JP2002514246A - Olefin polymerization method - Google Patents

Abstract

(57) The present invention relates to a method for polymerizing an olefin by contacting the olefin with a transition metal catalyst and a cocatalyst, wherein the cocatalyst has the formula XR _4, wherein X represents Si or Ge, and R is a compound having an alkyl, aryl, arylalkyl or alkylaryl group), or the co-catalyst is represented by the formula [XR ₅ ] ⁻ [Y] ⁺ (where X is Si, Ge, Which represents Sn or Pb, R represents hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group, and Y represents a cation).

Description

DETAILED DESCRIPTION OF THE INVENTION                 Olefin polymerization method   The present invention provides an olefin by contacting an olefin with a transition metal catalyst and a cocatalyst. The present invention relates to a method for polymerizing fins.   In the polymerization of olefins, co-catalysts, in addition to transition metal catalysts, are usually active Required to obtain a catalyst system.   Ziegler-Natta catalysts have been used for olefin polymerization since the 1950s Have been. These olefin polymerizations can lead to these Ziegler-Natta catalysts. To proceed more fully, a co-catalyst needs to be added. Usually, for example If an aluminum-containing cocatalyst such as diethylaluminum chloride Used in combination with La-Natta catalysts.   In recent years, other types of transition metal catalysts, such as metallocene catalysts, have also Used for fin polymerization. Olefin polymerization with the help of metallocene catalyst It is also necessary to use a co-catalyst in order to proceed sufficiently. Aluminoxa Is used as a promoter in combination with a metallocene catalyst. Aluminoxane An example is methylaluminoxane (MAO).   Aluminoki as cocatalyst in olefin polymerization with the aid of metallocene catalyst The disadvantage of using sun is the very large excess of aluminoxane over the metallocene catalyst. But, It must be used in order to obtain an active catalyst system. As a result Therefore, the produced polyolefin contains a high concentration of aluminum, and Luminium often must be washed away from polyolefins. Would.   It is an object of the present invention to provide a transition metal catalyst for olefin polymerization which does not have the disadvantages mentioned above. It is to provide a promoter suitable for use in combination with a medium.   The present invention relates to a compound of formula XR_FourWherein X represents Si or Ge; And R represents an alkyl, aryl, arylalkyl or alkylaryl group Alternatively, the present invention provides a compound of the formula [XR_Five]^-[Y]⁺Wherein X is Represents Si, Ge, Sn or Pb, and R is hydrogen or alkyl, aryl, Represents an alkylalkyl or alkylaryl group, and Y represents a cation.   In this method, as a co-catalyst suitable for olefin polymerization An active catalyst system comprising a transition metal catalyst with one of the compounds according to the invention is obtained . When the compounds according to the invention are used as cocatalysts for olefin polymerization Aluminoxane used as co-catalyst for transition metal catalyst Much less than when they are.   Lewis acids or ionic complexes may also be used as cocatalysts in combination with metallocene catalysts. Used. Examples of Lewis acids are Borane, such as tris (pentafluorophenyl) borane, and ions Examples of complexes are baudrates, for example dimethylanilinium tetrakis- (pentane Fluorophenyl) borate, triphenylcarbenium tetrakis- (pen Tafluorophenyl) borate and trityltetrakis (3,5-trifluoro) Romethylphenyl) baud rate. This type of boron-containing cocatalyst is, for example, EP-A-426,637, EP-A-277,003 and European It is disclosed in US Patent Application Publication No. 277,004.   Other advantages of using the compounds according to the invention as cocatalysts in olefin polymerization Is that the use of these compounds is less than the use of aluminoxanes, borane or baud rates. Usually less expensive.   Compounds which are suitable as cocatalysts have the formula XR_FourAnd a compound having the formula [ XR_Five]^-[Y]⁺Is a compound having X is an atom from group 14 of the periodic table And may be selected from the group comprising Si, Ge, Sn or Pb. Si is non-toxic Therefore, X is preferably Si.   Here and below, the periodic table is described in the Handbook of Chemistry and Physics. , 1989/1990, understand the periodic table (new IUPAC notation) inside the 70th edition cover Is done. The R groups can be the same or different And hydrogen and an alkyl, aryl, arylalkyl or alkylaryl group. May be selected from the group comprising: The R group is preferably a hydrocarbon containing 1 to 20 carbon atoms. Elementary group. Examples of suitable R groups are methyl, ethyl, propyl, isopropyl, Xyl, decyl and phenyl. Also, the two R groups are joined together to form a bridge Done R_TwoGroups such as biphenyl-2,2'-diyl and diphenyl-2,2 A 2'-diylmethane group may be formed. Preferably, at least two R groups are together To form a bridged aryl group. More preferably, the formula XR_FourOr expression [XR_Five] = [Y]⁺Have two such bridged aryl groups. Including one.   The cation Y is, for example, a Brönsted acid or a It is a cation or carbene of a rukari metal. Examples of cations are Li⁺, K⁺, Na⁺ , H⁺, Triphenylcarbenium, anilinium, guanidinium, glycini , Ammonium or substituted ammonium cations, where Three hydrogen atoms are hydrocarbyl groups having 1-20 carbon atoms or 1-20 Has been replaced by a substituted hydrocarbyl group having One or more of the halogen atoms is a halogen atom, a phosphonium group, Honium group, up to 3 hydrogen atoms of 1 to 20 carbon atoms original A substituted hydrocarbyl group having 1 to 20 carbon atoms And one or more of the hydrogen atoms has been replaced by a halogen Has been replaced by an atom. The cation is preferably dimethylanilinium , Triphenylcarbenium or Li⁺It is.   Formula XR_FourThe compound having is, for example, "The chemistry of organic silicon co mpounds, E.S. Patai et al., Wiley and Sons, 1989 ". Anionic Organic silicates are described in Angew. Chem. Int. Ed. Engl. 1996, 35, Issue 10 Explained for the first time. In this publication, lithium (2,2'-biphenyldiyl) (Trimethyl silicate) .4THF, lithium (2,2'-biphenyldiyldi) Methylphenyl silicate) 4THF, lithium (2,2'-biphenyldiyl) Dimethyl-t-butyl silicate) 4THF and lithium (pentaphenyl silicate) Kate) .4HMPA. (THF is tetrahydrofuran And HMPA is hexamethylphosphorous triamide. ) Heavy olefin The possibility of using these silicates as co-catalysts in If not, it is not suggested.   Formula XR_FourThe above compounds having are, for example, those mentioned in the above publications It can be synthesized according to a synthesis method. The compounds according to the invention can also be used for the polymerization of olefins. Hey As a co-catalyst on a carrier. SiO_Two, Al_TwoO_Three, MgCl_TwoAnd po Limmer particles, such as polystyrene microspheres, may be mentioned as a suitable carrier material. You. These carrier materials may also include, for example, silanes and / or aluminoxanes and / or Or it can be modified by aluminum alkyl. Supported cocatalysts are used prior to polymerization. Although they can be synthesized standing, they can also be formed in situ You.   Transition metal catalysts are suitable as catalysts for olefin polymerization. Of such a catalyst Examples are described in US Pat. No. 5,096,867, International Patent Application Publication No. 92/00 No. 333, European Patent Application Publication No. 347,129, European Patent Application Publication No. No. 344,887, European Patent Application Publication No. 129,368, European Patent Application No. 476,671 and European Patent Application Publication No. 468,651. State Patent Publication No. 416,815, European Patent Publication No. 351,391. Gazette, EP-A-351,392, EP-A-423 No. 101, European Patent Application Publication No. 503,422, European Patent Application Publication No. No. 516,018, European Patent Application Publication No. 490,256, European Patent Publication Application Publication No. 485,820, European Patent Application Publication No. 376,154, Patent Application Publication No. 4,015,254, International Patent Application Publication No. 96/135 No. 29, European Patent Application Publication No. 5 No. 30,908, International Patent Application Publication No. 94/11406, European Patent Application No. 672,676 and International Patent Application Publication No. 96/23010. Is described in. A transition metal catalyst comprising a metal from Group 3 of the Periodic Table; Lanthanides can also be used.   Supported transition metal catalysts can be used. SiO_Two, Al_TwoO_Three, MgCl_Twoas well as Polymer particles, such as polystyrene microspheres, are mentioned as suitable carrier materials. obtain. These carrier materials may also include, for example, silanes and / or aluminoxanes and And / or modified with aluminum alkyls. The supported transition metal catalyst is Can be synthesized prior to polymerization, but these are also formed in situ be able to. Preferably a metallocene catalyst is combined with a co-catalyst according to the invention Used for olefin polymerization. Metallocene catalysts may have one or more π A binding ligand such as cyclopentadiene ligand (Cp) or cyclopentadiene Ene-related ligands, such as those present in transition metal catalysts of indene and fluorene And characterized by:   As disclosed in WO 96/13529, the transition metal is Transition metal catalysts that are in a reduced oxidation state Use is more preferred.   Olefins, such as ethylene, propylene, butene, The polymerization of hexene, octene and their mixtures in combination with dienes is It can be carried out in the presence of a metal catalyst and a cocatalyst according to the invention. The above catalyst system also Polymerization of phenyl aromatic monomers such as styrene and p-methylstyrene, Nyl monomers such as alcohols, amines, alkyl halides, ethers, Polymerization of monomers containing amide, imine or anhydride groups, and cyclic olefins, eg For example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclone Looctene, norbornene, dimethanooctahydronaphthalene and substituted It can be used for the polymerization of rubornene.   The amount (mol: mol) of cocatalyst used relative to the amount of transition metal catalyst is usually 1: It is 100-1000: 1, preferably 1: 5-250: 1.   The polymerization can be carried out in a known manner and the use of a cocatalyst according to the invention is , No substantial improvement of these processes is required. Known polymerizations are suspended It is carried out in solution, emulsion, gas phase or bulk polymerization.   When the cocatalyst is used in a suspension or gas phase polymerization, a transition metal catalyst on the support or Preferably uses the cocatalyst according to the invention. Both catalyst and co-catalyst on the support It is also possible to use a person. The polymerization is carried out at a temperature between -50 ° C and + 350 ° C. Is performed. Preferably it is 50 degreeC-250 degreeC.   The pressure used is usually between atmospheric pressure and 250 MPa, and for bulk polymerizations: Especially at 50-250 MPa, for other polymerization methods, 0.5-25 MPa a. Examples of dispersants and solvents include pentane, heptane and mixtures thereof. Such substituted and unsubstituted hydrocarbons can be used, for example. Aromatic, Perhaps perfluorinated hydrocarbons can also be considered. Monomers to be used for polymerization Can also be used as dispersants.   The invention is illustrated by the following non-limiting examples.   Example I a ) Synthesis of bis-biphenylsilane   12.3 grams of biphenyl (80 mmol) are n- By adding butyllithium (100 ml, 160 mmol) Tylethylenediamine (TMEDA) (24.1 ml, 160 mmol) Dilithiated in When the addition is complete, the reaction mixture is brought to 60 ° C for 90 minutes. Held. After cooling to −20 ° C., 2,2 ″ -dilithiobiphenyl · 2TMEDA Was crystallized. The liquid is transferred to another container, and the crystals are Redissolved in diethyl ether. This solution contains approximately 100 milliliters of Tetrachlorosilane in ethyl ether (4.6 ml, 40 mmol) of The solution was added at room temperature in about 45 minutes. When the addition is complete, the mixture is Stirred for 1 day and refluxed for 2 days. After careful addition of water, the reaction mixture Was mixed with 1N HCl to remove TMEDA. The aqueous phase is diethyl ether After extraction with water, the organic layer is washed once with water,_FourDried on and filtered And concentrated under reduced pressure. Crystallization from ethyl acetate²⁹Si-,¹ H- and¹³Pure 9,9'-spirobi as investigated using C-NMR (9H, 9-silafluorene) (where we treat it as bis-biphenylsilane) U).   b )polymerization   0.01 mmol metallocene catalyst bis (2-methylindenyl) dimethyldi Ruconium was added to 0.02 mmol of bis-biphenylsilane at room temperature for 1 minute. And mixed in 100 milliliters of pentamethylheptane.   In a 1 liter stainless steel bench apparatus, a 750 ml pen Tamethylheptane was introduced, followed by 0.2 mmol of trioctylaluminum. Um (Witco GmbH) was introduced. The reactor is heated to 80 ° C and ethylene The pressure reached equilibrium at 20 bar overpressure (21 bar).   In the next step, the catalyst / promoter mixture was introduced. Ethylene pressure, polymerization Maintained constant at 20 bar during Was. After 20 minutes, the polymerization was stopped, the polymer was removed from the reactor, and the The weight was measured to be 3.63 grams.   Example II a ) Reaction of MeLi and (C ₆ H ₅ ) ₃ Cl with bis-biphenylsilane   1.31 mmol (436 grams) of bis-biphenylsilane was added to 100 mmol It was mixed with 50 ml of dry THF in a 1 liter Schlenk flask. The Schlenk flask is placed in a cold bath (dry ice / petroleum) and the reaction mixture is Cooled to -65 ° C. Bis-biphenylsilane was completely dissolved in THF . At -65 ° C, 1.31 mmol (885 microliter, 1.4 M) MeLi was added. During and after the addition, the reaction mixture remained colorless. The Schlenk flask was left at -65 ° C for 2 hours, during which time the reaction mixture was free. The color remained. After stirring for 2 hours, the reaction mixture was slowly brought to room temperature, And stirred overnight. After stirring overnight, the reaction mixture has a very bright yellow color I was   The reaction mixture was brought to -65 ° C and 1.31 mmol (9.56 mmol) Torr) (C₆H_Five)_ThreeCCl was added. After stirring overnight, the THF was evaporated And yellow crystals formed. Dry petroleum is added (three times) and then Evaporated. As a result, yellow A color / white powder was obtained. Dry toluene is added to the powder and the slurry is It was very well stirred. The toluene fraction is filtered off and the filtrate fraction The toluene in the solution was evaporated to yield a yellow solid. The solid is washed with petroleum, The petroleum was evaporated to give a light yellow solid. The yield is 774 milligrams there were.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, M W, SD, SZ, UG, ZW), EA (AM, AZ, BY) , KG, KZ, MD, RU, TJ, TM), AL, AU , BA, BB, BG, BR, CA, CN, CU, CZ, EE, GE, HU, ID, IL, IS, JP, KP, K R, LC, LK, LR, LT, LV, MG, MK, MN , MX, NO, NZ, PL, RO, SG, SI, SK, SL, TR, TT, UA, US, UZ, VN, YU (72) Klump, Gerhard, Willem             1185 GL Amstel, Netherlands             Fern, Strat Fan Sicily             D (no address)

Claims (1)

[Claims] 1. Contacting the olefin with a transition metal catalyst and a cocatalyst converts the olefin In the polymerization method, the co-catalyst is represented by the formula   XR_Four (Where X represents Si or Ge, and R is alkyl, aryl, aryl Alkyl or alkylaryl group) A compound having the formula: 2. Contacting the olefin with a transition metal catalyst and a cocatalyst converts the olefin In the polymerization method, the co-catalyst is represented by the formula   [XR_Five]^-[Y]⁺ (Where X represents Si, Ge, Sn or Pb, and R represents hydrogen or alkyl, A aryl, arylalkyl or alkylaryl group, and Y is a cation Show) A compound having the formula: 3. 3. The transition metal catalyst is a metallocene catalyst. the method of. 4. It is noted that the transition metal catalyst comprises a transition metal in a reduced oxidation state. 4. The method of claim 3, wherein the method comprises: 5. At least two R groups may together form a bridged aryl group. Claims 1 to 3, 5. The method according to any one of 4. 6. As a cocatalyst in olefin polymerization, the formula   XR_Four (Where X represents Si or Ge, and R is alkyl, aryl, aryl Alkyl or alkylaryl group) Using a compound having the formula: 7. As a cocatalyst in olefin polymerization, the formula   [XR_Five]^-[Y]⁺ (Where X represents Si, Ge, Sn or Pb, R is hydrogen or alkyl, A aryl, arylalkyl or alkylaryl group, and Y is a cation Show) Using a compound having the formula: 8. formula   [XR_Five]^-[Y]⁺ (Where X represents Si, Ge, Sn or Pb, R is hydrogen or alkyl, A aryl, arylalkyl or alkylaryl group, and Y is a cation Show) [However, a compound having lithium (2,2'-biphenyldiyltrimethyl) Silicate) .4THF, lithium (2,2'-biphenyldiyldimethyl) Phenyl) 4THF, lithium (2,2'-biphenyldiyldimethyl) -T-butyl silicate G) 4THF and lithium (bentaphenylsilicate) 4HMPA are excluded ].