WO2008038173A2 - Polymerisation (including oligomerisation) of olefinic compounds in the presence of catalyst, and a catalyst activator including a halogenated organic group - Google Patents

Abstract

According to the present invention there is provided a process for producing a polymenc (including oligomenc) product by the polymerisation (including oligomeπsation) of at least one olefinic compound, by contacting the at least one olefinic compound with the combination of a polymerisation (including ohgomensation) catalyst and a catalyst activator The catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium The polymeπsation (including ohgomensation) catalyst includes the combination of ι) a source of a transition metal, and n) a ligating compound of the formula (I). The invention also relates to a combination of a polymerisation (including ohgomensation) catalyst and a catalyst activator and to the use of such a combination in a polymerisation (including ohgomensation) process.

Description

POLYMERISATION (INCLUDING OLIGOMERISATION) OF OLEFINIC COMPOUNDS IN THE PRESENCE OF CATALYST, AND A CATALYST ACTIVATOR INCLUDING A HALOGENATED ORGANIC GROUP

Technical Field

This invention relates to the polymerisation (including oligomeπsation) of olefinic compounds in the presence of a polymeπsation (including oligomensation) catalyst, and a catalyst activator including a halogenated organic group

Background Art

A number of different oligomensation technologies are known to produce α-olefins Some of these processes, including the Shell Higher Olefins Process and Ziegler-type technologies, have been summaπzed in WO 04/056479 A1 The same document also discloses that the pπor art (e g WO 03/053891 and WO 02/04119) teaches that chromium based catalysts containing heteroaromatic hgands with both phosphorus and nitrogen heteroatoms, selectively catalyse the tnmeπsation of ethylene to 1-hexene

Processes wherein transition metals and heteroatomic ligands are combined to form catalysts for tnmeπsation, tetramensation, oligomensation and polymensation of olefinic compounds have also been described in different patent applications such as WO 03/053890 A1 , WO 03/053891 , WO 04/056479 A1 , WO 04/056477 A1 , WO 04/056480 A1 , WO 04/056478 A1 , US Complete Patent Application No 11/130,106, WO 05/123884 A2 and WO 05/123633 A1

The catalysts utilized in the abovementioned tπmeπsation, tetramensation, oligomensation or polymensation processes all include one or more catalyst activators to activate the catalyst Such an activator is a compound that generates an active catalyst when the activator is combined with the catalyst

Suitable activators include organoaluminium compounds, organoboron compounds, organic salts, such as methyl lithium and methyl magnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like

A common catalyst activator used in combination with Cr based catalysts for oligomensation of olefinic compounds is alkylaluminoxane, particularly methylaluminoxane (MAO) It is well known that MAO includes significant quantities of alkylaluminium in the form of tπmethylaluminium (TMA), and in effect the catalyst activator is a combination of TMA and MAO The MAO may also be replaced with modified MAO (MMAO)

The use of fluonnated boranes/borates as catalyst activators is also known In J Organomet Chem 683 (2003) 200 tπazacyclohexane CrCI₃ complexes were activated with AIR₃ and [PhN(Me)₂H]⁺ [B(C₆Fs)₄] to give catalysts active for tπmeπsation of alpha-olefins In J Am Chem Soc , 126 (2004) 1304, Cr-based ethylene tπmeπsation catalysts were activated by treating Cr-aryl complexes with fluonnated aryl-boranes (BARF) IPCOM000031729D discloses the use of fluonnated borate and borane activators in combination with chromium based catalyst in the oligomensation of olefins In WO 99/64476, catalysts (especially Ziegler-Natta and metallocene polymerisation catalysts) were activated by a combination of halogenated aryl containing Group13 metal or metalloid based Lewis acids and organo- Group13 metal compounds

Tπtyl tetrakis (pentafluorophenoxo) aluminate, [Ph₃C]⁺ [AI(OCeFs)₄] , has been prepared and employed as a co-catalyst for ethylene and propylene polymeπsation with metallocene complexes such as (CsHs^Zrlv^ in Organometallics, 19 (2000) 1625 and Organometallics, 21 (2002) 3691 Angew Chem lnt Ed 2004, 43, 2066 also discloses compounds such as [M(OCeFs)_n] and [AI(OC(CFa)₃J₄] and the use of the latter as an activator for ethene and propene polymensation with a Zr-alkyl complex in the presence of AI₁Bu₃ J Fluorine Chemistry 2001 , 112, 83 discloses the preparation of compounds such as [Ph₃C]⁺ [AI{OC(CF₃)₃}₄]

It has now been found that compounds of the present invention including at least one halogenated organic group bound to an aluminium central atom by means of one or more binding atoms can be used as activators of polymensation (including oligomensation) catalysts in polymensation (including ohgomeπsation) reactions In some cases the productivity of the polymerisation (including oligomensation) catalysts was found to have been improved.

Furthermore, it has been found that such activators are particularly suitable to activate polymensation (including oligomensation) catalysts which are in the form of a source of a transition metal and a ligating compound of the formula

Tπdent N-donor hgands, including some hgands of the above formula are known to be used in combination with transition metals to form oligomensation and/or polymerisation catalysts See for example US0177744,

US6291733, US2004068072, US4069273, US5196625, US5196624, WO2004/078799, WO2004/033398,

WO03/054038, WO98/30612, WO00/73249, WO99/02472, B L Small, et al , Organometallics, 2003, 22,

3178, B L Small, et al , Chem Eur J , 2004, 10, 1014, B L Small, et al , Organometallics, 2001 , 20, 5738, B

L Small, et al , Macromolecules, 2004, 37, 4375 These systems are highly active, but are limited by the large excess of aluminium co-activator (typically MAO or MMAO) required for effective activation Typically this excess is considered to be Al M of 500 1 or greater, see for example B L Small, ef al , Chem Eur J , 2004,

10, 1014 Alternatively, the activation of these systems using fluorinated boranes in conjunction with tnalkyl aluminium compounds is also demonstrated (in the above documents) although these generally appear to be less effective than MAO or MMAO based activators, as although a similar or even slightly greater rate is achieved, the catalysts produced are shorter lived leading to a lower overall productivity Journal of Orgaπometallic Chemistry, 621 (2001 ), 184 discloses the use of [Me₃NH]⁺ [B(OC₆Fs)₄] for polymerisation with iron catalysts including tπdentate N-donor ligands

Not only has the present invention shown that the aluminium based activators in question are suitable to activate polymerisation (including oligomensation catalysts) as set out above, but in at least some cases it will allow reduced levels of aluminium containing activators to be used, which results in lower Al costs and Al waste volumes In at least some cases increased activity has also been observed

Disclosure of the invention

According to the present invention there is provided a process for producing a polymenc (including oligomeπc) product by the polymerisation (including oligomensation) of at least one olefinic compound in the form of an olefin or a compound including a carbon to carbon double bond, by contacting the at least one olefinic compound with the combination of a polymensation (including oligomensation) catalyst and a catalyst activator, which catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymensation (including oligomensation) catalyst includes the combination of ι) a source of a transition metal, and n) a ligating compound of the formula

wherein A, in combination with Z¹, is a divalent heteroaromatic moiety, each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom, and a group 5A atom, each of n¹ and n² is 0, 1 or a larger interger, each of R¹ and R² is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 , and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R³ being the same or different when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1

It will also be appreciated that in some embodiments one or more R¹ groups may be bound to one or more R³ groups and/or one or more R² groups may be bound to one or more R⁴ groups

Accordingly to another aspect of the present invention there is provided the use of a combination of a catalyst activator and a polymeπsation (including oligomeπsation) catalyst in the polymeπsation (including oligomensation) of at least one olefinic compound in the form of an olefin or a compound including a carbon to carbon double bond by contacting the at least one olefinic compound with the combination of the polymensation (including oligomensation) catalyst and the catalyst activator, wherein the catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymerisation (including oligomensation) catalyst includes a combination of ι) a source of a transition metal, and n) a ligating compound of the formula

wherein A, in combination with Z¹, is a divalent heteroaromatic moiety, each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom and a group 5A atom, each of n¹ and n² is 0, 1 or a larger interger, each of R¹ and R² is selected from the group consisting of H an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H an organic moiety, and an inorganic moiety, R³ being the same or different when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1 Combination of catalyst and activator

The catalyst and activator may be combined pnor to being contacted with the olefinic compound The catalyst and activator may react with each other to form a reaction product of the catalyst and the activator The activator and catalyst may form part of the same compound The said reaction product may be an ionic reaction product

Activator

Preferably the activator is a Lewis acid

As stated above the one or more binding atoms are bound to a central atom in the form of aluminium

The, or each binding atom is preferably an atom selected from the group consisting of O, N, P and S Preferably it is O

In one embodiment of the invention the activator may include only one or more halogenated organic groups bound to one or more binding atoms as set out above, which one or more binding atoms are groups bound to the aluminium central atom In an alternative embodiment of the invention the activator may also include one or more atoms or groups of atoms other than said one or more halogenated organic groups bound to said one or more binding atoms

The at least one halogenated organic group may be bound to each binding atom by means of a carbon atom and/or a non-carbon atom The halogenated organic group may be a halogenated hydrocarbyl group or a halogenated heterohydrocarbyl group The halogenated organic group may be a halogenated organyl group or a halogenated organoheteryl group Preferably it is a halogenated hydrocarbyl group

In one embodiment of the invention the activator may be a compound of the formula, or the activator may include a moiety of the formula

wherein n is 1 or a larger integer, and

R is a halogenated organic group, and the respective R groups being the same or different when n is larger than 1

R may be bound to each O by means of a carbon atom and/or a non-carbon atom When R is monovalent it may be selected from the group consisting of a halogenated hydrocarbyl group, a halogenated heterohydrocarbyl group a halogenated organyl group, and a halogenated organoheteryl group, and when R is divalent it may be selected from the group consisting of a halogenated hydrocarbylene group, a halogenated heterohydrocarbylene group, a halogenated organyl-diyl group, and a halogenated organoheterylene group In one embodiment of the invention the activator may be a compound of the formula

wherein R and n are as defined above. Alternatively the activator may be a compound which includes a moiety of the formula

wherein R and n are as defined above, and Al is bound to at least one moiety Z which is not a

O\

OR or R O^

group as defined above. Preferably Z is a halide or a hydrocarbyl group or heterohydrocarbyl group. Preferably Z is a halide or an organoheteryl group. Preferably Z is -O(R¹⁰)₂ wherein R¹⁰ is a hydrocarbyl group, and R¹⁰ being the same or different. R¹⁰ may be alkyl and preferably it is ethyl. Alternatively Z may be halide, preferably in the form of F.

Alternatively, the activator may be a salt containing an anion which includes a moiety of the formula

preferably the anion is

wherein R and n are as defined above. Preferably when R is monovalent, R is a halogenated hydrocarbyl group or a halogenated organyl group The halogenated organyl group or halogenated hydrocarbyl group may compπse an organyl group or hydrocarbyl group wherein at least one hydrogen atom has been replaced with a halogen atom Preferably all the hydrogen atoms of the organyl group or hydrocarbyl group are replaced with halogen atoms Preferably all the halogen atoms are the same Preferably the halogen atom is F

Similarly, when R is divalent, R is a halogenated hydrocarbylene group or a halogenated organyl-diyl group The halogenated organyl-diyl group or halogenated hydrocarbylene group may compπse an organyl-diyl group or hydrocarbylene group wherein at least one hydrogen atom has been replaced with a halogen atom Preferably all the hydrogen atoms of the organyl-diyl group or hydrocarbylene group are replaced with halogen atoms Preferably all the halogen atoms are the same Preferably the halogen atom is F

The halogenated hydrocarbyl group may comprise a halogenated acylic hydrocarbyl group or a halogenated cyclic hydrocarbyl group The halogenated acyclic hydrocarbyl group may compπse a halogenated alkyl, preferably a halogenated branched alkyl, preferably halogenated isobutyl or tertiary-butyl The halogenated cyclic hydrocarbyl group may compπse a halogenated aromatic moiety, preferably a halogenated phenyl group

The halogenated hydrocarbylene group may comprise a halogenated acylic hydrocarbylene group or a halogenated cyclic hydrocarbylene group The halogenated acyclic hydrocarbylene group may comprise a halogenated alkylene, preferably a halogenated branched alkylene, preferably halogenated isobutylene or tertiary-butylene The halogenated cyclic hydrocarbylene group may comprise a halogenated aromatic moiety, preferably a halogenated phenylene group

In one embodiment of the invention the activator may be selected from the group consisting of a compound AI(OR)₃, a salt containing the anion

a compound including a moiety AI(OR)₃ wherein R is defined as above

In one embodiment of the invention the activator may be selected from the group consisting of AI(OC₆F₅)₃, X⁺[AI{OC(CF₃)₃}₄] , X⁺[AI(OC₆Fs)₄] , X⁺[AI(C₆F₄Oz)₂] , X⁺[AI{OC(CF₃)₂C(CF₃)₂O}2], X⁺[AIF{OC(CF₃)₃}₃], X⁺[AI₂F{OC(CF₃)₃}₆], (Z)AI{OCH(C₆F₅)₂}3, and (Z)AI{OC(CF₃)₃}₃ wherein X⁺ is a cation including Ph₃C⁺ , (Et₂O)₂H⁺ and Me₂PhNH⁺, and wherein Z is a moiety bound to Al which moiety Z is not an

(OR) group or R - group

where R is a halogenated organic group

The amount of activator used may be between 1-100 equivalents relative to the catalyst transition metal Preferably it is less than 5 equivalents relative to the catalyst transition metal, and most preferably between 1-3 equivalents relative to the catalyst transition metal

The activator may be prepared in situ, alternatively it may be preformed In one embodiment of the invention the activator may be preformed from the co-activator as descπbed herein below

Co-Activator

The process may also include the use of a co-activator which is a compound not falling within the definition of the activator Preferably the co-activator includes no halogenated organic group bound to aluminium via one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom Preferably the co-activator is a compound which includes at least one moiety selected from the group consisting of an organic group (preferably an organyl group), a halogenated organic group (preferably a halogenated organyl group) and hydrogen, and the moiety being bound to an atom selected from the group consisting of a group 3A atom, a group 4A atom, and a metal atom, including an alkali metal atom and an alkaline earth metal atom

Preferably the co-activator as set out above is an organoaluminium compound and/or an organoboron compound Alternatively it may be an organic salt such as methyl lithium and/or methyl magnesium bromide

Examples of suitable organoboron compounds are boroxines, tπethylborane, trιs(pentafluoropheny)borane, tributyl borane and the like

Suitable organoaluminium compounds include compounds of the formula AI(R⁹)₃ (R⁹ being the same or different), where each R⁹ is independently an organyl group, a halogenated organyl group or a halide, with at least one of R⁹ being an organyl group or a halogenated organyl group Examples include trimethylaluminium (TMA), tπethylaluminium (TEA), tri-isobutylaluminium (TIBA), tπ-n-octylaluminium, methylaluminium dichloπde, ethylaluminium dichloride, dimethylaluminium chloπde, diethylaluminium chloπde, aluminium isopropoxide, ethylaluminiumsesquichlonde, methylaluminiumsesquichloπde, and aluminoxanes

Aluminoxanes are well known in the art as typically oligomenc compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example tnmethylaluminium Such compounds can be linear, cyclic, cages or mixtures thereof Mixtures of different aluminoxanes may also be used in the process

The co-activator may compnse a compound of the formula

M(R)_n

wherein M is selected from the group consisting of a group 3A atom, a group 4A atom and a metal atom, including an alkali metal atom and an alkaline earth metal atom, n is 1 or a larger integer, and R is an organic group, R being the same or different when n is larger than 1 Preferably M is selected from the group consisting of a group 3A atom, a group 4A atom, and a transition metal atom Preferably the R group is bound to a group 3A atom Preferably the group 3A atom is selected from the group consisting of Al and B, preferably it is Al

The organic group R may be an organyl group, and preferably it compπses a hydrocarbyl group, preferably it compπses an alkyl group, preferably methyl, ethyl or a larger alkyl group

In one embodiment of the invention the co-activator compπses AIR ₃ wherein R is an alkyl group

The co-catalyst may be selected from the group consisting of tπmethylaluminium (TMA), tnethylaluminium (TEA), tπbutylaluminium, tπ-ιsobutylalumιnιum (TIBA) and tn-n-octylaluminium

It will be appreciated that TMA is relatively expensive and accordingly the use thereof may be wished to be avoided It has been found that by using an activator as defined in the present invention in combination with a co-activator as defined above (but excluding TMA and MAO) the use of TMA can be avoided as a co-catalyst

It is foreseen that a co-activator as defined heremabove will usually be used in combination with an activator as defined above However, it may be possible, by selecting a suitable source of transition metal (1) and/or a ligating compound (11), that the use of the co-activator may be avoided It is believed (without being bound thereto) that a co-activator such as TMA is used to alkylate the catalyst formed by the combination of (1) and (11) and that the activator then acts on alkyl abstracting agent of the alkylated catalyst to activate the said catalyst

The amount of co-activator employed may be up to 1000 equivalents relative to the transition metal catalyst, but preferable is less than 600 equivalents Preferably it is in the range between 30-300 equivalents relative to the transition metal catalyst

In use where both an activator and a co-activator are used, the co-activator may be added first and the activator may be added subsequently

Polvmeπc product

The polymeric product may be a product which includes the polymeπsation of more than four monomers

In an alternative embodiment of the invention the polymeπsation product may be an oligomeπc product The oligomenc product may be an olefin, or a compound including an olefinic moiety Preferably the oligomeπc product includes an olefin When ethylene is used as olefin feed the oligomenc product includes an olefin and preferably it includes an α-olefin When α-olefιns such as 1-hexene are used as feed olefin the oligomeπc product includes an olefin, preferably this is an internal olefin

In one embodiment of the invention the oligomenc product may comprise a dimeπc product such as the dimenc product of 1-hexene The dimeπc product may be either a terminal or an internal olefin Polymerisation

The polymerisation process may compnse the polymensation of more than four monomers

In one embodiment of the invention the polymerisation process may be an oligomeπsation process

The process may be oligomeπsation of two or more different olefinic compounds to produce an oligomer containing the reaction product of the two or more different olefinic compounds

In one preferred embodiment of the invention the oligomerisation process is oligomeπsation of a single α-olefιn to produce an oligomeric olefin When α-olefins such as 1-hexene are the olefin feed the oligomensation is preferably selective towards dimensation specifically

In one embodiment of the invention the oligomensation process may compnse dimensation of a single olefin to a dimeric olefin Preferably it comprises the dimensation of 1 -hexene

Olefinic compound to be polvmensed (including oliqomeπsation)

The olefinic compound may be polymeπsed, preferably it is oligomeπsed

The olefinic compound may comprise a single olefinic compound or a mixture of olefinic compounds In one embodiment of the invention it may compnse a single olefin

The olefin may include multiple carbon-carbon double bonds, but preferably it comprises a single carbon- carbon double bond The olefin may comprise an α-olefin with 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms The olefinic compound may be selected from the group consisting of ethylene, propene, 1-butene, 1- pentene, 1-hexene, 1-heptene, and 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 3-methyl-1-pentene, 4- methyl-1-pentene, styrene, p-methyl styrene, 1-dodecene or combinations thereof Preferably it comprises ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene or mixtures thereof

Catalyst

Source of transition metal U)

Preferably the source of transition metal as set out in (ι) above is a source of a Group 4B to 8B transition metal Preferably it is a source of Cr, V, Fe, or Co, more preferably Cr, V or Fe Most preferably it is a source of Fe

The source of the Group 4B to 8B transition metal may be an inorganic salt, an organic salt, a coordination compound or an organometallic complex

Liqatinq compound

Preferably the ligating compound is a compound of formula

wherein Z¹, Z², Z³, Y¹, Y², R¹, R², R³, R⁴, n¹, n², m³ and m⁴ are as defined above, R⁸ is any substituent that replaces H, and n⁸ is 0,1 or a larger integer The substituent R⁸ may be selected from H, an organic compound, and an inorganic moiety In one embodiment n may be 0°

Preferably each of Z\ Z² and Z³ is selected from N or O Preferably Z¹ is N Preferably each of Z¹, Z² and Z³ is N

Preferably each of Y¹ and Y² is selected from C, N, P or Si, preferably C or N, but preferably both Y¹ and Y² are C

Preferably Y¹ is bound to Z² by means of a double bond Preferably Y² is bound to Z³ by means of a double bond

Preferably the ligating compound is a compound of formula

R⁶

N N

R³ R⁴

wherein each of R¹ and R² is H or an organic compound, each of R³ and R⁴ is H or an organic compound, and each of R⁵, R⁶ and R⁷ is selected from H, an organic compound, and an inorganic moiety

It will be appreciated that R¹ and R³ may be bound to each other to form a cyclic moiety and/or R² and R⁴ may likewise be bound to each other to form a cyclic moiety

Preferably each of R¹ and R² is an organic group, preferably an organyl group, preferably a hydrocarbyl group, preferably an alkyl group such as methyl Preferably each of R³ and R⁴ is an aromatic or heteroaromatic moiety, preferably an aromatic moiety Each aromatic moiety may be a single ring structure and each πng structure may include one or more substituents thereon The one or more substituents may by any suitable substituents such as organic moieties The substituents in the form of organic moieties may be hydrocarbyl groups or fluorocarbyl groups, preferably alkyl groups

Each of R⁵ to R⁷ may be H or a hydrocarbyl group Preferably each of R⁵ to R⁷ is H

In one preferred embodiment of the invention the ligating compound is selected from the group consisting of

The ligating compounds may be prepared using procedures known to one skilled in the art and procedures forming part of the state of the art

Preferably all three atoms Z¹ , Z² and Z³ in use bind to the transition metal of the source of transition metal

The catalyst may be prepared in situ, that is in the reaction mixture in which the oligomeπsation reaction is to take place Alternatively the catalyst may be pre-formed or partly pre-formed Preferably the source of transition metal and ligating compound are reacted with each other pnor to contact with the olefinic compound and also before contacting it with the activator

The source of transition metal and ligating compound may be combined to provide any suitable molar ratio, preferably a transition metal to ligating compound molar ratio of 1 1 The process may also include combining one or more different sources of transition metal with one or more different ligating compounds

Process

The olefinic compound or mixture thereof to be polymensation (including ohgomeπsed) according to this invention can be introduced into the process in a continuous or batch fashion

The olefinic compound or mixture of olefinic compounds may be contacted with the catalysts at a pressure of 1 barg (100 kPa) or higher

The process may be carried out at temperatures from -100 ⁰C to 250 ⁰C Temperatures in the range of 10-150 ⁰C are preferred Particularly preferred temperatures range from 15-12O⁰C

The reaction products deπved from the reaction as descnbed herein, may be prepared using the disclosed catalysts by a homogeneous liquid phase reaction in the presence or absence of an inert solvent, and/or by slurry reaction where the catalysts and the polymeric product is in a form that displays little or no solubility, and/or a two-phase liquid/liquid reaction, and/or a bulk phase reaction in which neat reagent and/or product olefins serve as the dominant medium, and/or gas phase reaction, using conventional equipment and contacting techniques

The reaction may also be earned out in an inert solvent Any inert solvent that does not react with the activator can be used These inert solvents may include any saturated aliphatic and unsaturated aliphatic and aromatic hydrocarbon and halogenated hydrocarbon Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, methylcyclohexane, methylcyclopentane, cyclohexane, chlorobenzene, dichlorobenzene, ionic liquids as well as the product formed duπng the reaction in a liquid state and the like

The reaction may be earned out in a plant which includes reactor types known in the art Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors The plant may include, in combination a) a stirred or fluidised bed reactor system, b) at least one inlet line into this reactor for olefin reactant and the catalyst system, c) effluent lines from this reactor for polymensation reaction products, and d) at least one separator to separate the desired polymensation reaction products which may include a recycle loop for solvents and/or reactants and/or products which may also serve as temperature control mechanism

According to another aspect of the present invention there is provided a polymerisation (including ohgomensation) product prepared by a process substantially as descnbed hereinabove

According to another aspect of the present invention there is provided the combination of a polymensation (including ohgomensation) catalyst and a catalyst activator, which catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymerisation (including ohgomensation) catalyst includes the combination of iii) a source of a transition metal; and iv) a ligating compound of the formula

wherein: A, in combination with Z¹, is a divalent heteroaromatic moiety; each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to Y¹ and Y² respectively by means of a single or multiple bond; each of Y¹ and Y² is selected from the group consisting of a group 4A atom and a group 5A atom; each of n¹ and n² is 0, 1 or a larger interger; each of R¹ and R² is selected from the group consisting of H an organic moiety, and an inorganic moiety; R¹ being the same or different when n¹ is larger than 1 ; and R² being the same or different when n² is larger than 1 ; each of m³ and m⁴ is 0, 1 or a larger integer; each of R³ and R⁴ is selected from the group consisting of H, an organic moiety, and an inorganic moiety; R³ being the same or different when m³ is larger than 1 ; and R⁴ being the same or different when m⁴ is larger than 1.

The invention will now be further described by means of the following non-limiting examples.

Examples

In the examples that follow, all manipulations were carried out under inert conditions, using standard Schlenk techniques. All solvents were dried and degassed via normal procedures.

[(N3-Ph)FeBr₂] is the compound

[(N3-Ph)CrCI₃] is the compound

[(N3-Tol)VCI₃] is the compound

[(Ph-S-ThIaZoIe)CoCI₂] is the compound

[(N3-cyclo-Tol)FeCb] is the compound

[(N3-Dιpp)FeBr₂] is the compound

[(N3-Dipp)CrCb] is the compound

[(N3-Dιpp)CoCl2] is the compound

TEA is Tnethylaluminium

The above compounds were prepared by procedures known in the art such as B L Small and R Schmidt, Chem Eur J , 2004, 10, 1014-1020 and references therein Example 1. Ethylene oligomerisation with [(N3-Ph)FeBr₂], Et₃AI co-activator and [Ph₃C][AI(OC(CF₃)_S)₄] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Ph)FeBr₂] (5 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI{OC(CF3)3}4] (7 5 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20⁰C AIEt₃ (0 5 mmol, 100 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 33 minutes the ethylene supply was closed (The ethene supply was closed as the autoclave vessel had filled with liquid product, and notably the catalyst had shown no significant deteπoration in activity over this penod as assessed by ethene uptake) and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis There was no solid product The total product mass was 80 536g Pertinent data is shown in Tables 1 and 2

Comparative Example 2. Ethylene oligomerisation with [(N3-Ph)FeBr₂] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stirnng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Ph)FeBr₂] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20⁰C MMAO (5 0 mmol, 500 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 117 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis There was no solid product The total product mass was 24 902g Pertinent data is shown in Tables 1 and 2

Example 3. Ethylene oligomerisation with [(N3-Ph)CrCI₃], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}₄] activator

A 250ml stainless steel reactor equipped with mechanical stirnng, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Ph)CrCI₃] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI{OC(CF3)3}4] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to Cr) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 6 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dried at 100⁰C The total product mass was 8 783g, of which 0 05Og was polymer Pertinent data is shown in Tables 1 and 2 Comparative Example 4. Ethylene oligomerisation with [(NS-Ph)CrCb] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stirnng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(NS-Ph)CrCb] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20⁰C MMAO (5 0 mmol, 500 equivalents relative to Cr) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 42 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 10OOμL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100°C The total product mass was 9 39Og of which 0 206g was polymer Pertinent data is shown in Tables 1 and 2

Example 5. Ethylene oligomerisation with [(N3-Tol)VCI₃], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}4] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Tol)VCI₃] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI{OC(CF₃)₃}4] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to V) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 10 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dried at 100°C The total product mass was 3 202g, of which 0 86Og was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 6. Ethylene oligomerisation with [(NS-ToI)VCI₃] and MMAO activator A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(NS-ToI)VCb] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20⁰C MMAO (5 0 mmol, 500 equivalents relative to V) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 72 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100°C The total product mass was 11 638g of which 3 039g was polymer Pertinent data is shown in Tables 1 and 2

Example 7. Ethylene oligomerisation with [(Ph-S-Thiazole)CoCl₂], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}₄] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(Ph-S-ThiazoleJCoCb] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI{OC(CF₃)₃}₄] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 2O⁰C AIEt₃ (1 0 mmol, 100 equivalents relative to Co) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 1 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100⁰C The total product mass was 0 884g, of which 0 83Og was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 8. Ethylene oligomerisation with [(Ph-S-ThiazoleJCoCb] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(Ph-S-ThiazoleJCoCy (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20°C MMAO (5 0 mmol, 500 equivalents relative to Co) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 3 1 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis There was no solid product The total product mass was 0 418g Pertinent data is shown in Tables 1 and 2

Example 9. Ethylene oligomerisation with [(N3-cyclo-Tol)FeCI₂], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)3}4] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-cyclo-Tol)FeCl2] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI{OC(CF₃)₃}4] (15 μmol) was added to the reactor as a solution in chlorobenzene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 21 6 minutes the ethylene supply was closed as the autoclave had filled with product and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100°C The total product mass was 72 053g, of which 1 556g was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 10. Ethylene oligomerisation with [(NS-cyclo-ToOFeCh] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stirπng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature the reactor was charged with solid catalyst, [(N3-cyclo-Tol)FeCl2j^" (10 μmol) and replaced under an Ar atmosphere Chlorobenzene (100 ml) was added to the reactor and the temperature maintained at 20°C MMAO (5 0 mmol, 500 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 51 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100⁰C The total product mass was 56 283g, of which 1 648g was polymer Pertinent data is shown in Tables 1 and 2

Example 11. Ethylene oligomerisation with [(N3-Dipp)CrCI₃], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}₄] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)CrCl3] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph3C][AI{OC(CF₃)₃}4] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to Cr) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 3 1 minutes the ethylene supply was closed as the gas uptake had ceased, and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100⁰C The total product mass was 0 139g, of which

0 136g was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 12. Ethylene oligomerisation with [(N3-Dipp)CrCI₃] and MMAO activator A 250ml stainless steel reactor equipped with mechanical stirnng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)CrCl3] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20°C MMAO (5 0 mmol, 500 equivalents relative to Cr) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 3 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dried at 100⁰C The total product mass was 0 618g, of which 0 522g was polymer Pertinent data is shown in Tables

1 and 2

Example 13. Ethylene oligomerisation with [(N3-Dipp)CoCI₂], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}₄] activator A 250ml stainless steel reactor equipped with mechanical stirnng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)CoCl2] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][AI(OC(CF₃)S)₄] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to Co) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 13 minutes the ethylene supply was closed as the gas uptake had ceased, and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at 100⁰C The total product mass was 3 435g, of which 3 41Og was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 14. Ethylene oligomerisation with [(N3-Dipp)CoCI₂] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stirmng, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)CoCl2] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20°C MMAO (5 0 mmol, 500 equivalents relative to Co) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 10 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dned at

100°C The total product mass was 9 68Og, of which 9 68Og was polymer Pertinent data is shown in Tables 1 and 2

Example 15. Ethylene oligomerisation with [(N3-Dipp)FeBr₂], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)3}4] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)FeBr₂] (10 μmol) and replaced under an Ar atmosphere A solution of

[Ph₃C][AI{OC(CF₃)3}4] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt₃ (1 0 mmol, 100 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 7 7 minutes the ethylene supply was closed as the gas uptake had ceased, and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10%

HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dried at 100°C The total product mass was 5604g, of which 5 55Og was polymer Pertinent data is shown in Tables 1 and 2

Comparative Example 16. Ethylene oligomerisation with [(N3-Dipp)FeBr₂] and MMAO activator

A 250ml stainless steel reactor equipped with mechanical stimng, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Dιpp)FeBr₂] (10 μmol) and replaced under an Ar atmosphere Toluene (100 ml) was added to the reactor and the temperature maintained at 20°C MMAO (5 0 mmol, 500 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 12 minutes the ethylene supply was closed as uptake had ceased and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis while the solid polyethylene produced was collected by filtration, washed with MeOH and dπed at 100⁰C The total product mass was 6 17Og, of which 6 17Og was polymer Pertinent data is shown in Tables 1 and 2

Table 2: Product distributions obtained in examples 1-16.

Example 17: Dimerisation of 1-hexene with [(N3-Tol)VCI₃], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}4] activator

A 250 ml round-bottom flask was charged with solid catalyst, [(NS-ToI)VCb] (0 02 mmol) and placed under vacuum After backfilling with dry N₂, toluene (10 mL), [Ph₃C][AI{OC(CF₃)₃}4] (0 03 mmol), nonane (1 mL) and 1-hexene (10 OmL) were added and a sample taken for GC analysis The vessel was stirred and maintained at 2O⁰C Reaction was initiated by addition of AIEt₃ (2 mmol, 100 equivalents relative to V) and the reaction run for 30 minutes The run was terminated by addition of MeOH and HCI (aq) and a sample of the organic fraction taken for GC analysis Pertinent data is shown in Table 3

Comparative Example 18: Dimerisation of 1-hexene with [(NS-ToI)VCI₃] and MMAO activator

A 250 ml round-bottom flask was charged with solid catalyst, [(N3-Tol)VCI₃] (0 02 mmol) and placed under vacuum After backfilling with dry N₂, toluene (10 mL), nonane (1 mL) and 1-hexene (10 OmL) were added and a sample taken for GC analysis The vessel was stirred and maintained at 2O⁰C Reaction was initiated by addition of MMAO (10 mmol, 500 equivalents relative to V) and the reaction run for 4 hours The run was terminated by addition of MeOH and HCI (aq) and a sample of the organic fraction taken for GC analysis Pertinent data is shown in Table 3

Example 19: Dimerisation of 1-hexene with [(N3-cyclo-Tol)FeCI₂], Et₃AI co-activator and [Ph₃C][AI{OC(CF₃)₃}₄] activator A 250 ml round-bottom flask was charged with solid catalyst, [(N3-cyclo-Tol)FeCI₂] (0 02 mmol) and placed under vacuum After backfilling with dry N₂, chlorobenzene (10 mL), [Ph₃C][AI{OC(CF₃)₃}4] (0 03 mmol), nonane (1 mL) and 1-hexene (10 OmL) were added and a sample taken for GC analysis The vessel was stirred and maintained at 2O⁰C Reaction was initiated by addition Of AIEt₃ (2 mmol, 100 equivalents relative to Fe) and the reaction run for 30 minutes The run was terminated by addition of MeOH and HCI (aq) and a sample of the organic fraction taken for GC analysis Pertinent data is shown in Table 3

Comparative Example 20: Dimerisation of 1-hexene with [(N3-cyclo-Tol)FeCl₂] and MMAO activator

A 250 ml round-bottom flask was charged with solid catalyst, [(N3-cyclo-Tol)FeCI₂] (0 02 mmol) and placed under vacuum After backfilling with dry N₂, chlorobenzene (10 mL), nonane (1 mL) and 1-hexene (10 OmL) were added and a sample taken for GC analysis The vessel was stirred and maintained at 2O⁰C Reaction was initiated by addition of MMAO (10 mmol, 500 equivalents relative to Fe) and the reaction run for 30 minutes The run was terminated by addition of MeOH and HCI (aq) and a sample of the organic fraction taken for GC analysis Pertinent data is shown in Table 3

Table 3. Product distributions obtained in examples 17-20.

Comparative Example 21. Ethylene oligomerisation with [(N3-Ph)FeBr₂], Et₃AI co-activator and B(CeFs)₃ activator

A 250ml stainless steel reactor equipped with mechanical stimng, cooling loop and external heating/cooling jacket was heated to 80⁰C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Ph)FeBr₂] (20 μmol) and replaced under an Ar atmosphere A solution of B(C₆F₅)₃ (50 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEfc (2 mmol, 100 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 9 minutes the ethylene uptake had ceased and the supply was closed and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis There was no solid product The total product mass was 4 384g Pertinent data is shown in Tables 4 and 5

Comparative Example 22. Ethylene oligomerisation with [(N3-Ph)FeBr₂], Et₃AI co-activator and [Ph₃C][B(C₆Fs)₄] activator

A 250ml stainless steel reactor equipped with mechanical stirring, cooling loop and external heating/cooling jacket was heated to 80°C under Ar purge for 10 minutes After cooling to room temperature, the reactor was charged with solid catalyst, [(N3-Ph)FeBr₂] (10 μmol) and replaced under an Ar atmosphere A solution of [Ph₃C][B(C₆F₅)₄] (15 μmol) was added to the reactor as a solution in toluene (100 ml) and the reactor maintained at 20°C AIEt (1 mmol, 100 equivalents relative to Fe) was then added to the reactor and the vessel immediately charged with 8 bar (800 kPa) of ethylene (Linde 4 5 grade) and the pressure kept constant throughout the reaction by the continuous addition of ethylene After 52 minutes the ethylene uptake had ceased and the supply was closed and the reactor cooled in an ice/water bath Excess ethylene was bled and the reactor contents treated sequentially with 1000μL of nonane (GC internal standard), MeOH and 10% HCI A sample of the organic phase was taken for GC-FID analysis There was no solid product The total product mass was 20 205g Pertinent data is shown in Tables 4 and 5

Table 4. Activities and Productivities obtained in examples 21-22.

Table 5. Product distributions obtained in examples 21-22.

Discussion - ethylene oligomerisation / polymerisation

The above detailed examples reveal several advantages that can be achieved through the use of the activators and co-activators disclosed herein Firstly, compared to the conventional alumoxane activators (MAO or MMAO) a reduction in the total amount of aluminium that can be used while still maintaining acceptable productivity and selectivity is demonstrated This is significant as at the productivities observed the mam cost dnver is no longer the transition metal catalyst, but the aluminium activator

Secondly and surpnsingly, in a number of cases a significantly higher activity is also observed See for instance example 1 , TEA/aluminate versus (comparative) example 2, MMAO In example 2 an Al Fe ratio of

500 1 is employed giving a catalyst with an activity of 22,866 g/g Fe/hr versus example 1 where an Al Fe ratio of only 100 1 generates a catalyst with a 23-fold increase in activity at 524,396 g/g Fe/hr A more revealing way to examine these results is to consider the productivities and activities based upon Al, as this is the cost dnver for the process Thus example 1 shows an activity of 10,855 g/g Al/hr verses example 2 at 95 g/g Al/hr, clearly illustrating a 114-fold improvement

A similar situation is borne out with the chromium analogues (examples 3, aluminate vs 4, MMAO, see Table 1 ), where again a 5-fold reduction in aluminium usage is achieved switching to the TEA/aluminate activator combination, whilst a 6-fold increase in activity (based upon Cr) is also observed (157,273 vs 24,020 g/g Cr/hr, respectively), although the ultimate productivity (based upon Cr) achieved is similar However, the crucial factor here is the greater rate which correlates with a larger space-time yield in any potential process Again, a more revealing way to consider these results is based upon Al instead of the transition metal and here we see activities of 3,255 (ex 3, TEA/aluminate) vs 99 (ex 4, MMAO) g/g Al/hr, which represents a 33-fold increase in activity However, the key factor here is now the productivities, which instead of being similar when based upon Cr, are significantly different when based upon the cost dnver, that is the Al centre 326 (ex 3, TEA/aluminate) vs 70 (ex 4, MMAO) g/g Al/hr

Further examples demonstrate that this new activation method is equally applicable with other metals such as V (examples 5 vs 6) and Co (examples 7 vs 8) and also with other vaπants of ligand (examples 5 and 6 use the N3-tolyl ligand in place of N3-Ph, whilst examples 7 and 8 utilize the Ph-S-Thιazole variant of the ligand) In both these pairs of examples, there is again a clear activity (based upon the transition metal) advantage when using the TEA/aluminate activation method over MMAO, but more importantly, when consideπng both the activity and productivity based upon Al there is an even more distinct advantage in both cases

A further vanant of the ligand, specifically the N3-cyclo-Tol ligand, is demonstrated in examples 9 and 10 Again, it is clear that activation with the TEA/aluminate (example 9), gives a catalyst that is significantly more active (3-fold improvement) and productive than the MMAO (example 10) variant (see Table 1 ) based upon the transition metal catalyst When one considers the activities (2,671 vs 417 g/g Al/hr) and productivities (7,418 vs 494 g/g Al/hr) based upon the more meaningful Al centre however, the true improvement is revealed to be a 15 fold improvement in activity and > 6-fold in productivity

Use of the N3-Dιpp vanant of the ligand is demonstrated in examples 11-16 As can be seen from the data when this vanant of the ligand is employed with Co or Cr metal centres (examples 11-14), the MMAO activation method does give higher activities and productivities based upon the transition metal centre, but when one considers the important cost dnver, Al centre then TEA/aluminate activation method suddenly looks comparable However, with Fe (examples 15-16) the TEA/aluminate activation method again gives a more active, more productive catalyst whether assessed by transition metal centre (83,979 vs 59,331 g/g Fe/hr) or Al centre (1 ,617 vs 229 g/g Al/hr), example 15 vs 16

Notably examples 1-16 show a consistent advantage of employing the TEA/alummate activation method over MMAO, in that the yields of products per Al centre are consistently higher These example also show a range of catalyst selectivities from pure ethene polymeπsation to solid product through to pure oligomerisation to give entirely liquid products

Whilst a number of prior art documents demonstrate the use of fluoπnated boranes in conjunction with trialkylaluminium to also achieve this reduction in amount of aluminium used [US0177744, US6291733, US2004068072, US4069273, US5196625, US5196624, WO2004/078799, WO2004/033398, WO03/054038, WO98/30612, WO00/73249, WO99/02472, B L Small, et al , Organometallics, 2003, 22, 3178, B L Small, et al , Chem Eur J , 2004, 10, 1014, B L Small, et al , Organometallics, 2001 , 20, 5738, B L Small, er a/ , Macromolecules, 2004, 37, 4375, and W A Herrmann, J Organomet Chem , 2001 , 621 , 184-189 ], it should be noted that these catalysts are generally of similar activity to their MAO or MMAO analogues, but undergo more rapid deactivation

Indeed when this activation with TEA/borane was employed (see example 21 ) under analogous conditions to examples 1 and 2, a catalyst was generated that was similar in activity to example 2 (MMAO), but that displayed significant deactivation and indeed gave a productivity of only 3,900 g/g Fe, giving a significantly lower productivity than either example 1 or 2 However, when consideπng the activity based upon Al then the activity of example 21 (TEA/borane) is improved over example 2 (MMAO), but the productivity is in fact still lower Notably however, this illustrates the advantage of the new methodology descnbed herein, as example 1 is still supeπor in all respects, productivity and activity whether based upon the transition metal or Al

A further alternative method of activation is the use of fluorinated borates in conjunction with tπalkylaluminium to also achieve this reduction in amount of aluminium used [W A Herrmann, J Organomet Chem , 2001 , 621 , 184-189] Again similar activities to the parent (M)MAO system are observed (compare results from this source with V C Gibson, et al , Chem Commun , 1998, 849-850) For purposes of companson the use of borates was also examined, see example 22 As can be seen from the example 22 and data in Table 4, a catalyst with a greater activity (based upon Fe) than the MMAO analogue (example 2, Table 1 ) was generated, but the lifetime was shorter, leading to a similar overall productivity However, when consideπng the productivity and activity based upon Al example 22 (TEA/borate) is better than example 2 (MMAO), but still vastly infeπor to example 1 (TEA/aluminate) in all respects

Thus, notably and surprisingly, example 1 represents a significant improvement over all of the TEA/borane, TEA/borate and (M)MAO activators, by virtue of being significantly more active, but also showing a much slower rate of catalyst deactivation, leading to much greater rates and productivities whilst achieving the same reduction in aluminium usage compared to examples 21 and 22

Indeed, if one compares the productivities for examples 1 (fluoπnated aluminate), 2 (MMAO), 21 (fluorinated borane) and 22 (fluoπnated borate) then the figures of 288,418, 44,589, 3925, and 36178 g/g Fe, respectively, clearly show that the aluminate is far superior, given that this greatly increased productivity is also delivered at only 100 equivalents of Et₃AI and a rate that is also vastly elevated 524,396, 22,866, 26,169, and 41 ,744 g/g Fe/hr, respectively In fact, when one then considers this in terms of Al (the cost driver in these catalyst systems) the improvement is even more marked activities of 10,855, 95, 542, 864 g/g Al/hr, respectively (ex's 1 , 2, 21 , 22) and productivities of 5,970, 185, 81 , 749 g/g Al₁ respectively (ex's 1 , 2, 21 , 22) Thus, clearly, the yield of product per unit of Al activator is greatly increased

Discussion - α-olefin (1-hexene) dimerisation

This new activation methodology has also been examined for the dimeπsation of α-olefins This revealed that an increase in total productivity was seen, as compared to MMAO, concomitantly with a significant increase in activity (see example 17 vs 18 and 19 vs 20 in Table 3) A surpnsing additional benefit was also that selectivity to the dimer fraction was greatly increased through a significant reduction in heavies formation (83% vs 46% and 75% vs 65%, respectively) Furthermore, example 19 illustrates the TEA/aluminate combination with a further variant of the hgand system, specifically the N3-cyclo-Tol hgand

Claims

Claims

A process for producing a polymeric (including oligomeπc) product by the polymerisation (including oligomeπsation) of at least one olefinic compound in the form of an olefin or a compound including a carbon to carbon double bond, by contacting the at least one olefinic compound with the combination of a polymensation (including oligomeπsation) catalyst and a catalyst activator, which catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymensation (including oligomeπsation) catalyst includes the combination of ι) a source of a transition metal, and n) a ligating compound of the formula

wherein A, in combination with Z¹, is a divalent heteroaromatic moiety, each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom, and a group

5A atom, each of n¹ and n² is 0, 1 or a larger interger, each of R¹ and R² is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 , and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H, an organic moiety, and an iinnoorrggaanniicc mmooiieettyy,, RR³³ bbeeiinngg tthhee ssaammee oorr ddiiffffeerrent when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1

The process according to claim 1 , wherein the activator is a compound of the formula, or the activator includes a moiety of the formula

wherein n is 1 or a larger integer, and

R is a halogenated organic group, and the respective R groups are the same or different when n is larger than 1

The process according to claim 2, wherein R, when monovalent, is selected from the group consisting of a halogenated hydrocarbyl group, a halogenated heterohydrocarbyl group, a halogenated organyl group, and a halogenated organoheteryl group and when R is divalent it is selected from the group consisting of a halogenated hydrocarbylene group, a halogenated heterohydrocarbylene group, a halogenated organyl-diyl group, and a halogenated organoheterylene group

The process according to claim 3, wherein R is a halogenated hydrocarbyl or a halogenated organyl group

The process according to claim 4, wherein all hydrogen atoms of the hydrocarbyl group or organyl group are replaced with halogen atoms and all the halogen atoms are the same

The process according to claim 5, wherein all the halogen atoms are F

The process according to claim 2, wherein the activator is selected from the group consisting of a compound AI(OR)₃, a salt containing the anion

a compound including a moiety AI(OR)₃ wherein R is a halogenated organic group

The process according to claim 2, wherein the activator is selected from the group consisting of

AI(OC₆Fs)₃, X⁺[AI{OC(CF₃)₃}4] , X⁺[AI(OC₆Fs)₄] , X⁺[AI(C₆F₄O₂J₂] , X⁺[AI{OC(CF₃)2C(CF₃)2θ}2],

X⁺[AIF{OC(CF₃)₃}3], X⁺[AI₂F{OC(CF₃)₃}₆], (Z)AI{OCH(C₆F₅)₂}3, and (Z)AI{OC(CF₃)₃}₃ wherein X⁺ is a cation including Ph₃C⁺ , (Et₂O)₂H⁺ and Me₂PhNH⁺, and wherein Z is a moiety bound to Al which moiety Z is not an

(OR) group or R - group

where R is a halogenated organic group The process according to any one of claims 1 to 8 which includes a co-activator compπsing a compound of the formula

M (R )_n

wherein M is selected from the group consisting of a group 3A atom, a group 4A atom and a metal atom, including an alkali metal atom and an alkaline earth metal atom, n is 1 or a larger integer, and

R is an organic group, R being the same or different when n is larger than 1

The process according to claim 9, wherein the co-activator is an organoaluminium compound and/or an organoboron compound

The process according to claim 10, wherein the co-activator is an organoaluminium compound of the formula AI(R⁹)₃ (R⁹ being the same or different), where each R⁹ is independently an organyl group, a halogenated organyl group or a hahde, with at least one of R⁹ being an organyl group or a halogenated organyl group

The process according to claim 11 , wherein the co-activator is selected from the group consisting of trimethylaluminium (TMA), triethylaluminium (TEA), tπbutylaluminium, tπ-ιsobutylalumιnιum (TIBA) and tπ-n-octylalumιnιum

The process according to any one of the preceding claims, wherein the polymerisation process compnses the polymerisation of more than four monomers

The process according to any one of the preceding claims, wherein the source of the transition metal of the polymensation (including oligomeπsation) catalyst is a source of a Group 4B to 8B transition metal

The process according to any one of the preceding claims, wherein the hgating compound of the polymensation (including oligomensation) catalyst is a compound of formula

wherein each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to

Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom, and a group 5A atom, each of n¹ and n² is 0, 1 or a larger interger, each of R¹ and R² is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 , and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R³ being the same or different when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1 ,

R⁸ is any substituent that replaces H, and n⁸ is 0,1 or a larger integer

The process according to claim 15, wherein the ligating compound is selected from the group consisting of

A polymensation product prepared by the process according to any one of the preceding claims

Use of a combination of a catalyst activator and a polymerisation (including oligomeπsation) catalyst in the polymensation (including oligomeπsation) of at least one olefinic compound in the form of an olefin or a compound including a carbon to carbon double bond by contacting the at least one olefinic compound with the combination of the polymeπsation (including oligomeπsation) catalyst and the catalyst activator, wherein the catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom, which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymeπsation (including oligomeπsation) catalyst includes a combination of ι) a source of a transition metal, and n) a ligating compound of the formula

wherein A, in combination with Z¹, is a divalent heteroaromatic moiety, each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to

Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom and a group

5A atom, each of n¹ and n² is 0, 1 or a larger interger, each of R¹ and R² is selected from the group consisting of H an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 , and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H an organic moiety, and an inorganic moiety, R³ being the same or different when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1

A combination of a polymerisation (including ohgomeπsation) catalyst and a catalyst activator, which catalyst activator is a compound which includes at least one halogenated organic group which is bound to one or more binding atoms selected from the group consisting of a group 5A atom and a group 6A atom which one or more binding atoms are in turn bound to a central atom in the form of aluminium, and wherein the polymensation (including oligomensation) catalyst includes the combination of ι) a source of a transition metal, and ιι) a ligating compound of the formula

wherein A, in combination with Z¹, is a divalent heteroaromatic moiety, each of Z¹, Z² and Z³ is a group 5A or 6A atom, with each of Z² and Z³ being bound to Y¹ and Y² respectively by means of a single or multiple bond, each of Y¹ and Y² is selected from the group consisting of a group 4A atom and a group

5 A atom, each of n¹ and n² is 0, 1 or a larger intergeπ each of R¹ and R² is selected from the group consisting of H an organic moiety, and an inorganic moiety, R¹ being the same or different when n¹ is larger than 1 , and R² being the same or different when n² is larger than 1 , each of m³ and m⁴ is 0, 1 or a larger integer, each of R³ and R⁴ is selected from the group consisting of H, an organic moiety, and an inorganic moiety, R³ being the same or different when m³ is larger than 1 , and R⁴ being the same or different when m⁴ is larger than 1