USOO6337297B1 (12) United States Patent (10) Patent No.: US 6,337,297 B1 Mimura et al. (45) Date of Patent: Jan. 8, 2002
(54) CATALYST FOR TRIMERIZATION OF 5,780,698 A 7/1998 Barat et al. ETHYLENE AND PROCESS FOR 5,891.816 A * 4/1999 Wang et al...... 502/117 TRIMERIZING ETHYLENE USING THE 6,180,552 B1 * 1/2001 Hlatky ...... 502/117 CATALYST 6,197.901 B1 * 3/2001 Rohde et al...... 502/117 FOREIGN PATENT DOCUMENTS (75) Inventors: Hideyuki Mimura, Shinnanyo; Motohiro Oguri, Yokkaichi; Toshihide JP 10-7712 1/1998 Yamamoto, Yokkaichi; Hideyuki JP 10-71335 3/1998 Murakita, Yokkaichi; Hisanori Okada, JP 10-231.317 9/1998 Yokkaichi, Toru Yoshida, Kuwana, all JP 10-287690 10/1998 of (JP) JP 11-60627 3/1999 * cited by examiner (73) Assignee: Tosoh Corporation, Shinnanyo (JP) Primary Examiner Mark L. Bell (*) Notice: Subject to any disclaimer, the term of this Assistant Examiner J. Pasteczyk patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm-Oblon, Spivak, McClelland, U.S.C. 154(b) by 0 days. Maier & Neustadt, P.C. (57) ABSTRACT (21) Appl. No.: 09/457,522 A catalyst for trimerization of ethylene is disclosed which (22) Filed: Dec. 9, 1999 comprises (a) a chromium complex having a neutral multi (30) Foreign Application Priority Data dentate ligand having a tripod Structure, represented by the formula, ACrJOs, wherein A is a neutral multidentate Oct. 12, 1998 (JP) ...... 1O-351134 ligand having a tripod Structure, J is a carbonyl ligand or Nov. 12, 1998 (JP) ...... 1O-352540 halogen, n is an integer of 0–3, and Q is at least one member (51) Int. Cl...... B01J 31/00; B01J 37/00; Selected from hydrogen, a C-C hydrocarbon group, a CO8F 4/02; CO8F 4/60; CO7C 2/58 C-Clo carboxylate group, a C-Co diketonato group, an amide group, an imide group, an C-Clio alkoxide group, a (52) U.S. Cl...... 502/117; 585/721; 585/722; C-Co thioalkoxide group, an C-Cs arene ligand, an 585/726; 585/727; 585/730; 585/732; 502/123; C-Clio alkene ligand, an C-C is alkyne ligand, an amine 502/167; 502/168; 502/169; 502/170 ligand, an imine ligand, an isonitrile ligand, a phosphine (58) Field of Search ...... 502/117; 585/721, ligand, a phosphine oxide ligand, a phosphite ligand, an 585/722, 726, 727, 730, 732 ether ligand, a Sulfide ligand, a Sulfone ligand and a Sulfox ide ligand, and (b) a metal alkyl compound. The catalyst (56) References Cited optionally further comprises (c) at least one compound U.S. PATENT DOCUMENTS Selected from aromatic tertiary amine compounds, except for an imine, and nitrogen-containing heterocyclic 3,033,878 A 5/1962 Zeiss et al...... 502/117 3,149,080 A * 9/1964 Gluesenkamp et al...... 502/117 compounds, and (d) a radical anion compound. 3.223,688 A 12/1965 Badin ...... 502/117 3,316,235 A 4/1967 Yazima et al...... 502/117 13 Claims, No Drawings US 6,337,297 B1 1 2 CATALYST FOR TRIMERIZATION OF Such that it has a poor Solubility in an organic Solvent and the ETHYLENE AND PROCESS FOR catalyst is troubleSome to prepare, and further that it is not TRIMERIZING ETHYLENE USING THE readily commercially available and is expensive. CATALYST The catalyst of JP-AH6-298673 has a problem such that BACKGROUND OF THE INVENTION alminoxane used as one ingredient of the catalyst is difficult to Synthesize with a good reproducibility. The catalyst of (1) Field of the Invention JP-A H10-7712 has a poor activity for trimerization of This invention relates to a catalyst for trimerization of ethylene. The catalyst of JP-AH10-231317 has problems ethylene and a process for trimerizing ethylene using the Such that polyethylene is undesirably produced in an amount catalyst. More Specifically, it relates to a catalyst exhibiting larger than that of 1-hexene, and that the Selectivity to an enhanced activity for trimerization of ethylene to produce 1-hexene among oligomerS is low. 1-hexene, which is used as a comonomer for the production of linear low-density polyethylene (LLDPE), and further to SUMMARY OF THE INVENTION a process for trimerizing ethylene by which 1-hexene can be 15 In View of the foregoing, a primary object of the present produced effectively and highly Selectively. invention is to provide a catalyst having good handling (2) Related Art characteristics and exhibiting an enhanced activity for tri It is known to use a chromium compound as a catalyst for merization of ethylene to produce 1-hexene, which is used trimerization of ethylene to give 1-hexene. For example, a as a comonomer for the production of linear low-density catalyst System comprising a chromium compound, polyhy polyethylene (LLDPE). drocarbylaluminum oxide and a donor ligand is described in Another object of the present invention is to provide a Japanese Unexamined Patent Publication No. (hereinafter process for trimerizing ethylene by which 1-hexene can be abbreviated to “JP-A”) S62-265237. A catalyst system com produced effectively and highly Selectively. prising a chromium compound, a pyrrole-containing 25 In one aspect of the present invention, there is provided a compound, an alkyl metal compound and a halide is catalyst for trimerization of ethylene which comprises: described in JP-AH6-23.9920. A catalyst system comprising (a) a chromium complex having a neutral multidentate a chromium compound, an alkyl metal compound, and an ligand having a tripod Structure, represented by the acid amide or imide compound is described in JP-A following formula (1): HB-59732. A catalyst comprising (i) a complex of chro mium Salt with a multidentate ligand Selected from ACrO3, (1) phosphine, arsine and stibine, and (ii) aluminoxane is wherein A is a neutral multidentate ligand having a described in JP-AH6-298673. A catalyst comprising (i) a 35 tripod structure, J is a carbonyl ligand or a halogen chromium-chlorine complex or alkyl chromium complex atom, n is an integer of 0 to 3, and Q is at least one having a specific nitrogen ligand and (ii) an aluminum member Selected from the group consisting of a hydro compound is described in JP-AH10-7712. A catalyst com gen atom, a hydrocarbon group having 1 to 10 carbon prising (i) a chromium complex having a cyclic polyamine atoms, a carboxylate group having 1 to 10 carbon or hydro-tris(pyrazolyl)borate ligand and (ii) an alkyl alu 40 atoms, a diketonato group having 3 to 10 carbon atoms, minum compound is described in JP-AHIO-231317. an amide group, an imide group, an alkoxide group having 1 to 10 carbon atoms, a thioalkoxide group However, these chromium catalysts have problems as having 1 to 10 carbon atoms, an arene ligand having 6 explained below. to 15 carbon atoms, an alkene ligand having 2 to 10 When the catalyst of JP-A S62-265237 is used for trim 45 carbon atoms, an alkyne ligand having 2 to 15 carbon erization of ethylene, a Salient amount of polyethylene is atoms, an amine ligand, an imine ligand, a nitrile produced in addition to 1-hexene. Further, polyhydrocarbyl ligand, an isonitrile ligand, a phosphine ligand, a phos aluminum oxide (i.e., aluminoxane), which is one ingredient phine oxide ligand, a phosphite ligand, an ether ligand, of the catalyst, is a polymer prepared by reacting an alkyl a Sulfide ligand, a Sulfone ligand and a Sulfoxide ligand, 50 and aluminum with water, and therefore, it is difficult to prepare (b) a metal alkyl compound. aluminoxane having a predetermined quality, and this leads Preferably the catalyst further comprises (c) at least one to reduction of reproducibility of trimerization reaction of compound Selected from aromatic tertiary amine ethylene. compounds, except for an imine, and nitrogen-containing When the catalyst of JP-AH6-23.9920 is used, the amount 55 heterocyclic compounds, and/or (d) a radical anion com of polyethylene produced can be reduced. However, a pound. pyrrole-containing compound, which is one ingredient of the In another aspect of the present invention, there is pro catalyst, is extremely unstable to air, and readily deteriorated Vided a process for trimerizing ethylene, characterized in and colored. Thus, a pyrrole-containing compound is that ethylene is trimerized in the presence of the above troublesome to handle, and a treating process or apparatus 60 mentioned catalyst. for removing a coloring matter from the catalyst or purifying DESCRIPTION OF THE PREFERRED the catalyst is needed. EMBODIMENTS As for the catalyst of JP-A H8-59732, among the acid amide or imide compounds, which are one ingredient of the 65 Catalyst for Trimerization of Ethylene catalyst, maleimide is optimum for the catalytic activity for The catalyst of the invention comprises a chromium trimerization of ethylene. However, maleimide has problems complex having a neutral multidentate ligand having a US 6,337,297 B1 3 4 tripod structure, represented by the above formula (1) as one may have a Substituent on the ring thereof, Such as, for indispensable ingredient. The neutral multidentate ligand example, methyl, ethyl, propyl, butyl, octyl and phenyl. having a tripod Structure coordinated in the chromium R" in formula (2) is not particularly limited, and include, complex is not particularly limited, and includes, for for example, a hydrogen atom, alkyl groups having 1 to 10 example, those which are represented by the following carbon atoms Such as methyl, ethyl, propyl, butyl, benzyl, formulae (2) and (3). hydroxymethyl, cyanoethyl, allyl and trifluoropropyl, and aryl groups having 6 to 10 carbon atoms Such as phenyl, (2) p-methylphenyl and p-chlorophenyl. MD-L The neutral multidentate ligand having a tripod Structure, R-G-D-L1 represented by formula (2) or (3), which has a substituent D-L1 containing an element of group 14, 15, 16 or 17 of the periodic table, is not particularly limited. AS Specific examples of the neutral multidentate ligand, there can be wherein j, k and m independently represent an integer of 0 15 to 6, each D' independently represents a divalent hydrocar mentioned oxygen-containing tridentate ligands Such as bon group which may have a Substituent, each L' indepen tris(methoxymethyl)methane, 1,1,1-tris(methoxymethyl) dently represents a Substituent containing an element of ethane, 1,1,1-tris(methoxymethyl)propane, 1,1,1-tris group 14, 15, 16 or 17 of the periodic table, G' represents (methoxymethyl)butane, 1,1,1-tris(ethoxymethyl)ethane, a carbon or silicon atom, and R' represents a hydrogen atom, 1,1,1-tris(propoxymethyl)ethane, 1,1,1-tris(butoxymethyl) an alkyl group having 1 to 10 carbon atoms or an aryl group ethane and 1,1,1-tris(phenoxymethyl)ethane, Sulfur having 6 to 10 carbon atoms. containing tridentate ligands Such as 1,1,1-tris (methylthiomethyl)ethane, 1,1,1-tris(butylthiomethyl) (3) ethane and 1,1,1-tris(phenylthiomethyl)ethane, nitrogen p.-1. 25 containing tridentate ligands Such as 1,1,1-tris (dimethylamino methyl)ethane and 1,1,1-tris D2 -L2 (diphenylaminomethyl)ethane; and phosphorus-containing tridentate lig and S Such S 1,1,1-tris (diphenylphosphino methyl)ethane, 1,1,1-tris wherein a, b and c independently represent an integer of 0 to 6, u represents an integer of 0 or 1, each D’ independently (dimethylphosphinomethyl)ethane and 1,1,1-tris represents a divalent hydrocarbon group which may have a (diethylphosphinomethyl)ethane. substituent, each Lindependently represents a substituent AS Specific examples of the neutral multidentate ligand containing an element of group 14, 15, 16 or 17 of the having a tripod structure, represented by formula (2) or (3), periodic table, G' represents a nitrogen or phosphorus atom, 35 which has a heterocyclic Substituent containing an element and R represents an oxygen or Sulfur atom. of group 14, 15, 16 or 17 of the periodic table, there can be The divalent hydrocarbon groups D" in formula (2) and mentioned oxygen-containing tridentate ligands Such as D° in formula (3) are not particularly limited, and include, trifurylmethane, tris(5-methyl-2-furyl)methane, tris(5-ethyl for example, alkylene, cycloalkylene, phenylene, tolylene 2-furyl)methane, tris(5-butyl-2-furyl)methane, 1,1,1- and xylylene groups. D' and D may have a substituent, for 40 trifurylethane, trifurylamine, trifurylphosphine and trifu example, an alkyl group Such as methyl or ethyl, and an rylphosphine oxide, Sulfur-containing tridentate ligands alkoxy group Such as methoxy and ethoxy. Such as tris(thienyl)methane; and nitrogen-containing tri The substituents L' in formula (2) and L in formula (3), dentate ligands Such as tris(pyrazolyl)methane, tris(3,5- which contain an element of group 14, 15, 16 or 17 of the 45 dimethyl-1-pyrazolyl)methane, tris(3,5-diisopropyl-1- periodic table, are not particularly limited. AS Specific pyrazolyl)methane, tris(3,5-diphenyl-1-pyrazolyl)methane, examples of the substituents L and L, there can be men 1,1,1-tris(3,5-dimethyl-1-pyrazolyl)ethane, 1,1,1-tris(3,5- tioned alkoxy groupS Such as methoxy, ethoxy, propoxy and dimethyl-1-pyrazolyl)-propane, 1,1,1-tris(3,5-dimethyl-1- butoxy, aryloxy groups Such as phenoxy and 2,6- pyrazolyl)butane, tris(2-pyridyl)methane, tris(6-methyl-2- dimethylphenoxy; alkylthio groupS. Such as methylthio, 50 pyridyl)methane, tris(2-pyridyl)amine, tris(2-pyridyl) ethylthio, propylthio and butylthio; arylthio groupS Such as phosphine, tris(2-pyridyl)phosphine oxide, tris(2-pyridyl) phenylthio and tolylthio; dialkylamino groupS. Such as hydroxymethane and tris(1-imidazolyl)methane. dimethylamino, diethylamino and bis(trimethylsilyl)amino; AS Specific examples of B in formula (1), there can be diarylamino groupS. Such as diphenylamino; alkylarylamino 55 mentioned hydrocarbon groups having 1 to 10 carbon atoms groupS. Such as methylphenylamino; dialkylphosphino Such as methyl, ethyl, propyl, butyl, cyclohexyl, benzyl and groupS Such as dimethylphosphino and diethylphosphino; phenyl, carboxylate groups having 1 to 10 carbon atoms diarylphosphino groupS. Such as diphenylphosphino and Such as acetate, naphthenate and 2-ethylhexanoate, diketo ditolylphosphino; and alkylarylphosphino groupS Such as nato groups having 3 to 10 carbon atoms Such as acetylac methylphenylphosphino. 60 etonato, arene ligands having 6 to 15 carbon atoms Such as The substituents L' and Lf further include heterocyclic benzene, toluene, Xylene, trimethylbenzene, hexamethyl groups containing an element of group 14, 15, 16 or 17 of benzene and naphthalene; alkene ligands having 2 to 10 the periodic table, Such as furyl, benzofuryl, thienyl, carbon atoms Such as ethylene, propylene, butene, hexene benzothienyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, 65 and decene, alkyne ligands having 2 to 15 carbon atoms Such imidazolyl, benzoimidazolyl, indazolyl, quinolyl, as acetylene, phenylacetylene and diphenylacetylene, amine isoquinolyl, oxazolyl and thiazol. These heterocyclic groups ligands Such as triethylamine, tributylamine, N,N- US 6,337,297 B1 S 6 dimethylaniline, N,N-diethylaniline, N,N-dibutylaniline, tris(3,5-diisopropyl- 1-pyrazolyl)methane chromium diphenylmethylamine, triphenylamine, pyridine and quino tricarbonyl(0), tris(3,5-diphenyl-1-pyrazolyl)- line, imine ligands Such as benzophenone imine and methyl methanechromium tricarbonyl(0), 1,1,1-tris(3,5-dimethyl-1- ethyl-ketone imine, amide groupS Such as dimethylamide, pyrazolyl)ethanechromium tricarbonyl(0), 1,1,1-tris(3,5- diethylamide, diisopropylamide, dioctylamide, dimethyl-1-pyrazolyl)propanechromium tricarbonyl (O), didecylamide, didodecylamide, bis(trimethylsilyl)amide, 1,1,1-tris(3,5-dimethyl-1-pyrazolyl)butanechromium pyrrollido, indole, maleimide, phthalimide, diphenylamide, tricarbonyl(0), tris(2-pyridyl)methanechromium tricarbonyl N-methylanilide and anilide, alkoxide groups having 1 to 10 (0), tris(6-methyl-2-pyridyl)methanechromium tricarbonyl carbon atoms Such as methoxide, ethoxide, propoxide, (0), tris(2-pyridyl)aminechromium tricarbonyl(0), tris(2- butoxide and phenoxide; thioalkoxide groups having 1 to 10 pyridyl)phosphinechromium tricarbonyl(O), tris(2-pyridyl) carbon atoms Such as thiomethoxide, thioethoxide, phosphine-oxide-chromium tricarbonyl(0), tris(1- thiopropoxide, thiobutoxide and thiophenoxide, imide imidazolyl)methanechromium tricarbonyl(0), 1,1,1-tris groupS Such as benzophenone imide, nitrile groupS Such as (diphenylphosphinomethyl)ethanechromium tricarbonyl(0), acetonitrile and benzonitrile; isonitrile groupS Such as 15 1,1,1-tris(dimethylphosphinomethyl)ethane chromium t-butylisonitrile and phenylisonitrile; phosphine ligands tricarbonyl(0), 1,1,1-tris(diethylphosphinomethyl) Such as triphenylphosphine, tritolylphosphine, tricyclohexy ethanechromium tricarbonyl(0), tris(methoxymethyl) lphosphine and tributylphosphine; phosphite ligands Such as methane chromium tris(diisopropylamide) (III), tris triphenyl phosphite, tritolyl phosphite, tributyl phosphite (methoxymethyl)methanechromium tris(dizenzylamide) and triethyl phosphite, phosphine oxide ligands Such as (III), 1,1,1-tris(ethoxymethyl)ethane chromium tris tributylphosphine oxide and triphenylphosphine oxide, ether (diisopropylamide) (III), 1,1,1-tris(butoxymethyl) ligands Such as dimethyl ether, diethyl ether and tetrahydro ethane chromium tris(diisopropylamide) (III), 1,1,1-tris furan, Sulfide ligands Such as ethylsulfide and butylsulfide; (phenoxymethyl)ethanechromium tris(diisopropylamide) Sulfone ligands Such as dimethylsulfone and dibutylsulfone, 25 (III), triphenylmethanechromiumn tris(diisopropylamide) and Sulfoxide ligands Such as dimethylsulfoxide and dibu (III), 1,1,1-tris(methylthiomethyl)ethanechromium tris tylsulfoxide. (diisopropylamide)(III), 1,1,1-tris(dimethylaminomethyl) The halogen atom J in formula (1) is not particularly ethanechromium tris(diisopropylamide)(III), tris(pyrazolyl) limited, and includes, for example, fluorine, chlorine, bro methanechromium tris(diisopropylamide)(III), tris(3,5- mine and iodine atoms. dimethyl-1-pyrazolyl)methanechromium tris(diethylamide) AS Specific examples of the chromium complex of for (III), tris(3,5-dimethyl-1-pyrazolyl)methanechromium tris mula (1), there can be mentioned 1,1,1-tris(methoxymethyl) (diisopropylamide)(III), tris(3,5-dimethyl-1-pyrazolyl) ethanechromium tricarbonyl(0), trifurylmethanechromium methanechromium tris(dibenzylamide)(III), tris(3,5- tricarbonyl(0), tris(5-methyl-2-furyl)methanechromium 35 dimethyl-1-pyrazolyl)me thane chromium tris tricarbonyl(0), tris(5-butyl-2-furyl)methanechromium (diphenylamide) (III), tris(3,5-dimethyl-1-pyrazolyl) tricarbonyl(0), trifurylaminechromium tricarbonyl(0), trifu methanechromium tris(bis(trimethylsilyl)amide(III), tris(3, rylphosphine chromium tricarbonyl(0), trifurylphosphine 5-dimethyl-1-pyrazolyl)methanechromium triethoxide(III), oxidechromium tricarbonyl(0), 1,1,1-tris(methylthiomethyl) tris(3,5-dimethyl-1-pyrazolyl)methane chromium ethane chromium tricarbonyl(0), tris(thienyl) 40 tributoxide (III), tris(3,5-dimethyl-1-pyrazolyl) me thane chromium tricarbonyl(0), 1,1,1-tris methanechromium thiobutoxide(III), tris(3,5-dimethyl-1- (dimethylaminomethyl)ethanechromium tricarbonyl(0), tris pyrazolyl)methanechromium bis(diisopropylamide)(III), (pyrazolyl)methanechromium tricarbonyl(0), tris(3,5- tris(3,5-diphenyl-1-pyrazolyl)methane chromium tris dimethyl-1-pyrazolyl)methanechromium tricarbonyl(0), tris 45 (diisopropylamide)(III), tris(2-pyridyl)methanechromium (3,5-dimethyl-1-pyrazolyl)methanechromium (ethylene) tris(diisopropylamide)(III), tris(6-methyl-2-pyridyl) dicarbonyl(0), tris(3,5-dimethyl-1-pyrazolyl) methanechromium tris(diisopropylamide)(III), tris(2- methanechromium (phenylacetylene)dicarbonyl(0), tris(3,5- pyridyl)aminechromium tris(diisopropylamide)(III), tris(1- dimethyl-1-pyrazolyl)methanechromium (dimethylaniline) imidazolyl)methanechromium tris(diisopropylamide)(III), dicarbonyl(0), tris(3,5-dimethyl-1-pyrazolyl) 50 1,1,1-tris(dimethylphosphinomethyl)ethanechromium tris methanechromium (benzophenoneimine)dicarbonyl(0), tris (di is op ropylamide) (III), 1, 1,1-tris (3,5-dimethyl-1-pyrazolyl)methanechromium (acetonitrile) (diphenylphosphino methyl)ethane chromium tris dicarbonyl(0), tris(3,5-dimethyl-1-pyrazolyl) (diisopropylamide)(III), 1,1,1-tris(diethylphosphinomethyl) methanechromium (t-butylisonitrile)dicarbonyl(0), tris(3,5- 55 ethane chromium tris(diisopropylamide) (III), tris dimethyl-1-pyrazolyl)me thane chromium (methoxymethyl)methanechromium trichloride(III), 1,1,1- (tributylphosphine)dicarbonyl(0), tris(3,5-dimethyl-1- tris(methoxymethyl)ethanechromium trichloride(III), 1,1,1- pyrazolyl)methane chromium (tributylphosphine oxide) tris(methoxymethyl)ethane-tris(diisopropylamide) dicarbonyl(0), tris(3,5-dimethyl-1-pyrazolyl) chromium(III), 1,1,1-tris(methoxymethyl)ethane-tris methanechromium (triphenylphosphite)-dicarbonyl(0), tris 60 (dimethylamide)chromium(III), 1,1,1-tris(methoxymethyl) (3,5-dimethyl-1-pyrazolyl)methane chromium ethane-tris bis(trimethylsilyl)amidechromium(III), 1,1,1- (tetrahydrofuran)dicarbonyl(0), tris(3,5-dimethyl-1- tris(methoxymethyl)ethanechromium triethoxide(III), 1,1,1- pyrazolyl)methanechromium (dimethylsulfone)dicarbonyl tris(methoxymethyl)ethanechromium trithiobutoxide(III), 1, (0), tris(3,5-dimethyl-1-pyrazolyl)methanechromium 65 1,1-tris(ethoxymethyl)ethanechromium trichloride(III), 1,1, (dimethylsulfoxide)dicarbonyl(0), tris(3,5-dimethyl-1- 1-tris(butoxymethyl)ethanechromium trichloride(III), 1,1,1- pyrazolyl)methanechromium (dibutylsulfide)dicarbonyl(0), tris(phenoxymethyl)ethanechromium trichloride(III), tris(3, US 6,337,297 B1 7 8 5-dimethyl-1-pyrazolyl)methanechromium trichloride(III), The process for Synthesizing the chromium halogen com tris(3,5-dimethyl-1-pyrazolyl)methane-tris(diethylamide) pleX and other chromium complexes, which have a neutral chromium(III), tris(3,5-dimethyl-1-pyrazolyl)methane-tris multidentate ligand having a tripod structure, is not particu (diisopropylamide)chromium(III), tris(3,5-dimethyl-1- larly limited. For example, the chromium halogen complex pyrazolyl)methane-tris bis(trimethylsilyl)amidechromium can be Synthesized from a neutral multidentate ligand having (III), tris(3,5-dimethyl-1-pyrazolyl)methane-tris a tripod structure and a chromium compound by known (benzophenoneimide)chromium(III), tris(3,5-dimethyl-l- complex Synthesizing processes. pyrazolyl)methanechromium triethoixide(III), tris(3,5- The chromium compounds used as a raw material for the dimethyl-1-pyrazolyl)methanechromium trithiobutoxide Synthesis of the chromium halogen complex and other (III), 1,1,1-tris(diphenylphosphinomethyl)ethanechromium chromium complexes are not particularly limited, and trichloride(III), 1,1,1-tris(diethylphosphinomethyl) include, for example, chromium halides Such as chromium ethane chromium trichloride(III), and 1,1,1-tris chloride(III), chromium chloride(II), chromium bromide (diethylphosphinomethyl)ethane-tris(diisopropylamide) (III), chromium bromide(II), chromium iodide(III), chro 15 mium iodide(II), chromium fluoride(III), chromium fluoride chromium(III). (II); chromium chloride complexes such as tris Among the neutral multidentate ligands having a tripod (tetrahydrofuran) chromium trichloride(III), tris(1,4- Structure, represented by formula (1), tridentate ligands dioxane)chromiumtrichloride(III), tris(diethyl ether)- having a nitrogen-containing heterocyclic group are prefer chromium trichloride(III), tris(pyridine) chromium able in view of the selectivity to 1-hexene and the catalyst trichloride(III), tris(acetonitrile)chromium trichloride(III); activity. Tris(3,5-dimethyl-1-pyrazolyl)methane is espe chromium amide complexes Such as tris(tetrahydrofuran) cially preferable. chromium tris(diethylamide)(III), tris(tetrahydrofuran) AS preferable examples of the chromium carbonyl com chromium tris(diisopropylamide)(III), tris(tetrahydrofuran) plexes having a neutral multidentate ligand having a tripod chromium tris(diphenylamide) (III), and tris Structure, there can be mentioned tris(3,5-dimethyl-1- 25 (tetrahydrofuran)chromium tris bis(trimethylsilyl)amide pyrazolyl)methane chromium tricarbonyl(0), tris(3,5- (III); chromium carboxylate complexes Such as chromium dimethyl-1-pyrazolyl)methanechromium trichloride(III), tris(2-ethylhexanoate)(III) and chromium tris(acetate)(III); 1,1,1-tris(diphenylphosphinomethyl)ethane chromium chromium diketonato complexes. Such as chromium tricarbonyl(0), tris(3,5-dimethyl-1-pyrazolyl) acetylacetonato(III); chromium alkoxide complexes Such as methane chromium tris(diethylamide) (III), tris(3,5- chromium(IV) t-butoxide and tris(tetrahydrofuran) dimethyl-1-pyrazolyl)me thane chromium tris chromium triethoxide(III); and chromium thioalkoxide com (diisopropylamide)(III), tris(3,5-dimethyl-1-pyrazolyl) plexes such as chromium(IV) thiobutoxide and tris methanechromium tris(diphenylamide)(III), tris(3,5- (tetrahydrofuran)chromium trithioethoxide(III). dimethyl-1-pyrazolyl)methane chromium trisbis 35 The concentration of chromium metal in a reaction Solu (trimethylsilyl)amide(III), and 1,1,1-tris-(methoxymethyl) tion for Synthesis of the chromium complex is not particu ethanechromium tricarbonyl(0). larly limited. The solvent used for the chromium complex The process for Synthesizing the chromium carbonyl Synthesis is not particularly limited, and usually organic complex having a neutral multidentate ligand having a Solvents are used. AS Specific examples of the organic tripod Structure is not particularly limited. For example, the 40 Solvent, there can be mentioned aliphatic hydrocarbons Such chromium carbonyl complex can be Synthesized from a as pentane, hexane, heptane, octane, nonane, decane, cyclo neutral multidentate ligand having a tripod Structure and a hexane and decalin; aromatic hydrocarbons Such as benzene, chromium carbonyl compound by known complex Synthe toluene, Xylene, cumene and trimethylbenzene, etherS Such sizing processes (for example, by a process described in J. 45 as diethyl ether and tetrahydrofuran; and halogenated hydro Amer. Chem. Soc., 92, 5118. carbons Such as methylene chloride, chloroform and carbon The chromium carbonyl compound used as a raw material tetrachloride. Of these, aliphatic hydrocarbons and aromatic is not particularly limited, and includes, for example, chro hydrocarbons are preferable in View of handling properties. mium hexacarbonyl(0), pentacarbonyl(triphenylphosphine) Decalin, trimethylbenzene and toluene are especially pref chromium(0), tetracarbonylbis(ethylene)chromium(0), 50 erable. These organic Solvents may be used either alone or tricarbonyl(benzene)chromium(0), tricarbonyl(toluene) in combination. chromium(0), tricarbonyl(trimethylbenzene)chromium(0), The Synthesis of the chromium complex is usually carried tricarbonyl(hexamethylbenzene)chromium(0), tricarbonyl out at a temperature in the range of -80 C. to the boiling (naphthalene)chromium(0), tricarbonyl(cycloheptatriene) 55 point of solvent used, preferably in the range of 0 to 200 C. chromium(0), tricarbonyl tris(acetonitrile)chromium(0), tri A temperature higher than the boiling point of Solvent may carbonyl tris(triphenylphosphite)chromium(0) (ethylene) also be employed provided that the reaction is conducted dicarbonyl (trimethylbenzene) chromium(0), under pressure. The reaction time is not particularly limited cyclohexylisonitriledicarbonyl (trimethylbenzene) and is usually in the range of 1 minute to 48 hours, chromium(0), tributylphosphine dicarbonyl 60 preferably 5 minutes to 24 hours. The operation for the (trimethylbenzene) chromium(0), tricarbonyl chromium complex Synthesis is preferably carried out under (cyclopentadienyl)chromium(I) dimer, and hydridotricarbo conditions Such that the reactants are not in contact with air nyl (cyclopentadienyl)chromium(II). Of these, chromium and moisture. The raw materials used are preferably pre hexacarbonyl(0) and tricarbonyl(trimethylbenzene) 65 liminarily dried. chromium(0) are preferable in View of handling properties Another proceSS may be employed wherein the chromium and commercial availability. complex having a neutral multidentate ligand having a US 6,337,297 B1 9 10 tripod structure is Synthesized by allowing a chromium represents lithium, magnesium, Zinc, boron or aluminum, halogen complex having a neutral multidentate ligand hav each R independently represents an alkyl group having 1 to ing a tripod structure to react with a metal alkylamide, a 10 carbon atoms, and each X independently represents a metal alkoxide or a metal thioalkoxide in a Solvent. hydrogen atom, an alkoxide group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or a The chromium halogen complex having a neutral multi halogen atom. dentate ligand having a tripod Structure used is not particu AS examples of the alkyl group R having 1 to 10 carbon larly limited, and includes, for example, 1,1,1-tris atoms in formula (4), there can be mentioned methyl, ethyl, (methoxymethyl)ethanechromium trichloride(III), 1,1,1-tris propyl, butyl, cyclohexyl and octyl groups. AS Specific (methoxymethyl)propanechromium trichloride(III), 1,1,1- examples of X in formula (4), there can be mentioned tris(ethoxymethyl)ethanechromium trichloride(III), 1,1,1- alkoxide groupS. Such as methoxide, ethoxide, butoxide and tris(butoxymethyl)ethanechromium trichloride(III), 1,1,1- phenoxide, aryl groups Such as phenyl, and halogen atoms tris(methylthiomethyl)ethanechromium trichloride(III), 1,1, Such as fluorine, chlorine, bromine and iodine. 1-tris(dimethylaminomethyl)ethanechromium trichloride In formula (4), when E is aluminum, each of p and q is (III), 1,1,1-tris(diphenylphosphinomethyl)ethanechromium 15 1.5, the metal alkyl compound is represented by the formula trichloride(III), trifurylmethanechromium trichloride(III), AlRXs. Theoretically this compound does not exist, but, tris(5-methyl-2-furyl)methanechromium trichloride(III), tri it is popularly called as a Sesqui-compound of Al-RX and furylphosphine oxidechromium trichloride(III), tris can be used as the alkyl metal compound in the present (pyrazolyl)methanechromium trichloride(III), tris(3,5- invention. dimethyl-1-pyrazolyl)methanechromium trichloride(III), AS Specific examples of the alkyl metal compound, there tris(3,5-diisopropyl-1-pyrazolyl)methane chromium can be mentioned methyllithium, ethyllithium, trichloride(III), tris(2-pyridyl)methanechromium trichloride propyllithium, n-butyllithium, S-butyllithium, (III), and tris(6-methyl-2-pyridyl)methane chromium t-butyllithium, diethylmagnesium, ethylbutylmagnesium, trichloride(III). 25 ethylchloromagnesium, ethylbromo magnesium, The metal alkylamide, metal alkoxide and metal thio dimethylzinc, diethylzinc, dibutylzinc, trimethylborane, alkoxide also are not particularly limited, and include, for triethylborane, trimethylaluminum, triethylaluminum, example, lithium dimethylamide, lithium diethylamide, triisobutylaluminum, tri-n-hexylaluminum, tri-n- lithium diisopropylamide, lithium bis(trimethylsilyl)amide, octyl aluminum, tricyclohe Xylaluminum, Sodium bis(trimethylsilyl)amide, Sodium diphenylamide, dimethylethylaluminum, diethylaluminum hydride, diisobu Sodium methoxide, Sodium ethoxide, Sodium propoxide, tylaluminum hydride, diethylaluminum ethoxide, diethyla Sodium phenoxide, Sodium thiomethoxide, Sodium luminum phenoxide, dicyclohexylphenylaluminum, ethyla thioethoxide, sodium thiobutoxide and sodium thiophenox luminum ethoxychloride, diethylaluminum chloride, ide. 35 diethylaluminum bromide, diisobutylaluminum chloride, The thus-produced chromium complex having a neutral dicyclohexylaluminum chloride, methylaluminum multidentate ligand having a tripod structure usually SeSquichloride, ethylaluminum Sesquichloride, butylalumi precipitates, and therefore, can be separated from the Solvent num Sesquichloride, ethylaluminum dichloride and isobuty by filtration. If desired, the Separated chromium complex is laluminum dichloride. washed with the same solvent, and then dried. If the pro 40 Of these, alkyl aluminum compounds are preferable in duced chromium complex does not precipitate, it can be view of commercial availability and catalytic activity. Tri precipitated by removing the Solvent by distillation, adding ethylaluminum and triisobutylaluminum are especially pref a poor Solvent, or cooling the reaction product mixture. erable. These alkyl metal compounds may be used either Among the chromium complexes having a neutral mul 45 alone or in combination. tidentate ligand having a tripod Structure, those in which the The amount of the alkyl aluminum compound is usually multidentate ligand is facially coordinated are preferable in the range of 0.1 to 10,000 equivalent, preferably 3 to because production of Side-reaction products Such as poly 3,000 equivalent and more preferably 5 to 2,000 equivalent, ethylene is minimized. By the term “facially coordinated” per mol of the chromium complex. used herein, we mean that the neutral multidentate ligand 50 To enhance the activity of the catalyst of the present occupies the three coordinate Sites to form an isomer of invention, aromatic tertiary amine compounds, except for an six-coordinate octahedral complex (Kagaku-Sensho: imine, and/or nitrogen-containing heterocyclic compounds Organic Metal Chemistry, Fundamental and Application, p143, published by Shoukabou, Japan). That is, the three can be used as an additional ingredient of the catalyst. 55 AS Specific examples of the aromatic tertiary amine coordinate Sites occupied by the multidentate ligand take a compounds, except for an imine, there can be mentioned cis-form to each other. N,N-dimethylaniline, N,N-diethylaniline, N,N- The catalyst of the invention comprises a metal alkyl diisopropylaniline, N,N-dibutylaniline, N,N- compound as another indispensable ingredient, in addition dibenzylaniline, Diphenylmethylamine, Triphenylamine, to the chromium complex of formula (1) having a neutral 60 Tris(p-methylphenyl)amine, Tris(m-methylphenyl)amine, multidentate ligand having a tripod Structure. The alkyl Tris(o-methylphenyl)amine, N,N-dimethyl-o-toluidine, metal compound is not particularly limited, but those which N,N-dimethyl-m-toluidine, N,N-dimethyl-p-toluidine, N.N., are represented by the following formula (4) are preferable: 2,3-tetramethylaniline, N.N.,2,4-tetramethylaniline, N.N.2, REX, (4) 65 5-tetramethylaniline, N.N.2,6-tetramethylaniline, N,N.3,4- wherein p and q are numbers Satisfying the formulae: 0
TABLE 1.
Example 1. 2 3 4 5 6 Catalyst: Cr complex A. A. A. A. A. A. (umol) 16.O 16.O 8.0 4.0 1.O 4.0 Alkyl metal compound i-BusAl i-BusAl i-BusAl i-BusAl i-BusAl i-Bus Al (umol) 240 240 240 240 240 48O Solvent Toluene CyHe Toluene Toluene Toluene Toluene Reaction conditions:
Temperature ( C.) 8O 8O 8O 8O 8O 8O Pressure (kg/cm) 5 5 5 5 5 5 Time (min) 3O 3O 3O 3O 3O 3O Results: Catalytic activity (g-1-hexenefg-Cr. h) 445 281 1,830 3,870 6,780 4,870 Liquid (wt.%) 99.0 96.9 99.8 99.1 98.9 99.9 Solid (PE) (wt.%) 1.O 3.1 O.2 O.9 1.1 trace Products in liquid: (wt.%) 4.4 5.8 2.6 O.2 1.7 2.4 (wt.%) 77.9 76.3 91.8 96.1 97.1 95.6 (wt.%) 2.3 5.1 O.8 0.5 O.3 O.2 C10 (wt.%) 5.6 5.3 2.4 1.9 O.8 1.4 C12 (wt.%) 9.8 7.5 2.4 1.3 O.1 0.4 Purity of C6 (wt.%) 96.2 95.4 98.9 99.1 99.3 99.1
Note C4: Butene, C6: Hexene, C8: Octene, C10: Decene, C12+: Dodecene and higher olefins, PE: Polyethylene, Purity of C6: (1-hexene/sum of hexene isomers) x 100, CyHe: Cyclohexane, i-BusAl: Triisobutylaluminum 45 The reactor was heated to 80° C. and the rate of stirring EXAMPLES 7 was adjusted to 1,400 rpm, and ethylene was introduced in the reactor to an extent Such that the absolute pressure within Trimerization of ethylene was conducted by the same the reactor reached 5 kg/cm. The content was irradiated procedure as in Example 3 except that triethylaluminum was with light for 5 minutes by using an ultra-high pressure 50 used instead of triisobutylaluminum with all other condi mercury lamp (500W) supplied by Ushio Inc. to commence tions remaining the same. The results are shown in Table 2. trimerization of ethylene. Then 40 ml of dry toluene was EXAMPLES 8 injected into the reactor by ethylene. Ethylene was continu ously introduced So that the absolute preSSure within the Trimerization of ethylene was conducted by the same reactor was maintained at 5 kg/cm during the reaction. 55 procedure as in Example 3 except that tris(n-hexyl) When 30 minutes elapsed while the temperature was main aluminum was used instead of triisobutylaluminum with all tained at 80 C., water was injected by nitrogen into the other conditions remaining the Same. The results are shown reactor to deactivate the catalyst and terminate the reaction. in Table 2. The reactor was cooled to room temperature and then the preSSure was reduced to normal preSSure. The products 60 EXAMPLES 9 contained in the reaction liquid and in the gas collected from Trimerization of ethylene was conducted by the same the reactor were analyzed by gas chromatography. The Solid procedure as in Example 1 except that 12.2 mg of complex contained in the reaction liquid was filtered by filter paper. B, prepared in Reference Example 2, was used instead of The collected Solid was air-dried and further dried under a 65 complex A, and cyclohexane was used instead of toluene reduced pressure of 1 mmHg at 100° C., and then weighed. with all other conditions remaining the Same. The results are The results are shown in Table 1. shown in Table 2. US 6,337,297 B1 21 22 COMPARATIVE EXAMPLES 1 EXAMPLE 10 Trimerization of ethylene was conducted by the same A pressure-resistant glass reactor having an inner Volume procedure as described in Example 1 except that 4.1 mg of of 150 ml, provided with a thermometer and a stirring commercially available mesitylenechromium tricarbonyl(0) apparatus was charged with 10.4 mg of complex G, prepared (hereinafter referred to as “complex C”) was used instead of in Reference Example 5, and 80 ml of dry toluene, and the complex A with all other conditions remaining the Same. The content was stirred. results are shown in Table 2. The reactor was heated to 80 C. and the rate of stirring was adjusted to 1,400 rpm, and 1.6 ml of a solution of COMPARATIVE EXAMPLES 2 triisobutylaluminum/cyclohexane having a concentration of Trimerization of ethylene was conducted by the same 0.154 mol/l was introduced by the pressure of ethylene, procedure as in Example 1 except that 11.8 mg of complex whereby trimerization of ethylene was commenced. The D, prepared in Reference Example 3, was used instead of amount of ethylene introduced was controlled So that the complex A, and cyclohexane was used instead of toluene 15 absolute pressure within the reactor reached 5 kg/cm and with all other conditions remaining the Same. The results are the introduction of ethylene was continued So that this shown in Table 2. preSSure was maintained during the reaction. When 30 minutes elapsed while the temperature was maintained at COMPARATIVE EXAMPLES 3 80 C., water was injected by nitrogen into the reactor to Trimerization of ethylene was conducted by the same deactivate the catalyst and terminate the reaction. procedure as in Example 1 except that 9.0 mg of complex E, The reactor was cooled to room temperature and then the prepared in Reference Example 4, was used instead of preSSure was reduced to normal pressure. The products complex A, and cyclohexane was used instead of toluene contained in the reaction liquid and in the gas collected from with all other conditions remaining the Same. The results are 25 the reactor were analyzed by gas chromatography. The shown in Table 2. results are shown in Table 3.
TABLE 2 Example Comparative Example
7 8 9 1. 2 3 Catalyst:
Cr complex A. A. B C D E (umol) 4.0 4.O. 16.0 16.0 16.O 16.O Alkyl metal compound EtAl Hex Al i-BusAl i-BusAl i-BusAl i-Bus Al (umol) 48O 480 240 240 240 240 Solvent Toluene Toluene CyHe Toluene CyHe CyHe Reaction conditions: Temperature ( C.) 8O 8O 8O Pressure (kg/cm) 5 5 5 5 5 5 Time (min) 3O 3O 3O 3O 3O 3O Results:
Catalytic activity (g-1-hexene/g-Cr. h) 3,280 3,380 76 176 230 2O1 Liquid (wt.%) >99.O 99.9 91.1 87.1 60.6 38.2 Solid (PE) (wt.%) trace O.1 8.9 12.9 39.4 618 Products in liquid: C4 (wt.%) 7.3 O.8 12.2 4.9 12.4 O.9 C6 (wt.%) 90.5 87.8 51.O 68.4 63.1 90.3 C8 (wt.%) 0.5 1.7 13.3 5.5 4.4 6.O C10 (wt.%) 1.6 5.3 11.1 7.7 5.2 1.1 C12+ (wt.%) O.2 4.5 12.4 13.4 14.9 1.7 Purity of C6 (wt.%) 98.8 97.5 90.3 98.5 97.6 99.9
Note C4: Butene, C6: Hexene, C8: Octene, C10: Decene, C12+: Dodecene and higher olefins, PE: Polyethylene, Purity of C6: (1-hexene/sum of hexene isomers) x 100, CyHe: Cyclohexane i-BusAl: Triisobutylaluminum, EtAl: Triethylaluminum, Hex. Al: Tris(n-hexyl)aluminum US 6,337,297 B1 24 the reactor to an extent Such that the absolute pressure within TABLE 3 the reactor reached 5 kg/cm. The content was irradiated with light for 5 minutes by using an ultra-high preSSure Example 1O mercury lamp (500 W) supplied by Ushio Inc., and then, Catalyst: Solution A was injected by ethylene into the reactor. Ethyl ene was continuously introduced So that the inner absolute Cr complex G pressure was maintained at 5 kg/cm, while the temperature (umol) 16.O Alkyl metal compound i-BusAl was maintained at 80 C. When 30 minutes elapsed, water (umol) 240 was injected by nitrogen into the reactor to deactivate the Solvent Toluene catalyst and terminate the reaction. Reaction conditions: The reactor was cooled to room temperature and then the Temperature (C.) 8O preSSure was reduced to normal pressure. The products Pressure (kg/cm) 5 contained in the reaction liquid and in the gas collected from Time (min) 3O the reactor were analyzed by gas chromatography. The Solid Results: 15 contained in the reaction liquid was filtered by filter paper. Catalytic activity 8O The collected Solid was air-dried and further dried under a (g-1-hexenefg-Cr h) reduced pressure of 1 Torr at 100 C., and then weighed. The Products in liquid: results are shown in Table 4. C4 (wt.%) 27.0 EXAMPLE 12 C6 (wt.%) 67.1 C8 (wt.%) 4.4 Trimerization of ethylene was conducted by the same C10 (wt.%) 1.6 procedure as in Example 11 except that 0.29 ml of a Solution C12+ (wt.%) O.O of N,N-dimethylaniline/toluene having a concentration of Note Abbreviations are the same as defined in the preceding tables 0.028 mol/l was used instead of 1.4 ml of the same Solution 25 with all other conditions remaining the Same. The results are EXAMPLE 11 shown in Table 4. A StainleSS Steel reactor having an inner Volume of 50 ml EXAMPLE 13 was charged with 1.4 ml of a solution of N,N- Trimerization of ethylene was conducted by the same diemthylaniline/toluene Solution having a concentration of procedure as in Example 11 except that 2.9 ml of a Solution 0.028 mol/l, and 40 ml of dry toluene (the resultant solution of N,N-dimethylaniline/toluene having a concentration of is hereinafter referred to as “solution A"). 0.028 mol/l was used instead of 1.4 ml of the same Solution A preSSure-resistant glass reactor having an inner Volume with all other conditions remaining the Same. The results are of 150 ml, provided with a thermometer and a stirring shown in Table 4. apparatus was charged with 1.7 mg of complex A, prepared 35 in Reference Example 1, 2.0 ml of a solution of EXAMPLE 14-16 triisobutylaluminum/cyclohexane having a concentration of Trimerization of ethylene was repeated by the same 0.24 mol/l, and 40 ml of dry toluene, and the content was procedure as in Example 11 except that each of the aromatic stirred. 40 tertiary amines shown in Table 4 was used instead of The reactor was heated to 80° C. and the rate of stirring N,N-dimethylaniline with all other conditions remaining the was adjusted to 1,400 rpm, and ethylene was introduced in same. The results are shown in Table 4.
TABLE 4
Example 11 12 13 14 15 16 Catalyst:
Cr complex A. A. A. A. A. A. (umol) 4.0 4.0 4.0 4.0 4.0 4.0 Alkyl metal compound i-Bus Al i-BusAl i-Bus Al i-Bus Al i-Bus Al i-BusAl (umol) 48O 48O 48O 48O 48O 48O Tertery aromatic amine PhNMe, PhNMe, PhNMe, PhN(Pr-n), Ph.N.Me PhN (umol) 40 8 8O 40 40 40 Solvent Toluene Toluene Toluene Toluene Toluene Toluene Reaction conditions:
Temperature ( C.) 8O 8O 8O 8O 8O 8O Pressure (kg/cm) 5 5 5 5 5 5 Time (min) 3O 3O 3O 3O 3O 3O Results: Catalytic activity (g-1-hexene/g-Cr. h) 12,600 8,380 13,000 11,900 9,050 15,600 Liquid (wt.%) 99.9 >99.9 99.9 99.7 >99.9 >99.9 Solid (PE) (wt.%) O1 trace O1 O.3 trace trace Products in liquid: C4 (wt.%) 1.2 1.6 1.1 O.9 1.5 1.O C6 (wt.%) 97.6 96.5 96.9 96.6 96.4 97.0 C8 (wt.%) O.2 O1 O.2 O.2 O1 O.2 US 6,337,297 B1
TABLE 4-continued
Example 11 12 13 14 15 16 C10 (wt.%) O6 1.3 1.1 1.2 1.1 1.1 C12+ (wt.%) 0.4 0.5 O.7 1.2 O.8 O.7 Purity of C6 (wt.%) 99.1 99.1 99.1 99.2 99.2 99.1
Note PhNMe: N,N-dimethylaniline, PhN(Pr-n): N,N-bis(n-propyl)aniline, PhNMe: Methyldiphenylamine, PhN: Triphenylamine, Other abbreviations are the same as defined in the preceding tables.
COMPARATIVE EXAMPLE 4 15 apparatus was charged with 7.3 mg of complex F, prepared Trimerization of ethylene was conducted by the same in Reference Example 5, and 80 ml of dry toluene, and the procedure as in Example 11 except that N,N-dimethylaniline content was stirred. was not used with all other conditions remaining the same. The results are shown in Table 5. The reactor was heated to 80 C. and the rate of stirring COMPARATIVE EXAMPLE 5 2O was adjusted to 1,400 rpm, and 1.6 ml of a solution of Trimerizatlon of ethylene was conducted by the same triisobutylaluminum/cyclohexane having a concentration of procedure as in Example 11 except that 12 mg of N,N- 0.150 mol/l was introduced by the pressure of ethylene, dimethyloctadecylamine, i.e., a tertiary aliphatic amine, was whereby trimerization of ethylene was commenced. Ethyl used instead of N,N-dimethylaniline with all other condi- as ene was introduced to an extent Such that the absolute tions remaining the Same. The results are shown in Table 5. pressure within the reactor reached 5 kg/cm, and the COMPARATIVE EXAMPLE 6 introduction of ethylene was continued So that this preSSure Trimerization of ethylene was conducted by the same was maintained during the reaction. When 30 minutes procedure as in Example 11 except that 14 mg of elapsed while the temperature was maintained at 80 C., didodecylamine, i.e., a Secondary aliphatic amine, was used O water was injected by nitrogen into the reactor to deactivate instead of N,N-dimethylaniline with all other conditions the catalyst and terminate the reaction. remaining the same. The results are shown in Table 5. The reactor was cooled to room temperature and then the TABLE 5 35 preSSure was reduced to normal pressure. Any Solids Such as polyethylene were not found in the reaction liquid. The Comparative Example 4 5 6 products contained in the reaction liquid and in the gas Catalyst: collected from the reactor were analyzed by gas chroma Cr complex A. A. A. 40 tography. The results are shown in Table 6. (umol) 4.0 4.0 4.0 Alkyl metal compound i-BusAl i-Bus Al i-BusAl EXAMPLE 1.8 (umol) 48O 48O 48O Tertiary aromatic amine CH7NME (CHs)NH (umol) 40 40 Trimerization of ethylene was conducted by the same Solvent Toluene Toluene Toluene procedure as described in Example 17 except that 1.5 ml of Reaction conditions: 45 a Solution of n-butyllithium/cyclohexane having a concen Temperature (C.) 8O 8O 8O tration of 53.3 mmol/l was added prior to the addition of the Pressure (kg/cm) 5 5 5 Time (min) 3O 3O 3O solution of triisobutylaluminum/cyclohexane with all other Results: o 50 conditions remaining the same. The results are shown in Table 6. Catalytic activity 4,870 5,000 4,330 (g-1-hexene/g-Cr h) Liquid (wt.%) >99.9 99.O >99.9 TABLE 6 Solid (wt.%) trace 1.O trace Products in liquid: Example 17 18 55 C4 (wt.%) 2.4 1.9 2.7 Catalyst: C6 (wt.%) 95.6 94.4 95.0 C8 (wt.%) O.2 O.2 O.2 Cr complex F F C10 (wt.%) 1.4 18 1.3 (umol) 16.O 16.0 C12+ (wt.%) 0.4 1.7 O.8 Alkyl metal compound i-Bus Al i-Bus Al Purity of C6 (wt.%) 99.1 99.1 99.1 60 (umol) 240 240 n-BuLi Note CHNME: N,N-Dimethyloctadecylamine, (CHs)NH: N,N- Didocylamine Solvent Toluene Toluene Other abbreviations are the same as defined in the preceding tables Reaction conditions: Temperature ( C.) 8O 8O EXAMPLE 1.7 65 Pressure (kg/cm) 5 5 A preSSure-resistant glass reactor having an inner Volume Time (min) 3O 3O of 150 ml, provided with a thermometer and a stirring US 6,337,297 B1
TABLE 6-continued TABLE 7-continued Example 17 18 Example 19 2O Results: (umol) 12 12 Solvent Toluene Toluene Catalytic activity 3.0 18 Reaction conditions: (g-1-hexenefg-Cr h) Products in liquid: Temperature ( C.) 8O 8O Pressure (kg/cm) 5 5 C4 (wt.%) 49.5 71.5 Time (min) 3O 3O C6 (wt.%) 36.3 23.4 Results: C8 (wt.%) O.O 4.0 C10 (wt.%) 14.3 1.2 Catalytic activity 5,490 4,750 C12+ (wt.%) O.O O.O (g-1-hexene/g-Cr h) Purity of C6 (wt.%) >99.9 92.9 Products in liquid: 15 Note n-BuLi: n-butyllithium, Other abbreviations are the same as defined C4 (wt.%) 2.4 1.8 in the preceding tables C6 (wt.%) 96.1 97.0 C8 (wt.%) O.2 O.O C10 (wt.%) O.9 O.8 EXAMPLE 1.9 C12+ (wt.%) 0.4 0.4 Purity of C6 (wt.%) 99.1 99.2 A preSSure-resistant glass reactor having an inner Volume Note Na-na: Sodium naphthalene, Other abbreviations are the same as of 150 ml, provided with a thermometer and a stirring defined in the preceding tables apparatus was charged with 3.6 mg of complex F, prepared in Reference Example 5, 80 ml of dry toluene and 0.012 ml of a Solution of Sodium naphthalene/ethylene glycol dim 25 EXAMPLE 21 ethyl ether having a concentration of 1 mol/l, and the content was stirred. A Schlenk tube having an inner volume of 20 ml was charged with 12.1 mg of complex G, prepared in Reference The reactor was heated to 80° C. and the rate of stirring Example 5, and 15.7 ml of a solution of was adjusted to 1,100 rpm, and 4.0 ml of a solution of triisobutylaluminum/toluene having a concentration of triisobutylaluminum/toluene having a concentration of 0.238 mol/l, and the content was stirred. 0.240 mol/l was introduced by the pressure of ethylene, whereby trimerization of ethylene was commenced. Ethyl A pressure-resistant glass reactor having an inner volume ene was introduced to an extent Such that the absolute of 150 ml, provided with a thermometer and a stirring pressure within the reactor reached 5 kg/cm, and the 35 apparatus was charged with 4.0 ml of the above-mentioned introduction of ethylene was continued So that this pressure solution and 80 ml of dry toluene, and the content was was maintained during the reaction. When 30 minutes Stirred. Ethylene was introduced in the reactor to an extent elapsed while the temperature was maintained at 80° C., Such that the absolute pressure within the reactor reached 5 kg/cm, and the pressure was maintained at 5 kg/cm during water was injected by nitrogen into the reactor to deactivate 40 the catalyst and terminate the reaction. the reaction. When 30 minutes elapsed, water was injected The reactor was cooled to room temperature and then the by nitrogen into the reactor to deactivate the catalyst and preSSure was reduced to normal pressure. Any Solids Such as terminate the reaction. polyethylene were not found in the reaction liquid. The The reactor was cooled to room temperature and then the products contained in the reaction liquid and in the gas 45 preSSure was reduced to normal pressure. The products collected from the reactor were analyzed by gas chroma contained in the reaction liquid and in the gas collected from tography. The results are shown in Table 7. the reactor were analyzed by gas chromatography. The results are shown in Table 8. EXAMPLE 2.0 50 TABLE 8 Trimerization of ethylene was conducted by the same procedure as described in Example 19 except that the Example 21 amount of the triisobutylaluminum/toluene Solution was Catalyst: changed to 2.4 ml with all other conditions remaining the 55 same. The results are shown in Table 7. Cr complex G (umol) 4.0 Alkyl metal compound i-Bus Al TABLE 7 (umol) 960 Solvent Toluene Reaction conditions: Example 19 2O 60 Catalyst: Temperature (C.) 8O Pressure (kg/cm) 5 Cr complex F F Time (min) 3O (umol) 4.0 4.0 Results: Alkyl metal compound i-BusAl i-Bus Al (umol) 960 590 65 Catalytic activity 1,637 Radical anion Na-na Na-na (g-1-hexenefg-Cr h) US 6,337,297 B1 30
TABLE 8-continued (3) Example 21 p.-1. Oligomers (wt.%) 98.3 Solid (PE) (wt.%) 1.7 Products in oligomers: C4 (wt.%) 3.0 whereina, b and c independently represent an integer C6 (wt.%) 94.9 C8 (wt.%) O.O of 0 to 6; u represents an integer of 0 or 1; each D C10 (wt.%) 0.4 independently represents a divalent hydrocarbon C12+ (wt.%) O.O group which may have a Substituent; each Linde Purity of C6 (wt.%) 99.4 pendently represents a Substituent containing an ele Note Abbreviations are the same as defined in the preceding tables ment of group 14, 15, 16 or 17 of the periodic table, 15 with the proviso that all of the three Lifs are not concurrently a Substituent containing an element of What is claimed is: group 14 or 17; G represents a nitrogen or phos 1. A catalyst for trimerization of ethylene which com phorus atom when u is 0 or a phosphorus atom when prises: u is 1, and R represents an oxygen or Sulfur atom. 2. The catalyst for trimerization of ethylene according to (a) a chromium complex having a neutral multidentate claim 1, wherein the neutral multidentate ligand is facially ligand having a tripod Structure, represented by the coordinated in the chromium complex. following formula (1): 3. The catalyst for trimerization of ethylene according to claim 1, which further comprises (d) a radical anion com ACrO3, (1) 25 pound. 4. The catalyst for trimerization of ethylene according to wherein A is a neutral multidentate ligand having a tripod claim 1, wherein the alkyl group containing compound is Structure, J is a carbonyl ligand or a halogen atom, n is an represented by the following formula (4): integer of 0 to 3, and Q is at least one member Selected from the group consisting of a hydrogen atom, a hydrocarbon REX (4) group having 1 to 10 carbon atoms, a carboxylate group wherein p and q are numbers Satisfying the formulae: 0