Co-oligomerization process.

0001This invention relates to a co-oligomerization process and is particularly directed to the co-oligomerization of ethene and an alpha olefin.

0002Oligomerization processes for the production of linear olefins are well known. Thus for example C₆-C₂₀ linear olefins may be prepared from lower olefins such as ethene by oligomerization in the presence of a Ziegler catalyst system. Dependent on the conditions of temperature and pressure and the catalyst employed, some variation is possible in the resulting product composition. While linear olefins, especially linear alpha olefins, over a range of carbon chain lengths have found use as valuable intermediates in the preparation of polyolefins, detergents and lubricant additives, there is an increasing desire to shift the product slate towards the shorter chain length oligomers, eg C₆-C₁₀, which are more suited as intermediates in the preparation of linear low density polyethylene. However, the consequence of such a shift in product slate towards shorter chain length oligomers is a rise in the production of the less valuable ethene oligomerization product, 1-butene. There is therefore a need to provide a process for the conversion of 1-butene, and other lower alpha olefins, to useful linear olefin oligomers of increased chain length.

0003The applicants have found that lower linear alpha olefins such as propene, 1-butene and 1-pentene can be co-oligomerized with ethene to yield oligomeric products of high linearity and with a high alpha olefinic content in the presence of a catalyst system comprising a Group IVA organometallic compound and a boron compound such as a carborane. This is highly surprising, as such catalyst systems have previously been proposed as olefin polymerization catalysts, see for example, EP-A-277003, where the use of such a catalyst to copolymerize ethene and 1-butene resulted in a highly branched polymeric product. Other methods for the co-dimerization and co-oligomerization, of ethene and linear alpha olefins are known, but formation of higher linear alpha olefins is small and those linear olefins which are formed are predominantly internal olefins - see for example, "Comprehensive Organometallic Chemistry", 1982, published by Pergamon Press, Vol. 8, Section 52, and J. Pol. Sci. Part A: Polymer Chem., Vol. 27, 1989, pages 605-637.

0004According to the present invention, there is provided a process for the preparation of linear olefins comprising reacting ethene with at least one further alpha olefin under oligomerizing conditions, the reaction temperature being in the range of from 90 to 125 °C, in the presence of a catalyst system comprising a combination of a first component which is a bis(cyclopentadienyl) Group IVA metal compound containing a substituent capable of reacting with a cation and a second component which is a compound having a bulky anion containing a plurality of boron atoms and which is substantially non-coordinating under the reaction conditions and a cation and recovering an oligomeric product comprising linear olefins.

0005Metals of Group IVA are as defined in the Periodic Table of the Elements published in Kirk-Othmer, Encylopaedia of Chemical Technology, 2nd edition, Vol. 8, p. 94.

0006The starting reactants comprise ethene, which may be supplied in the form of an ethene-containing gas together with an inert diluent such as nitrogen or helium. The further alpha olefin is preferably a lower linear alpha olefin such as propene, 1-butene or 1-pentene. However it is also possible to employ branched alpha olefin co-monomers such as 4-methyl-1-pentene, or an aryl-substituted olefin such as styrene or allyl benzene, dependent on the desired oligomerization products. Mixtures of alpha olefins may be employed. A preferred alpha olefin co-monomer is 1-butene. A particularly suitable source of co-monomer is the C₄ olefin fraction derived from an ethene oligomerization process to produce alpha olefins having from 4 to 20 carbon atoms. Such processes are known from, for example, EP-A-295960, US 4486615 and EP-A-241596.

0007To effect oligomerization, the reaction is suitably carried out at elevated temperatures, in the range of from 90 to 125°C. The reaction is suitably carried out under conditions of moderate elevated pressure, preferably in the range of from 1 to 100 bar, more preferably from 5 to 60 bar. The optimum conditions of temperature and pressure used for a particular catalyst system to maximize the yield of oligomer and minimize competing reactions such as dimerization and polymerization can readily be established by the man skilled in the art. The conditions of temperature and pressure are preferably selected to yield a product slate with a "K factor" within the range of from 0.3 to 0.8. The K factor, which is indicative of the relative proportions of the product olefins, is the molar ratio of [C_n+2]/[C_n] calculated from the slope of the graph of log [c_nmol%] versus n, where n is the number of carbon atoms in a particular product olefin.

0008The relative proportions of starting monomers can vary over a wide range. Suitably the amount of ethene to alpha olefin co-monomer lies within the range of 0.01 to 100 moles of ethene per mole of alpha olefin co-monomer, preferably 0.1 to 10 moles of ethene per mole of alpha olefin co-monomer.

0009The catalyst system, which may be formed initially prior to introduction to the reaction vessel, or which may be formed in situ, comprises a combination of a first component, which is a bis(cyclopentadienyl) Group IVA metal compound having a substituent capable of reacting with a proton and a second component which is an ionic combination of a bulky anion containing a plurality of boron atoms and a proton-donating cation, the anion being such that it is substantially non-coordinating under the reaction conditions employed. Thus, it is intended that the anion should not coordinate, or at least coordinate only weakly, to the bis(cyclopentadienyl) metal entity which is formed by reaction of the donated proton and the acceptor substituent of the first compound. Examples of such catalyst systems, normally regarded as polymerization catalysts, are to be found in EP-A-277003 and the paper by Hlatky <u style="single">et</u><u style="single">al</u>, J. Am. chem. Soc., 1989, Vol. 111 p. 2728-2729.

0010The first component is preferably a compound of zirconium or hafnium. The compound preferably has the formula (Cp)₂MR₁ R₂ where each group Cp, which may be the same or different, represents a substituted or unsubstituted cyclopentadienyl group, M represents a Group IVA metal atom, preferably zirconium or hafnium, and R₁ and R₂ which may be the same or different, each represent a hydrogen atom or a substituted or unsubstituted hydrocarbyl group. Preferably each group cp represents an unsubstituted cyclopentadienyl group or a pentamethylcyclopentadienyl group. R₁ and R₂ are preferably alkyl groups such as methyl.

0011Such complexes are known and can be prepared for example by the routes described in "Chemistry of Organo-Zirconium and Hafnium Compounds", by Lappert et al., published by John Wiley &amp; Sons.

0012The second component preferably contains, as the boron containing substantially non-coordinating anion, a carborane anion, suitably a carborane anion of formula B₁₁CH₁₂⁻, while the cation is preferably a proton donating cation, preferably a quaternary ammonium cation such as tributyl ammonium. Alternatively the cation may be a metal cation, such as a silver ion. Such carboranes are known and can be prepared for example by methods such as that of Shelly et al, JACS, 1985, Vol. 107, p. 5955 to 5959. Other bulky boron containing anions may be used such as a tetra (perfluorophenyl) boron anion.

0013The catalyst system may be formed by mixing together the two components, preferably in solution in a solvent such as toluene to form a homogeneous catalyst system. The two compounds are generally employed in substantially equimolar amounts. However the mole ratio of the first compound to the second compound may vary within the range of from 0.1 to 5.0.

0014The oligomerization is generally, although not necessarily, carried out in an inert liquid solvent which is suitably also the solvent for the catalyst components. The reaction can be carried out in batch or continuous operation. Reaction times of from 1 minute to 5 hours have been found to be suitable, dependent on the activity of the catalyst. After a suitable reaction time, a conventional catalyst deactivating agent such as methanol, or other alcohol, may be added if desired to the reaction mixture to terminate the reaction. The resulting mixed olefins preferably have a chain length of from 5 to 20 carbon atoms. The reaction is preferably carried out in the absence of air or moisture.

0015Product olefins are recovered suitably by distillation and further separated as desired by distillation techniques dependent on the intended end use of the olefins.

0016The invention will now be further described with reference to the following examples.

Examples 1 to 9

0017Catalyst liquors A and B were prepared having the following compositions: <ul id="ul0001" list-style="none"><li>Catalyst liquor A. bis(cyclopentadienyl) zirconium dimethyl (0.251g; 1.00 mmol) tri-<u style="single">n</u>-butyl ammonium 1-carbadodecacarborate of formula Bu₃NHB₁₁CH₁₂ (0.329 g; 1.00 mmol) toluene 300ml.</li><li>Catalyst liquor B. bis(pentamethylcyclopentadienyl) zirconium dimethyl (0.391 g; 1.00 mmol) Bu₃NHB₁₁CH₁₂ (0.329 g ; 1.00 mmol) toluene 300 ml.</li><li>Catalyst liquor C. Bis(cyclopentadienyl) hafnium dichloride (1.0mmol) was mixed with methyl lithium (2.0mmol) in diethylether to give bis(cyclopentadienyl) hafnium dimethyl <u style="single">in</u><u style="single">situ</u>. The ether was removed and toluene (300ml) and tri-<u style="single">n</u>-butyl ammonium 1-carbadodecacarborate (1.0mmol) added to give catalyst liquor C.</li></ul>

0018Catalyst liquors A, B and C were employed in the co-oligomerization of ethene with 1-pentene (Examples 1 to 3 and 8), 1-butene (Example 4) and propene (Examples 5 and 6) under conditions of temperature, pressure and time given in Table 1 below. Examples 7 and 9 are comparative examples relating to ethene oligomerization with no added co-monomer. In each case the catalyst liquor was added to an autoclave (500 ml volume) containing the co-monomer together with toluene (300 ml), the reactor was then pressurized with ethene and rapidly heated to the reaction temperature. Pressure was maintained by continuous recharging of consumed ethene. At the end of the desired reaction time the reaction was terminated by treatment with methanol or exposure to air. The product distribution was determined by gas chromatography and the K factor, as previously defined, calculated by linear regression for each catalyst both for the even carbon number olefins ("<u style="single">e</u>-olefins") and the odd carbon number olefins ("<u style="single">o</u>-olefins"). The results are given in Table 1. It is to be noted that the distribution figures include the residual alpha olefin co-monomer. <tables id="tabl0001" num="0001"><img file="EP0443686B1_D0001.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0443686B1_D0002.tif" /></tables>