crystallinity of the polymer product compared to previously known catalysts when paired with previously used electron donors, but when the catalyst is paired with an electron donor as described in the present invention, This increases much more. The present invention improves and controls the properties of polymeric products such as xylene solubles.

The unexpected and most important results obtained from the combination of the catalysts described in U.S. Patent Nos. 4,784,983 and 4,861,847 and the combination of CMDS, DIDS, DTDS, CPDS and CIDS are that the crystallinity of the polymer produced by the present catalyst system in the propylene polymerization is dramatic . The catalyst system was found to exhibit efficiencies higher than 30 kg / g-cat · h per Si / Ti molar ratio within the range of 4 to 200.

The present invention also provides a process for the polymerization of propylene. This process comprises contacting the supported Ziegler-Natta catalyst component with an organoaluminum compound, preferably trialkyl aluminum, to form a catalyst; Contacting the catalyst with the organoaluminum or simultaneously with an electron donor which is an organosilicon compound of the above formula (1); An optional step of pre-polymerizing the catalyst by contacting the catalyst with a small amount of monomer; Introducing the catalyst into the reaction zone under polymerization conditions containing a monomer and an optional amount of an organoaluminum compound and an electron donor; And recovering the polymer product. When the monomer is propylene, the xylene solubles are from 0.6 to 3.00 wt%, and the Si / Ti ratio in the reaction zone is in the range of from 4 to 200. When the electron donor is dicyclopentyldimethoxysilane and the monomer is propylene, the crystallinity (% of the pentavalent element distribution of the xylene insoluble fraction) as defined by the isotacticity of the polymer product is greater than 98%.

The present invention relates to specific groups of compounds and combinations of catalysts as electron donors for use in the polymerization of propylene.

Certain groups of electron donors have been found to significantly improve the catalytic properties of existing supported Ziegler-Natta catalysts. Existing Ziegler-Natta transition metal compound catalyst components can be used in the present invention. Electron donors are typically used in two ways to form a Ziegler-Natta catalyst and a catalyst system. First, the internal electron donor can be used in the formation reaction of the catalyst as the transition metal halide reacts with the metal hydride or metal alkyl.

Suitable internal electron donor compounds for preparing conventional Ziegler-Natta catalyst components include ether, ketone, lactone and electron donating compounds having N, P and / or S atoms and certain types of esters. Phthalic acid esters such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate; Malonic acid esters such as diisobutyl and diethylmalonate; Alkyl and aryl pivalate; Alkyl, cycloalkyl, and aryl maleates; Alkyl and aryl carbonates such as diisobutyl, ethyl phenyl and diphenyl carbonate; Particularly suitable are succinic esters (e.g. mono and diethyl succinate). The above phthalic acid esters are preferred donors.

A second use for electron donors in catalyst systems is as external electron donors and stereoregulators in polymerization reactions. The same compounds can be used in both cases, although applications are typically different. A typical external electron donor is an organosilicon compound, for example, cyclohexylmethyldimethoxysilane (CMDS). A description of two types of electron donors is given in U.S. Patent 4,535,0638, which is incorporated herein by reference.

Existing Ziegler-Natta catalyst components include compounds of the formula MR ⁺ _X , where M is a metal, R is a halogen or a hydrocarboxyl, and x is the valence of a metal. Preferably, M is a transition metal, more preferably a Group IVB, VB or Group VIB metal, most preferably Group IVB, especially titanium. Preferably, R is chlorine, bromine, alkoxy or phenoxy, more preferably chlorine or ethoxy, most preferably chlorine. Exemplary transition metal catalyst components are TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti ₆ H ₁₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , and Ti (OC ₁₂ H ₂₅ ) ₃ Cl ₃ . Mixtures of transition metal compounds may be used. The number of transition metal compounds is not limited as long as at least one transition metal compound is present.

The support must be an inert solid chemically unreactive to any of the components of conventional Ziegler-Natta catalysts. The support is preferably a magnesium compound. Examples of the magnesium compound used to provide the support source of the catalyst component are magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium, oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and carboxylate of magnesium.

Wherein the organoaluminum compound acting as a cocatalyst is a compound wherein R 'is alkyl having 1 to 8 carbon atoms or halogen and R' is the same or different, and at least one R ¹ is alkyl and R 'is the same or different. Preferably the organoaluminum compound is an alkylaluminum, alkylaluminum dihalide or dialkylaluminum halide. More preferably, R 'is alkyl which makes the alkyl aluminum to trialkyl aluminum. Most preferably, the alkylaluminum is trialkylaluminum such as triethylaluminum (TEAI) or triisobutylaluminum (TIBAI).

One specific Ziegler-Natta catalyst component that can be used in the present invention is about 40 to 70 weight percent of a halide selected from the group consisting of about 1.5 to 6.0 weight percent titanium, about 10 to 20 weight percent magnesium, chlorine, bromine and iodine, From about 5 to about 25 weight percent of a polycarboxylic acid ester selected from the group consisting of esters of aromatic and alicyclic polycarboxylic acids, and from about 0.1 to 2.5 weight percent of organic phosphorus compounds selected from the group consisting of hydrocarbon esters of phosphoric and phosphorous acids of from 1 to 6 carbon atoms, A) a solvent mixture consisting of a) an organic epoxy compound selected from the group consisting of alcohols of aliphatic olefins and diolefins, oxides of halogenated aliphatic olefins and diolefins and glycidyl ethers of 2 to 8 carbon atoms, magnesium Halide and magnesium or magnesium in water or alcohol A magnesium halide compound selected from the group consisting of a magnesium halide compound and a magnesium halide derivative, and an alkyl phosphate, aryl phosphate, aralkyl phosphate, , aryl includes the steps of dissolving an organic phosphorus compound selected from the group consisting of and has 6 to 10 carbon atoms) to form a homogeneous solution, b) a liquid titanium compound in the homogeneous solution formula _{TiX n (OR) 4-n} ( wherein, X is halogen and R is the same or different alkyl groups and n is an integer from 0 to 4, c) adding at least one co-precipitant selected from the group consisting of carboxylic acid anhydride, carboxylic acid, ether and ketone, D) forming a polycarboxylic acid ester when the precipitate appears, Phase, e) a separate and remove the precipitate and the precipitate from a mixture of titanium _{compound, TiX n (OR) 4-} n ( wherein, X is halogen, R is a hydrocarbon group which may be the same or different, n is 0 to 4; In an inert diluent in the presence of a catalyst or a mixture thereof, and f) washing the treated precipitate with an organic inert diluent, wherein the Ziegler-Natta catalyst is a commercially available Ziegler-Natta catalyst for olefin polymerization Which is described in U.S. Patent Nos. 4,861,847 and 4,784,983, the disclosures of which are incorporated herein by reference.

A preferred co-precipitant useful for catalyst formation is an organic carboxylic acid anhydride, more preferably phthalic anhydride, which is added in an amount of 0.03 to 1.0 mole per mole of magnesium halide. Preferred polycarboxylic acid esters are selected from the group consisting of esters of aromatic polycarboxylic acids, preferably dibutyl phthalate and di-isobutyl phthalate. A preferred inert diluent for washing the precipitate is 1,2-dichloroethane. Suitable titanium tetra halides are TiCl ₄ , TiBr ₄ and TiI ₄ , and TiCl ₄ is preferred.

As the present invention is particularly concerned with external electron donors, the term " electron donor " as used herein relates to external donors. The external electron donor acts as a stereoregulator and regulates the amount of the resulting polymer in the form of an atactic. It is also possible to increase the production of isotactic polymers. Organosilicon compounds are known in the art for use as electron donors. Examples of electron donors which are organosilicon compounds are described in U.S. Pat. Nos. 4,218,339, 4,395,360, 4,328,122, 4,473,660 and 4,927,797. As noted, certain catalysts may produce better results when paired with a particular type of electron donor. Examples of combinations of catalysts and electron donors are described in U.S. Pat. Nos. 4,562,173, 4,454,552 and 4,927,797. The electron donor is a compound of the formula SiR _m (OR) _4-m wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R 'is an alkyl group, When R is an alkyl group, R is the same as R ', and when m is 0, 1 or 2, R' are the same or different and when m is 1, 2 or 3, the R groups are the same or different) to be. Preferably, the electron donor is selected from organosilicon compounds of formula (I).

[Chemical Formula 1]

In the above formula, R ₁ is an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom bonded to a silicon atom, R ₂ and R ₃ are alkyl or aryl groups, R ₄ is a bond to a silicon atom Wherein R ₁ and R ₄ are the same or different and R ₂ and R ₃ are the same or different.

In a preferred embodiment, R ₁ is a secondary alkyl group having 3 to 5 carbon atoms with mirror symmetry, R ₂ and R ₃ are methyl, ethyl, propyl or butyl groups but not necessarily identical, and R ₄ has a mirror image symmetry A secondary alkyl or cycloalkyl group having 3 to 6 carbon atoms. More preferably, R ₁ and R ₄ are the same and are a cycloalkyl group, especially a group of 5 carbon atoms, namely cyclopentyl. Particular electron donors include cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), di-t-butyldimethoxysilane (DTDS), dicyclopentyldimethoxysilane (CPDS), and cyclohexylisopropyl Dimethoxysilane (CIDS), and most preferred is dicyclopentyldimethoxysilane (CPDS). The combination of the above-mentioned electron donor and the conventional supported Ziegler-Natta catalyst exhibits totally unexpected results over previous known catalyst systems. The electron donor as described by the present invention will be limited by the stability of the compound and the ease of handling, including storage, transportation and use at the factory.

The catalyst system can achieve high efficiency for a wide range Si / Ti ratio (4-200) while increasing the isotactic index while inhibiting the formation of the atactic polymer or making the xylene solubles relatively low. When another catalyst is paired with the electron donor described above, the polymer product is rapidly increased in xylene solubles. The present catalyst systems using CMDS, DIDS, DTDS, CPDS or CIDS with a specific supported Ziegler-Natta catalyst component have a xylene solubility of about 0.6 to about 3.0 wt% as the Si / Ti ratio is reduced to 200 to 4 and less, .

Catalyst systems with CPDS impart a high degree of crystallinity to the polymer system. The percentage of the meso pentavalent element (mmmm) of the heptane-insoluble fraction of the polymer product is a very high value of 97% or more.

(B) contacting the catalyst with an organoaluminum compound; (c) contacting the catalyst with an electron donor as such; and < RTI ID = 0.0 & (D) introducing the catalyst into a polymerization reaction zone containing an organoaluminum compound, an electron donor and a monomer, and (e) extracting the polymer product from the reactor. To provide a polymerization method of the propylene to be used.

Although the catalyst system can be used in almost all polymerization methods known in the art, the preferred method of the present invention includes a method of pre-polymerizing the catalyst by bringing the catalyst into contact with the electron donor and then contacting a small amount of the monomer with the catalyst. One method of the prepolymerization process is described in U.S. Patent Nos. 4,767,335 and 4,927,797, which are incorporated herein by reference. As described in these documents, a carrier stream of the catalyst is provided, the catalyst is contacted with a cocatalyst or an organoaluminum compound, the catalyst is contacted with an electron donor, the catalyst stream is contacted with a relatively small amount of the total amount of monomers to be polymerized, The stream is passed through a tubular reactor and the pre-polymerized catalyst and catalyst stream are introduced into the polymerization reaction zone. The electron donor can be contacted with the catalyst simultaneously with the use of the cocatalyst. The polymer product is then removed from the reactor. When the catalyst described above is used together with the electron donor described in the above formula (1), the efficiency can be 30 kg / g · cat · h or more and the Si / Ti molar ratio in the reaction is in the range of 1 to 10. The polymer product may also be characterized by 2 to 10 weight percent xylene solubles.

The following examples and comparative examples illustrate the present invention and its various advantages in more detail. The results are summarized in Tables 1-2. Catalysts used in the examples are prepared using the materials and methods described in U.S. Patent Nos. 4,861,847 and 4,784,983, and sold by Catalyst Resources, Inc. under the trade name Lynx 1000 . The catalysts used in the comparative examples are described in U.S. Patent 4,927,799; 4,816,433 and 4,839,321, and are commercially available under the trade designation THC-32A by Toho Titanium, Inc.

[Example 1]

Prior to the polymerization run, the water and air are completely removed from the reactor by heating to a temperature above 100 ° C for at least 30 minutes while constantly purging the dry nitrogen. After heating, the reactor is cooled to room temperature (25 占 폚) under nitrogen. The reactor is stabilized at room temperature and 32 mmol of hydrogen and 1,45 l of propylene are added. The reactor is stirred at 1300 rpm and the temperature is raised to 70 占 폚. 1. mmol of TEAI and 0.1 mmol of cyclohexylmethyldimethoxysilane (CMDS) are added to a 40 cc tubular reaction vessel. TEAI and the donor are pre-contacted for about 1 minute. 100 mg of the catalyst in the mineral oil suspension is added to the 40 cc reaction cylinder. The catalyst is pre-contacted with a mixture of TEAI and donor for about 2 minutes. The tubular reactor is then attached to the reactor inlet portion, filled with liquid propylene at room temperature, and polymerized for about 5 seconds to pre-polymerize the catalyst. The contents of the vessel are then flushed with 1.45 L of room temperature propylene to the reactor. The total amount of liquid propylene present in the reactor is about 2.9 liters. The polymerization is allowed to proceed for one hour, at which point the excess propylene is discharged and the reactor is cooled to room temperature to terminate the reaction.

The reactor is then opened to collect the polymer product, which is then dried and weight analyzed. The Si / Ti molar ratio is calculated by dividing the molar amount of the electron donor by the molar amount of the catalyst. The xylene solubles are determined by dissolving the polymer in hot xylene, cooling the solution to 0 < 0 > C and precipitating in isotactic form. The xylene solubles are the weight percent of polymer that is soluble in cold xylene. The pentavalent element distribution is determined by NMR analysis. The polymer fluff is dissolved in boiling xylene and the polymer is then precipitated in methanol by dropwise addition of the xylene solution to methanol while stirring. The precipitate was collected by filtration and then extracted with boiling heptane overnight. The results are shown in Table 1.

Summary of polymerization conditions

Catalyst weight 10.0 mmole

TEAL amount (cocatalyst) 1.0mmole

CMDS amount (electron donor) 0.1 mg

Al / Ti200

Al / Si 10

Si / Ti 20

Hydrogen 240 psig

Propylene 2.9 L (1500 g)

Temperature 70 ° C

Hour 1 hour

[Examples 2 to 9]

The procedure of Example 1 is repeated except that the total amount of CMDS is converted from 1 mmol to 0.002 mmol as indicated in Table 1. The results are shown in Table 1.

[Examples 10 to 15]

The procedure of Example 1 is repeated except that diisopropyl dimethoxysilane (DIDS) is used instead of CMDS and the total amount of DIDS is changed from 2 mmol to 0.0033 mmol as indicated in Table 1. The results are shown in Table 1.

[Examples 16 to 18]

The procedure of Example 1 is repeated except that di-tert-butyl dimethoxysilane (DTDS) is used instead of CMDS and the total amount of DTDS is changed from 2 mmol to 0.5 mmol as indicated in Table 1. The results are shown in Table 1.

[Examples 19 to 24]

The procedure of Example 1 is repeated except that dicyclopentyldimethoxysilane (CPDS) is used instead of CMDS and the total amount of CPDS is changed from 2 mmol to 0.0033 mmol as indicated in Table 1. The results are shown in Table 1.

[Examples 25 to 30]

The procedure of Example 1 is repeated except that the CMDS is used again with cyclohexylisopropyldimethoxysilane (CIDS) and the total amount of CIDS is changed from 2 mmol to 0.0033 mmol as indicated in Table 1. The results are shown in Table 1.

[Comparative Examples 1 to 30]

The procedure of Example 1 is repeated except that other commercially available Ziegler-Natta catalyst components are used in place of the catalyst components used in Examples 1-30. The results are shown in Table 2.

[Effects of the Invention]

The crystallinity of the polypropylene is controlled by the stereoregularity, that is, the isotacticity (% mmmm) as well as the amount of the atactic polymer present. Generally, the isotacticity of the xylene and / or heptane insoluble fraction increases with decreasing xylene solubles. Certain electron donors, combined with certain catalytic components, as evidenced by the above data, produce relatively small amounts of xylene solubles. This phenomenon is added when CPDS is used with certain catalyst components.

As described in the above Examples and Tables 1 and 2, the xylene solubles generally have the specific catalytic components of Examples 1 to 27 and Table 1, as compared with the same electron donors of Comparative Examples 1 to 27 and Table 2, The case where an electron donor is blended is extremely low. As shown in Examples 16 to 21 and Tables 1 and 2, when used in conjunction with the catalyst component as described for CPDS, relatively low xylene solubles and propylene with relatively high crystallinity are produced. When combined with a catalyst component as described for CPDS, the activity is increased by combining with other electron donors and catalyst components.

Claims (29)

(a) from about 1.5 to 6.0% by weight of titanium, from about 10 to 20% by weight of magnesium, from about 40 to 70% by weight of a halide selected from the group consisting of chlorine, bromine and iodine, a group consisting of esters of aliphatic, aromatic and alicyclic polycarboxylic acids About 5 to 25% by weight of a selected polycarboxylic acid ester selected from the group consisting of hydrocarbon esters of phosphoric acid and phosphorous acid of 1 to 6 carbon atoms, a) mixing a solvent mixture consisting of a magnesium halide with water or an alcohol, in a solvent mixture consisting of a) an organic epoxy compound selected from the group consisting of aliphatic olefins of 2 to 8 carbon atoms and diolefins, oxides of halogenated aliphatic olefins and diolefins and diglycidyl ethers, A magnesium halide compound selected from the group consisting of a magnesium halide complex and a magnesium halide derivative, and an alkyl halide compound selected from the group consisting of alkyl phosphate, aryl phosphate, aralkyl phosphate, alkyl phosphite, aryl phosphite, and aralkyl phosphite, And aryl has from 6 to 10 carbon atoms) to form a homogeneous solution, b) mixing a homogeneous solution with a liquid titanium compound of the formula TiX _n (OR) _4-n , wherein X is halogen and R is the same or different alkyl groups and n is an integer from 0 to 4, c) adding at least one auxiliary precipitant selected from the group consisting of carboxylic acid anhydride, carboxylic acid, ether and ketone to form a precipitate, d) adding a polycarboxylic acid ester when a precipitate appears, e) the precipitate is separated from the mixture and the separated precipitate is treated with a titanium compound, TiX _n (OR) _4-n wherein X is halogen, R is a hydrocarbon group which may be the same or different and n is an integer from 0 to 4 ) Or mixtures thereof in an inert diluent and and f) washing the treated precipitate with an organic inert diluent, wherein the Ziegler- (b) an organoaluminum compound and (c) an electron donor of the formula SiR _m (OR) _4-m wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, R 'is an alkyl group, 3, and when R is an alkyl group, R is the same as R ', and when m is 0, 1 or 2, R' are the same or different, and when m is 1, 2 or 3, the R groups are the same or different ). ≪ / RTI > The catalyst system according to claim 1, wherein the electron donor is a compound of formula (1). [Chemical Formula 1] In the above formulas, R ₁ is an alkyl or cycloalkyl group containing a primary or secondary carbon atom bonded to a silicon atom, R ₂ and R ₃ are each independently an alkyl or aryl group, R ₄ is an alkyl or cycloalkyl group having a secondary or tertiary carbon atom bonded to a silicon atom, R ₁ and R ₄ may be the same or different. The method of claim 2, wherein, R ₁ is the number of carbon atoms having mirror image symmetry 3 or 5. Level 2 of the alkyl or cycloalkyl and R ₄ is alkyl or cycloalkyl second degree of catalyst systems having 1 to 6 carbon atoms having mirror image symmetry. 4. A catalyst system according to claim 3 wherein R < ₁ > and R < ₄ > are both cycloalkyl groups. 5. The catalyst system of claim 4 wherein R < ₁ > and R < ₄ > are cyclopentyl. The catalyst system according to claim 2, wherein R ₂ and R ₃ are selected from the group consisting of methyl, ethyl, propyl and butyl groups. 7. The catalyst system of claim 6 wherein R < ₂ > and R < ₃ > are both methyl groups. The catalyst system according to claim 1, wherein the electron donor is cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane or dicyclopentyldimethoxysilane. The catalyst system according to claim 8, wherein the electron donor is dicyclopentyldimethoxysilane. The process according to claim 1, wherein the organoaluminum compound is an aluminum alkyl of formula AIR ' ₃ wherein R' is alkyl of 1 to 8 carbon atoms or halogen and, if the at least one R 'is alkyl, R' Or different. 11. The catalyst system according to claim 10, wherein the organoaluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum dihalide, trialkoxyaluminum and dialkylaluminum halide. 12. The catalyst system according to claim 11, wherein the organoaluminum compound is trialkylaluminum. 13. The catalyst system according to claim 12, wherein the organoaluminum compound is triethylaluminum or triisobutylaluminum. (a) from about 1.5 to 6.0% by weight of titanium, from about 10 to 20% by weight of magnesium, from about 40 to 70% by weight of a halide selected from the group consisting of chlorine, bromine and iodine, a group consisting of esters of aliphatic, aromatic and alicyclic polycarboxylic acids About 5 to 25% by weight of a selected polycarboxylic acid ester selected from the group consisting of hydrocarbon esters of phosphoric acid and phosphorous acid of 1 to 6 carbon atoms, a) mixing a solvent mixture consisting of a magnesium halide with water or an alcohol, in a solvent mixture consisting of a) an organic epoxy compound selected from the group consisting of aliphatic olefins of 2 to 8 carbon atoms and diolefins, oxides of halogenated aliphatic olefins and diolefins and diglycidyl ethers, A magnesium halide compound selected from the group consisting of a magnesium halide complex and a magnesium halide derivative, and an alkyl phosphate, aryl phosphate, aralkyl phosphate, And aryl has from 6 to 10 carbon atoms) to form a homogeneous solution, b) mixing a homogeneous solution with a liquid titanium compound of the formula TiX _n (OR) _4-n , wherein X is halogen and R is the same or different alkyl groups and n is an integer from 0 to 4, c) adding at least one auxiliary precipitant selected from the group consisting of carboxylic acid anhydride, carboxylic acid, ether and ketone to form a precipitate, d) adding a polycarboxylic acid ester when a precipitate appears, e) separating the precipitate from the mixture and separating the precipitate from the titanium compound, TiX _n (OR) _4-n wherein X is halogen, R is a hydrocarbon group which may be the same or different and n is an integer from 0 to 4 ) Or mixtures thereof in an inert diluent and f) washing the treated precipitate with an organic inert diluent, selecting the conventional Ziegler-Natta catalyst component prepared by the process, (b) contacting the catalyst with an organoaluminum compound, (c) an electron donor of formula SiR _m (OR) _4-m , wherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group, either simultaneously with or after step (b) R is an alkyl group, m is 0 to 3, R is the same as R 'when R is an alkyl group, R' is the same or different when m is 0, 1 or 2, and m is 1, 2 or 3, the R groups are the same or different) (d) introducing the catalyst into a polymerization reaction zone containing a monomer. 15. The method according to claim 14, wherein the electron donor is represented by formula (1). [Chemical Formula 1] In Formula 1, R ₁ is an alkyl or cycloalkyl group containing a primary or secondary carbon atom, R ₂ , R ₃ are each independently an alkyl or aryl group, R ₄ is an alkyl or cycloalkyl group having a secondary or tertiary carbon atom bonded to a silicon atom, R ₁ and R ₁ are the same or different. R ₂ and R ₃ are the same or different. 16. The method of claim 15 wherein, R ₁ has a mirror image symmetry of silver having a carbon number of 3 or 5. Level 2 of the alkyl or cycloalkyl and R ₄ is alkyl or cycloalkyl second degree method of 1-6 carbon atoms having mirror image symmetry. 17. The method of claim 16 wherein R < ₁ > and R < ₄ > are both cycloalkyl groups. 18. The method of claim 17 wherein R < ₁ > and R < ₄ > are cyclopentyl. 19. The method of claim 18, wherein the electron donor is cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane, or dicyclopentyldimethoxysilane. 20. The method of claim 19, wherein the electron donor is dicyclopentyldimethoxysilane. The method of claim 14 wherein the organoaluminum compound is a formula AIR _'3 of aluminum alkyl (wherein, R' is an alkyl or halogen group having 1 to 8 carbon atoms, the same or different and at least one R ¹ is alkyl, R 'is the same Or different. 22. The method of claim 21 wherein the organoaluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum dihalide, trialkoxyaluminum, and dialkylaluminum halide. 24. The method of claim 22, wherein the organoaluminum compound is trialkylaluminum. 24. The process of claim 23, wherein the organoaluminum compound is triethylaluminum. 15. The process of claim 14, wherein the monomer is propylene. 15. The method of claim 14, further comprising the step of pre-polymerizing the catalyst by contacting the catalyst with a minor amount of monomer after step (c). 15. The method of claim 14, wherein the reaction zone contains an additional amount of an organoaluminum compound and an electron donor. 15. The process of claim 14, wherein the process produces a polymer product wherein the xylene-soluble fraction is in the range of 0.6 to 3.0 weight percent of the polymer product. 15. The method of claim 14, further comprising forming a copolymer by adding a second monomer.