CATALYTIC SUPPORT AND USES THEREOF
20190345273 ยท 2019-11-14
Inventors
- Dermot O'Hare (Oxford, GB)
- Jean-Charles Buffet (Oxford, GB)
- Alexander Kilpatrick (Oxford, GB)
- Ekisath SOMSOOK (Bangkok, TH)
- Nitiphat NEALMONGKOLRATTANA (Bangkok, TH)
- Sumate Charoenchaidet (Bangkok, TH)
- Saovalak Sripothongnak (Bangkok, TH)
Cpc classification
C08F4/65927
CHEMISTRY; METALLURGY
C08F4/52
CHEMISTRY; METALLURGY
C08F4/65922
CHEMISTRY; METALLURGY
International classification
Abstract
Solid-phase supported materials are described for use in supporting metallocene catalytic compounds. The supported metallocene catalytic compositions are efficient olefin polymerisation catalysts, which show notably higher catalytic activity compared to catalytic compounds employing conventional support materials.
Claims
1. A solid-phase support material suitable for supporting a metallocene catalytic compound, the solid-phase support material comprising a solid polymethylaluminoxane modified by reaction with a compound of formula (I) or (II) shown below: ##STR00026## wherein X is hydroxyl or a group B(Y).sub.2 or a group Al(Y).sub.2, wherein each Y is independently selected from hydroxyl, phenyl and naphthalenyl, any of which may be optionally substituted with one or more groups selected from halo, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and trihaloalkyl; R.sub.a and R.sub.b are independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo or trihaloalkyl, or R.sub.a and R.sub.b are linked, such that, when taken with the atoms to which they are attached, they form a 6-membered aromatic ring that is optionally substituted by one or more groups selected from halo, 1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and trihaloalkyl; R.sub.c, R.sub.d, and R.sub.e are each independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo or trihaloalkyl; Z is hydroxyl or a group NR.sub.xR.sub.y, wherein R.sub.x and R.sub.y are independently selected from hydrogen and (1-4C)alkyl; R.sub.f is (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, trihaloalkyl or a phenyl group that is optionally substituted with one or more groups selected from hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo and trihaloalkyl; wherein the mole ratio of the compound of formula (I) or (II) to the solid polymethylaluminoxane within the solid-phase support material ranges from 0.0001:1 to 0.3:1.
2. (canceled)
3. The solid-phase support material of claim 1, wherein when X is hydroxyl i) R.sub.a, R.sub.b, R.sub.c, R.sub.d and R.sub.e are each independently halo; or ii) R.sub.a and R.sub.b are linked, such that, when taken with the atoms to which they are attached, they form a 6-membered aromatic ring that is optionally substituted by one or more groups selected from halo, 1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and trihaloalkyl, and R.sub.c, R.sub.d, and R.sub.e are independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo or trihaloalkyl; or iii) R.sub.a, R.sub.b and R.sub.e are each independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo or trihaloalkyl, and R.sub.d and R.sub.e are each independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl or trihaloalkyl; or iv) R.sub.a, R.sub.b, R.sub.d and R.sub.e are each independently hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, halo or trihaloalkyl, and R.sub.c is hydrogen, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl or halo.
4. The solid-phase support material of claim 1, wherein each Y is independently selected from hydroxyl or a phenyl group that is optionally substituted with one or more groups selected from fluoro, hydroxyl, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and trifluoroalkyl.
5. (canceled)
6. (canceled)
7. The solid-phase support material of claim 1, wherein R.sub.a, R.sub.b, R.sub.c, R.sub.d and R.sub.e are each independently hydrogen, hydroxyl, (1-4C)alkyl, 2-4C)alkenyl, (2-4C)alkynyl, fluoro or trifluoroalkyl.
8. (canceled)
9. (canceled)
10. The solid-phase support material of claim 1, wherein R.sub.f is (1-4C)alkyl, trihaloalkyl or a phenyl group that is optionally substituted with one or more groups selected from hydroxyl, (1-4C)alkyl, halo and trihaloalkyl.
11. (canceled)
12. (canceled)
13. The solid-phase support material of claim 1, wherein the mole ratio of the compound of formula (I) or (II) to the solid polymethylaluminoxane within the solid-phase support material ranges from 0.0001:1 to 0.1:1.
14. (canceled)
15. (canceled)
16. The solid-phase support material of claim 1, wherein the compound of formula (I) or (II) is selected from one or more of the following: ##STR00027##
17. (canceled)
18. (canceled)
19. The solid-phase support material of claim 1, wherein the solid-phase support material has an aluminium content of 23 to 40 wt %.
20. The solid-phase support material of pfeceding claim 1, wherein the BET surface area of the solid-phase support material is 10.0 to 20.0 m.sup.2 mmol.sub.Al.sup.1.
21. A method of preparing a solid-phase support material of claim 1, the method comprising the steps of: a) providing a solid polymethylaluminoxane in a first solvent; b) contacting the solid polymethylaluminoxane of step a) with one or more compounds of formula (I) or (II) as defined in any preceding claim; and c) isolating the product formed from step b); wherein the mole ratio of the compound of formula (I) or (II) to the solid polymethylaluminoxane used in step b) ranges from 0.0001:1 to 0.3:1.
22. The method of claim 21, wherein the one or more compounds of formula (I) or (II) used in step b) is provided in a second solvent.
23. The method of claim 21, wherein step b) is conducted at a temperature of 18-150 C.
24.-26. (canceled)
27. The method of claim 21, wherein step b) further comprises the step of sonicating the mixture of the solid polymethylaluminoxane and the one or more compounds of formula (I) or (II).
28.-30. (canceled)
31. The method of claim 21, wherein the first solvent is selected from toluene, benzene and hexane.
32. (canceled)
33. The method of claim 21, wherein the second solvent is selected from toluene, benzene and hexane.
34. (canceled)
35. The method of claim 21, wherein the mole ratio of the compound of formula (I) or (II) to the solid polymethylaluminoxane used in step b) ranges from 0.0001:1 to 0.1:1.
36. (canceled)
37. (canceled)
38. The method of claim 21, wherein step a) comprises the steps: i. precipitating a solid polymethylaluminoxane from a reaction medium, ii. isolating the precipitated solid polymethylaluminoxane from the reaction medium, and iii. dispersing the isolated solid polymethylaluminoxane in the first solvent.
39. (canceled)
40. A catalytic composition comprising: a) a compound of formula (III) ##STR00028## wherein R.sub.1 and R.sub.2 are each independently hydrogen or (1-2C)alkyl; R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4 are linked such that, when taken in combination with the atoms to which they are attached, they form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and S(O).sub.2(1-6C)alkyl; R.sub.5 and R.sub.6 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4 are linked such that, when taken in combination with the atoms to which they are attached, they form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and S(O).sub.2(1-6C)alkyl; R.sub.7 and R.sub.8 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4 are linked such that, when taken in combination with the atoms to which they are attached, they form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and S(O).sub.2(1-6C)alkyl; Q is absent, or is a bridging group selected from CH.sub.2 or CH.sub.2CH.sub.2, either or which may be optionally substituted with one or more groups selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, or Q is a bridging group Si(R.sub.9)(R.sub.10), wherein R.sub.9 and R.sub.10 are independently (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl or aryl; X is zirconium or hafnium; and each Y group is independently selected from halo, hydride, (1-6C)alkyl, (1-6C)alkoxy, aryl or aryloxy, either or which is optionally substituted with one or more groups selected from (1-6C)alkyl and halo; and b) a solid-phase support material of claim 1.
41.-51. (canceled)
52. A process for the preparation of a polyolefin, comprising polymerizing at least one monomer in the presence of a catalytic composition of claim 40.
53. (canceled)
54. The process of claim 52, wherein the polyolefin is a copolymer formed from ethene monomers comprising 1-10 wt %, by total weight of the monomer, of one or more (4-8C) -olefin.
Description
EXAMPLES
[0190] One or more non-limiting examples of the invention will now be described, for the purpose of illustration only, with reference to the accompanying figures, in which
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EXAMPLE 1PREPARATION OF SOLID MAO
[0237] The solid MAO useful in the preparation of the solid-phase support material of the invention may be prepared via an adaptation of the optimised procedure in Kaji et al. in the U.S. Pat. No. 8,404,880 B2 embodiment 1 (Scheme 1). For brevity, each synthesised solid MAO is represented as solid MAO(Step 1 Al:O ratio/Step 2 temperature in C.,time in h/Step 3 temperature in C.,time in h). Hence, the synthesis conditions outlined in Scheme 1 would yield solid MAO(1.2/70,32/100,12).
##STR00020##
[0238] A Rotaflo ampoule containing a solution of trimethyl aluminium (2.139 g, 2.967 mmol) in toluene (8 mL) was cooled to 15 C. with rapid stirring, and benzoic acid (1.509 g, 1.239 mmol) was added under a flush of N.sub.2 over a period of 30 min. Effervescence (presumably methane gas, MeH) was observed and the reaction mixture appeared as a white suspension, which was allowed to warm to room temperature. After 30 min the mixture appeared as a colourless solution and was heated in an oil bath at 70 C. for 32 h (a stir rate of 500 rpm was used). The mixture obtained was a colourless solution free of gelatinous material, which was subsequently heated at 100 C. for 12 h. The reaction mixture was cooled to room temperature and hexane (40 mL) added, resulting in the precipitation of a white solid which was isolated by filtration, washed with hexane (240 mL) and dried in vacuo for 3 h. Total yield=1.399 g (71% based on 40 wt % Al).
EXAMPLE 2PREPARATION OF SOLID-PHASE SUPPORT MATERIALS
Method A
[0239] Typical experiment: To a Schlenk flask charged with solid MAO (Example 1) and the modifier was added toluene, and the resulting dispersion was heated at 80 C. for 2 h with regular swirling. The mixture was cooled to room temperature and the insoluble solids were allowed to settle. The supernatant solution was removed by decantation and the remaining slurry was washed three times with a 2:1 mixture of hexane:toluene and dried in vacuo overnight, to afford the modified solid MAO as a free-flowing solid.
Method B
[0240] Typical experiment: To a Schlenk flask charged with a dispersion of solid MAO (Example 1) in toluene was added a solution of the modifier in toluene and the flask was sonicated in a water bath at ambient temperature for 1 h. The resultant mixture was allowed to settle, the supernatant solution was removed by decantation and the remaining slurry was washed three times with a 2:1 mixture of hexane:toluene and dried in vacuo overnight, to afford the modified solid MAO as a free-flowing solid.
##STR00021##
EXAMPLE 3CHARACTERISATION OF SOLID-PHASE SUPPORT MATERIALS AND POLYMERISATION STUDIES
[0241] In order to assess the catalytic performance of the sold-phase support materials, a range of metallocene compounds were supported on a variety of the solid-phase support materials. In a typical experiment, the metallocene catalytic compound (e.g rac-ethylenebis(1-indenyl) zirconium dichloride, (EBI)ZrCl.sub.2) and the support (modified solid MAO) were loaded into a Schlenk flask and toluene (40 mL) was added. The mixture was heated at 80 C. in an oil bath and swirled regularly to ensure complete immobilisation of the metallocene complex (stirring was avoided to prevent aggregation). After 2 h the reaction was removed from the oil bath and allowed to settle, before decantation of the colourless supernatant and thorough drying in vacuo.
[0242] Once prepared, the ability of the supported metallocene catalysts to catalyse the polymerisation of ethylene to polyethylene was assessed. In a typical polymerisation experiment, the immobilised catalyst (10 mg), triisobutlyaluminium scavenger (150 mg), and hexane (40 mL) were added to a high-pressure Rotaflo ampoule. Ethylene gas was continuously fed into the ampoule at 2 bar overpressure during polymerisation at 70 C. After 30 min, the reaction was stopped by removing the ampoule from the oil bath, and degassing in vacuo. The polymer was isolated on a frit, washed with pentane (50 mL) and vacuum dried at room temperature for 1 h. Each polymerisation experiment was conducted at least twice to ensure the reproducibility of the corresponding outcome, and mean productivities are quoted in units of kg.sub.PEg.sub.CAT.sup.1 h.sup.1.
[0243] For large scale polymerisation studies, polymerization of ethylene was performed in a 2 L stainless steel autoclave reactor as the lines of nitrogen and ethylene gases were directly connected into the reactor. First, to clear up the system, the reactor was evacuated and purged by inert nitrogen gas for 1 hour and dried n-hexane was filled. Then, triethylaluminum (TEA) was fed by pipette into the reactor following by finished catalyst, which was prepared in a glove box into the specified sampling catalyst vessel under nitrogen atmosphere. After that, 3 barg of nitrogen was replaced with ethylene for 3 times and kept within the reactor at 3 barg before starting stirrer. When the reactor was heated until temperature below the set point for 5 C., catalyst was injected into the reactor by ethylene pressure flushed with dried n-hexane. Ethylene gas was introduced via a mass flow controller to fulfill the reactor reaching to the set point of total pressure at 8 barg and the temperature was also controlled at 80 C. Polymerisation was continued for 1 hour, while feeding rate was recorded. Lastly, reaction was cut down by depressurised and cooled down temperature. Resulting mixture was poured into tray and dried at room temperature to remove solvent from polymer.
Supported (EBI)ZrCl.SUB.2 .Complexes
[0244] ##STR00022##
[0245] Table 1 below shows characterisation and polymerisation data for solid MAO samples modified via Method A with B(C.sub.6F.sub.5).sub.3.
TABLE-US-00001 TABLE 1 Characterisation and polymerisation data for solid MAO samples modified via Method A with B(C.sub.6F.sub.5).sub.3, Al(C.sub.6F.sub.5).sub.3 and Al(C.sub.6F.sub.5).sub.2Cl. Polymerisation conditions: 2 bar, 50 mL hexanes, TIBA. Ratio Support M:Al Support BET/ Support Catalyst Activity/ Modifier mole % Yield m.sup.2mmol.sub.Al.sup.1 wt % Al kg.sub.PEmol.sub.Zr.sup.1h.sup.1 Control 0 88 17.8 40.0 13686 B(C.sub.6F.sub.5).sub.3 0.02 87 15.0 32.6 13972 Al(C.sub.6F.sub.5).sub.3 0.02 83 X 30.9 12670 Al(C.sub.6F.sub.5).sub.2Cl 0.02 80 X 32.5 11461
[0246] Although the Al-based modifiers gave rise to support materials having activities that are slightly lower than the control, it is presumed that this is attributable to the relatively high temperature employed in Method A. It is expected that such modifiers will yield improved results when the support material is prepared according to Method B, which uses softer conditions. Preliminary studies support this hypothesis.
[0247]
[0248] Table 2 below shows characterisation and polymerisation data for solid MAO samples modified via Method A with increased amounts of B(C.sub.6F.sub.5).sub.3 (compared with the data of Table 1).
TABLE-US-00002 TABLE 2 Characterisation and polymerisation data for solid MAO samples modified via Method A with B(C.sub.6F.sub.5).sub.3 at increased loadings. Polymerisation conditions: 2 bar, 50 mL hexanes, TIBA Ratio M:Al Support Support BET/ Support Catalyst Activity/ mole % Yield m.sup.2 mmol.sub.Al.sup.1 wt % Al kg.sub.PEmol.sub.Zr.sup.1h.sup.1 0 88 17.8 40.0 13686 0.01 88 14.6 35.3 10787 0.02 87 15.0 34.9 11533 0.04 58 10.6 23.0 11739 0.10 59 12.8 23.5 14028 0.20 48 9.6 19.0 14402
[0249] Although the modifier loadings of 0.01, 0.02 and 0.04 resulted in catalyst activities that are slightly lower than the control, it is expected that this is attributable to the relatively high temperature employed in Method A. It is expected that such loadings will yield improved results when the support material is prepared according to Method B, which uses softer conditions. Preliminary studies support this hypothesis. It is also noted that the results illustrated in Table 1 demonstrate that B(C.sub.6F.sub.5).sub.3 loadings of 0.02 may nonetheless give rise to improved activities when the support material is prepared via Method A.
[0250] SEM imaging (
[0251] Table 3 below shows characterisation and polymerisation data for solid MAO samples modified via Method B with two different modifiers, B(C.sub.6F.sub.5).sub.3 and C.sub.6F.sub.5OH.
TABLE-US-00003 TABLE 3 Characterisation and polymerisation data for solid MAO samples modified via Method B with (EBI)ZrCl.sub.2. Polymerisation conditions: 8 bar, 1000 mL hexanes, TEA. Ratio M:Al Support Support Catalyst Activity/ Modifier mole % Yield wt % Al kg.sub.PEmol.sub.Zr.sup.1h.sup.1 Control 0 93.2 35.1 143608 B(C.sub.6F.sub.5).sub.3 0.10 72.9 24.8 211559 C.sub.6F.sub.5OH 0.40 98.8 18 262977
[0252] SEM images of the solid MAO samples mounted on copper tape (
[0253] Table 4 below shows characterisation and polymerisation data for solid MAO samples modified at 10 mol % loading via Method B with two different modifiers, B(C.sub.6F.sub.5).sub.3 and C.sub.6F.sub.5OH.
TABLE-US-00004 TABLE 4 Characterisation and polymerisation data for solid MAO samples modified at 10 mol % loading via Method B with (EBI)ZrCl.sub.2. Polymerisation conditions: 2 bar, 50 mL hexanes, TIBA. Ratio Support Catalyst M:Al Support Support Support BET/ Activity/ Modifier mole Colour % Yield wt. % Al m.sup.2mmol.sub.Al.sup.1 kg.sub.PEmol.sub.Zr.sup.1h.sup.1 Control 0 Colourless 88 39.7 15.0 12515 B(C.sub.6F.sub.5).sub.3 0.10 Colourless 62 24.9 18.6 16009 {4-F}C.sub.6H.sub.4OH 0.10 Orange 92 36.7 12.0 11366 {4-CF.sub.3}C.sub.6H.sub.4OH 0.10 Green 87 34.8 14.9 6891 {3,5-F}.sub.2C.sub.6H.sub.3OH 0.10 Grey 93 37.0 14.7 9178 {3,5-CF.sub.3}.sub.2C.sub.6H.sub.3OH 0.10 Dark red 95 37.9 11.9 3945 C.sub.6F.sub.5OH 0.10 Colourless 92 36.5 14.4 13340
[0254] Table 5 shows polyethylene polymerisation data for solid MAO modified with varying quantities of pentafluorophenol via Method B.
TABLE-US-00005 TABLE 5 Summary data of modified solid MAO with pentafluorophenol (Al wt %) and modified solidMAO/(EBI)ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 36 36 0.4 18.8 0.38 180,109 4.30 0.01 27 27 0.3 32.8 0.44 186,827 4.78 0.05 24 24 0.3 34.2 0.44 182,812 4.42 0.1 21 21 0.4 32.0 0.37 192,566 4.47 0.4 17 17 0.3 57.9 0.38 147,578 3.88 0.8 15 15 0.5 16.8 0.37 158,497 4.11 1.2 10 10 0.3 19.7 0.33 193,992 4.59 Polymerisation conditions: 25 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes
[0255] The aluminum content (wt %) of modified solid MAO decreases from 27, 24, 21 to 17 when more modifier was used. It indicates the presence of phenol compound in modified product corresponding to amount of phenol addition. At ratio of 0.4 it performs 3 folds higher catalyst activity [activity: 18.8 vs 57.910.sup.4 Kg.sub.PE/mol.sub.Zr.Math.h] compared with non-modified solid MAO/(EBI)ZrCl.sub.2. Bulk density of obtained polymer is in the range of 0.33-0.44 ml/g which is acceptable for polymerization.
Supported (.sup.nBuCp).sub.2ZrCl.sub.2 complexes
##STR00023##
[0256] Table 6 shows polyethylene polymerisation data for solid MAO modified with varying quantities of pentafluorophenol via Method B.
TABLE-US-00006 TABLE 6 Summary data of modified solidMAO with pentafluorophenol (Al wt %) and modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 36 40 0.8 31.2 0.34 142,466 2.54 0.0005 40 34 0.6 38.2 0.35 138,051 2.54 0.001 35 35 0.6 34.9 0.01 27 33 0.4 53.7 0.39 139,519 2.51 0.05 24 33 0.4 40.9 0.1 21 37 0.5 30.7 0.4 17 30 0.3 36.9 0.8 15 14 0.2 53.1 1.2 10 12 0.3 37.6 1.6 9 12 0.2 45.9 Polymerisation conditions: 25 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes
[0257] The increase of modifier amount (modifier: Al ratio of 0.0005 to 1.6) results in lower Al content (wt %) of modified solid MAO and Al & Zr (wt %) content in modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2. At ratio of 0.01 it shows the highest activity of 53.710.sup.4 Kg.sub.PE/mol.sub.Zr.Math.h which is higher than non-modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2 of 31.210.sup.4 Kg.sub.PE/mol.sub.Zr.Math.h. The bulk density of polymer obtained is in the range of 0.35-0.39 ml/g which is acceptable for slurry polymerization. The modification of solid MAO has no significant effect to polymer properties such as molecular weight and molecular weight distribution as shown in Table 6. The morphology of modified solid MAO still well controls. They have popcorn shape with particle size of 4-7 micron (
[0258] Table 7 shows polyethylene polymerisation data for solid MAO modified with 4-fluorophenol via Method B.
TABLE-US-00007 TABLE 7 Summary data of modified solidMAO with 4-fluorophenol (Al wt %) and modified solidMAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0005 40 0.05 40 37 0.49 29.83 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0259] Table 8 shows polyethylene polymerisation data for solid MAO modified with phenol via Method B.
TABLE-US-00008 TABLE 8 Summary data of modified solid MAO with phenol (Al wt %) and modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0005 35 36 0.56 37.75 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0260] Higher amount of modifier addition (higher modifier: Al) provides lower Al and Zr content in modified solid MAO and modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2. The morphology of modified solid MAO was elucidated with SEM, (
[0261] Table 9 shows polyethylene polymerisation data for solid MAO modified with methanesulfonic acid via Method B
TABLE-US-00009 TABLE 9 Summary data of modified solid MAO with methanesulfonic acid (Al wt %) and modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0045 36 36 0.48 33.8 0.35 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0262] The modifier: Al of 0.0045 shows higher activity of 33.810.sup.4 Kg.sub.PE/mol.sub.Zr.Math.h with lower Zr content of 0.48 wt %. Bulk density is 0.35 ml/g acceptable for slurry polymerization.
[0263] Table 10 shows polyethylene polymerisation data for solid MAO modified with 4-fluorophenylboronic acid via Method B
TABLE-US-00010 TABLE 10 Summary data of modified solid MAO with 4-fluorophenylboronic acid (Al wt %) and modified solid MAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0005 33 36 0.48 33.1 0.30 Finish catalyst 0.0125 g, TEA (200 mmol/L) = 2.5 mL, T = 80 C., P = 8 Bar, solvent hexane 1 L
[0264] The modifier: Al of 0.0005 showed an increased activity of 33.110.sup.4 Kg.sub.PE/mol.sub.Zr.Math.h.
[0265] Table 11 shows polyethylene polymerisation data for solid MAO modified with 3,5-Bis(trifluoromethane)phenol via Method B
TABLE-US-00011 TABLE 11 Summary data of modified solid MAO with 3,5-Bis(trifluoromethane)phenol (Al wt %) and modified solidMAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0006 34 38 0.51 34.6 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0266] Table 12 shows polyethylene polymerisation data for solid MAO modified with p-toluene sulfonamide via Method B.
TABLE-US-00012 TABLE 12 Summary data of modified solidMAO with p-toluene sulfonamide (Al wt %) and modified solidMAO/(.sup.nBuCp).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 39 40 0.8 31.2 0.34 142,466 2.54 0.0005 32 36 0.58 28.40 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0267]
Supported (Ind).sub.2ZrCl.sub.2 complexes
##STR00024##
[0268] Table 13 shows polyethylene polymerisation data for solid MAO modified with pentafluorophenol via Method B.
TABLE-US-00013 TABLE 13 Summary data of modified solid MAO with pentafluorophenol (Al wt %) and modified solidMAO/(Ind).sub.2ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.W, MWD). Al (wt %)- Ratio ICP Finish catalyst Bulk M:Al Modified ICP (wt %) Activity 10.sup.4 density (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) (ml/g) M.sub.w MWD control 36 41 0.78 18.47 0.34 142,466 2.54 0.0005 40 0.32 0.4 17 19 0.44 28.4 Polymerisation conditions: 12.5 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes.
[0269] The modification of solid MAO with pentafluorophenol with modifier: Al ratio of 0.4 used as solid activator for (Ind).sub.2ZrCl.sub.2 is able to enhance in catalyst activity of 28.4 KgPE/gCat.Math.h.
Supported .sup.Ph2C(.sup.tBuFlu,Cp)ZrCl.sub.2 complexes
##STR00025##
[0270] Table 14 shows polyethylene polymerisation data for solid MAO modified with varying quantities pf pentafluorophenol via Method B.
TABLE-US-00014 TABLE 14 Summary data of modified solid MAO with pentafluorophenol (Al wt %) and modified solid MAO/.sup.Ph2C(.sup.tBuFlu,Cp)ZrCl.sub.2 (Al wt %, Zr wt %, activity, productivity) and polymer properties (bulk density, M.sub.w, MWD). Al (wt %)- Finish ICP catalyst Ratio Modified ICP (wt %) Activity 10.sup.4 M:Al (mole) solidMAO Al Zr (Kg.sub.PE/mol.sub.Zr .Math. h) control 36 38 0.58 5.3 0.0005 40 36 0.6 6.2 0.001 35 38 0.67 5.5 0.01 27 37 0.67 5.4 0.05 24 30 0.34 11.6 0.1 21 29 0.29 15.9 0.4 17 16 0.36 9.2 0.8 15 12 0.40 7.7 1.2 10 11 0.13 3.2 1.6 9 11 0.08 1.0 Polymerisation conditions: 25 mg Catalyst, 2.5 mL TEA, 80 C., 8 bar. 1 L hexanes
Further Studies
[0271] Table 15 shows characterisation and polymerisation data for solid MAO samples modified with B(C.sub.6F.sub.5).sub.3 via Method B at different loadings, and polymerisation activities with 2 different zirconocene precatalysts.
TABLE-US-00015 TABLE 15 Characterisation data for solid MAO samples modified with B(C.sub.6F.sub.5).sub.3 via Method B at different loadings, and polymerisation activities with 2 different zirconocene precatalysts. Support Ratio Support ICP-MS Support M:Al Yield (wt % BET Activity (kg.sub.PEmol.sub.Zr.sup.1h.sup.1) (mol) (%) Al) (m.sup.2mmol.sub.Al.sup.1) (EBI)ZrCl.sub.2 (.sup.nBuCp).sub.2ZrCl.sub.2 0.00 94 38.5 16.6 12692 11900 0.01 89 38.1 14.2 15662 10827 0.05 78 36.4 15.2 16718 9690 0.10 62 32.5 16.8 16106 9346 0.20 44 25.3 11.6 17834 9088
[0272] Table 15 shows the polymerisation activities using (EBI)ZrCl.sub.2 and (.sup.nBuCp).sub.2ZrCl.sub.2 when B(C.sub.6F.sub.5).sub.3 was used as modifier at different molar ratios. This demonstrates an increase with the former but a decrease with the latter.
[0273] Table 16 shows characterisation and polymerisation data for solid MAO samples modified with C.sub.6F.sub.5OH via Method B at different loadings, and polymerisation activities with 2 different zirconocene precatalysts.
TABLE-US-00016 TABLE 16 Characterisation data for solid MAO samples modified with C.sub.6F.sub.5OH via Method B at different loadings, and polymerisation activities with 2 different zirconocene precatalysts. Support Ratio Support ICP-MS Support M:Al Yield (wt % BET Activity (kg.sub.PEmol.sub.Zr.sup.1h.sup.1) (mol) (%) Al) (m.sup.2mmol.sub.Al.sup.1) (EBI)ZrCl.sub.2 (.sup.nBuCp).sub.2ZrCl.sub.2 0.00 94 38.5 16.6 12692 11900 0.01 93 37.5 15.6 12500 8119 0.05 83 36.8 14.8 13330 9099 0.10 91 34.4 14.4 13023 7655 0.20 93 25.4 11.9 14392 5153
[0274] Table 16 shows the polymerisation activities using (EBI)ZrCl.sub.2 and (.sup.nBuCp).sub.2ZrCl.sub.2 when C.sub.6F.sub.5OH was used as modifier at different molar ratios. This demonstrates an increase with the former but a decrease with the latter.
[0275] Tables 17 to 19 shows the molecular weights of the polyethylene using various modifiers on solid MAO and various complexes.
TABLE-US-00017 TABLE 17 Polymerisation Activities and GPC data for unmodified solid MAO (control) with 5 different zirconocene precatalysts. Activity M.sub.w Precatalyst (kg.sub.PEmol.sub.Zr.sup.1h.sup.1) (kg/mol) PDI (EBI)ZrCl.sub.2 12692 99.0 3.5 (.sup.nBuCp).sub.2ZrCl.sub.2 11900 254.8 2.7 .sup.Me2SB(.sup.tBu2Flu, I*)ZrCl.sub.2 5849 585.6 2.8 .sup.Me2SB(Cp, I*)ZrCl.sub.2 9468 178.2 2.7
TABLE-US-00018 TABLE 18 Polymerisation Activities and GPC data for B(C.sub.6F.sub.5).sub.3 modified solid MAO at 5 mol % loading via Method B with 5 different zirconocene precatalysts. Activity M.sub.w Precatalyst (kg.sub.PEmol.sub.Zr.sup.1h.sup.1) (kg/mol) PDI (EBI)ZrCl.sub.2 17512 101.6 4.0 (.sup.nBuCp).sub.2ZrCl.sub.2 9690 289.9 2.6 .sup.Me2SB(.sup.tBu2Flu, I*)ZrCl.sub.2 6319 633.6 3.0 .sup.Me2SB(Cp, I*)ZrCl.sub.2 7020 252.1 2.5
TABLE-US-00019 TABLE 19 Polymerisation activities and GPC data for C.sub.6F.sub.5OH modified solid MAO at 5 mol % loading via Method B with 5 different zirconocene precatalysts. Activity M.sub.w Precatalyst (kg.sub.PEmol.sub.Zr.sup.1h.sup.1) (kg/mol) PDI (EBI)ZrCl.sub.2 13330 132.9 3.7 (.sup.nBuCp).sub.2ZrCl.sub.2 9090 290.6 2.7 .sup.Me2SB(.sup.tBu2Flu, I*)ZrCl.sub.2 8016 662.2 3.3 .sup.Me2SB(Cp, I*)ZrCl.sub.2 7671 185.5 3.2
[0276] The results presented in Tables 17-19 show that the modification of the support has no direct effect on the molecular weight of the resulting polyethylene.
[0277] Table 20 shows characterisation data for solid MAO samples modified with various modifiers at 5 mol % loading via Method B, and polymerisation data with 3 different zirconocene precatalysts.
TABLE-US-00020 TABLE 20 Characterisation data for solid MAO samples modified at 5 mol % loading via Method B, and polymerisation activities with 3 different zirconocene precatalysts. Activity (Kg.sub.PEmol.sub.Zr.sup.1h.sup.1) Yield ICP-MS BET .sup.Me2SB(Cp, I*) Modifier (%) Al (wt %) (m.sup.2 g.sup.1) (EBI)ZrCl.sub.2 (.sup.nBuCp).sub.2ZrCl.sub.2 ZrCl.sub.2 Control 94 38.5 16.6 12692 11900 9468 BPh.sub.3 59 36.5 15.2 10898 6204 5753 B(C.sub.6F.sub.5).sub.3 89 36.4 14.3 15662 10827 7020 Al(C.sub.6F.sub.5).sub.3 76 33.3 12.9 5449 8047 9530 {4-F}C.sub.6H.sub.4B(OH).sub.2 87 38.4 15.0 4052 5414 5718 {3,5-F}.sub.2C.sub.6H.sub.3B(OH).sub.2 86 30.3 13.5 8036 4694 3930 C.sub.6F.sub.5B(OH).sub.2 86 33.7 15.2 3243 3617 7956 {4-F}C.sub.6H.sub.4OH 90 38.0 15.2 6203 7988 4674 {3,5-F}.sub.2C.sub.6H.sub.3OH 91 35.5 15.0 4158 9629 8066 C.sub.6F.sub.5OH 90 36.8 14.8 13330 9090 7671
[0278] Table 21 shows spectroscopic data for the different modified solid polymethylaluminoxane and complexes.
TABLE-US-00021 TABLE 21 Spectroscopic data for solid MAO samples modified at 5 mol % loading via Method B. NMR in THF-d.sub.8 .sup.1H .sub.H .sup.19F{.sup.1H} SSNMR (ppm) .sub.F .sup.1H .sub.iso .sup.19H .sub.iso .sup.11B .sub.iso FWHH DRIFT Modifier Me.sup.B (ppm) (ppm) (ppm) (ppm) (Hz) v(cm.sup.1) Control 0.60 n/a .sup.# BPh.sub.3 0.81 n/a 32 5604 .sup.# B(C.sub.6F.sub.5).sub.3 0.64 123.2, 166 84 674 2315, 158.3, (s), 1641 164.2 157 (w) Al(C.sub.6F.sub.5).sub.3 0.63 123.2, 1.18 165, 158.3, 124 164.1 {4-F}C.sub.6H.sub.4B(OH).sub.2 0.71 .sup. 0.82 111 18 (w) 8231 .sup.# {3,5-F}.sub.2C.sub.6H.sub.3B(OH).sub.2 0.70 112.2 1.23, 123 16 (w) 9346 .sup.# 114.2, 6.55 (w) C.sub.6F.sub.5B(OH).sub.2 0.64 .sup. 1.31, 166, 7.3 (m) 3183 1647 6.29 135 (w) {4-F}C.sub.6H.sub.4OH 0.68 130.0 121 n/a n/a .sup.# {3,5-F}.sub.2C.sub.6H.sub.3OH 0.80 113.5 1.45, 110 n/a n/a 2468, 5.68 2115 (w) C.sub.6F.sub.5OH 0.83 164.8, 166, n/a n/a 2473, 169.0, 157 1654 177.4 .sup.Spectrum not fully resolved due to poor solubility. .sup.#Spectrum shows no change from the control (v = 3550, 2951, 2632, 2391, 1593, 1531, 1441, 1252, 1211 cm.sup.1).
[0279]
[0280]
[0281]
[0282]
[0283] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.