# Patent

## Title
Supported catalyst composition for polymerization of olefins, method for preparing the same and process for polymerization using the same

## Abstract

Supported catalyst composition for polymerization of olefins comprising: (i) a titanium compound, a magnesium compound and at least one electron donor compound; (ii) a chlorine containing polymer support; and (iii) a cocatalyst comprising at least one aluminum compound, wherein the magnesium loading on the final catalyst is between about 0.20 and 6% by weight.

## Background
This application is the national stage of PCT/IB02/02832, filed Jan. 7, 2002, which claims priority under 35 U.S.C. §119 based on EP 01102891.7, filed Feb. 15, 2001.
FIELD OF THE INVENTION
The present invention relates to a supported catalyst composition for polymerization of olefins, a method for preparing the same and a process for polymerization using the same.
DESCRIPTION OF THE PRIOR ART
Supported heterogeneous catalyst compositions for the polymerization of olefins are well known in the art.
In many cases, silica supported titanium based catalysts have been used for the polymerization of olefins. However, their use does result in the presence of impurities in the final product. These impurities, in turn, cause the polymer to have an poor film appearance rating. Thus, while silica supported catalysts provide good particle morphology, a sacrifice is made in the quality of the polymer.
Therefore, a need existed to provide catalyst supports overcoming the drawbacks of using silica.
L. Sun, C. C. Hsu and D. W. Bacon, Journal of Polymer Science: Part A Polymer Chemistry, Vol. 32, 2127–2134, describe eleven polymers of different backbone structures and functional groups which are tested for their suitability for use as a catalyst support.
U.S. Pat. No. 5,102,841 discloses the use of polypropylene polymer as support to bond particulate of catalyst precursor based on titanium or vanadium. A catalyst preparation is used therein for a catalyst precursor which is already described in U.S. Pat. No. 4,303,771. In U.S. Pat. No. 5,102,841 a process for the production of polyethylene is disclosed utilizing a catalyst having a support which furnishes a particle morphology equivalent to silica and other organic oxide supports, but essentially avoids the presence of objectionable residue in the resin. The process of U.S. Pat. No. 5,102,841 comprises contacting ethylene or a mixture comprising ethylene and one or more alpha-olefins and, optionally, one or more diolefins, under polymerization conditions with a catalyst system comprising:

    (a) a particulate catalyst precursor containing titanium and/or vanadium.
    (b) polypropylene support particles to which the catalyst precursor particles are bonded; and
    (c) a hydrocarbyl aluminum cocatalyst.


However, use of the process of U.S. Pat. No. 5,102,841 will result in a low productivity for that catalyst composition. Moreover, a product clarity and resin morphology are obtained which are not satisfying. Further, the catalyst price is quite high.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a supported catalyst composition, which overcomes the drawbacks of the prior art, especially improving its productivity.
It is a further object of the present invention to provide a method for preparing such a supported catalyst composition with lower costs.
It is still a further object of the present invention to provide a process for polymerization of olefins utilizing the supported catalyst composition of the present invention producing a polymer having an improved product quality and morphology.
The present invention provides a supported catalyst composition for polymerization of olefins comprising:

    
    
        (i) a titanium compound, a magnesium compound and at least one electron donor compound;
        (ii) a chlorine containing polymer support; and
        (iii) a cocatalyst comprising at least one aluminum compound,
        wherein the magnesium loading in the final catalyst is between 0.20 and 6% by weight.
    
    


Moreover, the present invention provides a method for preparing a supported catalyst composition according to the present invention comprising the following steps:

    
    
        (i) forming a catalytic precursor comprising a magnesium compound, a titanium compound and at least one electron donor compound;
        (ii) mixing the catalytic precursor prepared in step (i) with a polymer support in a solvent;
        (iii) refluxing the mixture prepared in step (ii) for a certain period of time;
        (iv) optionally removing the solvent to form a solid powder of the supported catalyst composition; and
        (v) adding a cocatalyst comprising at least one aluminum compound.
    
    


Further, the present invention provides a process for homopolymerization of ethylene or copolymerization of ethylene with alpha-olefins and/or diolefins by contacting ethylene or ethylene and alpha-olefins and/or diolefins with a catalyst composition according to the present invention.
Surprisingly, it was found that a supported catalytic composition according to the present invention shows an increased productivity in the polymerization of olefins and has a low price in preparation. Moreover, the polymeric support will result in less product ash and in less catalyst residuals remaining in the polymer produced. Further, the properties concerning the polymer produced with the catalyst composition of the present invention show increased product clarity and resin morphology. Without wishing to be bound to any theory, the functionality of the polymeric support of the present invention seems to play a major role in anchoring or coordinating the catalyst precursor on the support surface and preventing precursor leaching which in turn would lead to form poor resin morphology as with polypropylene supports of the prior art.


DETAILED DESCRIPTION OF THE INVENTION
The catalyst precursor, in solid or dissoluted form, used in the present invention may be in principle identical to the one disclosed in U.S. Pat. No. 4,303,771.
This catalytic precursor has the formula MgaTi(OR)bXc(ED)d wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, or COR′ wherein R′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR group is the same or different; X is Cl, Br, or I, or mixtures thereof; ED is electron donor; a is 0.5 to 56; b is 0, 1 or 2; c is 2 to 116; and d is greater than 1.5a+2;
A titanium compound, which may be used in the method for preparing the supported catalyst composition of the present invention may have the formula Ti(OR)aXb wherein R and X are defined as for the catalytic precursor mentioned above; a is 0, 1, or 2; b is 1 to 4; a+b is 3 or 4. Suitable compounds are TiCl3, TiCl4, Ti(OC6H5)Cl3, Ti(OC2H5)Cl3, Ti(OCOCH3)Cl3 and Ti(OCOC6H5)Cl3.
A magnesium compound useful in preparing the precursor may have the formula MgX2 wherein X is defined as above. Suitable examples are MgCl2, MgBr2, and MgI2. Anhydrous MgCl2 is a preferred compound. About 0.5 to 56, and preferably about 1 to 10, moles of the magnesium compound are used per mole of titanium compound. The magnesium loading on the final catalyst is between 0.20 and 6% by weight.
A suitable electron donor is an organic compound, which is liquid at temperatures in the range of about 0° C. to 200° C. It is also known as a Lewis base. The compounds used in the preparation of the catalyst precursor are soluble in the electron donor.
The electron donor may be an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an aliphatic alcohol, an alkyl or a cycloalkyl ether, or mixture thereof, each electron donor having 2 to 20 carbon atoms. Among these electron donors alkyl and cycloalkyl ethers having 2 to 20 carbon atoms; dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms; and alkyl, alkoxy, and alkylalkoxy esters of alkyl and aryl carboxylic acids having 2 to 20 carbon atoms are preferred. The most preferred electron donor is tetrahydrofuran. Other examples of suitable electron donors are methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, ethyl propionate, hexyl ether, acetone, and methyl iso-butyl ketone.
The supports useful in the present invention are polymeric resins comprising chlorinated polymers wherein polyvinyl chloride is the preferred one. The supports have a particle size ranging between about 5 and 1000 microns and the preferred size range is between 50 and 80 microns. Furthermore, the supports have a particle pore volume of at least about 0.1 cm3/g as well as surface area of at least about 0.2 cm2.
On the final catalyst composition the titanium loading is preferably between about 0.15 and 5% by weight, and the electron donor loading is preferably between 1 and 45% by weight.
The cocatalyst may comprise aluminum alkyls, aluminoxanes and/or mixtures thereof.
Further, the polymer support may further comprise an oxygen containing polymer, such as polyketone and/or hydrolyzed polyketone.
Some polymeric supports may be incompatible with some electron donors during catalyst preparation. For instance, tetrahydrofuran can easily dissolves or agglomerate polyvinyl chloride. Therefore, a unique method was devised for preventing the support from getting agglomerated or swelled when contacted with the electron donor. First, the support is dried in vacuum between 40 and 90° C., then slurried in hydrocarbon materials such as isopentane, hexane, heptane, or isooctane. The catalyst precursor solution, which contains the electron donor, is poured slowly on the support slurry and all materials are heated to 60° C. for from 15 minutes to 90 minutes. Mixing and stirring are employed continuously and constantly during the entire process. Washing with light hydrocarbon solvents, such as hexane and isopentane at the end of each batch preparation is an option sometimes used, and otherwise the composition is dried directly without washing. This is performed to compare catalyst activity and productivity utilizing both routes and for facilitating the catalyst scaling up process later on. In both ways, active catalyst batches are obtained and may be excellently utilized in a process for slurry polymerization of olefins according to the present invention.
Initially, catalysts batches are dried with a slow flow of nitrogen over night. Drying is later progressed to a vacuum drying to reduce lumps formation and to shorten cycle time of catalyst preparation. Vacuum drying is introduced after the majority of the liquid phase in the flask was evaporated. Catalyst drying time was varied with varying the desired amounts of tetrahydrofuran on the catalyst. The performance of the catalyst varies with varying tetrahydrofuran contents as well as with varying magnesium/titanium ratio.
The catalyst composition according to the present invention may be also used for copolymerization of ethylene with alpha-olefin selected from the group comprising 1-butene, 1-hexene, and 1-octene and mixtures thereof.
EXAMPLES
Example 1
Preparation of Catalyst Precursor
2.0 grams of anhydrous magnesium chloride, 1.16 ml of titanium tetrachloride and 60 ml of dry THF were heated up to 55° C. in a two-necked round bottom flask equipped with a condenser. The reaction was conducted under an inert atmosphere with continuous stirring. After 150 minutes, the content of the flask was cooled down, 10 ml of hexane was added, and yellow solid powder precipitated in the bottom of the flask. The solid was washed four times with isopentane and dried with nitrogen flow overnight. The solid was analyzed to give a composition comprising Ti=5.4 wt %, Mg=5.8 wt % and THF=56.6 wt %.
Example 2
Preparation of Catalyst Composition
6.0 grams of polyvinyl chloride polymer was dried under vacuum at 50° C. for 30 minutes and placed in a two-necked round bottom flask. The polymer was slurried in hexane and 0.633 grams of the above dry precursor powder (Example 1) slurried in 8 ml of THF were added slowly to the polymer slurry. The temperature raised to 63° C. and the materials were stirred and heated continuously for 30 minutes. The excess liquid was then drained and the remaining solid was washed with hexane and dried with nitrogen. The yellow catalyst was powdered and analyzed to give a composition comprising Ti=0.16 wt %, Mg=0.39 wt % and THF=1.55 wt %.
Example 3
Catalyst Performance—Ethylene Homopolymerization using Catalyst Composition of Example 2
An ethylene polymerization was performed with the catalyst composition of Example 2 at 15 bars of ethylene including three bars of hydrogen partial pressure, and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 233 grams of homo-polyethylene resin with a catalyst productivity of 2.5 kg PE/g cat-hr and an activity of 1474 kg PE/g Ti hr. The obtained polymer was a high-density polyethylene resin with a bulk density equal to 0.25 g/cc.
Example 4
Preparation of Catalyst Precursor
In a two-necked round bottom flask equipped with a condenser and a magnet stirrer, 2.0 grams of anhydrous magnesium chloride, 2.0 grams of titanium tetrachloride and 70 ml of THF were placed. The materials were heated to 60° C. and stirred for two hours until a clear yellow solution was formed.
Example 5
Preparation of Catalyst Composition
35 ml of the catalyst precursor of Example 4 was transferred slowly into another two-necked round bottom flask containing 6.0 grams of PVC polymer slurried in hexane and heated to 60° C. The materials were stirred for 1 hour at the same temperature and were then cooled down. The solid was washed several times with hexane and dried with nitrogen at 60° C. The yellow catalyst powder was analyzed and the composition comprised of Ti=0.82 wt %, Mg=1.3 wt % and THF=16.7 wt.
Example 6
Catalyst Performance—Ethylene Homopolymerization Using Catalyst Composition of Example 5
Ethylene polymerization was performed with the catalyst composition of Example 5 at 15 bars of ethylene including three bars of hydrogen partial pressure, and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 566 grams of homo-polyethylene resin with a catalyst productivity of 9.7 kg PE/g cat-.hr and an activity of 1185 kg PE/g Ti hr. The obtained polymer resin was a high-density homopolyethylene with a bulk density equal to 0.30 g/cc.
Example 7
Preparation of Catalyst Composition
3.0 grams of PVC polymer was dried under vacuum at 50° C. for 30 minutes and placed in a two-necked round bottom flask. The polymer was slurried in hexane and 30 ml of the catalyst precursor of example 4 was added on top of the polymer. The flask content was heated for 1 hour at 60° C., then the excess liquid was drained and the remaining solid was washed with hexane and dried under nitrogen at the same temperature. The catalyst composition was analyzed and comprised Ti=2.8 wt %, Mg=3.8 wt % and THF=30.7 wt %.
Example 8
Catalyst Performance—Ethylene Homopolymerization Using Catalyst Composition of Example 7
Ethylene polymerization was performed with a catalyst compositon of example 7 at 15 bars of ethylene including three bars hydrogen partial pressure and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 572 grams of homo-polyethylene resin with a catalyst productivity of 33.4 kg PE/g cat-hr and an activity of 1194 kg PE/g Ti hr. The obtained polymer was a high-density polyethylene resin with a bulk density equal to 0.31 g/cc.
Example 9
Preparation of Catalyst Precursor
In a two-necked round bottom flask equipped with a condenser and a magnet stirrer, 1.0 grams of anhydrous magnesium chloride, 1.8 grams of titanium tetrachloride and 70 ml of THF were placed. The materials were heated to 60° C. and stirred for 90 minutes. A clear yellow solution was formed.
Example 10
Preparation of Catalyst Composition
6.0 grams of polyvinyl chloride polymer was dried under vacuum at 50° C. for 30 minutes and placed in a two-necked round bottom flask. The polymer was slurried in hexane and the catalyst precursor of Example 9 was added slowly to the polymer slurry. The temperature raised to 60° C. and the materials were stirred and heated continuously for 60 minutes. The excess liquid was then drained and the remaining solid was washed with hexane and dried with nitrogen. The yellow catalyst powder was analyzed and the composition comprised Ti=2.3 wt %, Mg=1.8 wt % and THF=30.3 wt %.
Example 11
Catalyst Performance—Ethylene Homopolymerization Using Catalyst Composition of Example 10
Ethylene polymerization was performed with catalyst composition of Example 10 at 15 bars of ethylene including three bars of hydrogen partial pressure and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 320 grams of homo-polyethylene resin with a catalyst productivity of 15.4 kg PE/g cat-hr and an activity of 668 kg PE/g Ti hr. The obtained polymer was a high-density polyethylene resin with a bulk density equal to 0.11 g/cc.
Example 12
Preparation of Catalyst Precursor
In a two-necked round bottom flask equipped with a condenser and a magnet stirrer, 2.0 grams of anhydrous magnesium chloride, 2.0 grams of titanium tetrachloride and 70 ml of THF were placed. The materials were heated to 60° C. and stirred for 90 minutes. A clear yellow solution was formed.
Example 13
Preparation of Catalyst Composition
6.0 grams of PVC polymer was dried under vacuum at 50° C. for 30 minutes and placed in a two-necked round bottom flask. The polymer was slurried in hexane and the catalyst precursor of Example 12 was added slowly to the polymer slurry. The temperature was raised to 60° C. and the materials were stirred and heated continuously for 60 minutes, then dried with nitrogen under vacuum. The yellow catalyst powder was analyzed and the composition comprised Ti=0.94 wt %, Mg=2.9 wt % and THF=43.0 wt %.
Example 14
Catalyst Performance—Ethylene Homopolymerization Using Catalyst Composition of Example 13
Ethylene polymerization was performed with catalyst composition of Example 13 at 15 bars of ethylene including three bars of hydrogen partial pressure and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 494 grams of homo-polyethylene resin with a catalyst productivity of 9.7 kg PE/g cat-hr and an activity of 1031.3 kg PE/g Ti hr. The obtained polymer was a high-density polyethylene resin with a bulk density equal to 0.24 g/cc.
Example 15
Preparation of Catalyst Precursor
In a two-necked round bottom flask equipped with a condenser and a magnet stirrer, 2.0 grams of anhydrous magnesium chloride, 1.4 grams of titanium tetrachloride and 70 ml of THF were placed. The materials were heated to 60° C. and stirred for 90 minutes. A clear yellow solution was formed.
Example 16
Preparation of Catalyst Composition
3.0 grams of PVC polymer (sieved at 120 mesh) was dried under vacuum at 50° C. for 30 minutes and placed in a two-necked round bottom flask. The polymer was slurried in a hexane and the catalyst precursor of Example 15 was added slowly to the polymer slurry. The temperature was raised to 60° C. and the materials were stirred and heated continuously for 30 minutes, then dried with nitrogen under vacuum. The yellow catalyst powder was analyzed and the composition comprised Ti=2.87 wt %, Mg=4.35 wt % and THF=45.0 wt %.
Example 17
Catalyst Performance—Ethylene Homopolymerization Using Catalyst Composition of Example 16
Ethylene polymerization was performed with catalyst composition of example 16 at 15 bars of ethylene including three bars of hydrogen partial pressure and triethylaluminum alkyl (TEAL) was used as the polymerization cocatalyst. The polymerization was run for one hour at a temperature of 85° C.
The polymerization run produced about 263 grams of homo-polyethylene resin with a catalyst productivity of 15.8 kg PE/g cat-hr and an activity of 549.1 kg PE/g Ti hr. The obtained polymer was a high-density polyethylene resin with a sieved bulk density equal to 0.28 g/cc.
The features disclosed in the foregoing description and/or in the claims may, both separately and in any combination thereof, be material for realising the invention in diverse forms thereof.

## Claims

1. A supported catalyst composition for polymerization of olefins consisting essentially of:
(i) a titanium compound of the selected from the group consisting of TiCl3, TiCl4, Ti(OC6H5)Cl3, Ti(OC2H5)Cl3, Ti(OCOCH3)Cl3 and Ti(OCOC6H5)Cl3, a magnesium compound and at least one electron donor compound;
(ii) a polyvinyl chloride support; and
(iii) a cocatalyst comprising at least one aluminum compound;

wherein the magnesium loading on the catalyst composition is between about 0.20 and 6% by weight.

2. The supported catalyst composition according to claim 1, wherein the titanium compound is titanium tetrachloride.

3. The supported catalyst composition according to claim 2, wherein the magnesium compound is magnesium chloride.

4. The supported catalyst composition according to claims 3, wherein said electron donor is tetrahydrofuran.

5. The supported catalyst composition according to claim 4, wherein the polyvinyl chloride support has a particle size between about 5 μm and about 1000 μm.

6. The supported catalyst composition according to claim 5, wherein the polyvinyl chloride support has a pore volume of at least about 0.1 cm3/g and a surface area of at least about 0.2 m2/g.

7. The supported catalyst composition according to claim 5, wherein the titanium loading on the catalyst composition is between about 0.15 and 5% by weight.

8. The supported catalyst composition according to claim 6, wherein the titanium loading on the catalyst composition is between about 0.15 and 5% by weight.

9. The supported catalyst composition according to claim 8, wherein the electron donor loading on the catalyst composition is between about 1 and 45% by weight.

10. The supported catalyst composition according to claim 9, wherein the cocatalyst comprises an aluminum alkyl or an aluminoxane.

11. A method for preparing a supported catalyst composition comprising the following steps:
(i) mixing a magnesium compound, a titanium compound selected from the group consisting of TiCl3, TiCl4, Ti(OC6H5)Cl3, Ti(OC2H5)Cl3, Ti(OCOCH3)Cl3 and Ti(OCOC6H5)Cl3 and at least one electron donor compound to form a catalyst precursor;
(ii) mixing the catalytic precursor prepared in step (i) with a polyvinyl chloride support in a hydrocarbon liquid;
(iii) removing the hydrocarbon liquid from the product of step (ii) and recovering a supported catalyst; and
(iv) adding a cocatalyst comprising at least one aluminum compound to the supported catalyst of step (iii).

12. The method according to claim 11, wherein the mixture of step (ii) is heated at about 60° C. for about 15 to 90 minutes.

13. The method according to claim 12, wherein said hydrocarbon liquid is hexane, isooctane or isopentane.

14. A process for the homopolymerization of ethylene or the copolymerization of ethylene with an alphaolefin or a diolefin to produce a polymer, comprising contacting ethylene or ethylene and an alphaolefin or a diolefin with a supported catalyst in the presence of a cocatalyst, said supported catalyst prepared according to a process comprising:
(i) treating a polyvinyl chloride support with a catalyst precursor comprising a mixture of a titanium compound selected from the group consisting of TiCl3, TiCl4, Ti(OC6H5)Cl3, Ti(OC2H5)Cl3, Ti(OCOCH3)Cl3 and Ti(OCOC6H5)Cl3, a magnesium compound and at least one electron donor in a hydrocarbon liquid;
(ii) removing said hydrocarbon liquid from the product of step (i).

15. The process of claim 14, wherein said titanium compound is titanium tetrachloride and said magnesium compound is magnesium chloride.

16. The process of claim 15, wherein said electron donor is tetrahydrofuran.

17. The process of claim 16, wherein said polyvinyl chloride support has a particle size between about 5 and 1,000 μm, a pore volume of at least about 0.1 cm3/g and a surface area of at least about 0.2 m2/g.

18. The process of claim 17, wherein the product of step (i) is heated at about 60° C. for about 15 to 90 minutes.

19. The process of claim 18, wherein the cocatalyst comprises an aluminum alkyl or an aluminoxane.