Catalyst system for polymerization of an olefin

Abstract

The invention relates to a process for preparing a catalyst system suitable for olefin polymerization. The present invention further relates to a catalyst system obtainable by such process. In addition, the invention relates to a polyolefin. The invention also relates to ashaped article. The catalyst system comprises a procatalyst, a co-catalyst and optionally at least one external electron donor.

Claims

1. A process for preparing a catalyst system for olefin polymerization, said catalyst system comprising a procatalyst, a co-catalyst and optionally at least one external electron donor said process comprising: A) providing said procatalyst obtained via a process comprising: i) contacting a compound R.sup.4.sub.zMgX.sup.4.sub.2?z with an alkoxy- or aryloxy-containing silane compound to give a first intermediate reaction product, being a solid Mg(OR.sup.1).sub.xX.sup.1.sub.2?x, wherein: R.sup.4 is the same as R.sup.1 being a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group is substituted or unsubstituted, and optionally comprises one or more heteroatoms; X.sup.4 and X.sup.1 are each independently selected from the group of consisting of fluoride (F.sup.), chloride (Cl.sup.), bromide (Br.sup.) or iodide (I.sup.); z is in a range of larger than 0 and smaller than 2, being 0<z<2; ii) optionally contacting the solid Mg(OR.sup.1).sub.xX.sup.1.sub.2-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M.sup.1(OR.sup.2).sub.v?w(OR.sup.3).sub.w or M.sup.2(OR.sup.2).sub.v?w(R.sup.3).sub.w, to obtain a second intermediate product; wherein: M.sup.1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M.sup.2 is a metal being Si; v is the valency of M.sup.1 or M.sup.2; R.sup.2 and R.sup.3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group is substituted or unsubstituted, and optionally comprises one or more heteroatoms; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and an internal electron donor to obtain said procatalyst; B) contacting said procatalyst with a co-catalyst and at least one external donor; characterized in that, the at least one external donor is a di-alkylaminoalkyl-trialkoxysilane according to Formula C
(R.sup.90).sub.2N-A-Si(OR.sup.91).sub.3Formula C wherein each R.sup.90 group is independently selected from an alkyl having 1-10 carbon atoms, wherein each R.sup.91 group is independently selected from an alkyl having 1-10 carbon atoms, wherein A is a either a direct NSi bond, or an alkyl spacer selected from an alkyl having 1-10 carbon atoms, and/or wherein the at least one external donor is an imidosilane according to formula I:
Si(L).sub.n(OR.sup.1).sub.4-nFormula I wherein: Si is a silicon atom with valency 4+; O is an oxygen atom with valency 2? and O is bonded to Si via a silicon-oxygen bond; n is 1, 2, 3 or 4; R.sup.1 is selected from the group consisting of linear, branched and cyclic alkyl groups having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl groups having 6 to 20 carbon atoms; and L is a group represented by Formula II: ##STR00017## wherein: L is bonded to the silicon atom via a nitrogen-silicon bond; L has a single substituent on the nitrogen atom, where this single substituent is an imine carbon atom; and X and Y are each independently selected from the group consisting of: a) a hydrogen atom; b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of Formula II, wherein the heteroatom is substituted with a group consisting of a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or with an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; c) a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or wherein the at least one external donor is an alkylimidosilane according to Formula I:
Si(L).sub.n(OR.sup.1).sub.4?n?m(R.sup.2).sub.mFormula I wherein: Si is a silicon atom with valency 4+; O is an oxygen atom with valency 2? and O is bonded to Si via a silicon-oxygen bond; n is 1, 2, 3 or 4; m is 0, 1 or 2; n+m?4 R.sup.1 is selected from the group consisting of linear, branched and cyclic alkyl having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; and R.sup.2 is selected from the group consisting of linear, branched and cyclic alkyl having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; and L is a group represented by Formula II ##STR00018## wherein: L is bonded to the silicon atom via a nitrogen-silicon bond; L has a single substituent on the nitrogen atom, where this single substituent is an imine carbon atom; and X and Y are each independently selected from the group consisting of: a) a hydrogen atom; b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of Formula II, wherein the heteroatom is substituted with a group consisting of a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or with an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; c) a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements.

2. The process according to claim 1, wherein the internal donor is an N-containing internal electron donor selected from the group consisting of benzamides, di-alkylaminoalkyl-trialkoxysilanes, imidosilanes, alkylimidosilanes and aminobenzoates.

3. The process according to claim 2, wherein the N-containing internal donor is an aminobenzoate according to Formula XI: ##STR00019## wherein: R.sup.80, R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85, and R.sup.86 are independently selected from a group consisting of hydrogen, C.sub.1-C.sub.10 straight and branched alkyl; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl group; wherein R.sup.81 and R.sup.82 are each a hydrogen atom and R.sup.83, R.sup.84, R.sup.85 and R.sup.86 are independently selected from a group consisting of C1-C.sub.10 straight and branched alkyl; C.sub.3-C.sub.10 cycloalkyl; C.sub.6-C.sub.10 aryl; and C.sub.7-C.sub.10 alkaryl and aralkyl group, and R.sup.87 is selected from a group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl and halophenyl group.

4. The process according to claim 1, wherein the N-containing internal and/or external donor is a di-alkylaminoalkyl-trialkoxysilane according to Formula C
(R.sup.90).sub.2N-A-Si(OR.sup.91).sub.3Formula C wherein each R.sup.90 group is independently selected from an alkyl having 1-10 carbon atoms, wherein each R.sup.91 group is independently selected from an alkyl having 1-10 carbon atoms, wherein A is an alkyl spacer selected from an alkyl having 1-10 carbon atoms, and/or wherein the N-containing internal and/or external donor is an imidosilane according to formula I:
Si(L).sub.n(OR.sup.1).sub.4?nFormula I wherein: Si is a silicon atom with valency 4+; O is an oxygen atom with valency 2? and O is bonded to Si via a silicon-oxygen bond; n is 1, 2, 3 or 4; R.sup.1 is selected from the group consisting of linear, branched and cyclic alkyl groups having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl groups having 6 to 20 carbon atoms; and L is a group represented by Formula II: ##STR00020## wherein: L is bonded to the silicon atom via a nitrogen-silicon bond; L has a single substituent on the nitrogen atom, where this single substituent is an imine carbon atom; and X and Y are each independently selected from the group consisting of: a) a hydrogen atom; b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of Formula II, wherein the heteroatom is substituted with a group consisting of a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or with an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; c) a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or wherein the N-containing internal and/or external donor is an alkylimidosilane according to Formula I:
Si(L).sub.n(OR.sup.1).sub.4?n?m(R.sup.2).sub.mFormula I wherein: Si is a silicon atom with valency 4+; O is an oxygen atom with valency 2? and O is bonded to Si via a silicon-oxygen bond; n is 1, 2, 3 or 4; m is 0, 1 or 2; n+m?4 R.sup.1 is selected from the group consisting of linear, branched and cyclic alkyl having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; and R.sup.2 is selected from the group consisting of linear, branched and cyclic alkyl having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; and L is a group represented by Formula II ##STR00021## wherein: L is bonded to the silicon atom via a nitrogen-silicon bond; L has a single substituent on the nitrogen atom, where this single substituent is an imine carbon atom; and X and Y are each independently selected from the group consisting of: a) a hydrogen atom; b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements, through which X and Y are each independently bonded to the imine carbon atom of Formula II, wherein the heteroatom is substituted with a group consisting of a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and/or with an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; c) a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; and d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements.

5. The process according to claim 3, wherein the N-containing internal donor is an aminobenzoate according to formula XI; and the N-containing external donor is a di-alkylaminoalkyl-trialkoxysilane according to Formula C
(R.sup.90).sub.2N-A-Si(OR.sup.91).sub.3Formula C wherein each R.sup.90 group is independently selected from an alkyl having 1-10 carbon atoms, wherein each R.sup.91 group is independently selected from an alkyl having 1-10 carbon atoms, wherein A is a either a direct NSi bond, or an alkyl spacer selected from an alkyl having 1-10 carbon atoms.

6. Process according to claim 1, wherein the process is essentially phthalate free.

7. Process according to claim 1, wherein the N-containing internal electron donor is activated by an activator wherein the activator is a benzamide according to formula X: ##STR00022## wherein: R.sup.70 and R.sup.71 are each independently selected from hydrogen or an alkyl; R.sup.72, R.sup.73, R.sup.74, R.sup.75, R.sup.76 are each independently selected from hydrogen, a heteroatom such as a halide, or a hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.

8. The process according to claim 7, wherein the benzamide according to formula X is present in the procatalyst in an amount from 0.1 to 4 wt. %.

9. A catalyst system obtained by the process of claim 1.

10. A process for the preparation of polyolefins, comprising contacting the catalyst system of claim 9 with an olefin, and optionally an external donor.

11. The process according to claim 1, wherein the N-containing internal electron donor is activated by an activator.

12. The process according to claim 11, wherein the activator is N,N-dimethylbenzamide.

13. The process according to claim 1, wherein R.sup.4 and R.sup.1 each have from 1 to 20 carbon atoms; and R.sup.2 and R.sup.3 each have from 1 to 20 carbon atoms.

14. The process according to claim 3, wherein R.sup.83, R.sup.84, R.sup.85 and R.sup.86 are independently selected from a group consisting of C.sub.1-C.sub.10 straight and branched alkyl and phenyl; and R.sup.80 is selected from the group consisting of substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisol group.

15. The process acccording to claim 3, wherein the N-containing internal donor is selected from the group consisting of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis(4-methoxy)benzoate), 3-[benzoyl(cyclohexyl)amino]-1-phenylbutyl benzoate, 3-[benzoyl(propan-2-yl)amino]-1-phenylbutyl, 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl, 3-(methylamino)-1,3-diphenylpropan-1-ol dibenzoate, 3-(methyl)amino-propan-1-ol dibenzoate; 3-(methyl)amino-2,2-dimethylpropan-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis (4-methoxy)benzoate).

16. The process of of claim 4, wherein the N-containing internal and/or external donor is diethylaminotriethoxysilane or diethylamino methyl triethoxysilane.

17. The process of claim 15, wherein the N-containing external donor is diethylaminotriethoxysilane or diethylamino methyl triethoxysilane.

18. The process of claim 16, wherein the N-containing internal electron donor is activated by N,N-dimethylbenzamide.

Description

EXAMPLES

Synthesis of the Procatalyst Components

(1) Procatalyst I

(2) A. Grignard Formation Step

(3) A stirred flask, fitted with a reflux condenser and a funnel, was filled with magnesium powder (24.3 g). The flask was brought under nitrogen. The magnesium was heated at 80? C. for 1 hour, after which dibutyl ether (DBE, 150 ml), iodine (0.03 g) and n-chlorobutane (4 ml) were successively added. After the colour of the iodine had disappeared, the temperature was raised to 80? C. and a mixture of n-chlorobutane (110 ml) and dibutyl ether (750 ml) was slowly added over a period of 2.5 hours. The reaction mixture was stirred for another 3 hours at 80? C. Then the stirring and heating were stopped and the small amount of solid material was allowed to settle for 24 hours. By decanting the colorless solution above the precipitate, a solution of butylmagnesiumchloride (reaction product of step A) with a concentration of 1.0 mol Mg/l was obtained.

(4) B. Preparation of the Intermediate Reaction Product

(5) 250 mL of dibutyl ether was introduced to a 1 L reactor fitted with a propeller stirrer and two baffles. The reactor was thermostated at 35? C. and the stirrer speed was kept at 200 rpm. Then a cooled (to 15? C.) 360 mL solution of the Grignard reaction product as prepared in step A and 180 ml of a cooled (to 15? C.) solution of tetraethoxysilane (TES) in dibutyl ether (consisting of 38 ml of TES and 142 ml of DBE) were dosed into the reactor over a period of 400 minutes with preliminary mixing in a minimixer of 0.15 ml volume, which was cooled to 15? C. by means of cold water circulating in the minimixer jacket. The premixing time was 18 seconds in the minimixer and the connecting tube between the minimixer and the reactor. The stirring speed in the minimixer was 1000 rpm. On the dosing completion, the reaction mixture was kept at 35? C. for 0.5 hours. Then the reactor was heated to 60? C. and kept at this temperature for 1 hour. Then the stirrer was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 300 ml of heptane. As a result, a white solid reaction product was obtained and suspended in 200 ml of heptane.

(6) Under an inert nitrogen atmosphere at 20? C. a 250 ml glass flask equipped with a mechanical agitator is filled with a slurry of 5 g of the reaction product of step B dispersed in 60 ml of heptane. Subsequently a solution of 0.86 ml methanol (MeOH/Mg=0.5 mol) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at 20? C. for 30 minutes the slurry was slowly allowed to warm up to 30? C. for 30 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product which was washed once with 90 ml of heptane at 30? C.

(7) C. Preparation of the Procatalyst Component

(8) A reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 90? C. and a suspension, containing about 5.5 g of the support obtained in step C in 15 ml of heptane, was added to it under stirring. The reaction mixture was kept at 90? C. for 10 min. Then, ethyl benzoate was added (EB/Mg=0.15 molar ratio). The reaction mixture was kept for 60 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 90? C. for 20 min. The washing solution was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 90? C. for 30 min. After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. Then di-n-butyl phthalate (DBP) (DBP/Mg=0.15 molar ratio) in 3 ml of chlorobenzene was added to reactor and the temperature of reaction mixture was increased to 115? C. The reaction mixture was kept at 115? C. for 30 min. After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115? C. for 30 min, after which the solid substance was allowed to settle. The supernatant was removed by decanting and the solid was washed five times using 150 ml of heptane at 60? C., after which the procatalyst component, suspended in heptane, was obtained.

(9) Procatalyst II

(10) A. Grignard Formation Step

(11) This step was carried out as described in Example XVI of EP 1 222 214 B1.

(12) A stainless steel reactor of 9 l volume was filled with magnesium powder 360 g. The reactor was brought under nitrogen. The magnesium was heated at 80? C. for 1 hour, after which a mixture of DBE (1 liter) and chlorobenzene (200 ml) was added. Then iodine (0.5 g) and n-chlorobutane (50 ml) were successively added to the reaction mixture. After the colour of the iodine had disappeared, the temperature was raised to 94? C. Then a mixture of DBE (1.6 liter) and chlorobenzene (400 ml) was slowly added for 1 hour, and then 4 liter of chlorobenzene was slowly added for 2.0 hours. The temperature of reaction mixture was kept in interval 98-105? C. The reaction mixture was stirred for another 6 hours at 97-102? C. Then the stirring and heating were stopped and the solid material was allowed to settle for 48 hours. By decanting the solution above the precipitate, a solution of phenylmagnesiumchloride reaction product A has been obtained with a concentration of 1.3 mol Mg/l. This solution was used in the further catalyst preparation.

(13) B. Preparation of the First Intermediate Reaction Product

(14) This step was carried out as described in Example XX of EP 1 222 214 B1, except that the dosing temperature of the reactor was 35? C., the dosing time was 360 min and the propeller stirrer was used. First 250 ml of DBE was introduced to a 1 liter reactor. The reactor was fitted by propeller stirrer and two baffles. The reactor was thermostated at 35? C.

(15) The solution of reaction product of step A (360 ml, 0.468 mol Mg) and 180 ml of a solution of tetraethoxysilane (TES) in DBE, (55 ml of TES and 125 ml of DBE), were cooled to 10? C., and then were dosed simultaneously to a mixing device of 0.45 ml volume supplied with a stirrer and jacket. Dosing time was 360 min. Thereafter the premixed reaction product A and the TES-solution were introduced to a reactor. The mixing device (minimixer) was cooled to 10? C. by means of cold water circulating in the minimixer's jacket. The stirring speed in the minimixer was 1000 rpm. The stirring speed in reactor was 350 rpm at the beginning of dosing and was gradually increased up to 600 rpm at the end of dosing stage.

(16) On the dosing completion the reaction mixture was heated up to 60? C. and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 500 ml of heptane. As a result, a pale yellow solid substance, reaction product B (the solid first intermediate reaction product; the support), was obtained, suspended in 200 ml of heptane. The average particle size of support was 22 ?m and span value (d90?d10)/d50=0.5.

(17) C. Preparation of the Second Intermediate Reaction Product

(18) Support activation was carried out as described in Example IV of WO/2007/134851 to obtain the second intermediate reaction product.

(19) In inert nitrogen atmosphere at 20? C. a 250 ml glass flask equipped with a mechanical agitator is filled with slurry of 5 g of reaction product B dispersed in 60 ml of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg=0.1) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at 20? C. for 30 minutes, a solution of 0.79 ml titanium tetraethoxide (TET/Mg=0.1) in 20 ml of heptane was added for 1 hour.

(20) The slurry was slowly allowed to warm up to 30? C. for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product (the second intermediate reaction product; activated support) which was washed once with 90 ml of heptane at 30? C.

(21) D. Preparation of the Catalyst Component

(22) A reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 90? C. and a suspension, containing about 5.5 g of activated support in 15 ml of heptane, was added to it under stirring. The reaction mixture was kept at 90? C. for 10 min. Then add 0.866 g of ethyl acetate (EA/Mg=0.25 mol). The reaction mixture was kept for 60 min (stage I of catalyst preparation). Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 100? C. for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The temperature of reaction mixture was increased to 115? C. and 0.64 g of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (aminobenzoate, AB, AB/Mg=0.05 mol) in 2 ml of chlorobenzene was added to reactor. Then the reaction mixture was kept at 115? C. for 30 min (stage II of catalyst preparation). After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115? C. for 30 min (stage III of catalyst preparation), after which the solid substance was allowed to settle. The supernatant was removed by decanting and the solid was washed five times using 150 ml of heptane at 60? C., after which the catalyst component, suspended in heptane, was obtained.

(23) Procatalyst III

(24) Example II was carried out in the same way as Example I, but in step D 0.886 g of ethyl benzoate (EB/Mg=0.15) at 100? C. and AB/Mg=0.15 were used instead of ethyl acetate (EA/Mg=0.25) at 90? C. and AB/Mg=0.05, respectively. This procatalyst contains an AB, n-containing ID.

(25) Procatalyst IV

(26) Procatalyst IV was prepared according to the method disclosed in U.S. Pat. No. 4,866,022. This patent discloses a catalyst component comprising a product formed by: A. forming a solution of a magnesium-containing species from a magnesium carbonate or a magnesium carboxylate; B. precipitating solid particles from such magnesium-containing solution by treatment with a transition metal halide and an organosilane having a formula: RnSiR4?n, wherein n=0 to 4 and wherein R is hydrogen or an alkyl, a haloalkyl or aryl radical containing one to about ten carbon atoms or a halosilyl radical or haloalkylsilyl radical containing one to about eight carbon atoms, and R is OR a halogen: C. reprecipitating such solid particles from a mixture containing a cyclic ether; and D. treating the reprecipitated particles with a transition metal compound and an DBP electron donor. This process for preparing a catalyst is incorporated into the present application by reference.

Synthesis of Compound A and Compound B, Which are Two Examples of Nitrogen Containing External Electron Donors

(27) Tetraethoxysilane, t-butyl lithium, trimethylacetonitrile were purchased at Sigma-Aldrich and used as purchased.

Synthesis of 1,1,1-triethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene)silanamine (ED A)

(28) ##STR00015##

(29) A solution of trimethylacetonitrile (7.5 g, 0.090 mol) in 150 ml n-heptane was added to a 1.3 M solution of t-butyl-lithium in n-pentane (91 mL, 0.81 mole) at ?10? C. over 1 hr. The reaction mixture was stirred for 2 hr at 0 to ?50? C. to give a pale yellow solution of lithium (2,2,4,4-tetramethylpentan-3-ylidene)amide. The solution was cooled to ?10? C. and tetraethoxysilane (28.1 gm, 0.135 mol) was added over 15 min, while slowly rising the temperature to 10? C. The reaction mixture was quenched using 25 mL of a saturated ammonium chloride solution in water. The organic layer was separated and dried over sodium sulfate. The solvents were removed in vacuo. The remaining crude oil (16.0 g) was distilled at 120? C./2 mbar to obtain 4.9 g of 1,1,1-triethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene)silanamine; clear colorless liquid; GC-MS (Cl), 304.12 (m+1); .sup.1H NMR (300 MHz, CDCl.sub.3) ?=1.20-1.23 (t, 9H), 1.25 (d, 18H), 3.81-3.87 (q, 6H); .sup.13C NMR (75.4 MHz, CDCl.sub.3) ?=195.0, 77.3, 77.0, 76.7, 58.9, 45.3, 30.3, 18.2 ppm.

Synthesis of 1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene)silanamine (ED B)

(30) ##STR00016##

(31) A solution of trimethylacetonitrile (7.5 g, 0.090 mole) in 150 ml n-heptane was added to a 1.3 M solution of t-butyl-lithium in n-pentane (100.0 mL, 0.09 mole) at ?60? C. over 1 hr. The reaction mixture was stirred for 2 hr at ?30 to ?50? C. to give a pale yellow solution of lithium (2,2,4,4-tetramethylpentan-3-ylidene)amide. The reaction mixture was cooled to ?60? C. and tetramethoxysilane (27.4 g, 0.180 mole) was added over 15 min, while slowly rising the temperature to 10? C. The reaction mixture was quenched using 25 mL of a saturated ammonium chloride solution in water. The organic layer was separated and dried over sodium sulfate. The solvents were removed in vacuo. The remaining crude oil (20.0 g) was distilled at 110? C./2 mbar to obtain 6.5 g 1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene)silanamine; clear colorless liquid; GC-MS (Cl), 261.98 (m+1), 203.92, 141.21; .sup.1H NMR (400 MHz, CDCl.sub.3) ?=1.24-1.27 (d, 9H), 3.59-3.60 (d, 18H); .sup.13C NMR (100.6 MHz, CDCl.sub.3) ?=196.4, 51.2, 45.5, 30.4 ppm.

(32) Batch Propylene-Ethylene Co-Polymerizations

(33) Propylene-ethylene co-polymerization experiments (Table 1) were performed using the procatalysts described above. Triethylaluminum was used as co-catalyst, and several external electron donors (Di BDMS, DEATES, EDA and EDB) were employed.

(34) The copolymerization of propylene and ethylene was carried out in a stainless steel reactor with a volume of 1800 mL. Under a nitrogen atmosphere, the co-catalyst (TEAL) and procatalyst component synthesized according to the procedure described above and the external electron donor were dosed to the reactor as heptane solutions or slurries; 10-15 mg of procatalyst were employed. The molar ratio of co-catalyst to titanium (from the procatalyst) was set either to 50 or 160, and the Si/Ti ratio was set to 9. During this dosing, the reactor temperature was maintained below 30? C. Subsequently, the reactor was pressurized using a set ratio of propylene, ethylene and hydrogen, and the temperature and pressure were raised to its setpoint (60? C. and 20 bar). After the pressure setpoint has been reached, the polymerization was continued for 60 minutes. During the polymerization reaction the gas cap composition of propylene, ethylene and hydrogen was controlled using mass flow meters and online-GC control. After reaching the polymerization time the reactor was depressurized and cooled to ambient condtitions. The propylene-ethylene random copolymer so obtained was removed from the reactor and stored in aluminum bags for further analysis.

(35) TABLE-US-00001 TABLE 1 Co-polymerization of propylene and ethylene. Catalyst Pro Yield Exp. # Cat ED ID Al/Ti (Kg/g/h) MFR CE1 I DiBDMS DBP 50 16.3 0.28 CE2 IV DiBDMS DBP 50 19.1 0.27 1 I DEATES* DBP 160 20.5 27 2 I DEATES* DBP 50 17.0 25 CE3 II DiBDMS AB* 50 19.8 0.25 3 II DEATES* AB* 50 23.7 18 4 III DEATES* AB* 160 20.3 23 5 III DEATES* AB* 50 25.2 24 6 III DiBDMS AB* 50 24.9 25 7 III DiBDMS AB* 50 22.0 0.23 8 III DEATES* AB* 50 18.3 0.21 9 I ED A* DBP 50 20.7 24 10 I ED B* DBP 50 25.3 16 C.sub.2-cont. Lump Exp. # (Wt. %) Cont. XS H.sub.2/C.sub.3 C.sub.2/C.sub.3 Statics CE1 4.09 0.2 11.5 0.0110 0.0193 2 CE2 3.92 0.0 11.0 0.0009 0.0161 2 1 3.87 0.10 8.2 0.0307 0.0184 1 2 3.80 0.0 10.1 0.0281 0.0158 1 CE3 3.85 1.3 n.d. 0.0045 0.0236 2 3 4.1 0.8 11.5 0.0388 0.0228 1 4 3.74 0.3 10.7 0.0340 0.0203 1 5 3.80 0.1 10.0 0.0425 0.0202 1 6 3.93 2.3 n.d. 0.1468 0.0247 1 7 4.06 2.9 10.0 0.0038 0.0233 1 8 4.08 0.6 n.d. 0.0023 0.0233 1 9 4.2 2.8 n.d. 0.0310 0.0168 1 10 7.1 9.0 n.d. 0.0320 0.0174 1 *N-containing donor
Abbreviations and Measuring Methods: catalyst yield, kg/g cat is the amount of polymer obtained per gram of catalyst component. H.sub.2/C.sub.3 is the molar ratio of hydrogen to propylene in the gas cap of the reactor, measured by on-line gas chromatography. C.sub.2/C.sub.3 is the molar ratio of ethylene to propylene in the gas cap of the reactor, measured by on-line gas chromatography. C2 content (wt. % on propylene-ethylene copolymer)

(36) Lump content: lump content as used in the present description means: the weight percentage of the total isolated polymer weight which does not pass through a sieve having a pore size of 2.8 mm.

(37) Statics are observed visually by inspecting the wall of the reactor. The following criteria are used: 1: no statics observed, meaning that polymer powder was neither visible on the stirrer nor on the reactor walls (after opening of the reactor); 2: statics observed, meaning polymer powder was visible on the stirrer and/or on the reactor walls (after opening of the reactor).

(38) As can be seen from Table 1 above, when an N-containing internal and/or external donor is used for the polymerization of a polyolefin, preferably a propylene polymer, statics in the reactor are significantly reduced.