WO2002066405A1

WO2002066405A1 - Catalyst system for the trimerisation of olefins

Info

Publication number: WO2002066405A1
Application number: PCT/NL2002/000119
Authority: WO
Inventors: Patrick Jozef Wilhelmus Deckers; Bart Hessen
Original assignee: Stichting Dutch Polymer Institute
Priority date: 2001-02-22
Filing date: 2002-02-22
Publication date: 2002-08-29
Also published as: BR0207835A; WO2002066405A8

Abstract

The invention relates to a catalyst system for the selective trimerisation of olefins, which system is based on a titanium complex of formula (Cp-B (R) nAr) TiR13, wherein: Cp is a cyclopentadienyl type ligand, optionally substituted, B is a bridging group, based on a single atom selected from the groups 13 to 16 inclusive of the Periodic System, Ar is a aromatic group, optionally substituted, R is, independently, hydrogen, or a hydrocarbon residue, optionally being substituted and optionally containing heteroatoms, or groups R and B are joined together to from a ring, N is an integer equal to the (valency of B minus 2), and R1 is a mono-anionic group, and further comprises an activator. The present catalyst system obviates the use of toxic chromium compounds.

Description

Title: Catalyst system for the trimerisation of olefins .

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of PCT-application PCT/NL01/00149, filed 22 February 2001, the disclosure thereof being incorporated by reference.

DESCRIPTION

The invention relates to a catalyst system for the selective trimerisation of olefins, which system comprises a transition metal complex.

Such a catalyst system for trimerisation of olefins is known from EP-A-06084 7 and consists of a combination of a transition metal source, a pyrrole containing compound and a metal alkyl in an electron donor solvent. The transition metal source consists of a chromium, nickel, cobalt, or iron compound, preferably a chromium compound is used.

Because chromium compounds are highly toxic, and therefore need special handling precautions, a catalyst system for the trimerisation of olefins, which is not based on a chromium compound is needed. A catalyst system has now been found which is not based on a chromium compound, but still shows a high selectivity in the trimerisation of olefins with respect to the trimerisation product .

More specifically,, the invention relates to a catalyst system as indicated above, which is characterized in that said catalyst system comprises a) a half-sandwich substituted cyclopentadienyl titanium complex of formula

(Cp-B(R)_nAr)TiR¹ ₃ wherein Cp is a cyclopentadienyl type ligand, optionally substituted,

B is a bridging group, based on a single atom selected from the groups 13 to 16 inclusive of the Periodic System, Ar is a aromatic group, optionally substituted, R is, independently, hydrogen, or a hydrocarbon residue, optionally being substituted and optionally containing heteroatoms, or groups R and B are joined together to form a ring, n is an integer equal to the (valency of B minus 2) , and

R¹ is a mono-anionic group, and b) an activator.

It is observed that the catalyst system as disclosed in EP-A-0608447 is preferably a chromium catalyst, but a catalytic system based on a titanium compound, more specifically TiO(acac)₂, was also tested as a catalyst for the trimerisation of ethylene. The selectivity for hexene-1 was in that case nevertheless rather low. A high selectivity for hexene-1 is industrially very important because of the use of hexene-1 as starting material for the preparation of different kinds of (co) polymers .

It is further observed that trimerisation is in the above- mentioned reference and in the present disclosure defined as the combination of one or more kinds of olefins, wherein the number of olefin, i.e. double, bonds is reduced by two. The term "trimerisation" is thus intended to include "co-trimerisation" . So, for example, the number of olefin bonds in the combination of three ethylene units is reduced by two, to one olefin bond, in 1-hexene.

A half-sandwich substituted cyclopentadienyl titanium complex as a catalyst, in the presence of a co-catalyst, is known for example from Macromol . 1999, 3_2, 4491-4493. This titanium complex does nevertheless not have a bridging group in its structure,- moreover, the catalyst system is used for the synthesis of polyethylenes containing significant amounts of butyl branches, and is thus used in a polymerisation process .

As is known from EP-A-0 780 353, the properties of a polymer do not change markedly with the addition or removal of one or a few repeating units, contrary to the properties of a product obtained by oligomerisation or trimerisation. A polymerisation catalyst thus results in completely different products than a trimerisation catalyst does .

Half-sandwich cyclopentadienyl titanium complexes of formula (CpB(R) ₂Ar)TiMe₃ and (CpB (R) Ar) TiCl₃ are known per se from

J. Saβmannshausen et al . , J. Organomet . Chem. 1999, 592, 84-94. In these known complexes B(R) Ar can be CMe₂Ph, CHPh₂ or SiMe₂Ph. These complexes were only used as polymerization catalysts; there is no indication at all that these known catalysts could effectively be used for the selective trimerisation of olefins. On the contrary: it is said that the effect of a comparatively weakly coordinated pendant ligand, such as phenyl, on the behaviour of a polymerisation catalyst is difficult to predict. Moreover, a possible favourable effect of a catalyst having a bridging group only consisting of a single atom, for a trimerisation process of ethene to obtain hexene-1, is not mentioned or suggested in this reference.

As mentioned before, Cp is a cyclopentadienyl type ligand, which is optionally substituted. More preferably, Cp is a cyclopentadienyl, indenyl or fluorenyl group, which may be substituted or not with one to five (cyclopentadienyl) , one to seven (indenyl) or one to nine (fluorenyl) substituent alkyl or silyl groups, especially methyl or trimethylsilyl groups. In the catalyst system according to the invention Ar is an aromatic group, which is optionally substituted; examples thereof are phenyl, naphthalene, anthracene or phenanthrene . This enumeration is not to be regarded as limitative; other aromatic groups can also be used, provided that a coordination complex, based on π-electrons of said group, together with titanium is present.

As mentioned above, B is a bridging group based on a single atom selected from the groups 13 to 16 inclusive, preferably B, C, N, O, Si, P, S; more preferably C or Si; most preferably C.

In a preferred embodiment of the invention, the catalyst system comprises a complex of the above given formula, wherein the single atom forming the basis of said group B consists of carbon or silicon, Ar is phenyl, optionally substituted or being part of a larger aromatic entity,

R¹ is a halide, or mono-anionic hydrocarbon residue optionally containing heteroatoms, and n is 2, then R is a mono-anionic hydrocarbon residue, optionally containing heteroatoms, or n is 1, then R is a di-anionic hydrocarbon residue, optionally containing heteroatoms . Expediently, the catalyst system of the invention comprises a titanium complex of the above given formula, wherein Cp is a cyclopentadienyl type ligand being substituted, besides said B-(R)n group, with 1 to 8 groups of formula -YR2R3R4 in which Y is C or Si and R2, R3 and R4 are, independently, H, halogen, lower alkyl, aryl, lower-alkyl-aryl, aryl-lower alkyl residue, wherein said alkyl and aryl are independently substituted or not with one or more lower alkyl residues, said alkyl and aryl residues being independently provided or not with at least one heteroatom, selected from halogen, nitrogen, oxygen, sulphur and phosphor. It is in this respect observed that by "provided" is to be understood that said heteroatom(s) can be incorporated in the hydrocarbon chain, as well as be present as or in a substituent group .

Expediently, said lower alkyl residues, being the same or different to each other, are linear or branched C₁-C₅ alkyl residues, more specifically methyl .

In a further preferred embodiment of the present catalyst system, said above mentioned aryl group in the alkyl aryl or aryl alkyl residue is a phenyl group. Said halogen is preferably fluorine or chlorine.

More preferably the catalyst system of the invention comprises a titanium complex of the above given formula, wherein Ar is a phenyl group, substituted or not at the meta-or para- position (s) , B is based on a carbon atom, n is 2, then groups R are, independently, methyl, or ethyl; or n is 1, then group R is =CH₂ , or forms when R is C₄Hg or C^EJ__Q together with group B a dianionic cyclic group, Cp is C₅H₄ or C₅H₃(Si e3), and R! is chlorine, methyl, or benzyl.

The half-sandwich, substituted cyclopentadienyl titanium complex, forming a part of the present catalyst system, is in a preferred embodiment supported by a carrier. This carrier consists expediently either of a metal oxide, which is selected from the group consisting of alumina, boria, magnesia, thoria, zirconia, silica, or mixtures thereof, or it consists of a polymeric material.

As indicated above, the present catalyst system comprises an activator. Said activator is preferably methylalumoxane, a salt of a non-coordinating anion, or a Lewis acid capable of abstracting an anion from said transition metal complex and thus generating a cationic transition metal species with a non-coordinating anion.

An example of a salt of a non-coordinating anion is N,N- dimethylanilinium tetrakis (pentafluorophenyl) borate, while such a Lewis acid is for example B(CgF₅)₃. It is in this respect observed that any activator can be used provided that it is able to generate a cationic transition metal species with a non-coordinating anion. The term "non-coordinating anion" is meant to indicate the anionic part or derivative of the activator, which not or only weakly coordinates to the cationic form of the present catalyst system.

Preferably the activator is methylalumoxane (also known as MAO) . The molar ratio of Ti.Al is expediently from 1:100 to 1:1000.

The present catalyst system can further also comprise a scavenger. Examples of a scavenger are i-Bu₃Al and (i-BuAl)₂0. A scavenger is normally used to scavenge impurities from a polymerisation medium to obtain a high productivity.

The invention further relates to a process to trimerize olefinic compounds which comprises carrying out said trimerisation in the presence of a catalyst system, as described above, under trimerisation conditions . Such a trimerisation als comprises co- trimerisation according to the definition given before.

The olefin to be trimerized is preferably selected from C₂-C _Q olefins or mixtures of two or more of these olefins. The preferred olefins are ethylene and 1-butene, more preferably ethylene. The temperature is preferably in the range of from 20-150 °C, at a pressure in the range of from 1,5 to 3 MPa.

The invention will further be explained in the following examples .

Experimental section General considerations

All experiments were performed under a nitrogen atmosphere using standard Schlenk and glovebox techniques. Deuterated solvents (Aldrich, Acros) were dried over Na/K alloy and vacuum transferred before use. Cyclooctane (Aldrich, used as internal standard) was distilled from Na prior to use. Toluene (Aldrich, anhydrous, 99,8%) was passed over columns of A1₂0₃ (Fluka) , BASF R3-11 supported Cu oxygen and molecular sieves (Aldrich, 4A) . Diethyl ether and THF (Aldrich) were dried over Al₂0₃ (Fluka) and the other solvents (Aldrich) were dried over molecular sieves (Aldrich, 4A) . Ethene (AGA polymer grade) was passed over BASF R3-11 supported Cu oxygen scavenger and molecular sieves (Aldrich, 4A) .

The compounds 6, 6-pentamethylenefulvene, C₅H5CH₂Ph,

(C₅H₄C(=CH₂)Ph)Li, (C₅H₄CMe₂Ph) TiCl₃ (the catalyst used in Example 1), (C₅H₄SiMe₂Ph) TiCl (the catalyst used in Example 3),

(C5H C e₂-3,5- eCgH₃)TiCl3 (the catalyst used in Example 2) and

B(CgF5)₃ were prepared according to procedures known as such. 6,6-

Diethylfulvene was prepared analogously to 6, 6-pentamethylenefulvene from cyclopentadiene and 3-pentanone. (C5H₄CMe2Ph) TiMe (used in

Examples 10 and 11) was prepared through modification of a known procedure by reaction of (C5H₄CMe₂P ) TiCl₃ with either Me₂Mg or

MeMgl . The preparations of other titanium complexes are disclosed here'after in the Preparation Examples A to F. A toluene solution of MAO (26 wt%, Akzo Nobel Chemicals) , MAO supported on silica (5 wt%, Witco) and [PhNMe₂H] [B (C₆F₅) ₄] . (Akzo

Nobel Chemicals) were used as such.

NMR spectra were recorded on Varian Gemini 200/300 and Unity 500 spectrometers. The ^•'-H NMR spectra were referenced to resonances of residual protons in the deuterated solvents. Chemicals shifts (δ) are given relative to tetramethylsilane (downfield shifts are positive) . GC analyses were performed on a HP 6890 instrument equipped with a HP-1 dimethylpolysiloxane column (19095 Z-123). GC-MS analyses were conducted using a HP 5973 mass-selective detector attached to a

HP 6890 GC instrument. Elemental analyses are the average of a least two independent determinations .

Preparation example A Preparation of (C₅H₄CHPh) TiCl₃, to be used in Example 4. a) Preparation of (C₅H₄CH₂PI1) Li

To a solution of 11.3 mmol n-BuLi in 30 ml of diethyl ether/hexane at -40 °C, 1.87 g (12.0 mmol) of CpHCH₂Ph [2] was added dropwise. The reaction mixture was allowed to warm to room temperature and stirred overnight. The solvents were removed in vacuo. The white residue was stripped with pentane. After rinsing with 3x 10 ml of pentane and after drying in vacuo 1.55 g (9.6 mmol, 85%) of a white solid was isolated. - ^XH NMR (300 MHz, THF-d₈) : δ 8.04-7.92 (m, 4H, Ph o- and m-H) , 7.82 (m, 1H, Ph p-H) , 6.33 (t, ³J_HH = 2.6 Hz, 2H, Cp) , 6.29 (t, ³J_HH = 2.6 Hz, 2H, Cp) , 4.61 (s, 2H, CH₂) - ¹³C NMR (75.4 MHz, THF-d₈) : δ 148.2 (Ph C ipso) , 130.5 (Ph o- or m- CH) , 129.5 (Ph o- or IΏ-CH) , 126.3 (Ph p-CH) , 120.0 (Cp C ipso) , 105.1 (Cp CH) , 103.9 (Cp CH) , 39.0 (CH₂) b) Preparation of (Cs^CHg h) TiCl₃

To a solution of 1.42 g (8.8 mmol) (CpCH₂Ph)Li in 40 ml of methylene chloride, cooled at -40 °C, 0.96 ml (1.7 g, 8.9 mmol) titanium (IV) chloride was added. The reaction mixture was stirred at

5 ambient temperatures overnigh . The methylene chloride was removed in vacuo and the green-brown residue was stripped with pentane. After extraction with toluene, the extract was evaporated in vacuo and the extract residue was dissolved in methylene chloride. Brown crystals were obtained after cooling to -40 °C. Yield: 1.58 g (5.1 mmol, 58%)

10 - ^XH NMR (300 MHz, C₆D₆) : δ 7.09-7.03 (m, 3H, Ph m- and p-H) , 6.82 (m, 2H, Ph O-H) , 5.98 (m, 4H, Cp) , 3.71 (s, 2H, CH₂) - ¹³C NMR (75.4 MHz, C₆D_S) : δ 142.9, 138.3 (Ph and Cp C ipso) , 128.9, 127.2 (Ph CH, one signal overlapped by solvent), 123.6, 123.2 (Cp CH) , 37.7 (CH₂) - Anal. Calcd for C^HnTiCla : C, 46.57; H, 3.58; Ti, 15.48. Found: C,

15 47.07; H, 3.75, Ti, 15.38.

Preparation example B

Preparation of (C₅H₄CEt₂Ph)TiCl₃, to be used in Example 5. a) Preparation of C₅H₄ (TMS) CEt₂Ph

20 To a solution of 4.85 g (58 mmol) PhLi in 200 ml of diethyl ether, cooled at -50 °C, 8.0 g (60 mmol) of 6,6-diethyl fulvene [1] was added dropwise. The reaction mixture was allowed to warm to room temperature and was stirred for 3 hours . After 3 hours the yellow solution was cooled with an ice bath and 7.6 ml (6.5 g, 60 mmol) of

25 trimethylsilyl chloride was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight . The reaction mixture was poured into 250 ml of ice water. The water layer was extracted with 2x 100 ml of light petroleum, after which the combined organic layers were rinsed with 200 ml of brine. The organic phase

30 was dried on MgS0₄. After evaporating the low-boiling volatiles in vacuo, the residue was distilled using a Kogelruhr-apparatus . The product distilled at 110 °C at 0.5 mm Hg as a mixture of isomers . Yield: 9.21 g (32 mmol, 55%) - ^XH NMR (300 MHz, CDC1₃, main isomer) : δ 7.28 (m, 4H, Ph o- and m-H) , 7.18 (m, IH, Ph p-H) , 6.40 (m, IH,

35 C₅H₄) , 6.31 (s, IH, C₅H₄) , 6.22 (m, IH, C₅H₄) , 3.27 (s, IH, C₅H₄) , 2.02 (m, 4H, C-CH₂-CH₃) , 0.72 (m, 6H, C-CH₂-CH₃) , 0.06 (s, 9H, TMS) b) Preparation of (CsRjCEtgPfcQTiCla

To a solution of 6.30 g (22 mmol) of A.l in 40 ml of methylene chloride, cooled at -40 °C, 2.45 ml (4.2 g, 22 mmol) of titanium chloride was added. The mixture was allowed to warm to room temperature and stirred overnight . The methylene chloride was removed in vacuo and the residue was stripped with pentane . Extraction with methylene chloride and cooling to -60 °C afforded red-brown crystals of the title compound. Yield: 5.63 g (15.3 mmol, 70%) - ^XH NMR (300 MHz, C₆D₆) : δ 7.24 (d, ³J_HH = 7.3 Hz, 2H, Ph o-H) , 7.17 (t, ³J_HH = 7.3 Hz, 2H, Ph m-H) , 7.06 (t, ³ _HH = 7.3 Hz, IH, Ph p-H) , 6.26 (t, ³JHH = 2.8 Hz, 2H, Cp) , 6.04 (t, ³J_HH = 2.8 Hz, 2H, Cp) , 2.06 (m (dq) , 2H, C- CH₂-CH₃) , 1.86 (m (dq) , 2H, C-CH₂-CH₃) , 0.51 (t, ³J_HH = 7.3 Hz, 6H, C- CH₂-CH₃) - ¹³C NMR (75.4 MHz, C₆D_S) : δ 154.8 (Ph C ipso) , 142.1 (Cp C ipso) , 128.8 (Ph o-CH) , 128.3 (Ph m-CH, overlap with solvent), 127.2 (Ph p-CH) , 123.1, 121.8 (Cp CH) , 48.6 (C(C₂H_S)₂ ipso) , 29.3 (C-CH₂- CH₃) , 8.5 (C-CH₂-CH₃) - Anal. Calcd for C₁₆H₁₉TiCl₃ : C, 52.57; H, 5.24. Found: C, 52.75; H, 5.27.

Preparation example C

Preparation of {CpC[ (CH₂) ₅] Ph}TiCl₃, to be used in Example 6 a) Preparation of C₅H₄ (TMS) C [ (CH₂) ₅] Ph To a solution of 4.00 g (48 mmol) PhLi in 200 ml of diethyl ether, cooled at -50 °C, 6.95 g (48 mmol) of 6,6- pentamethylenefulvene [1] was added dropwise. The reaction mixture was allowed to warm to room temperature and was stirred for 3 hours. After 3 hours the yellow solution was cooled with an ice bath and 6.4 ml (5.5 g, 51 mmol) of trimethylsilyl chloride was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was poured into 250 ml of ice water. The water layer was extracted with 2x 100 ml of light petroleum, after which the combined organic layers were rinsed with 200 ml of brine. The organic phase was dried on MgS0₄. After evaporating the low-boiling volatiles in vacuo, the residue was distilled using a Kogelruhr-apparatus. The product distilled at 165 °C at 0.4 torr as a mixture of isomers. Yield: 8.96 g (30 mmol, 63%) - R NMR (300 MHz, CDC1₃, main isomer) : δ 7.40 (m, 2H, Ph o-H), 7.33 (m, 2H, PH m-H) , 7.15 (m, IH, Ph p-H) , 6.43 (m, 2H, C_SH₄) , 6.15 (a, IH, C₅H₄) , 3.27

(s, IH, C₅H₄) , 2.17 (m, 4H, α-CH₂) , 1.65-1.40 (m, 6H, β- and γ-CH₂) , - 0.03 (s, 9H, TMS) b) Preparation of {C₅H₄C[ (CH₂) ₅] Ph)TiCl₃ Titanium chloride (1.4 ml, 2.4 g, 12.7 mmol) was added to a solution of 3.70 g (12.5 mmol) of C₅H₄ (TMS) C [ (CH₂) ₅] Ph in 40 ml of methylene chloride, cooled at -40 °C. The reaction mixture was allowed to warm to room temperature and was stirred overnight . The 5 methylene chloride was removed in vacuo and the residue was stripped with pentane. The residue was extracted with methylene chloride. Crystallization from a 1:1 mixture of CH₂C1₂ :pentane afforded red- brown crystals of the desired compound in 78% yield (3.68 g, 9.7 mmol) . - ²H NMR (300 MHz, C_SD₆) : δ 7.16-7.06 (m, 4H, Ph o- and JΠ-H) ,

10 7.01 (m, IH, Ph p-H) , 6.31 (t, ³J_HH = 2.8 Hz, 2H, Cp) , 5.97 (t, ³J_HH = 2.8 Hz, 2H, Cp) , 2.45 (d, ²J_HH = 13.2 Hz, 2H, α-CH₂ (eq) ) , 1.88 (m, 2H, α-CH₂ (ax)), 1.37 (br, 3H, β- and γ-CH₂) , 1.25-1.05 (m, 3H, β- and γ-CH₂) - ¹³C NMR (75.4 MHz, C_SD₆) : δ 156.0 (Ph C ipso) , 142.1 (Cp C ipso) , 129.2 (Ph o-CH) , 127.9 (Ph m-CH) , 126.8 (Ph p-CH) , 123.2,

15 120.9 (Cp CH) , 45.1 (C_[(CH₂)₅] ipso) , 35.8 (α-CH₂) , 26.1 (γ-CH₂) , 22.4 (β-CH₂) - Anal. Calcd for C₁₇H₁₉TiCl₃ : C, 54.08; H, 5.07; Ti, 12.69. Found: C, 53.93; H, 4.90; Ti , 12.62.

Preparation example D 20 Preparation of [C₅H₄C(=CH₂) Ph] TiCl₃, to be used in Example 7

To a solution of 0.61 ml (1.06 g, 5.6 mmol) titanium chloride in 40 ml of methylene chloride, cooled at -50 °C, 1.80 g (5.6 mmol) [C₅H₄C (=CH₂) Ph] Li was added. The reaction mixture was allowed to warm to room temperature and was stirred overnight . The volatiles were

25 removed in vacuo and the green-black residue was stripped with pentane. Extraction with pentane afforded small analytically pure amounts of the desired compound. - ^XH NMR (300 MHz, C₆D_e) : δ 7.2-7.05 (m, 5H, Ph) , 6.35 (t, ³J_HH = 2.7 Hz, 2H, Cp) , 6.01 (t, ³J_HH = 2.7 Hz, 2H, Cp) , 5.58 (s, IH, =CH₂) , 5.20 (s, IH, =CH₂) - ¹³C NMR (75.4 MHz,

30 C₆D₆) : δ 142.5 (Ph C ipso) , 139.7 (Cp C ipso) , 139.6

ipso) , 128.8, 128.7, 128.5 (Ph CH) , 123.4, 121.1 (Cp CH) , 120.5 (C(=CH₂) - Anal. Calcd for C₁₃H_1:LTiCl₃ : C, 48.57; H, 3.45; Ti, 14.90. Found: C, 48.71; H, 3.55; Ti , 14.78.

35 Preparation Example E

Preparation of C₅H₃ (3-Si e₃) CMe₂Ph] TiCl₃, to be used in Example 8 a) Preparation of C₅H₃ (SiMe₃) ₂CMe₂Ph

To a solution of 2.25 g (11.8 mmol) (C₅H₄CMe₂Ph) Li [5] in 50 ml of diethyl ether and 20 ml of THF, cooled in ice water, 1.5 ml (1.3 g, 11.9 mmol) TMSC1 was added dropwise. The mixture was allowed to warm to room temperature and was stirred overnight . The yellow solution was cooled in ice water and 4.8 ml (12 mmol) of a 2.5M n- BuLi solution in hexanes was added. After warming up to room temperature the mixture was stirred for 4 hours . The white suspension was cooled in ice water and 1.6 ml (1.4 g, 12.7 mmol) TMSCl was added dropwise . The mixture was allowed to warm to room temperature and stirred overnight. The yellow suspension was poured into 125 ml ice water. The water layer was extracted with 50 ml of light petroleum and the combined organic layers were dried on MgS0₄. After evaporation of low-boiling volatiles, the residue was distilled using a Kogelruhr-apparatus. The product distilled at 115 °C at 0.8 Torr. Yield: 2.87 g (8.7 mmol, 74%) - ^XH NMR (200 MHz, CDC1₃) : δ 7.4-7.1 (m, 5H, Ph) , 6.40 (d, ³J_HH = 2.2 Hz, 2H, Cp) , 6.20 (t, ³J_HH = 2.1 Hz, IH, Cp) , 1.53 (s, 6H, CMe₂) , -0.03 (s, 18H, TMS) b) Preparation of [C₅H₃ (3-SiMe₃) CMe₂Ph] TiCl₃

To a solution of 0.92 ml (1.6 g, 8.4 mmol) TiCl₄ in 50 ml of methylene chloride, cooled at -50 °C, 2.75 g (8.4 mmol) of C₅H₃ (SiMe₃)₂CMe₂Ph was added. The reaction mixture was allowed to warm to room temperature and was stirred overnight . The volatiles were removed in vacuo and the residue was stripped with pentane. Extraction with methylene chloride and cooling down to -60 °C afforded 2.76 g (6.7 mmol, 80%) of the desired compound. - ¹H NMR (300 MHz, C₆D₆) : δ 7.1-6.85 (m, 5H+1H, Ph+Cp), 6.57 (m, IH, Cp) , 6.53 (m, IH, Cp) , 1.63 (s, 6H, CMe₂) , 0.12 (s, 9H, TMS) - ¹³C NMR (75.4 MHz, C_SD₆) : δ 158.5 (Ph C ipso) , 148.5 (Cp C ipso) , 144.1 (Cp C(TMS) ipso) , 128.7, 128.6, 126.7, 126.1, 124.6 (Ph+Cp CH) , 41.2 (CMe₂ ipso) , 29.3, 29.0 (CMe₂) , -0.8 (TMS) - Anal. Calcd for C₁₇H₂₃SiTiCl₃ : C, 49.84; H, 5.66; Ti, 11.69. Found: C, 49.70; H, 5.68; Ti , 11.59.

Preparation example F

Preparation of [C₅H₃ (3 -SiMe₃) C e₂-3 , 5 -Me₂C₆H₃] TiCl₃ , to be used in Example 9 a) Preparation of CgH₃ (SiMe₃) ₂CMe₂-3 , 5 -Me₂C₆H₃

To a solution of 1 . 15 g (5 .3 mmol ) [CpCMe₂-3 , 5 -Me₂C_sH₃] Li in 50 ml of diethyl ether, cooled with ice water , 0 . 7 ml ( 0 . 6 g, 5 . 5 mmol) trimethylsilyl chloride was added dropwise . The reaction mixture was allowed to warm to room temperature and was stirred overnight . The white suspension was cooled to -30 °C and 5.4 mmol of a 2.5M solution of n-BuLi in hexanes was added dropwise. After stirring for 3 hours at ambient temperature, the reaction vessel was placed in ice water and 0.8 ml (0.7 g, 6.4 mmol) trimethylsilyl chloride was added. The reaction mixture was allowed to warm up to room temperature and was stirred overnight. The mixture was poured into 100 ml of ice water. The water layer was extracted twice with 50 ml portions of light petroleum, and the combined organic layers were dried over MgS0₄. Kogelruhr-distillation at 160 °C and 0.4 Torr yielded 1.26 g (3.5 mmol, 66%) of the title compound - ^XH NMR (200 MHz, CDC1₃) : δ 6.90 (s, 2H, Ar o-H), 6.78 (s, IH, Ar p-H) , 6.37 (m, 2H, Cp) , 6.19 (m, IH, Cp) , 2.24 (s, 6H, ArMe) , 1.51 (s, 6H, CMe₂) , -0.05 (s, 18H, TMS) b) Preparation of [C₅H₃ (3-SiMe₃) CMe₂-3 , 5-Me₂C₆H₃] TiCl₃ To a solution of 0.35 ml (0.6 g, 3.2 mmol) titanium chloride in 40 ml of methylene chloride, cooled at -40 °C, 1.18 g (3.3 mmol) of C₅H₃ (SiMe₃) ₂CMe₂-3 , 5-Me₂C₆H₃ was added dropwise. The reaction mixture was allowed to warm to room temperature and was stirred overnight . The volatiles were removed in vacuo and the residue was stripped with pentane. Extraction with pentane yielded 1.02 g (2.3 mmol, 72%) of light-brown crystals. - ¹H NMR (300 MHz, C₆D₆) : δ 6.96 (m, IH, Cp) , 6.69 (s, 2H, Ar o-H), 6.64 (m, 1+1H, Cp + p-H), 6.55 (m, IH, Cp) , 2.08 (s, 6H, ArMe), 1.70 (s, 6H, CMe₂) , 0.13 (s, 9H, TMS) - ¹³C NMR (75.4 MHz, C₆D_S) : δ 159.1 (Ar C ipso) , 148.5 (Cp C ipso) , 144.1 (Cp C(TMS) ipso) , 137.9 (Ar a-C ipso) , 128.8, 128.4, 127.8, 124.7 (Cp CH + Ar p-CH) , 124.1 (Ar J7J-H) , 41.2 (CMe₂ ipso) , 29.3, 29.2 (CMe₂) , 21.5 (ArMe), -0.9 (TMS)

Preparation example G Preparation of (C₅H₄C e₂Ph) Ti (CH₂Ph) ₃, to be used in Example 10

To a stirred solution of 0.52 g of (C₅H₄CMe₂Ph) TiCl₃ (1.54 mmol) in 30 ml of diethyl ether, cooled at -40 °C, a solution of benzyl magnesium bromide (4.62 mmol) in diethyl ether was added dropwise. The mixture was allowed to warm to room temperature and was stirred for 3 hours. The solvent was removed in vacuo. The red solid was extracted with pentane. Cooling to -40 °C yielded red crystals of the desired product (560 mg, 1.11 mmol, 72%) - ^XH NMR (500 MHz, C₆D₆) : δ 7.17-7.11 (m, 10H, Ph m-and o-H and Bz m-H) , 7.02 (m, IH, Ph p-H), 6.90 (t, ³J_HH = 7.5 Hz, 3H, Bz p-H), 6.81 (d, ³J_HH = 7.5 Hz, 6H, Bz o- H) , 5.74 (ps. t, ³J_HH = 2.8 HZ, 2H, Cp) , 5.50 (ps . t, ³ _HH = 2.8 Hz,

2H, Cp) , 2.97 (s, 6H, Ti-CH₂) , 1.38 (s, 6H, CMe₂)- - ¹³C-NMR (125.7 MHz, C₆D_S) : δ 149.6 (s, Ph C ipso) , 149.1 (s, Bz C ipso) , 146.7 (s, Cp C ipso) , 128.8 (dd, ¹J_CH=158 Hz, Bz m-CH, overlap with solvent) , 128.5 5 (d, ¹J_αι=151 Hz, Ph m-CH, overlap with solvent) , 127.0 (dm, ^^=161 Hz, Bz o-CH) , 126.5 (dm, \T_CH=156 Hz, Ph o-CH) , 126.4 (dm, ¹J_CH=156 Hz, Ph p-CH) , 123.0 (dt,

Hz, Cp CH) , 113.5 (dm, ¹J_CH=172 Hz, Cp CH) , 93.5 (t, ^^=123 Hz, Ti-CH₂) , 40.5 (s, CMe₂) , 30.2 (q, ¹J_CH=122 Hz, CMe₂) - Anal. Calcd for C₃₅H₃₆Ti : 10 C, 83.32; H, 7.19; Ti , 9.49. Found: C, 82.63; H, 7.32; Ti, 9.35.

Preparation example H

Preparation of [C_SH₃-1,3- (C e₂Ph)₂] TiCl_3/ to be used in Example 15 a) Preparation of [C_SH₃-1, 3- (CMe₂Ph) ₂] Li

15 To a suspension of 2.28 g (27.1 mmol) PhLi in 50 ml of n- hexane, 6.14 g (27.4 mmol) of 3-α, α-dimethylbenzyl-6 , 6- dimethylfulvene was added. The mixture was refluxed for 5 hours. The precipitate was poured onto a glass frit and rinsed with 2x 20 ml of pentane. Drying in vacuo yielded 4.18 g (13.6 mmol, 50%) of the title

20 compound as an off-white solid. - ^XH NMR (300 MHz, C_sD₆/THF-d₈) : δ 7.55 (d, ³J_HH = 8.2 Hz, 4H, Ph o-H) , 7.16 (m, 4H, Ph m-E) , 7.01 (m, 2H, Ph p-H) , 5.87 (m, IH, Cp) , 5.83 (m, 2H, Cp) , 1.79 (s, 12H, CMe₂) - ¹³C NMR (75.4 MHz, C₆D₆/THF-d₈) : δ 154.9, 129.0 (Ph and Cp C ipso) , 127.8, 126.7, 124.7 (Ph CH) , 100.8, 99.8 (Cp CH) , 39.8 (CMe₂ C ipso) ,

25 32.5 (CMe₂) . b) Preparation of [η^s-C₃H₃-l, 3- (CMe₂Ph) ₂] TiCl₃

To a solution of 1.31 g (4.2 mmol) of [C₅H₃-1, 3- (CMe₂Ph) ₂] Li in 30 ml of methylene chloride, cooled at -40 °C, 0.47 ml (0.8 g, 4.2 mmol) TiCl₄ was added dropwise. The dark brown solution was allowed

30 to warm to room temperature and was stirred overnight. The solvent was removed in vacuo and the residue was stirred with 40 ml of pentane, which was subsequently pumped off. The residue was extracted with 50 ml of toluene, which was replaced by a 1:1 mixture of methylene chloride/pentane (30 ml in total) . Cooling to -40 °C

35 afforded 0.22 g (0.5 mmol, 12%) of the title compound. - ^XH NMR (300 MHz, C₆D_e) : δ 6.98 (m, 2H, Ph p-H) , 6.96 (m, 4H, Ph m- or o-H), 6.70 (m, 4H, Ph m- or o-H), 6.50 (m, IH, Cp) , 6.40 (d, ³J_HH = 2.6 Hz, 2H, Cp) , 1.60 (s, 6H, CMe₂) , 1.54 (s, 6H, CMe₂) - ¹³C NMR (75.4 MHz, C_SD_S) : δ 156.2, 148.8 (Ph and Cp C ipso) , 128.4, 126.5, 126.0 (Ph CH) , 121.5, 120.5 (Cp CH) , 41.7 (CMe₂ C ipso) , 28.5, 28.4 (CMe₂) - Anal. Calcd for C₂₃H₂₅TiCl₃ : C, 60.62; H, 5.53. Found: C, 60.16; H, 5.56.

Example 1: Catalytic ethene conversion with (C₅H₄CMe₂Ph)TiCl₃/ AO

The reactions were performed in a stainless steel 1L autoclave (Medimex) , fully temperature and pressure controlled and equipped with solvent and catalyst injection systems. In a typical experiment, the autoclave was evacuated and heated for 45 min at 90 °C prior to use.

The reactor was then brought to the desired temperature, charged with 200 ml of toluene and pressurized with ethene. After equilibrating for 15 min, the appropriate amount of MAO/toluene was injected together with 25 ml of toluene. Subsequently a mixture of 2.50 g cyclooctane (internal standard) and 1.0 ml (0.87 g) of a 15 mM stock solution of the titanium complex in toluene was injected, together with 25 ml of toluene, to start the reaction. During the run the ethene pressure was kept constant to within 0.2 bar of the initial pressure by replenishing flow. After the specified run time, the reactor was vented and the residual MAO was destroyed by addition of 20 ml of ethanol . Samples of the reaction mixture were taken to analyze and quantify the soluble components . Polymeric product was stirred for 90 min in acidified ethanol and repeatedly rinsed with ethanol and light petroleum on a glass frit. The polymer was initially dried in air and subsequently in vacuo at 70 °C overnight. The results of the catalytic experiments are summarized in Table 1 (ethene conversion with the (C₅H₄CMe₂Ph) TiCl₃/MA0 catalyst system) and Table 2 (ethene conversion with the (C_sH₄CMe₂Ph) TiCl₃/MAO catalyst system) . In these experiments, the C_s fraction consists predominantly of 1-hexene (99+ %) , with traces of 2- and 3-hexenes. The only detectable product of the C₈ fraction is 1-octene. The C₁₀ fraction is a mixture of isomers with either vinyl (90%) , vinylidene (5%) or internal olefinic (5%) unsaturation, and consists predominantly of 5- methylnon-1-ene (75-85%) . Higher olefins (C₁₂-C₂₄) constitute less than 0.5 wt% of the total amount of product formed. Table 1:

Test P (ethene) T c₆ C_B Cio PE Productivity nr . MPa °C g (wt%) g (wt%) g (wt%) g (wt%) kg(C₆) mol(Ti)^"1 h^"1

1 0.2 30 δ.O (87) 0.1 (0.8) 1.0 (11) 0.2 (1.6) 1066

2 0.5 30 20.9 (83) 0.3 (1.2) 3.5 (14) 0.5 (1.8) 2787

3 1.0 30 47.2 (86) 0.9 (1.6) 5.1 ( 9) 1.4 (2.6) 6292

4 0.5 50 12.4 (83) 0.2 (1.1) 1.6 (11) 0.7 (4.6) 1653

5 0.5 so 3.3 (76) 0.05(0.9) 0.2 ( 4) 0.8 (19) 440

Toluene solvent, 15 μmol Ti, Al:Ti = 1000, 30 min run time

Table 2:

Test Run time Al:Ti c₆ c₈ Cio PE Productivity nr . min g (wt%) g (wt%) g (wt%) g (wt%) kg(C₆) ol(Ti)-¹ h^"1

15 1000 16.6 (89) 0.2 (1.0) 1.4 ( 8) 0.4 (2.2) 4413 30 1000 20.9 (83) 0.3 (1.2) 3.5 (14) 0.5 (1.8) 2787 60 1000 27.1 (80) 0.4 (1.2) 5.5 (16) 0.9 (2.7) 1809 30 500 15.2 (86) 0.2 (1.2) 1.8 (10) 0.5 (2.8) 2029 Toluene solvent, 15 μmol Ti, 30 °C, 0.5 MPa ethene

Comparative example A: Catalytic ethene conversion with (C_sH₄CMe₃) TiCl₃/MAO

The general procedure and conditions of example 1 were followed, using the (C₅H₄CMe₃) TiCl₃/MA0 catalyst system. The results of the catalytic experiment are listed in Table 3.

Table 3:

Test P (ethene) T C₆ Ca Cio PE Productivity nr . MPa °C g (wt%) g ( t%) g ( t%) g ( t%) g(Cβ) mol(Ti)^"1 h^"1 a 0.5 30 0.5 (17) 0.1 (3) 0.1 (4) 2.4 (76) 72

Example 2: Catalytic ethene conversion with (C₅H₄CMe₂-3 , 5- e₂C₅H₃)TiCl₃/MAO

The general procedure and conditions of example 1 were followed, using the (C₅H₄CMe₂-3 , 5-Me₂C₆H₃) TiCl₃/MA0 catalyst system. The results of the catalytic experiments are listed in Table 4.

Table 4:

Test P (ethene) T Cs Cβ Cio PE Productivity nr . MPa °C g (wt%) g (wt%) g ( t%) g ( t%) kg(C₆) mol(Ti)-¹ h^"1

10 0.5 30 7.9 (94) 0.02 (0.2) 0.4 (5) 0.1 (1.3) 1052

11 0.5 50 4.5 (93) 0.03 (0.6) 0.2 (4) 0.1 (2.1) 599 Example 3: Catalytic ethene conversion with (C₅H₄Si e₂Ph)TiCl₃/ AO

The general procedure and conditions of example 1 were followed, using the (C₅H₄SiMe₂Ph) TiCl₃/MA0 catalyst system. The results of the catalytic experiments are listed in Table 5. Higher olefins (C₁₂-C₂₄) are also formed, constituting about 8 wt% of the total amount of product formed.

Tab: Le 5:

Test P (ethene) T Cs Cβ Cio C12-C2 PE Productivity nr. MPa °C g (wt%) g (wt%) g (wt%) g ( t%) g (wt%) kg(C₆) mol(Ti)^"1 h^"1

12 0.5 30 2.1 (36) 0.3 (5) 0.4 (7) 0.5 (8) 2.6 (44) 284 13 0.5 50 2.6 (47) 0.4 (7) 0.4 (7) 0.4 (7) 1.7 (32) 352

Example 4: Catalytic ethene conversion with (C₅H₄CH₂Ph)TiCl₃/ A0 The general procedure and conditions of example 1 were followed, using the (C₅H₄CH₂Ph) TiCl₃/MA0 catalyst system. The results of the catalytic experiments are listed in Table 6. Higher olefins (C₁₂-C₂₄) are also formed, constituting about 9 wt% of the total amount of products formed.

Table 6:

Test (ethene) T c₆ c₈ Cio 12-C24 PE Product i - ity nr . MPa °C g ( t%) g ( t%) g ( t%) g ( t%) g ( t%) kg(C₆) mol(Ti)^"1 h^"1

14 0.5 30 2.7 (42) 0.4 (6) 0.6 (9) 0.6 (9) 2.2 (34) 361

15 0.5 50 3.0 (54) 0.3 (6) 0.5 (9) 0.5 (9) 1.2 (22) 405

Example 5: Catalytic ethene conversion with (C₅H₄CEt₂Ph) TiCl₃/MAO

The general procedure and conditions of example 1 were followed, using the (C₅HCEt₂Ph) TiCl₃/MAO catalyst system. The results of the catalytic experiments are listed in Table 7.

Table 7:

Test P (ethene) T C₆ Ca Cio PE Productivity nr. MPa °C g (wt%) g ( t%) g ( t%) g (wt%) kg(C₆) mol(Ti)^"1 IT¹

16 0.5 30 18.5 (88) 0.05 (0.3) 1.4 (7) 1.0 (4.6) 2462

17 0.5 50 8.7 (84) 0.03 (0.3) 0.6 (5) 1.0 (9.9) 1159

Example 6: Catalytic ethene conversion with {CpC [ (CH₂) ₅] Ph}TiCl₃/ AO The general procedure and conditions of example 1 were followed, using the {C₅H₄C [ (CH₂) ₅] Ph}TiCl₃/MAO catalyst system. The results of the catalytic experiments are listed in Table 8.

Table 8

Test P (ethene) T Ce Ca Cio PE Productivity nr. MPa °C g (wt%) g ( t%) g ( t%) g (wt%) kg(C_s) rαol(Ti)-¹ IT¹

18 0.5* 30 24.4 (87) 0.1 (0.3) 2.9 (10) 0.6 (2.0) 3248 19 0.5* 50 12.0 (86) 0.1 (0.4) 1.2 ( 9) 0.7 (5.2) 1593 20 0.5** 30 16.4 (91) 0.04 (0.2) 1.4 ( 8) 0.2 (1.3) 4362

* 30 min run time, ** 15 min run time

Example 7: Catalytic ethene conversion with [C₅H₄C{=CH₂)Ph]TiCl₃/ AO

The general procedure of example 1 was followed, using the [C₅H₄C(=CH₂) Ph]TiCl₃/MAO catalyst system. The conditions and results of the catalytic experiments are listed in Table 9.

Table 9: Catalytic ethene conversion with the [C₅H₄C (=CH₂) Ph] TiCl₃/MA0 system (toluene solvent, 15 μmol Ti, Al:Ti = 1000, 30 min run time)

Test P (ethene) T c. Cβ Cio PE Productivity nr . MPa °C g ( t%) g (wt%) g (wt%) g ( t%) kg(C₆) moKTi)^"1 h^'1

21 0.5 30 17.3 (88) 0.1 (0.3) 1.4 (7) 0.9 (4.7) 2307 22 0.5 50 10.9 (86) 0.03 (0.2) 0.7 (6) 1.1 (8.3) 1449

Example 8: Catalytic ethene conversion with [C₅H₃ (3-SiMe₃) CMe₂Ph] - TiCl₃/MAO

The general procedure and condictions of example 1 were followed, using the [C_SH₃ (3-SiMe₃) CMe₂Ph] TiCl₃/MA0 catalyst system. The results of the catalytic experiments are listed in Table 10.

Table 10

Test P (ethene) T c_s Ca Cio PE Productivity nr. MPa °C g ( t%) g ( t%) g ( t%) g ( t%) kg(C₆) moKTi)^"1 h^"1

23 0.5 30 25.2 (85) 0.6 (2.1) 3.3 (11) 0.4 (1.2) 3357 24 0.5 50 20.1 (84) 0.4 (1.5) 3.3 (14) 0.3 (1.3) 2683 25 0.5 80 8.0 (88) 0.1 (1.4) 0.8 ( 8) 0.2 (2.1) 1069

Example 9: Catalytic ethene conversion with [C₅H₃ (3-SiMe₃) CMe₂-3, 5- Me₂C₆H₃]TiCl₃/ AO

The general procedure and conditions of example 1 were followed, using the [Cp (TMS) CMe₂-3 , 5-Me₂C_sH₃] TiCl₃/MA0 catalyst system. The results of the catalytic experiments are listed in Table 11. For the run at 30°C, the C_s fraction consists of 99.9% 1-hexene, and the Cι₀ fraction of 94% 5-methylnon-l-ene .

Table 11:

Test P (ethene) T c₆ C₈ Cio PE Productivity nr. MPa °C g (wt%) g (wt%) g ( t%) g ( t%) kg(C_β) mol(Ti)^"1 h^"1

26 0.5 30 40.1 (84) 0.1 (0.2) 7.0 (15) 0.3 (0.6) 5347 27 0.5 50 25.7 (82) 0.1 (0.3) 4.8 (15) 0.6 (1.9) 3427

Example 10 : Catalytic ethene conversion with (C₅H₄CMe₂Ph) Ti (CH₂Ph) ₃/ AO

The general procedure and conditions of example 1 were followed, using the (C_sH₄CMe₂Ph) Ti (CH₂Ph) ₃/MAO catalyst system. The results of the catalytic experiments are listed in Table 12.

Table 12:

Test P (ethene) T C₆ Ca Cio PE Productivity nr . MPa °C g ( t%) g (wt%) g ( t%) g ( t%) kg(C_s) mol(Ti)-¹ h^-1

28 0.5 30 23.8 (82) 0.3 (1.1) 4.6 (16) 0.5 (1.6) 3175

29 0.5 50 18.6 (78) 0 . 3 (1.1) 4.0 (17) 0.8 (3.3) 2480

Example 11: Catalytic ethene conversion with (C₅H₄CMe₂Ph)Ti e₃/MAO

The general procedure and conditions of example 1 were followed, using the (CHCMe₂Ph) TiMe₃/MAO catalyst system. The results of the catalytic experiment are listed in Table 13.

Table 13:

Test P (ethene) T C_G Ca Cio PE Productivity nr . MPa °C g (wt%) g ( t%) g (wt%) g (wt%) kg(C₆) moKTi)^"1 h^"1

30 0.5 30 25.7 (81) 0.4 (1.2) 5.2 (16) 0.5 (1.5) 3428

31 0.5 50 18.1 (79) 0.2 (1.0) 3.8 (17) 0.7 (3.2) 2412

Example 12: Catalytic ethene conversion with

(C₅H₄C e₂Ph) TiMe₃/MAO/Si0₂

The reaction was performed in a stainless steel 1 1 autoclave (Medimex) , fully temperature and pressure controlled and equipped with solvent and catalyst injection systems. Prior to use the autoclave was preheated in vacuo for 45 min at 90 °C. The reactor was cooled to 30 °C, charged with 200 ml of toluene and pressurized with ethene. After equilibrating for 15 min, a slurry of 2.05 g of 5 wt% MAO/Si0₂ in 10 ml of toluene was injected together with 30 ml of toluene. Subsequently a mixture of 2.50 g cyclooctane (internal standard) and 1.0 ml (0.87 g) of a 15 mM stock solution of

(C₅H₄CMe₂Ph) TiMe₃ in toluene was injected, together with 25 ml of toluene, to start the reaction. During reaction the ethene pressure was kept constant to within 0.2 bar of the initial pressure by replenishing flow. After 30 min the reactor was vented and the remaining residual MAO was destroyed by addition of 20 ml of ethanol. Samples of the reaction mixture were taken to analyze and quantify the soluble components. The solids (polyethene and silica support) were stirred in acidified ethanol for 90 min and rinsed repeatedly with ethanol and light petroleum on a glass frit. The material was dried in air overnight and subsequently in vacuo at 70 °C overnight, yielding 1.7 g of which the polyethene fraction was not determined. The results of the catalytic experiment are listed in Table 14; the conditions were: toluene solvent, 15 μmol Ti, Al:Ti = 250, 30 min run time. Weight percentages calculated on C₃-C₁₀ products only.

Table 14:

Test P (ethene) T c₆ Ca Cio PE Productivity nr. MPa °c g ( t%) g (wt%) g (wt%) g (wt%) kg(Cβ) mol(Ti)^"1 h^-1

32 0.5 30 13.8 (95) 0.1 (0.8) 0.6 (4) n.d. 1837

Example 13: Catalytic ethene conversion with (C₅H₄C e₂Ph) Ti e₃/ [PhNMe₂H] [B (C₆F₅) ₄]

The reactions were performed in a stainless steel 500 mL autoclave (Medimex) , fully temperature and pressure controlled and equipped with solvent and catalyst injection systems. Prior to use the autoclave was preheated in vacuo for 45 min at 90 °C. The reactor was cooled to the desired temperature, charged with 150 ml of toluene and pressurized with ethene. After equilibrating for 15 min, a suspension of 16.5 μmol [PhNMe₂H] [B(C₆F₅)₄] in 5 ml of toluene was injected together with 25 ml of toluene. Subsequently a mixture of 2.50 g cyclooctane (internal standard) and 1.0 ml (0.87 g) of a 15 mM stock solution of the titanium trimethyl complex in toluene was injected, together with 25 ml of toluene, to start the reaction. During reaction the ethene pressure was kept constant to within 0.2 bar of the initial pressure by replenishing flow. After the desired run time, the reactor was vented and samples of the reaction mixture were taken to analyze and quantify the soluble components . The polymer was repeatedly rinsed with ethanol and light petroleum on a glass frit . The polymer was dried in air overnight and subsequently dried in vacuo at 70 °C overnight. The results of the catalytic experiments are listed in Table 15. The conditions were: toluene solvent, 15 μmol Ti, B:Ti = 1.1, 30 min run time

Table 15:

Test P (ethene) T Cs Ca io PE Productivity nr. MPa °C g (wt%) g (wt%) g (wt%) g ( t%) kg (C_s) mol (Ti) -¹ h^"1

33 0 . 5 30 14 . 6 (90) 0 . 2 (1 .3 ) 1.2 ( 7) 0 . 3 (2 . 0) 1948 34 0 . 5 50 14 . 0 ( 82) 0 . 2 (1.1) 2 .2 (13 ) 0 . 6 (3 .4) 1867

Example 14: Catalytic ethene conversion with (C₅H₄C e₂Ph) Ti e₃/B (C₆F₅) ₃ The reaction was performed in a stainless steel 500 mL autoclave (Medimex) , fully temperature and pressure controlled and equipped with solvent and catalyst injection systems. Prior to use the autoclave was preheated in vacuo for 45 min at 90 °C. The reactor was cooled to the desired temperature, charged with 150 ml of toluene and pressurized with ethene. After equilibrating for 15 min, 1.0 ml (0.87 g) of a 16.5 mM stock solution of B(C₆F₅)₃ in toluene was injected together with 25 ml of toluene. Subsequently a mixture of 2.50 g cyclooctane (internal standard) and 1.0 ml (0.87 g) of a 15 mM stock solution of the titanium trimethyl complex in toluene was injected, together with 25 ml of toluene, to start the reaction.

During reaction the ethene pressure was kept constant to within 0.2 bar of the initial pressure by replenishing flow. After the desired run time, the reactor was vented and samples of the reaction mixture were taken to analyze and quantify the soluble components . The polymer was repeatedly rinsed with ethanol and light petroleum on a glass frit . The polymer was dried in air overnight and subsequently dried in vacuo at 70 °C overnight. The results of the catalytic experiment are listed in Table 16. The conditions were: toluene solvent, 15 μmol Ti, B:Ti = 1.1, 30 min run time. Table 16:

Test P (ethene) T Cs C_a Cio PE Productivity nr. MPa °C g (wt%) g (wt%) g ( t%) g (wt%) kg(Cs) mol(Ti)-¹ h^"1

35 0.5 30 5.8 (88) 0.1 (0.9) 0.3 ( 5) 0.4 (6.6) 776

Example 15: Catalytic ethene conversions with [C₅H₃-1,3- (CMe₂Ph) ₂] TiCl₃/MAO

The general procedure and conditions of example 1 were followed, using the [C₅H₃-1, 3- (CMe₂Ph) ₂] TiCl₃/MAO catalyst system. The results of the catalytic experiments are listed in Table 17.

Table 17:

Test P (ethene) T Run time Cs Cio PE Productivity nr . MPa °C min g ( t%) g ( t%) g ( t%) kg(C₆) mol(Ti)^"1 h^"1

36 0.5 30 30 11.9 (91) 0.6 (5) 0.3 (2.3) 1575 37 0.5 30 120 46.6 (89) 4.1 (8) 0.8 (1.5) 1550

Claims

C L A I M S

1. A catalyst system for the selective trimerization of olefins comprising a transition metal complex characterized in that said catalyst system comprises a) a half-sandwich substituted cyclopentadienyl titanium complex of formula

(Cp-B(R)_nAr)TiR¹ ₃ wherein

Cp is a cyclopentadienyl type ligand, optinally substituted,

B is a bridging group, based on a single atom selected from the groups 13 to 16 inclusive of the Periodic System,

Ar is a aromatic group, optionally substituted, R is, independently, hydrogen, or a hydrocarbon residue, optionally being substituted and optionally containing heteroatoms, or groups R and B are joined together to form a ring, n is an integer equal to the (valency of B minus 2) , and

R-¹- is a mono-anionic group, and b) an activator.

2. A catalyst system according to claim 1, wherein the single atom forming the basis of group B is selected from B, C, N, 0, Si, P and S.

3. A catalyst system according to any of the claims 1 or 2 wherein the single atom forming the basis of said group B consists of carbon or silicon,

Ar is phenyl, optionally substituted or being part of a larger aromatic entity,

R¹ is a halide, or mono-anionic hydrocarbon residue optionally containing heteroatoms, and n is 2, then R is a mono-anionic hydrocarbon residue, optionally containing heteroatoms, or n is 1, then R is a di-anionic hydrocarbon residue, optionally containing heteroatoms .

4. A catalyst system according to any of the claims 1 to 3 , wherein Cp is a cyclopentadienyl type ligand being substituted, besides said B-(R)n group, with 1 to 8 groups of formula -YR2R3R4 in which Y is C or Si and R2, R3 and R4 are, independently, H, halogen, lower alkyl, aryl, lower-alkyl-aryl, aryl-lower alkyl residue, wherein said alkyl and aryl are independently substituted or not with one or more lower alkyl residues, said alkyl and aryl residues being independently provided or not with at least one heteroatom, selected from halogen, nitrogen, oxygen, sulphur and phosphor.

5. A catalyst system according to any of the claims 1 to 4, wherein said lower alkyl residues, being the same or different to each other, are linear or branched C -C5 alkyl residues, more specifically methyl.

6. A catalyst system according to any of the claims 1 to 5, wherein said aryl group in the alkylaryl or arylalkyl residue is a phenyl group .

7. A catalyst system according to any of the claims 1 to 6, wherein said halogen is fluorine or chlorine.

8. A catalyst system according to any of the claims 1 to 7, wherein

Ar is a phenyl group, substituted or not at the meta-or para- position,

B is based on a carbon atom, n is 2, then groups R are, independently, methyl, or ethyl; or n is 1, then group R is

or forms when R is C H₈ or C₅H₁₀ together with group B a dianionic cyclic group Cp is C₅H₄ or C₅H₃(SiMe₃), or C5H3 (CMe₂Ph) , and

R¹ is chlorine, methyl, or benzyl.

9. A catalyst system according to any of the claims 1 to 8, wherein said catalyst complex is supported on a carrier.

10. A catalyst system according to any of the claims 1 to 9, wherein said activator is methylalumoxane, a salt of a non- coordinating anion, or a Lewis acid capable of abstracting an anion from said transition metal complex.

11. A catalyst system according to any of the claims 9 and 10 wherein the activator is methylalumoxane and the molar ratio of Ti:Al is from 1:100 to 1:1000.

12. A catalyst system according to any of the claims 1 to 11, wherein said catalyst system further comprises a scavenger.

13. A catalyst system according to claim 12, wherein said scavenger is selected from i-Bu₃Al and (i-BU₂Al)2θ.

14. A process to trimerize olefinic compounds, which comprises carrying out said trimerization in the presence of a catalyst system according to any of the preceding claims under trimerization conditions .

15. A process according to claim 14, wherein said olefin is selected from C2-C₂0 olefins or mixtures of two or more of these olefins .