Process for producing liquid ethylene-type random copolymers

Abstract: A process is disclosed for producing liquid ethylene-type random copolymers by copolymerizing ethylene and a C₃-C₂₀ alpha-olefin in the presence of a catalyst comprising an alumoxane and a stereorigid metallocene compound described by the formula : R''(CpR₅)(CpR'₅)MeQ₂ wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R and R' is the same or different and is hydrogen or a hydrocarbyl radical having 1-20 carbon atoms or two R or two R' together form a hydrocarbyl radical having 2-20 carbon atoms; R'' is a structural bridge between the two Cp rings imparting stereorigidity to the compound; Me is a transition metal of Group IVb of the periodic table; and each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen. Lower amounts of alumoxane are required, and it is possible to operate at higher temperatures. The alumoxane may be partly replaced by an alkylaluminium.

Description: This invention relates to a process for producing liquid ethylene-type random copolymers. More specifically, it relates to a process for producing a liquid ethylene-type random copolymers having a narrow molecular weight distribution and a narrow composition distribution making it suitable for use as a lubricant oil. Liquid ethylene/alpha-olefin copolymers, typically liquid ethylene/propylene copolymer, have been expected to find applications as synthetic lubricant oils or various resin modifiers. They are known to be produced by methods comprising copolymerizing ethylene with alpha-olefins in the presence of titanium-type catalysts composed of titanium compounds and organoaluminium compounds or vanadium-type compounds composed of vanadium compounds and organoaluminium compounds. Liquid ethylene/alpha-olefin copolymers produced in the presence of the titanium-type catalysts generally have poor randomness, broad molecular weight and composition distributions, and poor properties for use as synthetic lubricant oils. Liquid ethylene/alpha-olefin copolymers obtained in the presence of the vanadium-type catalysts have higher randomness, narrower molecular weight and composition distributions than the copolymers obtained with the titanium-type catalysts, and therefore have fairly improved properties for use as synthetic lubricant oils. It is still desired however to improve the quality of such copolymers for applications which must meet rigorous requirements. Catalysts comprising zirconium compounds and aluminoxanes are disclosed in a series of prior art publications as new Ziegler-type olefin polymerization catalysts. But most of these publications fail to give any description which suggests liquid ethylene/alpha-olefin copolymers. European Patent EP-200351-B discloses (i) liquid ethylene-type random copolymer consisting essentially of units derived from ethylene and an alpha-olefin having 3 to 20 carbon atoms, said copolymer being characterized in that (a) it has an ethylene unit content of from 10 to 85 mole% and an alpha-olefin unit content of from 15 to 90 mole%, (b) it has a number average molecular weight ( M n ), measured by gel permeation chromatography, of from 3 x 10 2 to 1 x 10 4 , (c) it has a molecular weight distribution ( M w / M n ), determined by gel permeation chromatography, of not more than 2.5, (d) it has a B value, defined by the following equation (I), as defined by the following equation (II) B ≡ P OE 2P O ·P E wherein P E represents the molar fraction of the ethylene component in the copolymer, P O is the molar fraction of the alpha-olefin component in the copolymer, P OE is the molar fraction of alpha-olefin/ethylene chains in the total dyad chains, 1.05≦B≦2 (e) signals of αβ and β γ based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not substantially observed in the 13 C-NMR spectrum of the copolymer, and (f) it has an iodine value of from 0 to 85. European Patent EP-200351-B discloses further (ii) a process for producing said copolymers which comprises copolymerizing ethylene and said alpha-olefin in the presence of a catalyst comprising a compound of a transition metal of Group IVb of the periodic table and an alumoxane, and (iii) use of said copolymers or of the hydrogenation product thereof as a synthetic lubricating oil. WO91/1488 application discloses the use of a copolymer as a fuel additive effective both to improve low temperature flow of the fuel and also to inhibit wax settling. The Applicant has now found a new process for producing liquid ethylene-type random copolymers which consist essentially of units derived from ethylene and an alpha-olefin having 3 to 20 carbon atoms, whereby less alumoxane is required, to yield products having good or even improved properties, more particularly for use as synthetic lubricating oil. The process of the invention for producing liquid ethylene-type random copolymers as defined in claim 1 by copolymerizing ethylene and an alpha-olefin having 3 to 20 carbon atoms in the presence of a catalyst comprising a compound of a transition metal of Group IVb of the periodic table and an alumoxane is characterised by the use as compound of a stereorigid metallocene compound described by the formula : R"(CpR 5 ) (CpR' 5 )MeQ 2 wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R and R' is the same of different and is hydrogen or hydrocarbyl radical having 1-20 carbon atoms or two R or two R' together from a hydrocarbyl radical having 2-20 carbon atoms; R'' is a structural bridge between the two Cp rings imparting stereorigidity to the compound; Me is a transition metal of Group IVb of the periodic table; and each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen, and by the possibility to replace part of the alumoxane by an alkylaluminium. Methods for preparing such stereorigid metallocene compounds are well known in the art. Me is preferably zirconium, and Q is preferably chlorine. Exemplary hydrocarbyl radicals include alkyl radicals such as isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl and cetyl. Other hydrocarbyl radicals include aryl, alkenyl, alkylaryl or arylalkyl radicals. Further, R and R' may be radicals that are bonded to two carbon atoms in the ring. R'' is preferably selected from the group consisting of alkylene radicals having 1-4 carbon atoms and their substituted analogues. Preferred catalysts include isopropyl (fluorenyl) (cyclopentadienyl) Zr dichloride, and its counterpart with an ethyl bridge. The transition metal compound may be used directly. Preferably, those transition metal compounds which are difficulty soluble in solvents such as toluene (for example, bis(cyclopentadienyl)zirconium monochloride monohydride) are used after they are contacted with organoaluminium compounds. This operation renders the sparingly solvent-soluble transition metal compounds readily soluble in solvents, as known in the art. Preferred examples of the alumoxane as an ingredient constituting the catalyst used in this invention are : wherein R* is an alkyl group such as methyl, ethyl, propyl or butyl group, preferably the methyl and ethyl groups, especially preferably the methyl group, m is preferably more than 20, especially preferably at least 25, most preferably 30 to 100. Methods for preparing aluminoxanes are well known in the art. Alkylaluminiums are well known in the art and need not be described here. Preferred ones include trialkylaluminiums wherein the alkyl group is ethyl or isobutyl. In the process of this invention, the starting material to be fed to the polymerization reaction system is a mixture of ethylene and an alpha-olefin having 3 to 20 carbon atoms. The content of ethylene in the starting material is usually 2 to 80 mole %, preferably 4 to 55 mole %, and the content of the alpha-olefin is usually 20 to 98 mole %, preferably 45 to 96 mole %. Specific examples of the alpha-olefin having 3 to 20 carbon atoms used in the starting material in the process of this invention are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. The polymerization reaction of the olefins in the process of this invention is usually carried out in a hydrocarbon solvent. Examples of the hydrocarbon solvent used for this purpose are aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, kerosene and light oils. The starting olefins may themselves serve as the hydrocarbon medium. Among these hydrocarbon media, the aromatic hydrocarbons and the starting olefins are preferably used in the process of this invention. The polymerization temperature in the process of this invention is, for example, -50 to 200°C, preferably -30 to 100°C, especially preferably -20 to 80°C. The proportion of the transition metal compound (A) used in practising the process of this invention is, for example, 10 -8 to 10 -2 gram-atom/liter, preferably 10 -7 to 10 -3 gram-atom/liter, as the concentration of the transition metal in the polymerization reaction system. The proportion of the aluminoxane (B) used is, for example, 10 -4 to 10 -2 gram-atom/liter, preferably 10 -7 to 10 -3 gram-atom/liter, as the concentration of the transition metal in the polymerization reaction system. The molar ratio of the aluminium atom to the transition metal in the polymerization reaction system is, for example, in the range of 50 to 500 and preferably 75 to 125; it is indeed a characteristic of the process of this invention that less alumoxane is required. Also, up to 90% of the aluminium can be in the form of alkylaluminium; this is unexpected since olefin polymerization was long thought impossible therewith at significant levels. The molecular weight of the copolymer can be controlled by using hydrogen, and/or by adjusting the polymerization temperature. When the copolymerization reaction in the process of this invention is carried out in the absence of hydrogen, a liquid ethylene-type random copolymer having a high iodine value can be obtained. When it is carried out in the presence of hydrogen, a liquid ethylene-type random copolymer having a low iodine value or an iodine value of substantially zero can be obtained. After the polymerization reaction by the process of this invention, the polymerization reaction mixture is worked up in a customary manner to give the liquid ethylene-type random copolymer of the invention. When the liquid ethylene-type random copolymer having a high iodine value obtained by the aforesaid process is hydrogenated in the presence of a hydrogenating catalyst, a liquid ethylene-type random copolymer having a lower iodine value or an iodine value of substantially zero can be obtained. Examples of the hydrogenating catalyst that can be used are metals of Group VIII of the periodic table such as iron, cobalt, nickel, rhodium, palladium and platinum. Of these, nickel is preferred. Raney nickel is especially preferred. The hydrogenation reaction may be carried out in the presence or absence of solvent. Examples of the solvent are hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane and cyclooctane. The temperature in the hydrogenation reaction is, for example, 50 to 250°C, preferably 100 to 200°C. The hydrogenation reaction pressure is, for example, in the range of 0.5 to 9.8 MPa-G. The liquid ethylene-type random copolymer of this invention has an ethylene unit content of 10 to 85 mole %, preferably 20 to 80 mole %, especially preferably 30 to 70 mole %, and an alpha-olefin unit content of 15 to 90 mole %, preferably 20 to 80 mole %, especially preferably 30 to 70 mole %. For use as a lubricant oil, the liquid ethylene-type random copolymers should have an iodine value of 0 to 0.3 preferably 0 to 0.2 especially preferably 0 to 0.1. The liquid ethylene-type random copolymers prepared by the process of this invention have various excellent properties required of lubricant oils. When liquid ethylene-type random copolymer prepared by the process of the invention is hydrogenated, there is obtained a hydrogenated polymer having a high viscosity index, a high ignition point, a low pour point, excellent shear stability, excellent oxidation stability, excellent thermal stability and high oil film strength. The hydrogenated polymer is superior in various properties which are considered necessary to lubricating oils, and may thus be used as a synthetic lubricant. The following examples specifically illustrate the present invention. EXAMPLE 1 A 2 liter continuous polymerization reactor was charged with 300 ml of cyclohexane, 13.1 mmol of methylaluminoxane and 0.036 mmol of ethylene bis(indenyl) zirconium dichloride. Ethylene and propylene were simultaneously fed continuously into the reactor at a rate of 700 ml/min and 1400 ml/min, respectively, and polymerized at 60°C and 5.8 bar pressure with a residence time of 61 min under such conditions as to provide 100 g of polymer. The resulting polymer solution was continuously withdrawn for the reactor, and the polymerization was stopped by adding a small amount of methanol. The polymer solution was washed four times with a large amount of water. Subsequent removal of toluene from the polymer solution gave a liquid polymer. EXAMPLES 2-6 AND COMPARATIVE EXAMPLES A-B Example 1 was repeated except that the conditions indicated in the Table were employed. The metallocene used was the same except in examples 2 and comparative examples A and B wherein isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, bis (indenyl) zirconium dichloride and bis (cyclopentadienyl) zirconium dichloride were used respectively. Methylalumoxane (MAO) was used in all examples, except in example 6 and comparative examples A and B wherein 1.3 mmol MAO and 11.8 mmol (triisobutylaluminium) TIBA, were used and in examples 12 and 13 wherein 13.1 mmol ethylalumoxane (EAO) were used. In examples 4, 5, 11 and 13, hydrogen was used at a rate of 400, 200, 100 and 200 ml/min respectively. In examples 5, 8 to 14 and comparative example C, toluene was used instead of cyclohexane. The yield and appearance of the polymer produced are also indicated in the Table. Example Exp.No. Solvent ml Zr mmol MAO mmol TIBA mmol C 2 ml/min C 3 ml/min H 2 ml/min T °C Time min Yield g Appearance 1 Lub389 300 0.036 13.1 0 700 1400 0 60 61 100.0 Waxy 2 Lub388 300 0.036 13.1 0 700 1400 0 60 55 75.0 Waxy 3 Lub425 300 0.036 13.1 0 700 1400 0 100 75 103.0 Very viscous 4 Lub456 150 0.018 6.6 0 700 1400 400 90 75 200.0 Liquid 5 Lub433 300 0.036 13.1 0 700 1400 200 120 75 121.0 Liquid 6 Lub390 300 0.036 1.3 11.8 700 1400 0 60 75 94.3 Very viscous 7 Lub427 300 0.036 9.0 0 700 1400 0 100 75 115.6 Very viscous 8 FIE49 150 0.018 4.5 0 700 1400 0 120 60 51.6 Very viscous 9 FIE82 300 0.072 5.4 0 700 1400 0 100 53 197.6 Waxy 10 FIE85 300 0.072 3.6 0 700 1400 0 100 75 147.4 Waxy 11 Lub468 150 0.036 2.7 0 700 1400 100 90 75 158.0 Very viscous 12 FIE57 300 0.036 EAO=13.1 700 1400 0 60 75 111.6 Waxy 13 Lub443 300 0.036 EAO=13.1 700 1400 200 60 75 72.0 Waxy 14 FIE48 300 0.030 10.9 0 960 1920 0 120 40 102.5 Very viscous A Lub395 300 0.036 1.3 11.8 700 1400 0 60 75 37.5 Polymer B FIE27 300 0.036 1.3 11.8 700 1400 0 60 75 0.0 C FIE84 300 0.072 2.7 0 700 1400 0 100 75 7.4 Waxy These examples show that other types of alkylaluminiums can be used than MAO at constant Al/Zr ratio. They also show that increasing the reaction temperature decreases the molecular weight of the oligomers without affecting the catalyst activity too much. They further show that hydrogen has a very positive effect on catalyst activity and stability (e.g. the yield in example 4 is of about 10 5 g/g Zr.h and 900 g/g Al.h, and in example 11 of 1734 g/g Al.h); whilst not wishing to be bound by a theory, it would seem that this is due to an increased stability of the catalyst in the presence of hydrogen.

Claims: Process for producing liquid ethylene-type random copolymers by copolymerizing ethylene and an alpha-olefin having 3 to 20 carbon atoms in the presence of a catalyst comprising a compound of a transition metal of Group IVb of the periodic table and a mixture of alumoxame and an alkyl aluminium in an amount to produce a molar ratio of aluminium to transition metal of 50 to 500, said liquid ethylene-type random copolymer consisting essentially of units derived from ethylene and an alpha-olefin having 3 to 20 carbon atoms and being characterized in that (a) it has an ethylene unit content of from 10 to 85 mole% and an alpha-olefin unit content of from 15 to 90 mole%, (b) it has a number average molecular weight ( M n ), measured by gel permeation chromatography, of from 3 x 10 2 to 1 x 10 4 , (c) it has a molecular weight distribution ( M w / M n ), determined by gel permeation chromatography, of not more than 2.5, (d) it has a B value, defined by the following equation (I), as defined by the following equation (II) B ≡ P OE 2P O ·P E wherein P E represents the molar fraction of the ethylene component in the copolymer, P O is the molar fraction of the alpha-olefin component in the copolymer, P OE is the molar fraction of alpha-olefin/ethylene chains in the total dyad chains, 1.05≦B≦2 (e) signals of αβ and β γ based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not substantially observed in the 13 C-NMR spectrum of the copolymer, and (f) it has an iodine value of from 0 to 85, characterised by the use as compound of a stereorigid metallocene compound described by the formula : R"(CpR 5 )(CpR' 5 )MeQ 2 wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R and R' is the same or different and is hydrogen or a hydrocarbyl radical having 1-20 carbon atoms or two R or two R' together form a hydrocarbyl radical having 2-20 carbon atoms; R" is a structural bridge between the two Cp rings imparting stereorigidity to the compound; Me is a transition metal of Group IVb of the periodic table; and each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen. Process according to claim 1, wherein up to 90% of the aluminium present comes from an alkylaluminium. Process according to claim 1, wherein the molar ratio of aluminium to transition metal is of from 75 to 125.

Inventors: BREMS PATRICK, HINNEKENS HERVE, VERMEIREN WALTER, BREMS, PATRICK, HINNEKENS, HERVE, VERMEIREN, WALTER
Applicants: FINA RESEARCH, FINA RESEARCH S.A.
Application year: 1992
Main classification: C08F210
IPC codes: C08F210, C08F4