Catalyst comprising permethylpentalene ligands
10888854 ยท 2021-01-12
Assignee
Inventors
- Dermot O'Hare (Oxford, GB)
- Jean-Charles Buffet (Oxford, GB)
- Zoe Turner (Oxford, GB)
- Duncan Fraser (Oxford, GB)
Cpc classification
C08F4/65912
CHEMISTRY; METALLURGY
C08F2500/03
CHEMISTRY; METALLURGY
C08F2500/04
CHEMISTRY; METALLURGY
C08F4/65925
CHEMISTRY; METALLURGY
C08F2500/03
CHEMISTRY; METALLURGY
C08F4/65925
CHEMISTRY; METALLURGY
C08F4/65916
CHEMISTRY; METALLURGY
C08F2500/04
CHEMISTRY; METALLURGY
B01J31/2295
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08F4/659
CHEMISTRY; METALLURGY
C08F4/6592
CHEMISTRY; METALLURGY
Abstract
Catalytic compositions comprising permethylpentalene based metallocene complexes supported on solid methylaluminoxane are disclosed. The compositions are effective catalysts/initiators in the polymerisation of olefins. Also disclosed are uses of the compositions in olefin polymerisation.
Claims
1. A composition comprising a solid methyl aluminoxane support material and compound of the formula ##STR00041## .
2. The composition of claim 1, wherein the compound is: ##STR00042##
3. The composition of claim 1, further comprising a suitable activator.
4. The composition according to claim 3, wherein the activator is an alkyl aluminium compound.
5. The composition according to claim 3, wherein the activator is methylaluminoxane (MAO), triisobutylaluminium (TIBA), diethylaluminium (DEAC) or triethylaluminium (TEA).
6. A process for polymerising one or more olefins, said process comprising the step of polymerising the one or more olefins in the presence of: (i) a composition as claimed in claim 1; and (ii) a suitable activator.
7. The process of claim 6, wherein the activator is an alkyl aluminium compound.
8. The process of claim 6, wherein the activator is methylaluminoxane (MAO), triisobutylaluminium (TIBA), diethylaluminium (DEAC) or triethylaluminium (TEA).
9. The process of claim 6, wherein the olefins are a mixture of olefins containing 90-99 wt % of ethene monomers and 1-10 wt % of (4-8C) -olefin monomers.
10. The process of claim 6, wherein the olefins are ethylene.
Description
EXAMPLES
(1) Examples of the invention will now be described, for the purpose of illustration only, by reference to the accompanying figures, in which:
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EXAMPLE 1SYNTHESIS OF PRE-CATALYST
Example 1aSynthesis of Pn*ZrCp.SUP.Me.Cl
(17) ##STR00024##
(18) [ZrPn*(-Cl).sub.3/2].sub.2(Cl).sub.2Li.Et.sub.2O.sub.(1.21) (300 mg, 0.362 mmol) was dissolved in Et.sub.2O (20 mL) and cooled to 78 C. Et.sub.2O (15 mL) was added to LiCp.sup.Me (62.3 mg, 0.724 mmol), cooled to 78 C. and the contents slurried onto the solution of [ZrPn*(-Cl).sub.3/2].sub.2(-Cl).sub.2Li.Et.sub.2O.sub.(1.21). The schlenk was allowed to warm to room temperature over the course of an hour, and then stirred for a further hour. The Et.sub.2O was then removed under vacuum, and the solids dissolved sparingly in benzene (32 mL) before being filtered into a small schlenk. The benzene was frozen at 78 C., removed from the cold bath, and exposed to dynamic vacuum overnight causing the solvent to sublime. The solid was then washed with 78 C. pentane (23 mL) and dried under vacuum for 4 h giving the product in 54% yield (152 mg, 0.388 mmol).
(19) .sup.1H NMR (C.sub.6D.sub.6) (ppm): 1.66 {(2,6)-Me.sub.2, 6H, s}; 1.81 {(3,5)-Me.sub.2, 6H, s}; 2.12 {(1,7)-Me.sub.2, Cp-Me, 9H, s); 5.13 {Cp(2,5)-CH, 2H, t (.sup.3J.sub.H-H=2.6 Hz)}; 5.59 {Cp(3,4)-CH, 2H, t (.sup.3J.sub.H-H=2.6 Hz)}
(20) .sup.13C NMR (C.sub.6D.sub.6) (ppm): 10.8 {(2,6)-Me.sub.2}; 12.4 {(1,7)-Me.sub.2}; 13.0 {(3,5)-Me.sub.2}; 14.5 (Cp-Me); 106.1 {Cp(2,5)}; 113.6 {Cp(3,4)} 124.3 (Cp(1)}
Example 1bSynthesis of ZrPn*Cp.SUP.Me3.Cl
(21) ##STR00025##
(22) [ZrPn*(-Cl).sub.3/2].sub.2(-Cl).sub.2Li.THF.sub.(1.02) (250 mg, 0.308 mmol) was dissolved in Et.sub.2O (20 mL) and cooled to 78 C. A slurry of 1,2,3-CpMe.sub.3 (70.2 mg, 0.615 mmol) in 78 C. Et.sub.2O (15 mL) was transferred to this solution via cannula and the contents stirred at this temperature for 1 h. The schlenk was then slowly warmed to room temperature before being stirred for a further hour. The solvent was removed in vacuo, the contents dissolved in benzene (32 mL) and filtered via cannula into a small schlenk. This solution was frozen at 78 C., exposed to dynamic vacuum, then removed from the cool bath to allow the benzene to sublime overnight. This solid was washed with 78 C. pentane (23 mL) and dried under vacuum overnight giving the product as a light tan powder in 53% yield (137 mg, 0.326 mmol).
(23) .sup.1H NMR (C.sub.6D.sub.6) (ppm): 1.64 {(2,6)-Me.sub.2, 6H, s}; 1.76 {Cp(1,3)-Me.sub.2, 6H, s}; 1.90 {(3,5)-Me.sub.2, 6H, s}; 2.03 {Cp(2)-Me, 3H, s}; 2.14 {(1,7)-Me.sub.2, 6H, s}; 4.82 {Cp(4,5)-CH}
(24) .sup.13C NMR (C.sub.6D.sub.6) (ppm): 10.5 {(2,6)-Me.sub.2}; 11.8 {(Cp(2)-Me.sub.2}; 12.1 {Cp(1,3)-Me.sub.2}; 12.6 {(1,7)-Me.sub.2}; 13.2 {(3,5)-Me.sub.2}; 104.2 (3,5); 105.1 {Cp(4,5)}; 112.1 (1,7); 118.9 {Cp(1,3)}; 119.3 (4); 125.1 (2,6); 126.8 (8); 127.3 {Cp(2)}
Example 1cSynthesis of ZrPn*IndCl
(25) ##STR00026##
(26) [ZrPn*(-Cl).sub.3/2].sub.2(Cl).sub.2Li.THF.sub.(1.02) (300 mg, 0.369 mmol) was dissolved in Et.sub.2O (20 mL) and cooled to 78 C. A slurry of IndLi (90.1 mg, 0.738 mmol) was transferred to this solution via cannula and the contents stirred for 1 h. The vessel was allowed to warm to room temperature, then stirred for a further hour, before the solvent was removed under vacuum. The solid was redissolved sparingly in benzene (32 mL) and filtered via cannula into a small schlenk. The solvent was frozen at 78 C., removed from the cold bath, and exposed to dynamic vacuum overnight. The resultant powder was washed with 78 C. pentane (32 mL) and dried under vacuum for 4 hours giving the product as an orange-green powder in 75% yield (239 mg, 0.558 mmol).
(27) .sup.1H NMR (C.sub.6D.sub.6) (ppm): 1.49 {(2,6)-Me.sub.2, 6H,s}; 1.91 {(3,5)-Me.sub.2, 6H, s}; 1.94 {(1,7)-Me.sub.2, 6H, s}; 5.51 {Ind(2,9), 2H, d (.sup.3J.sub.H-H=3.4 Hz)}; 5.78 {Ind(1), 1H, t (.sup.3J.sub.H-H=3.4 Hz)}; 6.93 {Ind(5,6), 2H, m}; 7.51 {Ind(4,7), 2H, m}
(28) .sup.13C NMR (C.sub.6D.sub.6) (ppm): 10.4 {(2,6)-Me.sub.2}; 12.5 {(3,5)-Me.sub.2}; 13.1 {(1,7)-Me.sub.2}; 95.2 {Ind(2,9)}; 105.8 (3,5); 112.4 (1,7); 119.1 {Ind(1)}; 119.8 (4); 123.4 {Ind(4,7)}; 124.0 {Ind(5,6)}; 126.3 (2,6); 126.5 {Ind(3,8); 128.6 (8)
Example 1dSynthesis of Pn*ZrCp.SUP.n..SUP.
(29) ##STR00027##
(30) LiCp.sup.n.sup.
(31) Single crystals suitable for an X-ray diffraction study were grown from a saturated (Me.sub.3Si).sub.2O solution at 35 C. Anal Calcd (found) for C.sub.23H.sub.31ClZr: C, 63.63 (63.71); H, 7.20 (7.21).
(32) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 0.87 (t, 3H, .sup.3J.sub.H-H=7.2 Hz, CH.sub.3(CH.sub.2).sub.3-Cp); 1.30 (m, 2H, CH.sub.3CH.sub.2(CH.sub.2).sub.2-Cp); 1.42 (m, 2H, CH.sub.3CH.sub.2CH.sub.2CH.sub.2-Cp); 1.70 (s, 6H, 2,6-Me-Pn*); 1.84 (s, 6H, 3,5-Me-Pn*); 2.11 (s, 6H, 1,7-Me-Pn*); 2.6 (m, 2H,CH.sub.3CH.sub.2CH.sub.2CH.sub.2-Cp); 5.15 (t, 2H, .sup.3J.sub.H-H=2.7 Hz, 3,4-H-Cp); 5.68 (t, 2H, .sup.3J.sub.H-H=2.7 Hz, 2,5-H-Cp).
(33) .sup.13C{.sup.1H} NMR (100 MHz, C.sub.6D.sub.6) (ppm): 11.3 (2,6-Me-Pn*); 12.6 (1,7-Me-Pn*); 13.3 (3,5-Me-Pn*); 14.3 (CH.sub.3CH.sub.2CH.sub.2CH.sub.2-Cp); 23.0 (CH.sub.3CH.sub.2(CH.sub.2)-Cp); 29.3 (CH.sub.3CH.sub.2CH.sub.2CH.sub.2-Cp); 33.8 (Cp-CH.sub.2CH.sub.2); 105.2 (3,5-Pn*); 106.0 (3,4-Cp); 112.2 (1,7-Pn*); 113.4 (2,5-Cp); 119.5 (4-Pn*); 125.6 (2,6-Pn*); 128.6 (8-Pn*); 130.0 (1-Cp).
Example 1eSynthesis of Pn*ZrCp.SUP.M.e(Me)
(34) ##STR00028##
(35) A solution of Pn*ZrCp.sup.MeCl (200 mg, 0.510 mmol) in toluene (15 mL) at 78 C. was added to a solution of MeLi (1.6 M in Et.sub.2O, 319 L, 0.510 mmol) in toluene at 78 C. Thea reaction mixture was stirred for 1 h before being exposed to dynamic vacuum while still in the cold bath. The solution was removed from the cold bath so that the removal of the solvent kept the temperature below 0 C. The solid was extracted with hexane (45 mL) and the combined extracts concentrated to 15 mL and cooled to 80 C. in a freezer overnight, yielding a yellow microcrystalline solid. The supernatant was removed and the solid dried in vacuo for 4 h to yield Pn*ZrCp.sup.Me(Me) in 50% yield (95 mg, 0.256 mmol).
(36) Single crystals suitable for an X-ray diffraction study were grown from slow-evaporation of a benzene solution. Anal Calcd (found) for C.sub.21H.sub.28Zr: C, 67.86 (67.73); H, 7.59 (7.71).
(37) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 0.74 (s, 3H, Zr-Me); 1.63 (s, 6H, 2,6-Me-Pn*); 1.85 (s, 3H, Me-Cp, 3H, s); 1.99 (s, 6H, 3,5-Me-Pn*); 2.00 (s, 6H, 1,7-Me-Pn*); 5.15 (t, 2H, .sup.3J.sub.H-H=2.6 Hz, 2,5-H-Cp); 5.37 (t, 2H, .sup.3J.sub.H-H=2.6 Hz, 3,4-H-Cp).
(38) .sup.13C{.sup.1H} NMR (C.sub.6D.sub.6) (ppm): 10.6 (ZrCH.sub.3); 10.9 (2,6-Me-Pn*); 12.4 (3,5-Me-Pn*); 13.4 (1,7-Me-Pn*); 14.0 (Me-Cp); 102.2 (1,7-Pn*); 105.5 (3,4-Cp); 106.4 (3,5-Pn*); 111.4 (2,5-Cp); 116.9 (8-Pn*); 119.8 (1-Cp); 123.1 (2,6-Pn*); 123.4 (4-Pn*).
Example 1fSynthesis of Pn*ZrCp(Me)
(39) ##STR00029##
(40) A solution of Pn*ZrCpCl (250 mg, 0.661 mmol) in toluene (15 mL) at 78 C. was added to a solution of MeLi (1.6 M in Et.sub.2O, 415 L, 0.664 mmol) in toluene at 78 C. The reaction mixture was stirred for 1 h before being exposed to dynamic vacuum while still in the cold bath. The solution was removed from the cold bath so that the removal of the solvent kept the temperature below 0 C. The solid was extracted with hexane (45 mL) and the combined extracts concentrated to 15 mL and cooled to 80 C. in a freezer overnight, yielding a yellow microcrystalline solid. The supernatant was removed and the solid dried in vacuo for 4 h to yield Pn*ZrCp(Me) in 68% yield (160 mg, 0.447 mmol).
(41) Single crystals suitable for an X-ray diffraction study were grown from slow-evaporation of a benzene solution.
(42) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 0.72 (s, 1H, Zr-Me); 1.64 (s, 6H, 2,6-Me-Pn*); 1.96 (s, 6H, 3,5-Me-Pn*); 1.97 (s, 6H, 1,7-Me-Pn*); 5.46 (s, 5H, Cp);
(43) .sup.13C{.sup.1H} NMR (C.sub.6D.sub.6) (ppm): 10.0 (ZrCH.sub.3); 11.2 (2,6-Me-Pn*); 12.3, 13.4 (3,5-Me-Pn* & 1,7-Me-Pn*-indistinguishable by HSQC); 102.5 (1,7-Pn*); 106.4 (3,5-Pn*); 108.9 (Cp); 116.9 (8-Pn*); 123.3 (2,6-Pn*); 123.6 (4-Pn*).
Example 1gSynthesis of Pn*ZrCp(H)
(44) ##STR00030##
(45) An ampoule was charged with a solution of Pn*ZrCpCl (150 mg, 0.397 mmol) in toluene (15 mL) and potassium triethylborohydride (1.0 M solution in THF, 417 L, 0.417 mmol) and stirred for 48 h. The volatiles were removed in vacuo, the solid extracted with pentane (45 mL) and the combined extracts concentrated to 15 mL before being cooled to 80 C. in a freezer overnight. The supernatant was removed and the solid dried under vacuum for 4 h to yield Pn*ZrCp(H) in 42% yield (57 mg, 0.166 mmol).
(46) Single crystals suitable for an X-ray diffraction study were grown from slow-evaporation of a benzene solution.
(47) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 0.69 (d, 1H, J=1.6 Hz, ZrH); 1.69 (s, 6H, 2,6-Me-Pn*); 2.05 (s, 6H, 3,5-Me-Pn*); 2.59 (s, 6H, 1,7-Me-Pn*); 5.54 (s, 5H, Cp);
(48) .sup.13{.sup.1H} NMR (C.sub.6D.sub.6) (ppm): 10.8 (2,6-Me-Pn*); 12.8 (3,5-Me-Pn*); 14.4 (1,7-Me-Pn*); 103.9 (3,5-Pn*); 105.5 (Cp); 108.6 (1,7-Pn*); 117.5 (4-Pn*); 121.4 (8-Pn*); 121.4 (2,6-Pn*).
Example 1hSynthesis of Pn*ZrCp(.SUP.n.Bu)
(49) ##STR00031##
(50) A solution of Pn*ZrCpCl (200 mg, 0.529 mmol) in toluene (15 mL) at 78 C. was added to a solution of .sup.nBuLi (1.6 M in Et.sub.2O, 347 L, 0.555 mmol) in toluene at 78 C. The reaction mixture was stirred for 1 h, allowed to slowly warm to room temperature and stirred for a further hour. The volatiles were then removed under dynamic vacuum and the solid extracted with pentane (45 mL) and the combined extracts concentrated to 15 mL and cooled to 80 C. in a freezer overnight, yielding a yellow microcrystalline solid. The supernatant was removed and the solid dried in vacuo for 4 h to yield Pn*ZrCp(.sup.nBu) in 57% yield (120 mg, 0.300 mmol).
(51) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 0.14 (m, 2H, ZrCH.sub.2); 1.16 (t, 3H, .sup.3J.sub.H-H=7.3 Hz, Zr(CH.sub.2).sub.3CH.sub.3); 1.42 (m, 2H, ZrCH.sub.2CH.sub.2); 1.58 (m, 2H, Zr(CH.sub.2).sub.2CH.sub.2); 1.63 (s, 6H, 2,6-Me-Pn*); 1.96 (s, 6H, 3,5-Me-Pn*); 1.99 (s, 6H, 1,7-Me-Pn*); 5.50 (s, 5H, Cp);
(52) .sup.13C{.sup.1H} NMR (C.sub.6D.sub.6) (ppm): 11.0 (2,6-Me-Pn*); 12.1 (3,5-Me-Pn*); 13.6 (1,7-Me-Pn*); 14.6 (Zr(CH.sub.2).sub.3CH.sub.3); 28.9 (ZrCH.sub.2); 32.4 (Zr(CH.sub.2).sub.2CH.sub.2); 36.7 (ZrCH.sub.2CH.sub.2); 102.4 (3,5-Pn*); 106.4 (1,7-Pn*); 108.5 (Cp); 116.7 (4-Pn*); 123.1 (8-Pn*); 123.5 (2,6-Pn*).
Example 1iSynthesis of Pn*ZrCp(NMe.SUB.2.)
(53) ##STR00032##
(54) An ampoule was charged with Pn*ZrCpCl (100 mg, 0.27 mmol), LiNMe.sub.2 (19 mg, 0.37 mmol) and benzene (20 mL) at room temperature. The resultant yellow solution was stirred for 3 days, filtered and the supernatant frozen at 78 C. and lyophilized under dynamic vacuum. Pn*ZrCp(NMe.sub.2) was isolated as a yellow powder in 83% yield (85 mg, 0.22 mmol).
(55) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 1.82 (s, 6H, 2,6-Me-Pn*); 1.89 (s, 6H, 3,5-Me-Pn*); 2.09 (s, 6H, 1,7-Me-Pn*); 2.40 (s, 6H, N-Me.sub.2); 5.72 (s, 5H, Cp)
(56) .sup.13C{.sup.1H} NMR (C.sub.6D.sub.6) (ppm): 11.3 (2,6-Me-Pn*); 12.2 (1,7-Me-Pn*); 13.8 (3,5-Me-Pn*); 48.2 (N-Me.sub.2); 104.2 (3,5-Pn*); 108.0 (Cp); 112.5 (1,7-Pn*); 120.3 (4-Pn*); 125.1 (2,6-Pn*); 126.7 (8-Pn*).
Example 1jSynthesis of Pn*ZrCp(NPh.SUB.2.)
(57) ##STR00033##
(58) THF (20 mL) was cooled to 78 C. and added to Pn*ZrCpCl (100 mg, 0.27 mmol) and KNPh.sub.2.THF.sub.0.27 (70 mg, 0.31 mmol). The solution was allowed to warm to room temperature, stirred for 16 h then filtered and dried under dynamic vacuum. The yellow solid was redissolved in a pentane (20 mL) and toluene (10 mL) mixture, then filtered. The filtrate was reduced to a minimum volume and placed in a freezer at 80 C. for 3 days. The resultant yellow crystalline solid was isolated by filtration and dried in vacuo to give Pn*ZrCp(NPh.sub.2) in 60% yield (81 mg, 0.16 mmol).
(59) .sup.1H NMR (400 MHz, THF d.sup.8) (ppm): 1.58 (s, 6H, 3,5-Me-Pn*); 2.12 (s, 6H, 2,6-Me-Pn*); 2.20 (s, 6H, 1,7-Me-Pn*); 5.62 (s, 5H, Cp); 6.58 (m, 6H, N-Ph.sub.meta & N-Ph.sub.para); 7.00 (m, 4H, N-Ph.sub.ortho).
(60) .sup.13C{.sup.1H} NMR (THF d.sup.8) (ppm): 11.0 (3,5-Me-Pn*); 11.5 (2,6-Me-Pn*); 13.6 (1,7-Me-Pn*); 106.3 (1,7-Pn*); 111.2 (Cp); 112.0 (3,5-Pn*); 117.7 (N-Ph meta/para); 118.3 (8-Pn*); 118.3 (2,6-Pn*); 124.1 (N-Ph meta/para) 128.3 (4-Pn*); 128.5 (N-Ph ortho); 159.1 (N-Ph ipso).
Example 1kSynthesis of ZrPn*FluCl
(61) ##STR00034##
(62) [ZrPn*(Cl).sub.3/2].sub.2(-Cl).sub.2Li.THF.sub.(1.02) (51 mg, 0.060 mmol) and LiFlu (21 mg, 0.12 mol) were introduced into an NMR tube and dissolved in 0.5 mL of C.sub.6D.sub.6 and the solution turned bright yellow instantly. The reaction mixture was heated to 80 C. for 96 h and the benzene was filtered through celite. The benzene was removed to afford Pn*ZrFluCl as a pale green solid. Yield: 26 mg (80% yield).
(63) .sup.1H NMR (benzene-d.sub.6, 400 MHz): 1.25 1.76 2.07 (s, 6H, Pn-CH.sub.3), 4.69 (s, 1H, Flu-H), 7.04 (m, 2H, Flu-H), 7.08 (m, 2H, Flu-H), 7.17 (d, 2H, Flu-H, .sup.3J.sub.HH=7.72 Hz), 8.31 (d, 2H, Flu-H, .sup.3J.sub.HH=8.29 Hz).
(64) .sup.13C{.sup.1H} NMR (benzene-d.sub.6, 100 MHz): 9.5 12.5 12.8 (Pn-CH.sub.3), 75.5 (Flu(C)), 118.5 (Flu(C)), 121.9 (Flu(C)), 126.5 (Flu(C)), 127.0 (Flu(C)).
Example 1lSynthesis of Pn*ZrCp.SUP.Me.(OAm)
(65) ##STR00035##
(66) Pn*ZrCp.sup.MeCl (0.020 g, 0.051 mmol) and KO-2,6-.sup.iPrC.sub.6H.sub.3 (0.006 g, 0.051 mmol) were combined in C.sub.6D.sub.6 (0.5 mL) and sonicated for 230 minutes to afford a yellow solution and colourless precipitate. Analysis of the solution using 1H NMR spectroscopy indicated the formation of Pn*ZrCp.sup.Me(OAm).
(67) .sup.1H NMR (benzene-d.sub.6, 23 C.): 5.70 5.55 (app.t, 2H each, J.sub.H-H=2.7 Hz, C.sub.5H.sub.4Me), 2.07 (s, 6H, CH.sub.3-Pn*), 2.02 (s, 3H, C.sub.5H.sub.4Me), 1.95 1.89 (s, 6H each, CH.sub.3-Pn*), 1.48 (q, 2H, .sup.3J.sub.HH=7.4 Hz, C(CH.sub.3).sub.2CH.sub.2CH.sub.3), 1.13 (s, 6H, C(CH.sub.3).sub.2CH.sub.2CH.sub.3), 0.86 (t, 2H, .sup.3J.sub.HH=7.4 Hz, C(CH.sub.3).sub.2CH.sub.2CH.sub.3).
Example 1mSynthesis of Pn*ZrCp.SUP.Me.(O-2,6-Me-C.SUB.6.H.SUB.3.)
(68) ##STR00036##
(69) Pn*ZrCp.sup.MeCl (0.018 g, 0.046 mmol) and KO-2,6-Me-C.sub.6H.sub.3 (0.0090 g, 0.046 mmol) were combined in C.sub.6D.sub.6 (0.5 mL) and sonicated for 230 minutes to afford a yellow solution and colourless precipitate. After was followed by drying of the filtrate in vacuo to afford Pn*ZrCp.sup.Me(O-2,6-Me-C.sub.6H.sub.3) as a pale yellow solid. Single crystals suitable for an X-ray diffraction study were grown from a pentane solution at 30 C.
(70) .sup.1H NMR (benzene-d.sub.6, 23 C.): 7.17 (d, 2H, .sup.3J.sub.HH=7.4 Hz, 3,5-C.sub.6H.sub.3), 6.82 (t, 1H, .sup.3J.sub.HH=7.4 Hz, 4-C.sub.6H.sub.5), 5.47 5.20 (app.t, 2H each, J.sub.HH=2.7 Hz, C.sub.5H.sub.4Me), 2.08 1.92 1.88 1.84 (s, 6H each, CH.sub.3-Pn* or 2,6-Me-C.sub.6H.sub.3), 1.83 (s, 3H, C.sub.5H.sub.4Me).
Example 1nSynthesis of Pn*ZrCp.SUB.Me.(O-2,6-.SUP.i.PrC.SUB.6.H.SUB.3.)
(71) ##STR00037##
(72) Pn*ZrCp.sub.MeCl (0.020 g, 0.051 mmol) and KO-2,6-.sup.iPrC.sub.6H.sub.3 (0.011 g, 0.051 mmol) were combined in C.sub.6D.sub.6 (0.5 mL) and sonicated for 230 minutes to afford a yellow solution and colourless precipitate. After was followed by drying of the filtrate in vacuo to afford Pn*ZrCp.sup.Me(O-2,6-.sup.iPrC.sub.6H.sub.3) as a pale yellow solid.
(73) .sup.1H NMR (benzene-d.sub.6, 23 C.): 7.17 (d, 2H, .sup.3J.sub.HH=7.5 Hz, 3,5-C.sub.6H.sub.3), 6.96 (t, 1H, .sup.3J.sub.HH=7.5 Hz, 4-C.sub.6H.sub.5), 5.63 5.22 (app.t, 2H each, J.sub.HH=2.7 Hz, C.sub.5H.sub.4Me), 2.93 (sept., 2H, .sup.3J.sub.HH=6.8 Hz, CH(CH.sub.3).sub.2), 2.01 1.90 (s, 6H each, CH.sub.3-Pn*), 1.89 (s, 3H, C.sub.5H.sub.4Me), 1.87 (s, 6H, CH.sub.3-Pn*), 1.35 1.21 (d, 2H each, .sup.3J.sub.HH=6.8 Hz, CH(CH.sub.3).sub.2).
Example 1oSynthesis of Pn*ZrCp.SUP.Me.(O-2,4-.SUP.t.Bu-C.SUB.6.H.SUB.3.)
(74) ##STR00038##
(75) Pn*ZrCp.sup.MeCl (0.032 g, 0.082 mmol) and KO-2,4-.sup.tBu-C.sub.6H.sub.3 (0.020 g, 0.082 mmol) were combined in C.sub.6D.sub.6 (0.5 mL) and sonicated for 230 minutes to afford a yellow solution and colourless precipitate. After was followed by drying of the filtrate in vacuo to afford Pn*ZrCp.sup.Me(O-2,6-.sup.tBu-C.sub.6H.sub.3) as a pale yellow solid.
(76) .sup.1H NMR (benzene-d.sub.6, 23 C.): 7.57 7.26 (m, 1H each, 3,5,6-C.sub.6H.sub.3), 5.99 5.66 5.58 5.30 (m, 1H each, C.sub.5H.sub.4Me), 2.19 1.99 1.93 1.92 1.90 1.90 1.85 (s, 3H each, CH.sub.3-Pn* or C.sub.5H.sub.4Me), 1.60 1.43 (s, 9H each, O-2,4-.sup.tBu-C.sub.6H.sub.3).
Example 1pSynthesis of Pn*ZrCp.SUP.Me.(NMe.SUB.2.)
(77) ##STR00039##
(78) Pn*ZrCp.sup.MeCl (0.045 g, 0.11 mmol) and LiNMe.sub.2 (0.0058 g, 0.11 mmol) were combined in C.sub.6D.sub.6 (0.5 mL) and sonicated 30 minutes to afford a yellow solution and colourless precipitate. After was followed by drying of the filtrate in vacuo to afford Pn*ZrCp.sup.Me(NMe.sub.2) as a pale yellow solid.
(79) .sup.1H NMR (benzene-d.sub.6, 23 C.): 5.66 5.50 (m, 2H each, C.sub.5H.sub.4Me), 2.43 2.11 1.92 (s, 6H each, CH.sub.3-Pn* or NMe.sub.2), 1.92 (s, 3H, C.sub.5H.sub.4Me) 1.82 (s, 6H each, CH.sub.3-Pn* or NMe.sub.2).
COMPARATIVE EXAMPLESYNTHESIS OF Pn*ZrCp.SUP.t..SUP.
(80) ##STR00040##
(81) To [Pn*Zr(-Cl).sub.3/2].sub.2(-Cl).sub.2Li.Et.sub.2O.sub.(1.21) (300 mg, 0.362 mmol) in Et.sub.2O (20 mL) at 78 C. was added a slurry of LiCp.sup.t.sup.
(82) Single crystals suitable for an X-ray diffraction study were grown from slow-evaporation of a benzene solution. Anal Calcd (found) for C.sub.23H.sub.31ClZr: C, 63.63 (63.55); H, 7.20 (7.33).
(83) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) (ppm): 1.33 (s, 9H, .sup.tBu-Cp); 1.71 (s, 6H, 2,6-Me-Pn*); 1.83 (s, 6H, 3,5-Me-Pn*); 2.09 (s, 6H, 1,7-Me-Pn*); 5.04 (t, 2H, .sup.3J.sub.H-H=2.8 Hz, 2,5-H-Cp); 5.96 (t, 2H, .sup.3J.sub.H-H=2.8 Hz, 3,4-H-Cp).
(84) .sup.13C{.sup.1H} NMR (100 MHz, C.sub.6D.sub.6) (ppm): 11.6 (2,6-Me-Pn*); 12.6 (1,7-Me-Pn*); 13.3 (3,5-Me-Pn*); 32.2 (CMe.sub.3-Cp); 104.2 (2,5-Cp); 105.0 (3,5-Pn*); 112.3 (1,7-Pn*); 113.9 (3,4-Cp); 119.4 (4-Pn*); 126.1 (2,6-Pn*); 128.6 (8-Pn*); 138.8 (1-Cp).
EXAMPLE 2SYNTHESIS OF CATALYTIC COMPOSITIONS
Example 2aSupporting Pre-Catalyst on Solid Polymethylaluminoxane
(85) The compounds of Examples 1 a-c were supported on solid MAO according to the following general method:
(86) Toluene (40 ml) was added to a Schlenk tube containing solid aluminoxane (300 mg, 5.172 mmol) (solid MAO) (produced by TOSOH, Lot no. TY130408) and Pn*ZrCp.sup.MeCl (10.1 mg, 0.0258 mmol) (shown above) at room temperature. The slurry was heated to 80 C. and left, with occasional swirling, for two hours during which time the solution turned colourless and the solid colourised. The resulting suspension was then left to cool down to room temperature and the toluene solvent was carefully filtered and removed in vacuo to obtain solid MAO/Pn*ZrCp.sup.MeCl catalyst as a free-flowing powder in 88% yield (273 mg).
Example 2bAlternative Approach for Supporting Pre-Catalyst on Solid Polymethylaluminoxane
(87) The compounds of Examples 1a-j were supported on solid polymethylaluminoxane according to the following general method:
(88) The polymethylaluminoxane was combined with the pre-catalyst and stirred together dry for 5 minutes. The stirring was halted and toluene (10 mL) was added to the mixture and heated to 60 C. for 1 h. The contents were manually swirled every 5 minutes and after 1 h were allowed to settle leaving a colored solid and a colorless solution. The supernatant was removed via cannula and the solid dried under vacuum for 4 h.
(89) The resulting supported pre-catalysts were characterised as follows: Pn*ZrCpCl-sMAO .sup.13C CPMAS (10 KHz) (ppm): 13.3 (sMAO-Me); 6.3 (Pn*-Me); 106.2 (Cp-ring; Pn*-ring); 123.0 (sMAO-benzoate); 126.4 (sMAO-benzoate); 172.0 (sMAO-benzoate -C(O)O). .sup.27Al DPMAS (15 KHz) (ppm): 387.4; 250.7; 83.1; 75.7; 211.2; 347.0. Pn*ZrCp.sup.MeCl-sMAO .sup.13C CPMAS (10 KHz) (ppm): 13.3 (sMAO-Me); 6.7 (Pn*-Me); 15.1 (Cp-Me); 106.7 (Cp-ring; Pn*-ring); 122.9 (sMAO-benzoate); 126.0 (sMAO-benzoate); 130.8 (sMAO-benzoate); 172.4 (sMAO-benzoate -C(O)O). .sup.27Al HAHNECHO (15 KHz) (ppm): 242.4; 86.4; 97.6; 179.2; 330.3. Pn*ZrCp.sup.t.sup.
EXAMPLE 3POLYMERISATION STUDIES
Example 3aGeneral Procedure for Slurry-Phase Polymerization of Ethylene
(90) An ampoule is charged with TiBA (150 mg, 0.756 mmol), toluene (50 mL) and the supported catalyst (10 mg). The contents are placed in an oil bath at the required temperature and allowed to equilibrate for 5 minutes while the headspace is degassed. The flask is opened to ethylene (2 bar) and stirred at 1200 rpm for the duration of the experiment. The polymer is then filtered, washed with pentane (220 mL) and dried at 5 mbar overnight.
Example 3bEthylene Polymerisation Activity (Solid MAO Supported Slurry Phase)
(91) Four zirconium complexes were reacted with Solid MAO and used in the Solid MAO supported slurry polymerisation of ethylene in the conditions [M]:[TIBA] of 1:200, 50 mL toluene, 60 C. and 30 minutes. The results are shown in
(92) TABLE-US-00001 TABLE 1 Summary of the Solid MAO slurry polymerisation of various Pn*ZrCp.sup.RCl complexes T Time Activity Complex ( C.) (minutes) Kg.sub.PE/mol.sub.Zr/h/bar Pn*ZrCpCl 50 30 2833 82 Pn*ZrCpCl 70 30 3055 7 Pn*ZrCpCl 60 30 3630 257 Pn*ZrCpCl 60 60 2648 41 Pn*ZrCpCl 60 15 3837 156 Pn*ZrCpCl 60 5 4295 186 Pn*ZrCp.sup.MeCl 60 30 4288 184 Pn*ZrCp.sup.1,2,3-MeCl 60 30 1984 507 Pn*ZrIndCl 60 30 1971 76
Example 3cEthylene Polymerisation Activity (Solid MAO Supported Slurry Phase)
(93) Following the procedure outlined in Example 3a, the catalytic activity of various solid MAO-supported pre-catalysts in the polymerisation of ethylene was assessed. The results are outlined in Table 2 and
(94) TABLE-US-00002 TABLE 2 Summary of the solid MAO slurry polymerisation using various Pn*ZrCp.sup.RCl (Cp.sup.R = Cp, Cp.sup.Me, Cp.sup.t.sub.Bu, Cp.sup.n.sub.Bu, Cp.sup.Me.sub.3, Ind) and Pn*ZrCp.sup.MeMe. Polymerisation conditions: [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 60 C.; 30 minutes. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCpCl 60 30 3624 256 Pn*ZrCp.sup.MeCl 60 30 4209 73 Pn*ZrCp.sup.tBuCl 60 30 294 86 Pn*ZrCp.sup.nBuCl 60 30 4096 72 Pn*ZrCp.sup.Me3Cl 60 30 1981 507 Pn*ZrIndCl 60 30 1971 77 Pn*ZrCp.sup.Me(Me) 60 30 4486 300
(95) Table 2 shows that significant rate enhancements can be observed with variation of Cp.sup.R.
Example 3dPolyethylene Characteristics
(96) The molecular weight (M.sub.w, and M.sub.n) and polydispersity index (PDI) of polyethylenes prepared using various solid MAO-supported pre-catalysts were determined. The results are outlined in Table 3 and
(97) TABLE-US-00003 TABLE 3 Polymer molecular weight, M.sub.w for polymethylaluminoxane supported ethylene polymerization at 60 C. with Pn*ZrCp.sup.RCl (Cp.sup.R = Cp, Cp.sup.Me, Cp.sup.tBu, Cp.sup.Me3, Ind). PDIs are given in parentheses. Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 60 C.; 30 minutes. Temperature Time M.sub.w M.sub.n Complex ( C.) (minutes) (Kg/mol) (Kg/mol) PDI Pn*ZrCpCl 60 30 325000 137000 2.4 Pn*ZrCp.sup.MeCl 60 30 250000 103000 2.4 Pn*ZrCp.sup.tBuCl 60 30 310000 44000 7 Pn*ZrCp.sup.Me3Cl 60 30 505000 133000 3.8 Pn*ZrIndCl 60 30 290000 86000 3.4
(98) The molecular weight distribution of polyethylene prepared using solid-MAO supported Pn*ZrCp.sup.tBuCl was determined by GPC. The results are illustrated in
(99) Table 3 shows that molecular weight can be controlled by variation of Cp.sup.R.
Example 3eEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp.SUP.Me.Cl
(100) The temperature dependence of ethylene polymerisation activity with solid MAO-supported Pn*ZrCp.sup.MeCl was assessed. The results are outlined in Table 4 and
(101) TABLE-US-00004 TABLE 4 Temperature dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp.sup.MeCl. Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 30 minutes. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp.sup.MeCl 40 30 2563 103 Pn*ZrCp.sup.MeCl 50 30 2988 34 Pn*ZrCp.sup.MeCl 60 30 4209 73 Pn*ZrCp.sup.MeCl 70 30 3368 164 Pn*ZrCp.sup.MeCl 80 30 2841 62
(102) Table 4 shows that the maximum activity for Pn*ZrCp.sup.MeCl was observed at 60 C.
Example 3fEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp.SUP.nBu.Cl
(103) The temperature dependence of ethylene polymerisation activity with solid MAO-supported Pn*ZrCp.sup.nBuCl was assessed. The results are outlined in Table 5 and
(104) TABLE-US-00005 TABLE 5 Temperature dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp.sup.nBuCl. Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 30 minutes. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp.sup.nBuCl 40 30 4786 156 Pn*ZrCp.sup.nBuCl 50 30 5025 213 Pn*ZrCp.sup.nBuCl 60 30 4096 72 Pn*ZrCp.sup.nBuCl 70 30 3446 195 Pn*ZrCp.sup.nBuCl 80 30 3502 62
(105) Table 5 shows that the maximum activity for Pn*ZrCp.sup.nBuCl was observed at 50 C.
Example 3gEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp.SUP.Me.(Me)
(106) The temperature dependence of ethylene polymerisation activity with solid MAO-supported Pn*ZrCp.sup.Me(Me) was assessed. The results are outlined in Table 6 and
(107) TABLE-US-00006 TABLE 6 Temperature dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp.sup.Me(Me). Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 30 minutes. Temperature Time Activity Complex ( C.) (minutes) (kg.sup.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp.sup.Me(Me) 40 30 2644 252 Pn*ZrCp.sup.Me(Me) 50 30 5012 50 Pn*ZrCp.sup.Me(Me) 60 30 4376 441 Pn*ZrCp.sup.Me(Me) 70 30 3074 66 Pn*ZrCp.sup.Me(Me) 80 30 2968 70
(108) Table 6 shows that the maximum activity for Pn*ZrCp.sup.Me(Me) was observed at 50 C.
Example 3hEffect of Reaction Duration on Catalytic Activity of Solid-MAO Supported Pn*ZrCpCl and Characteristics of Resulting Polyethylene
(109) The time dependence of ethylene polymerization activity and polymer molecular weight (M.sub.w) with solid MAO-supported Pn*ZrCpCl was assessed. The results are outlined in Table 7 and
(110) TABLE-US-00007 TABLE 7 Time dependence of ethylene polymerization activity and polymer molecular weight, M.sub.w with polymethylaluminoxane supported pre-catalyst, Pn*ZrCpCl. PDIs are also given. Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 60 C. Temperature Time Activity Mw Mn Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) (kg/mol) (kg/mol) PDI Pn*ZrCpCl 60 5 4296 187 415000 158000 2.6 Pn*ZrCpCl 60 15 3837 156 320000 131000 2.4 Pn*ZrCpCl 60 30 3624 256 325000 137000 2.4 Pn*ZrCpCl 60 60 2649 42 295000 123000 2.4
(111) Table 7 shows that the molecular weight of the polyethylene can be controlled by varying the duration of polymerisation, with concomitant effects observed for activity.
Example 3iEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp.SUP.Me.(Me) and Characteristics of Resulting Polyethylene
(112) The temperature dependence of ethylene polymerization activity and polymer molecular weight (M.sub.w) with solid MAO-supported Pn*ZrCpCl was assessed. The results are outlined in Table 8 and
(113) TABLE-US-00008 TABLE 8 Temperature dependence of ethylene polymerization activity and polymer molecular weight, M.sub.w with polymethylaluminoxane supported pre-catalyst, Pn*ZrCpCl. PDIs are also given. Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene. Temperature Time Activity Mw Mn Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) (kg/mol) (kg/mol) PDI Pn*ZrCpCl 50 30 2833 82 385000 156000 2.5 Pn*ZrCpCl 60 30 3624 257 325000 137000 2.4 Pn*ZrCpCl 70 30 3056 6 230000 98000 2.4
(114) Table 8 shows that the molecular weight of the polyethylene can be controlled by varying the duration of polymerisation, with concomitant effects observed for activity.
Example 3jEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp(NMe.SUB.2.)
(115) The temperature dependence of ethylene polymerisation activity with solid MAO-supported Pn*ZrCp(NMe.sub.2) was assessed. The results are outlined in Table 9 and
(116) TABLE-US-00009 TABLE 9 Temperature dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp(NMe.sub.2). Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 30 minutes. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp(NMe.sub.2) 40 30 2905 83 Pn*ZrCp(NMe.sub.2) 50 30 2426 195 Pn*ZrCp(NMe.sub.2) 60 30 2337 86 Pn*ZrCp(NMe.sub.2) 70 30 2197 5 Pn*ZrCp(NMe.sub.2) 80 30 1645 27
(117) Table 9 shows that in contrast to compositions where YCl or methyl, when YNMe.sub.2 the maximum activity was observed at 40 C.
Example 3kEffect of Temperature on Catalytic Activity of Solid-MAO Supported Pn*ZrCp(NPh.SUB.2.)
(118) The temperature dependence of ethylene polymerisation activity with solid MAO-supported Pn*ZrCp(NPh.sub.2) was assessed. The results are outlined in Table 10 and
(119) TABLE-US-00010 TABLE 10 Temperature dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp(NPh.sub.2). Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 30 minutes Temperature Time Activity Complex ( C.) (minutes) (kg.sup.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp(NPh.sub.2) 40 30 2361 291 Pn*ZrCp(NPh.sub.2) 50 30 1945 212 Pn*ZrCp(NPh.sub.2) 60 30 1715 366 Pn*ZrCp(NPh.sub.2) 70 30 1332 301 Pn*ZrCp(NPh.sub.2) 80 30 1090 384
(120) Table 10 shows that in contrast to compositions where YCl or methyl, when YNPh.sub.2 the maximum activity was observed at 40 C.
Example 3lEffect of Reaction Duration on Catalytic Activity of Solid-MAO Supported Pn*ZrCp(NMe.SUB.2.)
(121) The time dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp(NMe.sub.2) was assessed. The results are outlined in Table 11 and
(122) TABLE-US-00011 TABLE 11 Time dependence of ethylene polymerization activity with polymethylaluminoxane supported pre-catalyst, Pn*ZrCp(NMe.sub.2). Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 40 C. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp(NMe.sub.2) 40 5 5989 63 Pn*ZrCp(NMe.sub.2) 40 15 3786 159 Pn*ZrCp(NMe.sub.2) 40 30 2949 105 Pn*ZrCp(NMe.sub.2) 40 60 2350 15
(123) Table 11 suggests that activity decreases with increasing time of the polymerisation.
Example 3mEffect of Reaction Duration on Catalytic Activity of Solid-MAO Supported Pn*ZrCp(NPh.SUB.2.)
(124) The time dependence of ethylene polymerization activity with solid MAO-supported Pn*ZrCp(NPh.sub.2) was assessed. The results are outlined in Table 12 and
(125) TABLE-US-00012 TABLE 12 Time dependence of ethylene polymerization activity with polymethylaluminoxane supported pre-catalyst, Pn*ZrCp(NPh.sub.2). Polymerisation conditions [Zr]:[sMAO] = 1:200; 150 mg TiBA co-catalyst; 2 bar ethylene; 10 mg catalyst loading; 50 mL toluene; 40 C. Temperature Time Activity Complex ( C.) (minutes) (kg.sub.PE/(mol.sub.Zr .Math. h .Math. bar)) Pn*ZrCp(NPh.sub.2) 40 5 4213 95 Pn*ZrCp(NPh.sub.2) 40 15 2618 11 Pn*ZrCp(NPh.sub.2) 40 30 2361 147 Pn*ZrCp(NPh.sub.2) 40 60 1718 37
(126) Table 12 suggests that activity decreases with increasing time of the polymerisation.
Example 3nMorphology Studies
(127)
(128)
(129) 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.