Process for the Oligomerisation of Olefins by Coordinative Chain Transfer Polymerisation

Abstract

The present invention relates to a process for the oligomerisation of olefins, in particular ethylene, via coordinative chain transfer polymerisation (CCTP) and alkyl elimation reaction. A preferred embodiment of the invention relates to CCTP of olefins, in particular ethylene, with the use of guanidinato, amidinato or hydrocarbyl-2-pyridyl amine complexes of titanium, zirconium or lanthanides, a nickel or cobalt compound as chain displacement catalyst (CDC) and one or more chain shuttling agents (CSA) such as a main group metal alkyl.

Claims

1. Process for the manufacture of oligomerised olefins i) by bringing in contact with each other (a) one or more C2 to C8 olefins, (b) a coordinate chain transfer polymerization catalyst (CCTP catalyst) comprising one or more organo metallic transition metal compounds and one or more ligands, (c) a chain shuttling agent (CSA) being one or more metal alkyls selected from the group II, XII and XIII, (d) a chain displacement catalyst (CDC) being one or more member selected from the group consisting of a nickel salt, a cobalt salt, an organo metallic nickel complex and an organo metallic cobalt complex, or ii) by bringing in contact with each other (a), (b), (c) and (d), wherein (c) is (c-1) the chain shutting agent (CSA) comprises two metal alkyls one being one or more Zn alkyl compounds (CSA(1)) the other being one or more XIII metal alkyls (CSA(2)), to form a growth composition thereby obtaining oligomerised olefins having an oligomerisation degree of 2 to 100, wherein for process i) (d) is brought in contact only at a later point in time with the growth composition when the oligomerisation has commenced or has come to an end and (b) is at least partially or completely transformed into an inactive reaction product or inactive degradation product.

2. The process according to claim 1, wherein the growth composition further comprises an activator for the coordinative chain transfer polymerization catalyst (CCTP catalyst) being an aluminium or boron containing compound comprising at least one hydrocarbyl group.

3. The process according to claim 1, wherein the olefin is one or more member selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene and 1-hexene.

4. The process according to claim 1, wherein the one or more organo metallic transition metal compounds comprises one or two transition metals.

5. The process according to claim 1, wherein one or two ligands are selected from cyclopentadienyl, indenyl, fluorine, diamide ligands, phenoxy-imine-ligand, indolide-imine-ligands, amidinate, guanidinate, amidopyridine, pyrrdinimine and alcoholate each optionally substituted.

6. The process according to claim 1, wherein for process i) the CCTP catalyst is deactivated during or after the oligomerisation by heating the growth composition or by bringing the CCTP catalyst in contact with a catalyst poison.

7. The process according to claim 1 wherein the chain shuttling agent (CSA) is a C1 to C30 hydrocarbyl metal compound, methyl-alumoxane or both, the metal being aluminium, zinc, magnesium, indium or gallium.

8. The process according to claim 1 wherein the chain displacement catalyst (CDC) is selected from nickel halogenides, cobalt halogenides, nickel cyclooctadiene, cobalt cyclooctadiene, nickel acetylactonate, C1 to C30 carboxylic acid salts of nickel and mixtures thereof.

9. The process according to claim 2 wherein the activator is methyl aluminoxan, or a perfluorated aluminate or a boron containing compound or combinations thereof.

10. The process according to claim 1 wherein the molar ratio of the coordinative chain transfer polymerization catalyst (CCTP catalyst) to the chain shuttling agent (CSA) is 1:>50000 or 1:50 to 1:10000, except for methyl alumoxane as the CSA.

11. The process according to claim 1 wherein the molar ratio of the coordinative chain transfer polymerization catalyst (CCTP catalyst) to the chain displacement catalyst (CDC) prior or during the oligomerisation is 1:0.5 to 1:50, and after the oligomerisation in the concentration of the chain displacement catalyst (CDC) is between 1 to 10000 ppm (w/w) relative to the growth composition.

12. The process according to claim 2 wherein the molar ratio of the coordinative chain transfer polymerization catalyst (CCTP catalyst) to the activator is 1:1 to 1:4, except in case where methyl alumoxane acts as the activator.

13. The process according to claim 1 wherein the growth composition further comprises a liquid reaction medium, the liquid reaction medium comprising aromatic hydrocarbons.

14. The process according to claim 1 wherein the reaction is carried out at a C2 or C3 or C2 and C3 olefin pressure of 0.2 to 60 bar, or a C4 pressure of 0.2 to 20 bar.

15. The process according to claim 1, wherein the coordinative chain transfer polymerization catalyst comprises as transition metal Ti, Zr or Hf and one ligand per metal of the following formula ##STR00026## the ligand being bound to the metal, wherein Z1, Z2 and Z3=are independently hydrocarbon or heteroatom containing hydrocarbon moieties, wherein the heteroatom, if present, for Z1 or Z3 is not directly adjacent to the N-atom and, wherein Z1, Z2 and Z3 independently from each other are optionally linked with one or more of each other.

16. The process according to claim 1, wherein the coordinative chain transfer polymerization catalyst comprises as transition metal Ti, Zr or Hf and one ligand per metal having the following sub-structural element: ##STR00027## wherein Z1, Z3=each are independently from each other a di-ortho substituted aromatic moiety, each being independently hydrocarbon moieties or heteroatom containing hydrocarbon moieties, wherein the heteroatom, if present, is not directly adjacent to the N-atom, Z2=is a hydrocarbon moiety or a heteroatom containing hydrocarbon moiety, Z1, Z2 and Z3 independently from each other are optionally linked with one or more of each other, M=Titanium, Zirconium or Hafnium X=halogen, hydrocarbyl, hydride; alkoxide, amide, optionally substituted and independent of each m, and m=1 to 4.

17. The process of claim 15 wherein Z2 is NR1R2 with R1 and R2 independently from each other are C1 to C40 hydrocarbon moieties, optionally comprising one or more heteroatoms.

18. The process according to claim 1 wherein for process ii) in step (c-1) the chain shutting agent (CSA(2)) is an aluminium alkyl compound.

19. The process according to claim 18 wherein the process does not include that (d) is brought in contact with the growth composition only at a later point in time when the oligomerisation has commenced or has come to an end and (b) is at least partially or completely transformed into an inactive reaction product or inactive degradation product.

20. The process according to claim 18, wherein the metal has a hydrocarbyl-2-pyridyl amine ligand and an, optionally substituted, cyclopentadienyl ligand.

21. The process according to claim 18, wherein the molar ratio of the coordinative chain transfer polymerization catalyst (CCTP catalyst) to the chain shuttling agent (CSA(1)), being a zinc hydrocarbyl compound is 1/10 to 1/500.

22. The process according to claim 18, wherein the molar ratio of the coordinative chain transfer polymerization catalyst (CCTP catalyst) to the chain shuttling agent (CSA(2)), being an aluminium alkyl compound, is 1/50 to 1/500.

23. The process according to claim 18, wherein the molar ratio of the (CSA(1)) to the (CSA(2)) is 1/49 to 5/1.

24. The process according to claim 20, wherein the zirconium cyclopentadienyl hydrocarbyl-2-pyridyl amine alkyl compound is ##STR00028## wherein R1 and R2=independent from each other is hydrocarbyl, or halogen, wherein R2 is branched at the 2-position; R3=is independently from each other zero to three hydrocarbyl and M=titanium, zirconium or hafnium. X=independent of each other halogen; hydrocarbyl, C1 to C40, and alkysubstituted cyclopentadiene.

Description

FIGURES

[0315] The following is depicted in the attached figures:

[0316] FIG. 1: Reaction scheme illustrating the assumed mechanism of the tandem catalyst oligomerisation process of ethylene via single chain shuttling

[0317] FIG. 1a: Reaction scheme illustrating the assumed mechanism of dual chain shuttling via two CSAs

[0318] FIG. 2: Molecular structure of III in the formula as displayed above.

[0319] FIG. 3: Molecular structure of IV as described in the formula as displayed above.

[0320] FIG. 4: 1H NMR spectrum (C2Cl.sub.4D.sub.2, 120 C.) of oligomers obtained with GuaTiMe.sub.3 (I) precatalyst in absence (entry 1, table 1, above) and presence of Ni(COD).sub.2 (entry 5, table 2, below). In the absence of a CDC no olefins are observed. With Ni(COD).sub.2 only alpha-olefins were observed.

[0321] FIG. 5: 1H NMR spectrum (C.sub.2Cl.sub.4D2, 120 C.) of oligomers obtained with GuaZrMe.sub.3 (III) precatalyst in absence (entry 2, below, table 1) and presence of Ni(COD).sub.2 (entry 9, above, table 2). In absence of a CDC no olefins are observed.

[0322] FIG. 6: 1H NMR spectrum (C.sub.2Cl.sub.4D.sub.2, 120 C.) of oligomers obtained with GuaZrMe.sub.3 (III) precatalyst in presence of Ni(COD).sub.2 (entry 9, below, table 2), Ni(acac).sub.2 (entry 6, middle, table 2) and Ni(stea).sub.2 (entry 7, above, table 2). From top to the bottom the ratio between terminal to internal olefins increases.

[0323] FIG. 7: Oligomerised olefin distribution at different ethylene pressures; 8 mol GuaZrMe.sub.3, 16 mol Dimethylaniliniumborat, 32 mol Ni(COD).sub.2, 8000 mol TEAL, T=60 C.

[0324] FIG. 8: Oligomerised olefin distribution at different temperatures; 8 mol GuaZrMe3, 16 mol Dimethylaniliniumborat, 32 mol Ni(COD).sub.2, 8000 mol TEAL, p=2 bar.

[0325] FIG. 9 Oligomerised olefin distribution at different temperatures; 4 mol GuaZrMe3, 4 mol Trioctyammonium borate, 8 mol Ni(COD).sub.2, 40000 mol TEAL, p=2 bar, 22 g ethylene.

[0326] FIG. 9a Oligomerised olefin distribution using the yttrium complexes of Example S6; 10 mol yttrium pre-catalyst, 10.0 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (RC.sub.16H.sub.33C.sub.18H.sub.37), 2 mol Ni(COD).sub.2, 500 mol TEAL, p=5 bar, T=80 C.

[0327] FIG. 10: .sup.1H NMR spectrum (C.sub.2Cl.sub.4D.sub.2, 120 C.) of oligomers obtained with CpApZrMe.sub.2 (II) precatalyst and in the presence of 2 mol Ni(COD).sub.2 (Table 8, entry 6).

[0328] FIG. 11: .sup.1H NMR spectrum (C.sub.2Cl.sub.4D.sub.2, 120 C.) of oligomers obtained with Cp Ap.sup.ClZrMe.sub.2 (II) precatalyst and in the presence of 24 mol Ni(COD).sub.2 (Table 8, entry 13).

[0329] FIG. 12: Influence of DEZn content on the oligomerised olefin obtained with CpApZrMe.sub.2 (I) precatalyst in presence of Ni(COD).sub.2 (Table 8, entry 1, Table 8, entries 3-7).

EXPERIMENTAL SECTION

[0330] The following abbreviations were used: [0331] MeMethyl (CH.sub.3) [0332] EtEthyl (CH.sub.3CH.sub.2) [0333] TEALTriethyl aluminium (Et.sub.3Al) [0334] GuaH2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidine [0335] i-Priso-Propyl (Me.sub.2CH) [0336] i-Buiso-Butyl (Me.sub.2CHCH.sub.2) [0337] CyCyclohexyl (C.sub.6H.sub.11) [0338] TMATrimethylaluminium (Me.sub.3Al) [0339] TEATriethylaluminium (Et.sub.3Al) [0340] DEACDiethylaluminiumchloride [(Et.sub.2AlCl).sub.2] [0341] Pipicis-2,6-Dimethylpiperidin-1-yl [cis-2,6-Me.sub.2C.sub.5H.sub.8N] [0342] CODCyclooctadiene (C.sub.8H.sub.12) [0343] acacAcetylacetonate (CH.sub.3COCHCOCH.sub.3.sup.) [0344] steaStearate (O.sub.2C(CH.sub.2).sub.16CH.sub.3.sup.) [0345] Ni(acac).sub.2Nickel(II) acetylacetonate (Ni(C.sub.5H.sub.7O.sub.2).sub.2) [0346] Ni(COD).sub.2Bis(1,5-cyclooctadiene)nickel(0) (Ni(C.sub.8H.sub.12).sub.2) [0347] Ni(stea).sub.2Nickel(II) stearate (Ni(O.sub.2C(CH.sub.2).sub.16CH.sub.3).sub.2) [0348] DEZnDiethyl zinc (Et.sub.2Zn) [0349] ApH N-(2,6-diisopropylphenyl)pyridin-2-amine [2-(NC.sub.5H.sub.4)(2,6-Pr.sup.iC.sub.6H.sub.3)NH] [0350] Ap.sup.ClH6-Chloro-N-(2,6-diisopropylphenyl)pyridin-2-amine [2-(6-ClNC.sub.5H.sub.3)(2,6-Pr.sup.iC.sub.6H.sub.3)NH] [0351] CpH1,3-di-tert-butylcyclopenta-1,3-diene (1,3-Bu.sup.tC.sub.5H.sub.4)

[0352] All ratios herein are molar ratios except when specifically mentioned otherwise.

[0353] General: All manipulations of air- or moisture-sensitive compounds were carried out under N.sub.2 using glove-box, standard Schlenk, or vacuum-line techniques. Solvents and reagents were purified by distillation from LiAlH.sub.4, potassium, Na/K alloy, or sodium ketyl of benzophenone under nitrogen immediately before use. Toluene (Aldrich, anhydrous, 99.8%) was passed over columns of Al.sub.2O.sub.3 (Fisher Scientific), BASF R.sup.3-11 supported Cu oxygen scavenger, and molecular sieves (Aldrich, 4 ). Ethylene and Propylene (AGA polymer grade) were passed over BASF R3-11 supported Cu oxygen scavenger and molecular sieves (Aldrich, 4 ). NMR spectra were recorded on a Varian Inova 400 (.sup.1H: 400 MHz, .sup.13C: 100.5 MHz) or Varian Inova 300 (1H: 300 MHz, 13C: 75.4 MHz) spectrometer. The .sup.1H and .sup.13C NMR spectra, measured at 26 C., were referenced internally using the residual solvent resonances, and the chemical shifts () reported in ppm. High temperature NMR measurements of polymer samples were carried out in deutero tetrachloroethane at 120 C.

[0354] Gel permeation chromatography (GPC) analysis was carried out on a PL-GPC 220 (Agilent, Polymer Laboratories) high temperature chromatographic unit equipped with LS, DP and RI detectors and three linear mixed bed columns (Olexis, 13-micron particle size) at 150 C. using 1,2,4-trichlorobenzene as the mobile phase. The samples were prepared by dissolving the polymer (0.05 wt.-%, conc.=1 mg/mL) in the mobile phase solvent in an external oven and were run without filtration. The molecular weight was referenced to polyethylene (Mw=520-3200000 gmol.sup.1) and polystyrene (Mw=580-2800000 gmol.sup.1) standards.

[0355] The reported values are the average of at least two independent determinations. GC analysis was performed with an Agilent 6850 gas chromatograph and/or Agilent 7890A GC with an inert MSD 5975C with Triple Axis Detector. Both GC's are equipped with an Agilent 19095J-323E capillary column (HP-5; 5% phenyl methyl siloxane; 30 m; film 1.5 m, diameter 0.53 mm) and a flame ionization detector.

[0356] N,N-Dimethylanilinium (tetrapentafluorophenyl) borate ([PhNMe.sub.2H][B(C.sub.6F.sub.5).sub.4]), Nickel(II) stearate, Bis(1,5-cyclooctadiene)nickel(0), Nickel(II) pentanedionate (anhydrous; 95%), Titanium(IV)chloride and Zirconium(IV)chloride are commercially available from abcr GmbH & Co. KG. Triethyl aluminium (SASOL Germany GmbH) and Bis(2,6-diisopropylphenyl)carbodiimide (TCI Deutschland GmbH) were used as received. The ligand precursor 2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidine (G. Jin, C. Jones, P. C. Junk, K.-A. Lippert, R. P. Rose, A. Stasch, New J. Chem, 2008, 33, 64-75) and the metal precursors diethylaminotrichloridozirconium(IV) etherate (E. V. Avtomonov, K. A. Rufanov, Z. Naturforsch. 1999, 54 b, 1563-1567) and 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido titanium(IV) (GuaTiMe.sub.3, I, J. Obenauf, W. P. Kretschmer, R. Kempe, Eur. J. Inorg. Chem. 2014, 1446-1453) were prepared according to published procedures.

Comparative Example 1: Synthesis of {2,3-bis[2,6-di(isopropyl)phenyl]-1,1-diethyl-guanidinato}-(diethylamido)-dichlorido-zirconium(VI) (Aa; Mixtures Of Isomers)

[0357] Method A:

[0358] Bis(diethylamido)-dichlorido-zirconium(IV)-bis(tetrahydrofurane) (0.036 g, 80 mol) and Bis(2,6-diisopropylphenyl) carbodiimide (0.029 g, 80 mol) were subsequently added to a Schlenk flask filled with 10 mL of toluene and stirred at RT. After 24 h the mixture was filtered and diluted with toluene to reach 40 mL. This solution was used in oligomerisation without further purification.

##STR00017##

[0359] Alternative Method B can be used: Bis(diethylamido)-dichlorido-zirconium(IV)bis(tetrahydrofurane) (0.036 g, 80 mol) and (Z)-2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidine (0.035 g, 80 mol) were subsequently added to a Schlenk flask filled with 10 mL of toluene and stirred at RT. After 24 h the mixture was filtered and diluted with toluene to reach 40 mL. This solution was used in oligomerisation without further purification.

Comparative Example 2

[0360] General description of ethylene oligomerisation experiments for Runs 1-6

[0361] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for 1 h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive TEAL co-catalyst solution, activator (perfluorophenylborate) and 1 mL of a zirconium pre-catalyst stock solution in toluene was injected, to start the reaction.

[0362] After the desired reaction time the reactor was vented and the residual aluminium alkyls were destroyed by addition of 50 mL of ethanol. Polymeric product was collected, stirred for 30 min in acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 80 C. Oligomeric product was collected by washing the toluene solution with water and removing the solvent under reduced pressure. The oily product was analyzed by GC-MS.

TABLE-US-00004 TABLE 1 Ethylene oligomerisation with Zr pre-catalyst Aa, TEAL co-catalyst and perfluorophenylborate activator..sup.a t m.sub.product. Activity M.sub.n Entry Precat Al/Zr [min] [g] [kg.sub.PEmol.sub.cat.sup.1h.sup.1bar.sup.1] [kgmol.sup.1] M.sub.w/M.sub.n 1 Aa 250 15 1.68 1680 1300 1.9 2 Aa 500 15 1.70 1700 1140 1.5 3 Aa 750 15 3.54 3540 1030 1.5 4 Aa 1000 15 6.48 6480 1290 1.3 5 Aa 10000 30 6.50 3270 350 1.3 6 Aa 10000 60 21.00 5250 370 1.5 .sup.aPre-catalyst: 2.0 mol; ammonium borate: 2.2 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (R = C.sub.16H.sub.33C.sub.18H.sub.37), Zr/B = 1/1.1; toluene: 150 mL; T = 50 C., p = 2 bar.

Example 1: Synthesis of 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato diethylamino trichiorido zirconium(IV) (Ia)

[0363] ##STR00018##

[0364] 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidine (2.55 g, 5.85 mmol) and diethylamido-trichloridozirconium(IV) etherate (2.01 g, 5.85 mmol) were dissolved in toluene (100 mL) and stirred overnight. Diethylamine (0.86 mg, 11.16 mmol) was added to the filtered reaction solution and the mixture was stirred for one hour. After filtration and concentration of the reaction solution, colourless crystals were obtained at 30 C. .sup.1H NMR (300 MHz, C.sub.6D.sub.6): =0.15 (t, 6H, CH.sub.3), 0.67 (t, 6H, CH.sub.3), 1.26 (d, 12H, CH.sub.3), 1.59 (d, 12H, CH.sub.3), 2.49 (br s, 4H, CH.sub.2), 2.77 (q, 4H, CH.sub.2), 3.60 (s, 1H, NH), 3.91 (m, 4H, CH), 7.13 (d, 6H, CH.sub.arom) ppm.

Example 2: Synthesis of 2,3-bis(2,6-diisopropylphenyl)-C-(cis-2,6-dimethylpiperidyl)guanidinato diethylamido trichlorido zirconium(IV) (Id)

[0365] ##STR00019##

[0366] 2,3-bis(2,6-diisopropylphenyl)-C-(cis-2,6-dimethylpiperidyl)guanidine (11.2 g, 23.5 mmol) and diethylamido-trichloridozirconium(IV) etherate (8.1 g, 23.5 mmol) were dissolved in toluene (300 mL) and stirred overnight. The reaction solution is filtered, diethylamine (3.0 mL, 28.7 mmol) is added and stirred for one hour. After filtration and concentration of the reaction solution, colourless crystals could be obtained at 30 C. .sup.1H NMR (300 MHz, C.sub.6D.sub.6): =0.73 (d, 6H, CH.sub.3); 0.75 (t, 6H, CH.sub.3); 1.29-1.72 (m, 6H, CH.sub.2); 1.04 (d, 6H, CH.sub.3); 1.40 (d, 6H, CH.sub.3); 1.47 (d, 6H, CH.sub.3); 1.71 (d, 6H, CH.sub.3); 2.54 (q, 4H, CH.sub.2); 3.23 (s, 1H, NH); 3.99 (sept, 4H, CH); 3.60-3.74 (m, 2H, CH); 6.93-7.19 (m, 6H, CH.sub.arom) ppm.

Example 3: Synthesis of 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato diethylamido-dimethanido zirconium(IV) (IId)

[0367] ##STR00020##

[0368] To a suspension of bis(2,6-diisopropylphenyl)-C-(cis-2,6-dimethylpiperidyl)guanidinato-diethylamido-trichlorido-zirconium (2.5 g, 3.4 mmol) in ether (50 mL) methylmagnesium chloride (3 M in THF, 4.9 mL, 14.7 mmol) was added dropwise at 78 C. The mixture was warmed to room temperature and stirred overnight. Storage of the concentrated filtrate at 30 C. led to colourless crystals. Yield 1.9 g (85%). .sup.1H NMR (300 MHz, C.sub.6D.sub.6): =0.53 (s, 6H, CH.sub.3); 0.74 (d, 6H, CH.sub.3); 0.90 (t, 6H, CH.sub.3); 0.80-1.46 (m, 6H, CH.sub.2); 1.09 (d, 6H, CH.sub.3); 1.23 (d, 6H, CH.sub.3); 1.29 (d, 6H, CH.sub.3); 1.37 (d, 6H, CH.sub.3); 3.24 (q, 4H, CH.sub.2); 3.63 3.99 (sept, 4H, CH); 3.88-3.98 (m, 2H, CH); 7.04-7.14 (m, 6H, CH.sub.arom) ppm.

Example 4

[0369] General Description of Ethylene Oligomerisation Experiments for Runs 7-15

[0370] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.

[0371] In a typical semi-batch experiment, the autoclave was evacuated and heated for 1 h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive TEAL co-catalyst solution, activator (perfluorophenylborate) and 1 mL of a zirconium pre-catalyst stock solution in toluene was injected, to start the reaction. After the desired reaction time the reactor was vented and the residual aluminium alkyls were destroyed by addition of 50 mL of ethanol. Polymeric product was collected, stirred for 30 min in acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 80 C. Oligomeric product was collected by washing the toluene solution with water and removing the solvent under reduced pressure. The oily product was analyzed by GC-MS.

TABLE-US-00005 TABLE 2 Ethylene oligomerisation with Zr pre-catalysts example 1-3, TEAL co-catalyst and perfluorophenylborate activator..sup.a t m.sub.roduct. Activity M.sub.n Entry Precat Al/Zr [min] [g] [kg.sub.PEmol.sub.cat.sup.1h.sup.1bar.sup.1] [kgmol.sup.1] M.sub.w/M.sub.n 7 Ia 500 15 0.63 1150 650 1.14 8.sup.b Ia 5000 15 1.13 1080 liquid.sup.d 9 Id 500 15 1.45 2900 1181 1.5 10 Id 1000 15 4.58 9160 860 1.5 11.sup.c Id 1000 15 10.87 21800 2590 2.5 12.sup.c,f Id 72000 60 68.2 14200 650 1.6 13.sup.b,f Id 79000 15 28.1 14080 liquid.sup.d 14.sup.b,e Id 75000 15 28.5 17070 280 1.6 15 IId 500 15 3.7 7400 12450 1.9 .sup.aPrecatalyst: 1.0 mol; ammonium borate: 1.1 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (R = C.sub.16H.sub.33C.sub.18H.sub.37), Zr/B = 1/1.1; toluene: 150 mL; T = 50 C., p = 2 bar; t = 15 min. .sup.bPrecatalyst: 2.0 mol. .sup.canilinium borate: 1.1 mmol [PhN(CH.sub.3).sub.2H].sup.+[B(C.sub.6F.sub.5).sub.4].sup.. .sup.doligomeric products. .sup.e3 bar ethylene. .sup.f4 bar ethylene.

Example 5: Synthesis of Di--chlorido-bis[2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato]-tetrachlorido-dizirconium(IV) (III)

[0372] ##STR00021##

[0373] Diethylamido-trichloridozirconium(IV) etherate (0.68 g, 2.0 mmol) and Bis(2,6-diisopropylphenyl) carbodiimide (0.55 g, 1.5 mmol were dissolved in toluene (100 mL) and stirred overnight at 60 C. After filtration and concentration of the reaction solution, colourless crystals were obtained at 30 C. .sup.1H NMR (300 MHz, C.sub.6D.sub.6): =0.20 (t, 6H, CH.sub.3), 1.18 (d, 12H, CH.sub.3), 1.50 (d, 12H, CH.sub.3), 2.59 (q, 4H, CH.sub.2), 3.55 (m, 4H, CH), 7.06 (d, 6H, CH.sub.arom) ppm. .sup.13C NMR (75.4 MHz, C.sub.6D.sub.6): =20.5 (CH.sub.3), 25.3 (CH.sub.3), 37.8 (CH), 48.7 (CH.sub.2), 121.1 (Carom), 123.6 (Carom), 125.6 (Carom) ppm.

Example 6 Synthesis of 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido zirconium(IV) (IV)

[0374] ##STR00022##

[0375] To a suspension of dimeric .sup.2-Chlorido-[2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato]trichloridozirconium(IV) (1176 mg, 0.93 mmol) in hexane (50 mL) methylmagnesium chloride (1.9 mL, 5.58 mmol) was added dropwise at 78 C. The mixture was warmed to room temperature and stirred overnight. Storage of the concentrated filtrate at 30 C. led to colourless crystals. Yield 903 mg (85%). .sup.1H NMR (300 MHz, C.sub.6D.sub.6): =0.26 [t, J=7.1 Hz, 6H, N(CH.sub.2CH.sub.3).sub.2]; 0.86 [s, 9H, Zr(CH.sub.3).sub.3]; 1.24 [d, J=6.9 Hz, 12H, CH(CH.sub.3).sub.2]; 1.36 [d, J=7.1 Hz, 12H, CH(CH.sub.3).sub.2]; 2.74 [q, J=7.1 Hz, 4H, N(CH.sub.2CH.sub.3).sub.2]; 3.62 [sept, J=6.8 Hz, 4H, CH(CH.sub.3).sub.2]; 7.09 (s, 6H, ArH) ppm. .sup.13C NMR (75.4 MHz, C.sub.6D.sub.6): =11.3 [N(CH.sub.2CH.sub.3).sub.2]; 24.0 [CH(CH.sub.3).sub.2]; 25.9 [CH(CH.sub.3).sub.2]; 28.5 [CH(CH.sub.3).sub.2]; 40.8 [N(CH.sub.2CH.sub.3).sub.2]; 51.4 [Zr(CH.sub.3).sub.3]; 124.3, 125.5, 142.7, 143.3 (ArC); 169.5 (NCN) ppm.

Example 7: Synthesis of Di--methylene-bis[2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato]-dimethanido-dizirconium(IV) (V)

[0376] To a suspension of Di--chlorido-bis[2,3-bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato]-tetrachlorido-dizirconium(IV) (1.92 g, 1.52 mmol) in THF (30 mL) methylmagnesium chloride (3.05 mL, 9.12 mmol) was added dropwise at 78 C. The mixture was warmed to room temperature and stirred overnight. Solvent was removed under reduced pressure and the residue extracted twice with hexane (220 mL). Storage of the concentrated filtrate at 30 C. led to light yellow crystals. Yield 1.68 g (88%). .sup.1H NMR (300 MHz, C6D6): =0.21-0.27 (m, 6H, N(CH.sub.2CH.sub.3).sub.2); 0.58 (s, 3H, Zr(CH.sub.3).sub.3); 1.26 (d, 6H, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.31 (d, 6H, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.39 (d, 6H, J=6.7 Hz, CH(CH.sub.3).sub.2); 1.48 (d, 6H, J=6.7 Hz, CH(CH.sub.3).sub.2); 2.76 (m, 4H, N(CH.sub.2CH.sub.3).sub.2); 3.62 (sept., 2H, J=6.8 Hz, CH(CH.sub.3).sub.2); 3.83 (sept., 2H, J=6.8 Hz, CH(CH.sub.3).sub.2); 5.25 (s, 2H, Zr(CH.sub.2)Zr); 7.05 (m, 6H, ArH) ppm.

Example 8

[0377] General Description of Ethylene Oligomerisation Experiments for Runs 16-21

[0378] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with, separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for 1 h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive TEAL co-catalyst solution, activator (perfluorophenylborate) and 1 mL of a 0.001 M zirconium pre-catalyst stock solution in toluene was injected, to start the reaction. After the desired reaction time the reactor was vented and the residual aluminium alkyls were destroyed by addition of 50 mL of ethanol. Polymeric product was collected, stirred for 30 min in acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 80 C. Oligomeric product was collected by washing the toluene solution with water and removing the solvent under reduced pressure. The oily product was analyzed by GC-MS.

TABLE-US-00006 TABLE 3 Ethylene oligomerisation with Zr pre-catalyst III and IV, TEAL co-catalyst and perfluorophenylborate activator..sup.a t m.sub.product. Activity M.sub.n Entry Precat Al/Zr [min] [g] [kg.sub.PEmol.sub.cat.sup.1h.sup.1bar.sup.1] [kgmol.sup.1] M.sub.w/M.sub.n 16.sup.b III 2000 15 1.00 500 560 1.2 17.sup.b III 1000 15 1.40 700 780 1.5 18.sup.b III 500 15 3.24 1620 990 1.5 19 IV 2000 15 12.73 25480 3000 1.5 20.sup.c,e IV 72000 22 28.13 25598 liquid.sup.d 21 IV 1000 15 13.38 26800 2480 1.9 .sup.aPrecatalyst: 1.0 mol; ammonium borate: 1.1 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (R = C.sub.16H.sub.33C.sub.18H.sub.37), Zr/B = 1/1.1; toluene: 150 mL; T = 50 C., p = 2 bar; t = 15 min. .sup.bPrecatalyst: 2.0 mol, t = 30 min. .sup.canilinium borate: 1.1 mmol [PhN(CH.sub.3).sub.2H].sup.+[B(C.sub.6F.sub.5).sub.4].sup.. .sup.doligomeric products. .sup.e3 bar ethylene.

Example 9

[0379] General Description of Ethylene Oligomerisation Experiments for Entries 22-24

[0380] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems.

[0381] During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for 1 h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive TEAL co-catalyst solution, activator (perfluorophenylborate), Diethyl aluminium chloride and 1 mL of a 0.001 M zirconium pre-catalyst stock solution in toluene was injected, to start the reaction. After the desired reaction time the reactor was vented and the residual aluminium alkyls were destroyed by addition of 50 mL of ethanol. Polymeric product was collected, stirred for 30 min in acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 80 C.

TABLE-US-00007 TABLE 4 Ethylene oligomerisation with Zr pre-catalyst IV in presence of DEAC, TEAL co-catalyst and perfluorophenylborate activator..sup.a TEAL DEAC M.sub.product Activity M.sub.n Entry Al/Zr Cl/Zr [g] [kg.sub.PEmol.sub.cat.sup.1h.sup.1bar.sup.1] [kgmol.sup.1] M.sub.w/M.sub.n 22 2000 1 8.64 17300 1790 1.5 23 2000 3 3.11 6230 950 1.6 24 2000 6 0.88 1750 630 1.5 .sup.aPrecatalyst IV: 1.0 mol; ammonium borate: 2.2 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (R = C.sub.16H.sub.33C.sub.18H.sub.37), Zr/B = 1/1.1; toluene: 150 mL; T = 50 C., p = 2 bar; t = 15 min.

Example S1 (In-Situ)

[0382] General Description of Ethylene Oligomerisation Experiments for Entries 25+26 (Table 5)

[0383] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.

[0384] In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive chain transfer agent, activator, and 1 mL of a 0.001 M pre-catalyst stock solution in toluene was injected, to start the reaction. After 15 min reaction time the reactor was vented and the residual CSA alkyls were destroyed by addition of 20 mL of ethanol. Polymeric product was collected by filtration at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 50 C. The soluble residue was analyzed by GC and/or GC-MS.

Example S2 (In-Situ): General Description of Ethylene Oligomerisation Experiments for Entries 27+28 (Table 5)

[0385] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 150 mL of toluene. After pressurizing with ethylene to reach 2 bar total pressure the autoclave was equilibrated for 10 min. Successive chain transfer agent, activator and chain displacement catalyst, all dissolved in toluene, were injected, to start the reaction. After 15 min reaction time the reactor was vented and the residual CSA alkyls were destroyed by addition of 20 mL of ethanol. The toluene solution was analyzed by GC and/or GC-MS.

Example S3 (In-Situ): General Description of Ethylene Oligomerisation Experiments for Runs 29-38 (Table 6)

[0386] The catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems.

[0387] During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with the desired amount of toluene. After pressurizing with ethylene to reach the desired total pressure the autoclave was equilibrated for 10 min. Successive chain transfer agent, activator, chain displacement catalyst and pre-catalyst, all dissolved in toluene, were injected, to start the reaction. After the appropriate reaction time the reactor was vented and the residual CSA alkyls were destroyed by addition of 20 mL of ethanol. Polymeric product was collected by filtration at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The polymer was initially dried on air and subsequently in vacuum at 50 C. The soluble residue was analyzed by GC and/or GC-MS.

Example S4 (In-Situ)

[0388] The catalytic ethylene oligomerisation reaction was performed in a 1000 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During the oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 100 C. prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 300 mL toluene. After pressurizing with ethylene to reach the desired total pressure the autoclave was equilibrated for 10 min. 1000 mol TEAL, 4 mol of 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido zirconium(IV), 6 mol of Dimethylaniliniumborate and 8 mol of Bis(cyclooctadienyl)nickel(0), was added to start the reaction. 30 g of ethylene was dosed into the reactor.

[0389] The temperature was maintained at 60 C. After the appropriate reaction time the reactor was vented and the residual TEAL was destroyed by addition of 20 mL of ethanol. A sample is taken from the solution and analyzed via GC with nonane as internal standard.

TABLE-US-00008 TABLE 5 Comparative ethylene oligomerisation with GuaTiMe.sub.3 (I) and GuaZrMe.sub.3 (IV) precatalysts or Ni(stea).sub.2 and Ni(COD).sub.2 CDC's only..sup.a Entry precat. [mol] CSA [mol] CDC [mol] C2 sump. [I] con- yield [g] Activity [00002]$\left[\frac{{\mathrm{Kg}}_{\mathrm{PE}}}{{\mathrm{mol}}_{\mathrm{cat}}.Math.h.Math.\mathrm{bar}}\right]$ m(C4) [g] m(C6) [g] m(C8) [g] m(C10) [g] m(C12) [g] m.sub.solid [g] M.sub.n [00003]$\left[\frac{g}{\mathrm{mol}}\right]$ M.sub.w/ M.sub.n 25 I (Ti)* 10000 1.92 3.36 3360 1.92 1120 1.6 2 26 IV (Zr) 1000 12.14 15.18 30360 15.18 2480 1.9 1 27 1000 Ni(stea).sub.2 0.00 0 0 2 28 1000 Ni(COD).sub.2 0.10 0.12 125 0.10 2 .sup.aactivator: [Me.sub.2NPhH][B(C.sub.6F.sub.5).sub.4], Zr/B = 1/2; toluene: 150 mL; p.sub.ethylene = 2 bar; t = 15 min; *2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido titanium(IV) (GuaTiMe3, I, J. Obenauf, W. P. Kretschmer, R. Kempe, Eur. J. Inorg. Chem. 2014, 1446-1453) was prepared according to published procedures.

TABLE-US-00009 TABLE 6 Ethylene oligomerisation with GuaTiMe.sub.3 (I) and GuaZrMe.sub.3 (IV) precatalysts in presence of CDC's..sup.a Entry precat. [mol] CSA [mol] CDC [mol] C2 sump. [I] con- yield [g] Activity [00004]$\left[\frac{{\mathrm{Kg}}_{\mathrm{PE}}}{{\mathrm{mol}}_{\mathrm{cat}}.Math.h.Math.\mathrm{bar}}\right]$ m(C6) [g] m(C8) [g] m(C10) [g] m(C12) [g] m(C14) [g] m.sub.solid [g] M.sub.n [00005]$\left[\frac{g}{\mathrm{mol}}\right]$ M.sub.w/ M.sub.n 29 I (Ti)* 10000 Ni(COD).sub.2 6.68 8.35 8350 6.33 840 1.5 2 2 30 IV (Zr) 1000 Ni(acac).sub.2 10.40 13.00 26000 1.64 1.42 1.20 1.01 0.83 0.18 1 7.8 31 IV (Zr) 1000 Ni(stea).sub.2 10.77 13.46 26925 0.42 0.43 0.43 0.44 0.45 6.90 810 1.6 1 1 32.sup.b IV (Zr) 1000 Ni(stea).sub.2 17.50 21.88 21875 1.67 1.58 1.50 1.38 1.19 1.69 740 1.5 1 2 33.sup.b IV (Zr) 1000 Ni(COD).sub.2 17.23 21.54 21540 1.37 1.32 1.24 1.08 0.97 4.88 790 1.5 1 1 34.sup.b IV (Zr) 520 Ni(COD).sub.2 15.20 19.00 19000 0.72 0.72 0.72 0.71 0.70 0.22 370 41.5.sup.g 1 2 35.sup.b IV (Zr) 330 Ni(COD).sub.2 15.10 18.88 18875 1.01 0.99 0.98 0.92 0.86 0.40 520 133.7.sup.g 1 2 36.sup.b IV (Zr) 300 Ni(COD).sub.2 15.00 18.75 18750 1.04 1.02 0.98 0.94 0.87 1.95 390 2.3 1 2 37.sup.c IV (Zr) 280 Ni(COD).sub.2 16.80 21.00 21000 0.91 0.91 0.92 0.91 0.89 8.34 390 2.0 1 2 38.sup.d IV (Zr) 650 Ni(COD).sub.2 0.80 1.50 3000 0.36 .sup.0.26.sup.e 0.16 .sup.0.10.sup.f 0.05 n.d. n.d. 1 2 .sup.aactivator: [Me.sub.2NPhH][B(C.sub.6F.sub.5).sub.4], Zr/B = 1/2; toluene: 150 mL; p.sub.ethylene = 2 bar; t = 15 min. .sup.bt = 30 min, CSA = . Yield was calculated from ethylene consumption, m(C4) was not determined. .sup.cp.sub.ethylene = 4 bar. .sup.dp.sub.propylene = 2 bar. .sup.eCg. .sup.fC.sub.15. .sup.gbimodal;* 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido titanium(IV) (GuaTiMe3, I, J. Obenauf, W. P. Kretschmer, R. Kempe, Eur. J. Inorg. Chem. 2014, 1446-1453) was prepared according to published procedures.

[0390] Waxy product was collected by filtration (0.2 m) at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The filtrate was initially dried on air and subsequently in vacuum at 50 C. and analyzed via GPC. The permeate was analyzed by GC and/or GC-MS.

[0391] The effect of applied pressure and temperature are shown in FIGS. 7 and 8.

Example S5 (Sequential Process)

[0392] The catalytic ethylene oligomerisation reaction was performed in a 1000 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 100 C. prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 300 mL toluene. After pressurizing with ethylene to reach the desired total pressure the autoclave was equilibrated for 10 min. 40000 mol TEAL, 4 mol of 2,3-Bis(2,6-diisopropylphenyl)-1,1-diethylguanidinato trimethanido zirconium(IV), 4 mol of trioctylammonium borate was added to start the reaction. 22 g of ethylene was dosed into the reactor and the temperature was maintained at 60 C.

[0393] After the desired amount of ethylene was consumed the reactor was depressurized and the reactor flushed with argon. Subsequently the temperature was raised to 100 C. for 1 hour. 8 mol Bis(cyclooctadienyl)nickel(0), was added to the reactor via a syringe. A temperature of 120 C. was set and maintained via a thermostat. The reactor was pressurized with ethylene again and the reaction monitored until no more ethylene was consumed. The residual TEAL was destroyed by addition of 20 mL of ethanol. A sample was taken from the solution and analyzed via GC with nonane as internal standard. Waxy product was collected by filtration (0.2 m) at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The filtrate was initially dried on air and subsequently in vacuum at 50 C. and analyzed via GPC. The permeate was analyzed by GC and/or GC-MS. The distribution of the obtained linear -olefins are shown in FIG. 9.

Example S6 (In-Situ): Single Chain Shuttling Using Yttrium Complexes as CCTP Catalysts (Table 7)

[0394] The following yttrium pre-catalysts were employed in the ethylene oligorimerisation experiments:

##STR00023##

[0395] The catalytic ethylene oligomerization reactions were performed in an 800 mL autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 80 C. prior to use. The reactor was then brought to 80 C., stirred and charged with 250 mL of toluene. After pressurizing with ethylene to reach the 5 bar the autoclave was equilibrated for 3 min. Successive TEAL co-catalyst solution, activator (methyldialkylammonium-tetrakis(pentafluorophenyl)borate) and after an additional equilibration yttrium pre-catalyst stock solution in toluene was injected, to start the reaction. After the 15 min the reactor was vented and the residual TEAL was destroyed by addition of 20 mL of ethanol. A sample was taken from the solution and analyzed via GC with cumene as internal standard. Waxy product was collected by filtration (0.2 m) at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The permeate was analyzed by GC and/or GC-MS. The distribution of the obtained linear oligomerised alpha olefins are shown in FIG. 9a.

TABLE-US-00010 TABLE 7 Ethylene oligomerisation with Y pre-catalysts Ya and Yb, TEAL co-catalyst and methyldialkylammoniumtetrakis(pentafluorophenyl)borate activator..sup.a Entry Catalyst n(Al(Et).sub.3) [mol] n(Ni(cod).sub.2) [mol] activity [00006]$\left[\frac{\mathrm{kg}}{\mathrm{mol}.Math.h.Math.\mathrm{bar}}\right]$ 39 Ya 500 2 128 40 Yb 500 2 175 .sup.aPre-catalyst: 10.0 mol; ammonium borate: 10.0 mol [R.sub.2N(CH.sub.3)H].sup.+[B(C.sub.6F.sub.5).sub.4].sup. (R = C.sub.16H.sub.33-C.sub.18H.sub.37); Y/B = 1/1; CDC 2 mol Ni(COD).sub.2; toluene: 250 mL; T = 80 C., p = 5 bar.

[0396] Experimental Section Dual Chain Shuttling

[0397] N,N,N-trialkylammonium (tetrapentafluorophenyl)borate ([R.sub.2NMeH][B(C.sub.6F.sub.5).sub.4], RC.sub.16H.sub.33C.sub.18H.sub.37, 6.2 wt-% B(C.sub.6F.sub.5).sub.4 in Isopar, DOW Chemicals), Bis(1,5-cyclooctadiene)nickel(0), and Zirconium(IV)chloride are commercially available from abcr GmbH & Co. KG. Triethyl aluminum (SASOL Germany GmbH) and Diethyl zinc (15 wt-% in toluene, Sigma-Aldrich) were used as received. The ligand precursor N-(2,6-diisopropylphenyl)pyridine-2-amine (A. Noor, W. P. Kretschmer, R. Kempe, Eur. J. Inorg. Chem. 2006, 2683), 6-Chloro-N-(2,6-diisopropylphenyl)pyridin-2-amine (M. Hafeez, W. P. Kretschmer, R. Kempe, Eur. J. Inorg. Chem. 2011, 5512-5522) and the metal precursor (1,3-di-tert-butylcyclopenta-1,3-dienyl)-trimethanidozirconium(IV) (J. Amor, T. Cuenca, M. Galakhov, P. Royo, J. Organomet. Chem 1995, 497, 127-131) were prepared according to published procedures.

Synthesis of Pre-Catalyst 1

[0398] ##STR00024##

Synthesis of (1,3-di-tert-butylcyclopenta-1,3-dienyl)-(N-(2,6-diisopropylphenyl)pyridin-2-amidinato)-dimethanidozirconium(IV) (I)

[0399] To a solution of ApH (88 mg, 0.35 mmol) in benzene (0.5 mL) was added (1,3-di-tert-butylcyclopenta-1,3-dienyl)-trimethanidozirconium(IV) (109 mg, 0.35 mmol). The mixture was shaken for 15 min, until the formation of methane gas was finished, filtrated and used without further purification. NMR spectroscopic analysis showed an almost quantitative formation of the desired complex II. .sup.1H NMR (300 MHz, C.sub.6D.sub.6):=0.47 [s, 6H, H.sup.14,15], 1.07 (d, J=6.6 Hz, 6H, H.sup.7,8), 1.13 (s, 18H, H.sup.16,16), 1.32 (d, J=6.6 Hz), 3.44 (sept, J=6.6 Hz, 2H, H.sup.9,9), 5.56 (d, J=8.8 Hz, 1H, H.sup.3), 5.82 (m, 1H, H.sup.5), 5.99 (d, J=2.2 Hz, 2H, H.sup.19,20), 6.45 (t, J=2.3 Hz, 1H, H.sup.22), 6.67 (t, J=7.3 Hz, 1H, H.sup.4), 6.98-7.31 (m, 3H, H.sup.10,11,12), 7.48 (d, J=5 Hz, 1H, H.sup.24). .sup.13C NMR (300 MHz, C.sub.6D.sub.6):=24.68 (s, 2C, C.sup.7,8), 26.05 (s, 2C, C.sup.7,8), 28.66 (s, 2C, C.sup.9;9), 31.97 (s, 6C, C.sup.16;16), 33.26 (s, 2C, C.sup.14,15), 107.55 (s, 1C, C.sup.3), 108.37 (s, 2C, C.sup.19,20), 109.67, 109.74, 124.07, 124.88, 126.04, 126.33, 128.91 (s, 10C, C.sup.1,2,4,6,18,21,22), 129.67, 140.21, 141.63, 144.08, 145.01 (s, 5C, C.sup.10,11,12,13,23)

Synthesis of Pre-Catalyst II

[0400] ##STR00025##

Synthesis of (1,3-di-tert-butylcyclopenta-1,3-dienyl)-(6-chloro-N-(2, 6-diisopropylphenyl)pyridin-2-amidinato)-dimethanidozirconium(IV) (II)

[0401] To a solution of Ap.sup.ClH (45 mg, 0.15 mmol) in benzene (0.5 mL) was added (1,3-di-tert-butylcyclopenta-1,3-dienyl)-trimethanidozirconium(IV) (49 mg, 0.15 mmol). The mixture was shaken for 15 min, until the formation of methane gas was finished, filtrated and used without further purification. NMR spectroscopic analysis showed an almost quantitative formation of the desired complex III. .sup.1H NMR (300 MHz, C.sub.6D.sub.6):=0.60 [s, 6H, H.sup.14,15], 1.01 [d, J=6.4 Hz, 6H, H.sup.7,8], 1.17 [s, 18H, H.sup.16,16], 1.29 [d, J=7.0 Hz, 6H, H.sup.7,8], 3.46 [sept, J=6.5 Hz, 2H, H.sup.9,9], 5.33 [d, J=8.2 Hz, 1H, H.sup.3], 5.88 [d, J=6.3 Hz, 1H, H.sup.5 ], 6.29 [d, J=2.9 Hz, 2H, H.sup.19,20] 6.3 [t, J=8.2 Hz, 1H, H.sup.22], 6.62 [t, J=2.6 Hz, 1H, H.sup.22], 6.95-7.19 [m, 3H, H.sup.10,11,12].

[0402] .sup.13C NMR (300 MHz, C.sub.6D.sub.6):=24.48 (s, 2C, C.sup.7,8), 26.04 (s, 2C, C.sup.7,8), 28.80 (s, 2C, C.sup.9;9), 32.70 (s, 6C, C.sup.16;16), 45.58 (s, 2C, C.sup.14,15), 105.58 (s, 1C, C.sup.3), 108.51 (s, 2C, C.sup.19,20), 110.20 (s, 1C, C.sup.4), 111.23, 125.02, 128.07, 128.92, 129.67, 141.34, 142.43, 143.31, 144.67, 147.40, (s, 10C, C.sup.1,2,6,18,21,22,10,11,12,13), 171.87 (s, 1C, C.sup.23). CHN anal. C.sub.32H.sub.46Cl.sub.1N.sub.2Zr (585.40): C, 65.65; H, 7.92; N, 4.79. Found: C, 65.94, H, 8.21, N, 4.45.

[0403] Examples for Dual Chain Shuttling

[0404] General Description of Ethylene Oligomerisation Experiments for Runs D1 to D12 (Table 8)

[0405] The catalytic ethylene oligomerization reactions were performed in a 300 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant). The reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously. In a typical semi-batch experiment, the autoclave was evacuated and heated for h at 80 C. prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with the desired amount of toluene. After pressurizing with ethylene to reach the desired total pressure the autoclave was equilibrated for 3 min. Successive chain transfer agent, activator, chain displacement catalyst and pre-catalyst, all dissolved in toluene, were injected, to start the reaction. After the appropriate reaction time the reactor was vented and the residual CSA alkyls were destroyed by addition of 20 mL of ethanol. Solid product was collected by filtration at 50 C., washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The wax was initially dried on air and subsequently at 50 C. The soluble residue was analyzed by GC and/or GC-MS.

TABLE-US-00011 TABLE 8 Ethylene oligomerisation examples with CpApZrMe.sub.2 (I) and CpAp.sup.ClZrMe.sub.2 (II) precatalysts, Ni(COD).sub.2 as CDC and DEZn/TEAL mixtures as CSA..sup.a Entry precat. (M) [mol] CSA [mol] time [min] C2 con- sump. [I] yield [g] Activity [00007]$\left[\frac{{\mathrm{Kg}}_{\mathrm{PE}}}{{\mathrm{mol}}_{\mathrm{cat}}.Math.h.Math.\mathrm{bar}}\right]$ m(C6) [g] m(C8) [g] m(C10) [g] m(C12) [g] m(C14) [g] m.sub.solid [g] M.sub.n [00008]$\left[\frac{g}{\mathrm{mol}}\right]$ M.sub.w/ M.sub.n D1 I 500 12.0 2 2.50 2940 0.014 0.015 0.017 0.020 0.022 1.77 1380 1.4 (Ap, 2) (10/490) D2 I 500 11.3 2 2.50 3320 0.046 0.057 0.066 0.072 0.075 1.12 920 1.2 (Ap, 2) (40/460) D35 I 500 9.4 2 2.50 3990 0.112 0.120 0.129 0.122 0.116 (Ap, 2) (100/400) D46 I 500 9.9 2 2.50 3800 0.196 0.208 0.200 0.185 0.169 0.39 377 1.1 (Ap, 2) (250/250) D5 I 500 11.1 2 2.50 3380 0.239 0.244 0.254 0.233 0.210 (Ap, 2) (400/100) D6 II 300 30 2.81 3.52 1760 0.012 0.014 0.015 0.018 0.021 2.85 1460 1.4 (Ap.sup.Cl, 2) (50/250) D7 II 300 30 2.99 3.74 1870 0.028 0.030 0.035 0.042 0.047 2.68 1050 1.5 (Ap.sup.Cl, 2) (100/200) D8 II 300 30 3.11 3.89 1950 0.068 0.081 0.089 0.098 0.105 1.71 870 1.3 (Ap.sup.Cl, 2) (150/150) D9 II 300 30 2.30 2.88 1440 0.041 0.053 0.058 0.065 0.071 1.31 1000 1.2 (Ap.sup.Cl, 2) (200/100) D10 II 300 30 1.82 2.28 1140 0.062 0.074 0.081 0.088 0.092 0.53 950 1.9 (Ap.sup.Cl, 2) (250/50) D11.sup.b II 300 30 1.74 2.18 1080 0.049 0.062 0.061 0.066 0.070 0.61 1010 1.3 (Ap.sup.Cl, 2) (150/150) D12 II 500 30 1.72 2.15 1080 0.121 0.124 0.134 0.139 0.138 0.02 840 2.2 (Ap.sup.Cl, 2) (250/250) .sup.atoluene: 150 mL; CDC: 2 mol Ni(COD).sub.2; activator: 2.2 mol [R.sub.2NMeH][B(C.sub.6F.sub.5).sub.4] (R = C.sub.16H.sub.33-C.sub.18H.sub.37), Zr/B = 2/2.2; p.sub.ethylene = 2 bar; t = 15 min. .sup.bCDC: 24 mol Ni(COD).sub.2.