Catalyst system for polymerisation of an OLEFIN

Abstract

The present invention relates to a catalyst system comprising a procatalyst, a co-catalyst and an external electron donor, wherein the external electron donor comprises a compound having the structure according to Formula I: Si(L).sub.n(OR.sup.11).sub.4-n (Formula 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 the silicon-oxygen bond; n is 1, 2, 3 or 4; R.sup.11 is a 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; L is a group represented by (Formula II), wherein, L is bonded to the silicon atom via the 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 independently selected from the group consisting of a hydrogen atom; a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; 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 an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 7 of the IUPAC Periodic Table of the Elements. ##STR00001##

Claims

1. A catalyst system suitable for olefin polymerization comprising a Ziegler-Natta type procatalyst, a co-catalyst and at least one external electron donor, wherein the external electron donor comprises a compound having the structure according to Formula I:
Si(L).sub.n(OR.sup.11).sub.4-n(Formula 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.11 is a 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; L is a group represented by the following structure ##STR00025## 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 groups 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 groups 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 catalyst system according to claim 1, wherein L is guanidine, amidine or ketimide.

3. The catalyst system according to claim 1, wherein R.sup.11 is an alkyl having at most 10 carbon atoms.

4. A process for preparing the catalyst system according to claim 1, comprising contacting a Ziegler-Natta type procatalyst, a co-catalyst and at least one external electron donor comprising the compound according to Formula I.

5. The process according to claim 4, said process comprising the steps of: A) providing a Ziegler-Natta procatalyst obtained via a process comprising the steps of: 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, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; X.sup.4 and X.sup.1 are each independently selected from the group of consisting of fluoride (F), chloride (Cl), bromide (Br) or iodide (I), preferably chloride; 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 ii) with at least one activating compound selected from the group formed of 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 may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has from 1 to 20 carbon atoms; iii) contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a halogen-containing Ti-compound and optionally an internal electron donor to obtain said procatalyst; B) contacting said procatalyst with a co-catalyst and at least one external electron donor being a compound having the structure according to Formula I.

6. The process according to claim 5, wherein Mg(OR.sup.1).sub.xX.sup.1.sub.2-x is contacted in step ii) with titanium tetraalkoxide and an alcohol as activating compounds.

7. The process according to claim 4, wherein the co-catalyst is a hydrocarbyl aluminum compound represented by the formula R.sup.21.sub.mAIX.sup.21.sub.3-m wherein m=1 or 2, R is an alkyl, and X is a halide or alkoxide.

8. A process for preparing a polyolefin by contacting at least one olefin with the catalyst system according to claim 1.

9. The process according to claim 8, wherein the at least one olefin is propylene or a mixture of propylene and ethylene.

10. A method for the polymerization of an olefin, comprising: polymerizing the olefin using the compound having the structure according to Formula I according to claim 1 as an external electron donor in a Ziegler-Natta type catalyst system.

Description

EXAMPLES

Synthesis of Si(L)n(OR1)4-n Compounds

(1) 1,1,3,3-Tetramethylguanidine, tetraethoxysilane, tert-butyl lithium, trimethylacetonitrile were purchased at Sigma-Aldrich and used as purchased. Ketimines, amidines and guanidines were synthesized according to literature procedures.

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

(2) ##STR00020##

(3) 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 (yield, 20%; purity, 93%); 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.

Compound B: 1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene) silanamine

(4) ##STR00021##

(5) 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 (yield, 27%; purity, 93.7%); 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.

Compound C: N,N,N,N-tetramethylguanidine triethoxysilane

(6) To a solution of N,N,N,N-tetramethylguanidine (5.0 g, 0.043 mol) in 40 ml of hexane a 2.5 M solution of n-butyl-lithium (17.4 ml, 0.043 mol) was added at 78 C. A white precipitate was observed immediately upon addition. The mixture was subsequently allowed to heat up to room temperature by removing the cooling bath and stirred for an additional 30 minutes. The obtained suspension was slowly added to a solution of tetraethoxysilane (9.7 ml, 0.043 mol) in 50 ml hexane at 78 C., 40 ml of extra hexane was used to transfer the slurry to the reaction mixture. The reaction mixture was allowed to slowly heat up to room temperature and was stirred overnight. The suspension was filtered and the solvent in the obtained residue was removed under a nitrogen flow. The remaining crude oil was distilled at 130 C./0.34 mbar to obtain 8.9 g of N,N,N,N-tetramethylguanidine triethoxysilane (yield, 74%; purity, 99+%); clear colorless liquid; .sup.1H NMR (300 MHz, CDCl.sub.3) =1.11-1.06 (t, 9H), 2.67 (s, 12H), 3.70-3.72 (q, 6H); .sup.13C NMR (75.4 MHz, CDCl.sub.3) =161, 59, 40, 19 ppm.

Compound D: N,N,N,N-tetramethylguanidine trimethoxysilane

(7) ##STR00022##

(8) To a solution of N,N,N,N-tetramethylguanidine (10.0 g, 0.087 mole) in 80 ml of hexane, a 1.6 M solution of n-butyl-lithium (54.2 ml, 0.087 mole) was added at 78 C. Immediately after addition, a white precipitate was observed. The mixture was subsequently allowed to heat up to room temperature by removing the cooling bath and stirred for an additional 30 minutes.

(9) The obtained suspension was slowly added to a solution of tetramethoxysilane (12.8 ml, 0.087 mole) in 100 ml hexane at 78 C., 80 ml of extra hexane was used to transfer the slurry to the reaction mixture. The reaction mixture was allowed to slowly heat up to room temperature and was stirred overnight. The suspension was filtered and the solvent in the obtained residue was removed under a nitrogen flow. The remaining crude reaction mixture was distilled at 128 C./0.15 mbar to obtain 9.5 g of N,N,N,N-tetramethylguanidine trimethoxysilane (yield, 46.5%; purity, 97+%); Pale yellow liquid; .sup.1H NMR (300 MHz, CDCl.sub.3) =2.71-2.73 (d, 12H), 3.70-3.72 (d, 9H). Anal. Calcd for C.sub.8H.sub.21N.sub.3O.sub.3Si (235.36): C, 40.78; H, 8.92; N, 17.84. Found: C, 39.46; H, 8.55; N, 17.455.

Compound E: Di tetramethylguanidine dimethoxysilane

(10) ##STR00023##

(11) To a solution of N,N,N,N-tetramethylguanidine (20.0 g, 0.174 mole) in 200 ml of hexane a 1.6 M solution of n-butyl-lithium (108.5 ml, 0.174 mole) was added at 78 C. A white precipitate was observed immediately upon addition. The mixture was subsequently allowed to heat up to room temperature by removing the cooling bath and stirred for an additional 30 minutes.

(12) The obtained suspension was slowly added to a solution of tetramethoxysilane (13.2 ml, 0.087 mole) in 200 ml hexane at 78 C., 160 ml of extra hexane was used to transfer the slurry to the reaction mixture. The reaction mixture was allowed to slowly heat up to room temperature and was stirred for 16 h. The suspension was filtered and the solvent in the obtained residue was removed under a nitrogen flow. The remaining crude reaction mixture was distilled at 135 C./0.2 mbar to obtain 10.3 g of Di tetramethylguanidine dimethoxysilane (yield, 18.7%; purity, 95+%); clear colorless liquid; .sup.1H NMR (300 MHz, CDCl.sub.3) =2.677-2.679 (d, 24H), 3.542-3.544 (d, 6H). Anal. Calcd for C.sub.12H.sub.30N.sub.6O.sub.2Si (318.5): C, 45.25; H, 9.49; N, 26.38. Found: C, 44.87; H, 10.02; N, 25.12.

Compound F: Tetra tetramethylguanidine silane

(13) ##STR00024##

(14) To a solution of N,N,N,N-tetramethylguanidine (10.0 g, 0.087 mol) in 100 ml of hexane a 1.6 M solution of n-butyl-lithium (59.0 ml, 0.087 mol) was added at 78 C. A white precipitate was observed immediately upon addition. The mixture was subsequently allowed to heat up to room temperature by removing the cooling bath and stirred for an additional 30 minutes.

(15) The obtained suspension was slowly added to a solution of tetramethoxysilane (2.52 ml, 0.017 mol) in 100 ml hexane at 78 C., 100 ml of extra hexane was used to transfer the slurry to the reaction mixture. The reaction mixture was allowed to slowly heat up to room temperature and was stirred for 24 h. The suspension was filtered and the solvent in the obtained residue was removed under a nitrogen flow. The remaining crude reaction mixture was distilled at 100 C./0.25 mbar to obtain 10.8 g of Tetra tetramethylguanidine silane (yield, 26.4%; purity, 95+%); clear colorless liquid; .sup.1H NMR (300 MHz, CDCl.sub.3) =2.69-2.70 (d, 48H). Anal. Calcd for C.sub.19H.sub.45N.sub.12Si (469.74): C, 49.55; H, 9.98; N, 34.67. Found: C, 48.43; H, 10.95; N, 33.075.

Synthesis of the Procatalyst Component

A. Grignard Formation Step (Step o))

(16) 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 for 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.

B. Preparation of the Intermediate Reaction Product (Step i))

(17) 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 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 for 400 min. 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.

(18) 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.

C. Preparation of the Procatalyst Component (Phase C)

(19) 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 (DNB) (DNB/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.

Propylene-ethylene co-polymerization

(20) All polymerization experiments were performed using a magnesium/titanium/chloride containing catalyst which was prepared according to EP1838741B.

(21) The copolymerization of propylene and ethylene was carried out in a stainless steel reactor with a volume of 1800 mL. The co-catalyst (TEAL) and procatalyst component synthesised according to the procedure described above (steps A to C) and the external electron donor were dosed as heptane solutions or slurries to the reactor (Al/Titanium molar ratio=50 and Si/Ti ratio=4.5), which is under a nitrogen atmosphere, while the reactor temperature is 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 barg). After the pressure setpoint has been reached, the polymerization was continued for 75 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 conditions. The propylene-ethylene random copolymer so obtained was removed from the reactor and stored in aluminium bags.

Polymer Analysis

(22) Polymer yield is expressed as total mass of polymer isolated from the reactor.

(23) Catalyst yield is expressed as kilogram of polymer isolated per gram of catalyst after the 75 minutes of polymerization time.

(24) H.sub.2/C.sub.3 is the percentage of hydrogen over propylene in the gas cap of the reactor.

(25) C.sub.2/C.sub.3 is the percentage of ethylene over propylene in the gas cap of the reactor.

Results of the Polymerization Experiments

(26) The following propylene-ethylene co-polymerization experiments were performed using the above reactor conditions. In a reference experiment a standard external donor was used, being diisobutyl dimethoxysilane (DIBDMS); this is comparative example C1. For Example 1 Compound A prepared as discussed above was used. For Example 2 Compound B prepared as discussed above was used. For Example 3 Compound C prepared as discussed above was used. For Example 4 Compound D prepared as discussed above was used. For Example 5 Compound E prepared as discussed above was used. For Example 6 Compound F prepared as discussed above was used.

(27) Compound A=Si(L)(OEt).sub.3 wherein L=N-(2,2,4,4-tetramethylpentan-3-ylidene)

(28) Compound B=Si(L)(OMe).sub.3 wherein L=N-(2,2,4,4-tetramethylpentan-3-ylidene)

(29) Compound C=Si(L)(OEt).sub.3 wherein L=N,N,N,N-tetramethylguanidine

(30) Compound D=Si(L)(OMe).sub.3 wherein L=N,N,N,N-tetramethylguanidine

(31) Compound E=Si(L).sub.2(OMe).sub.2 wherein L=N,N,N,N-tetramethylguanidine

(32) Compound F=Si(L).sub.4 wherein L=N,N,N,N-tetramethylguanidine

(33) The difference between compound A and compound B is in the OR groups wherein for compound A R is ethyl and for compound B R is methyl.

(34) The difference between compound C and compound D is in the OR groups wherein for compound C R is ethyl and for compound D R is methyl.

(35) The difference between compound A and compound C is in the L group wherein for compound A L is N-(2,2,4,4-tetramethylpentan-3-ylidene) and for compound C L is N,N,N,N-tetramethylguanidine.

(36) The difference between compound B and compound D is in the L group wherein for compound B L is N-(2,2,4,4-tetramethylpentan-3-ylidene) and for compound D L is N,N,N,N-tetramethylguanidine.

(37) The difference between compounds D, E and F is that compound F has four L groups, compound E has two L groups whereas compound D has one L group.

(38) From the table below it is clear that with all of the compounds according to the present invention, compared with the comparative example, the lump content is remarkable decreased from 28.7 of the comparative example (C1) to a value between 2.8 and 11.7 for Examples 1-5.

(39) Furthermore, one can for example see from the comparison between the compounds C to F on one hand as well as A and B on the other hand, that depending on the L group, the number and/or bulk/length of the OR can either decrease or increase the lump formation as well as the yield.

(40) For the compounds C to F, one sees that decreasing the number and/or the bulk/length of the OR group(s) tends to decrease the tendency to form lumps formation. However, for Compound F it was not possible to measure the actual lump content because of the formation of one big viscous mass (a big lump). Moreover, decreasing the hinderance arising for example from bulky groups around the Si increases yield. Compound D thereby for example combines a good yield with a low tendency to lump formation

(41) In contrast, for the compounds A and B, with another L group, one sees that increasing the number and/or the bulk/length of the OR group(s) decreases lump formation here. Yield increases again when hinderance arising for example from bulky groups around the Si is decreased.

(42) Especially, compounds A and B thereby showed excellent yields together with a low tendency to form lumps.

(43) This is accordingly an exemplary way that one can tune for example the tendency to form lumps and/or the yield.

(44) The results are shown in Table 1.

(45) TABLE-US-00001 TABLE 1 Polymer Catalyst C2 Lump External H.sub.2/C.sub.3 C.sub.2/C.sub.3 yield yield MFR content content XS Exp. donor vol. % vol. % (gram) Kg/g g/10 min wt. % wt. % wt % C1 DIBDMS 5.1 1.9 188 22.6 22.61 8.6 28.7 10.6 1 Compound A 3.1 1.7 311 20.7 23.8 4.2 2.8 11.7 2 Compound B 3.2 1.7 378 25.3 16.1 7.1 9.0 7.6 3 Compound C 5.0 2.8 60 4.0 52.3 5.6 11.7 22.2 4 Compound D 4.7 2.2 203 13.5 18.9 4.8 4.4 16.7 5 Compound E 5.0 2.2 150 10.0 28.9 5.1 4.0 21.1 6 Compound F 4.9 2.0 75 5.0 75.7 5.8 not 27.5 measured