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(11) | EP 1 999 165 B9 |
| (12) | CORRECTED EUROPEAN PATENT SPECIFICATION |
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TRANSITION METAL COMPLEX, CATALYST COMPOSITION INCLUDING THE SAME AND OLEFIN POLYMER USING CATALYST COMPOSITION ÜBERGANGSMETALLKOMPLEX, KATALYSATORZUSAMMENSETZUNG DAMIT UND OLEFINPOLYMER MIT DER KATALYSATORZUSAMMENSETZUNG COMPLEXE DE MÉTAL DE TRANSITION, COMPOSITION CATALYTIQUE COMPRENANT CE COMPLEXE ET POLYMÈRE OLÉFINIQUE FAISANT APPEL À CETTE COMPOSITION CATALYTIQUE |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Technical Field
[0001] The present invention relates to a novel transition metal complex where a monocyclopentadienyl ligand to which an amido group is introduced is coordinated, a catalyst composition including the same, and an olefin polymer using the catalyst composition, and more particularly, to a novel transition metal complex containing a phenylene bridge, a catalyst composition including the same, and an olefin polymer using the catalyst composition.
Background Art
[0002] In the early 1990s, Do5.21w Chemical Co. developed Me2Si(Me4C5)(NtBu)TiCl2 (Constrained-Geometry Catalyst, hereinafter referred to as CGC) (US Patent No. 5,064,802). CGC shows excellent properties in a copolymerization reaction of ethylene and α-olefin, compared to conventional metallocene catalysts. For example, (1) CGC can be used to form high molecular weight polymers due to its high reactivity at high polymerization temperature, and (2) CGC can be used for copolymerization of α-olefin having large steric hindrance, such as 1-hexene and 1-octene. Due to many useful properties, in addition to these properties described above, obtained from use of CGC, research into synthesis of CGC derivatives as a polymerization catalyst is substantially increasing in academic and industrial fields.
[0003] For example, synthesis of metal complexes comprising other various bridges instead of a silicon bridge and containing a nitrogen substituent, and polymerization using these metal complexes were performed. Examples of such metal compounds include Complexes 1 through 4 (Chem. Rev. 2003, 103, 283).
[0005] Complexes 1 through 4 respectively contain a phosphorus bridge, an ethylene or propylene bridge, a methylidene bridge, and a methylene bridge, instead of the silicon bridge of the CGC structure. However, these complexes show low activity or poor copolymerization performance when ethylene is polymerized or when ethylene and α-olefin are copolymerized, compared to CGC.
[0006] In addition, the amino ligand in CGC can be replaced with an oxido ligand. Some of such complexes were used for polymerization. Examples of such complexes include the following Formulae.
[0008] In Complex 5, which was developed by T. J. Marks et al., a cyclopentadiene (Cp) derivative is bridged to an oxido ligand by ortho-phenylene group (Organometallics 1997, 16, 5958). A complex having the same bridge and polymerization using the complex were suggested by Mu et al. (Organometallics 2004, 23, 540). A complex in which an indenyl ligand is bridged to an oxido ligand by an ortho-phenylene group was developed by Rothwell et al. (Chem. Commun. 2003, 1034). In Complex 6, which was developed by Whitby et al., a cyclopentadienyl ligand is bridged to an oxido ligand by three carbon atoms (Organometallics 1999, 18, 348). It was reported that Complex 6 showed reactivity in syndiotactic polystylene polymerization. Similar complexes to Complex 6 were developed by Hessen et al. (Organometallics 1998, 17, 1652). Complex 7, which was developed by Rau et al., showed reactivity when being used for ethylene polymerization and ethylene/1-hexene copolymerization at high temperature and high pressure (210 °C, 150Mpa) (J. Organomet. Chem. 2000, 608, 71). Complex 8, which has a similar structure to Complex 7 and was developed by Sumitomo Co. (US Patent No. 6,548,686), can be used for high temperature and high pressure polymerization.
[0009] However, only some of these catalysts described above are used commercially. Accordingly, there is still a need to develop a catalyst inducing high polymerization performance.
Disclosure of Invention
Technical Solution
[0012] The present invention also provides a catalyst composition including the transition metal complex.
[0014] The present invention also provides a method of preparing an olefin polymer using the catalyst composition.
[0016] According to an aspect of the present invention, there is provided a transition metal complex represented by Formula 1 below.
[0018] Here, R1s and R2s are each independently a hydrogen atom; a C1-20 alkyl, C6-20 aryl or silyl radical; a C2-20 alkenyl, C7-20 alkylaryl, or C7-20 arylalkyl radical; or a metalloid radical of Group 14 substituted with a C1-20 hydrocarbyl, wherein R1 and R2 can be connected to each other by an alkylidene radical containing a C1-20 alkyl or aryl radical to form a ring;
[0019] each of the R3s are independently a hydrogen atom; or a halogen radical; or a C 1-20 alkyl, C6-20 aryl, C1-20 alkoxy, C6-20 aryloxy, or amido radical, wherein at least two R3's can be connected to each other to form an aliphatic or aromatic ring;
[0022] Q1 and Q2 are each independently a halogen radical; a C1-20 alkylamido, or C6-20 arylamido radical; a C1-20 alkyl, C2-20 alkenyl, C6-20 aryl, C7-20 alkylaryl, or C7-20 arylalkyl radical; or a C 1-20 alkylidene radical.
[0025] Here, R4s and R5s are each independently a hydrogen atom; or a C1-20 alkyl, C6-20 aryl or silyl radical;
[0026] each of the R6s are each independently a hydrogen atom; or a C1-20 alkyl or C6-20 aryl radical; a C2-20 alkenyl, C7-20 alkylaryl or C7-20 arylalkyl radical; or a C1-20 alkoxyl, C6-20 aryloxyl or amido radical, wherein at least two R6's can be connected to each other to form an aliphatic or aromatic ring;
[0027] Q3 and Q4 are each independently a halogen radical; a C1-20 alkylamido or C6-20 arylamido radical; or a C1-20 alkyl radical; n is a integer such as 0 or 1; and
[0029] The transition metal complex represented by Formula 1 may be represented by one of the following Formulae.
[0033] According to another aspect of the present invention, there is provided an amine-based compound represented by Formulae 3 and 4 below.
[0036] According to another aspect of the present invention, there is provided a catalyst composition including: a transition metal complex represented by Formula 1; and at least one cocatalyst compound selected from the group consisting of compounds represented by Formulae 5, 6, and 7 below.
[0041] Here, each of the R8s are independently a halogen radical; a C1-20 hydrocarbyl radical; and a C1-20 hydrocarbyl radical substituted with a halogen atom, or a is an integer of 2 or greater.
[0047] Here, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; and each of the As are independently a C6-20 aryl or C1-20 alkyl radical in which at least one hydrogen atom is substituted with a halogen atom, or a C1-20 hydrocarbyl, C1-20 alkoxy, or phenoxy radical.
[0048] The transition metal complex represented by Formula 1 of the catalyst composition may be one of compounds represented by the following Formulae.
[0051] According to another aspect of the present invention, there is provided a method of preparing a catalyst composition including: bringing the transition metal complex represented by Formula 1 below into contact with a compound represented by Formula 5 or 6 below to obtain a mixture; and adding a compound represented by Formula 7 below to the mixture.
[0056] The transition metal complex represented by Formula 1 in the method of preparing the catalyst composition may be one of compounds represented by the following Formulae.
[0059] The molar ratio of the transition metal complex to the compound represented by Formula 5 or 6 may be in the range of 1:2 to 1:5000, and the molar ratio of the transition metal complex to the compound represented by Formula 7 may be in the range of 1:1 to 1:25.
[0060] According to another aspect of the present invention, there is provided a method of synthesizing an olefin polymer, wherein the catalyst composition is brought into contact with a monomer.
[0061] The monomer may be at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.
[0062] According to another aspect of the present invention, there is provided an olefin polymer synthesized using the method of synthesizing an olefin polymer.
[0063] The monomer that is used to synthesize the olefin polymer may include: ethylene; and at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
[0064] A transition metal complex according to an embodiment of the present invention has an amido group connected by a phenylene bridge, so that a sterically hindered monomer easily approaches the transition metal complex and a pentagon ring structure of the transition metal complex is stably maintained, compared to a conventional transition metal complex having a silicon bridge and an oxido ligand. By using a catalyst composition including the transition metal complex according to an embodiment of the present invention, a polyolefin copolymer having a very low density less than 0.910 g/cm3 can be obtained.
Advantageous Effects
[0065] A transition metal complex of the present invention has a pentagon ring structure having an amido group connected by a phenylene bridge in which a stable bond is formed in the vicinity of the metal site, and thus, a sterically hindered monomer can easily approach the transition metal complex. By using a catalyst composition including the transition metal complex according to the present invention, a linear low density polyolefin copolymer having a high molecular weight and a very low density polyolefin copolymer having a density of 0.910 g/cm3 or less can be produced in a polymerization of monomers having large steric hindrance. Further, the reactivity for the olefin monomer having large steric hindrance is excellent.
Best Mode
[0066] Hereinafter, the present invention will be described in detail by explaining embodiments of the invention.
[0067] A transition metal complex according to an embodiment of the present invention may be represented by Formula 1 below.
[0069] Here, R1s and R2s are each independently a hydrogen atom; a C1-20 alkyl, C6-20 aryl or silyl radical; a C2-20 alkenyl, C7-20 alkylaryl, or C7-20 arylalkyl radical; or a metalloid radical of Group 14 substituted with a C1-20 hydrocarbyl, wherein R1 and R can be connected to each other by an alkylidene radical containing a C1-20 alkyl or aryl radical to form a ring;
[0070] each of the R3s are independently a hydrogen atom; a halogen radical; or a C 1-20 alkyl, C6-20 aryl, C1-20 alkoxy, C6-20 aryloxy, or amido radical, wherein at least two R3 scan be connected to each other to form an aliphatic or aromatic ring;
[0073] Q1 and Q2 are each independently a halogen radical; a C1-20 alkylamido, or C6-20 arylamido radical; a C 1-20 alkyl, C2-20 alkenyl, C6-20aryl, C7-20 alkylaryl, or C7-20 arylalkyl radical; and a C1-20 alkylidene radical.
[0074] A metal site of the transition metal complex represented by Formula 1 according to the current embodiment of the present invention is connected to a cyclopentadienyl ligand which is connected to a phenylene bridge to which a ring shaped amido group is introduced. Thus, by its structural inherence the angle of Cp-M-N structure tends to be narrow, and a wide angle tends to be maintained in the Q1-M-Q2 structure to which a monomer approaches. In addition, compared to a CGC structure that includes a silicon bridge, the transition metal complex represented by Formula 1 has a stable and strong ring in which Cp, a phenylene bridge, nitrogen, and a metal site forms a pentagon structure. That is, a securer complex compound structure can be obtained since the nitrogen atom in the amido group is cyclically connected to the phenylene bridge through two bonds. Accordingly, when the complex compound which is activated by a cocatalyst such as methylaluminoxane or B(C6F5)3, is applied to the synthesis of polyolefin, a polyolefin which has a high activity, a high molecular weight, and a high degree of copolymerization can be obtained even at a high reaction temperature. In particular, a very low density polyolefin copolymer having a density of 0.910 g/cm3 or less as well as 0.910 - 0.930 g/cm3 can also be prepared since the structure of the catalyst can contain a great amount of α-olefin. Various substituents can be included in a cyclopentadienyl ring and a quinoline-based ring. Thus, the structures and properties of the polyolefin can be controlled since electronic and steric environments in the vicinity of the metal can be easily controlled. The transition metal complex according to the current embodiment of the present invention may be used to prepare a catalyst that is used to polymerize olefin monomers. However, use of the transition metal complex is not limited thereto.
[0075] The transition metal complex represented by Formula 1 may have a structure represented by Formula 2. The compound represented by Formula 2 can control electronic and steric environments in the vicinity of metal.
[0077] Here, R4s and R5s are each independently a hydrogen atom; and a C1-20 alkyl, C6-20 aryl or silyl radical;
[0078] each of the R6s are independently a hydrogen atom; a C1-20 alkyl or C6-20 aryl radical; a C2-20 alkenyl, C7-20 alkylaryl or C7-20 arylalkyl radical; and a C1-20 alkoxyl, C6-20 aryloxyl or amido radical, wherein at least two R6 scan be connected to each other to form an aliphatic or aromatic ring;
[0079] Q3 and Q4 are each independently a halogen radical; a C1-20 alkylamido or C 6-20 arylamido radical; and a C1-20 alkyl radical; n is a integer such as 0 or 1; and
[0081] The transition metal complex represented by Formula 1 or 2 may be one of the compounds represented by the following Formulae. These compounds can control electronic and steric environments in the vicinity of metal.
[0085] According to another embodiment of the present invention, there is provided an amine-based compound represented by Formulae 3 and 4 below as a ligand of the transition metal complex of Formula 1 or 2.
[0089] When these ligands are coordinated with metal, a phenylene bridge is formed, and nitrogen and cyclopentadiene are coordinated with metal. These compounds may be used as ligands of the transition metal complex. However, use of the compounds is not limited thereto. That is the compounds can be used in any applications.
[0090] According to an embodiment of the present invention, there is provided a catalyst composition including: a transition metal complex represented by Formula 1 or 2; and at least one cocatalyst compound selected from the group consisting of compounds represented by Formulae 5, 6, and 7 below.
[0094] Here, each of the R8s are independently a halogen radical; a C1-20 hydrocarbyl radical; or a C1-20 hydrocarbyl radical substituted with a halogen atom, and a is an integer of 2 or greater.
[0100] Here, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; and each of the As are independently a C6-20 aryl or C1-20 alkyl radical in which at least one hydrogen atom is substituted with a halogen atom, or a C1-20 hydrocarbyl, C1-20 alkoxy, or phenoxy radical.
[0101] The transition metal complex represented by Formula 1 of the catalyst composition may be one of the compounds represented by the following Formulae.
[0103] Here, each of the R7s are independently a hydrogen atom or a metal radical, and Q5 and Q6 are each independently a methyl, dimethylamido or chloride radical.
[0104] A method of preparing the catalyst composition according to an embodiment of the present invention includes: bringing the transition metal complex represented by Formula 1 into contact with a compound represented by Formula 5 or 6 to obtain a mixture; and adding a compound represented by Formula 7 to the mixture.
[0105] A method of preparing the catalyst composition according to another embodiment of the present invention includes bringing the transition metal complex represented by Formula 1 into contact with a compound represented by Formula 7.
[0106] In the former method, the molar ratio of the transition metal complex to the compound represented by Formula 5 or 6 may be in the range of 1:2 to 1:5,000, more preferably in the range of 1:10 to 1:1,000, and most preferably in the range of 1:20 to 1:500.
[0107] Meanwhile, the molar ratio of the transition metal complex to the compound represented by Formula 7 may be in the range of 1:1 to 1:25, more preferably in the range of 1:1 to 1:10, and most preferably in the range of 1:1 to 1:5.
[0108] When the molar ratio of the transition metal complex to the compound represented by Formula 5 or 6 is less than 1:2, the metal compound is insufficiently alkylated since the amount of an alkylating agent is too small. On the other hand, when the molar ratio of the transition metal complex to the compound represented by Formula 5 or 6 is greater than 1:5,000, the metal compound is alkylated, but excess alkylating agent can react with the activator of Formula 7 so that the alkylated metal compound is less activated. When the molar ratio of the transition metal complex to the compound represented by Formula 7 is less than 1:1, the amount of the activator is relatively small so that the metal compound is less activated. On the other hand, when the molar ratio of the transition metal complex to the compound represented by Formula 7 is greater than 1:25, the metal compound may be completely activated but excess activator remains, that is, the preparation process for the catalyst composition is expensive, and the obtained polymer purity is poor.
[0109] In the latter method, the molar ratio of the transition metal complex to the compound represented by Formula 7 may be in the range of 1:10 to 1:10,000, more preferably in the range of 1:100 to 1:5,000, and most preferably in the range of 1:500 to 1:2,000. When the molar ratio of the transition metal complex to the compound represented by Formula 7 is less than 1:10, the metal compound is insufficiently alkylated since the amount of an alkylating agent is relatively small. On the other hand, when the molar ratio of the transition metal complex to the compound represented by Formula 7 is greater than 1:10,000, the metal compound may be completely activated but excess activator remains, that is, the preparation process for the catalyst composition is expensive, and the obtained polymer purity is poor.
[0110] A reaction solvent used in the preparation of the activated catalyst composition may be a hydrocarbon solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene and toluene, but is not limited thereto and any solvent that is used in the art can be used.
[0111] In addition, the transition metal complex represented by Formula 1 or 2 and the cocatalyst may be loaded on silica or alumina.
[0112] The compound represented by Formula 5 may be an alkylaluminoxane, more preferably one of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and most preferably methylaluminoxane.
[0113] The compound represented by Formula 6 may be one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, trip-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, dripropylboron, and tributylboron, and more preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum.
[0114] Examples of the compound represented by Formula 7 may include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N- diethylanilinium tetraphenylboron, N,N-diethyl anilinium tetraphenylboron, N,N-diethyl anilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tripropylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluo romethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tributylammoniumtetrapentafluorophenylaluminum, NN-diethyl anilinium tetraphenylaluminum, N,N-diethyl anilinium tetraphenylaluminum, N,N-diethyl anilinium tetrapentafluorophenylaluminum, diethylammoniumtetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethyl anilinium tetraphenylboron, N,N-diethyl anilinium tetraphenylboron, N,N-diethyl anilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, and triphenylcarboniumtetrapentafluorophenylboron.
[0115] According to an embodiment of the present invention, there is provided a method of synthesizing an olefin polymer using the catalyst composition.
[0116] In the method, the catalyst composition including a transition metal complex represented by Formula 1 or 2 and at least one compound selected from the group consisting of compounds represented by Formulae 5, 6, and 7 is brought into contact with an olefin-based monomer to prepare a p olyolefin homopolymer or copolymer.
[0117] The transition metal complex that is used in the method of preparing the homopolymer or copolymer may be represented by one of the following Formulae.
[0121] A polymerization process using the catalyst composition may be a solution process, but when the catalyst composition is used together with an inorganic support, such as silica, the polymerization process can also be a slurry or gas phase process.
[0122] In the method, the catalyst composition may be dissolved or diluted in a solvent suitable for olefin polymerization, before being used. Examples of the solvent may include a C5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane, and derivatives thereof; an aromatic hydrocarbon solvent such as toluene or benzene; and a hydrocarbon solvent substituted with a chlorine atom such as dichloromethan or chlorobenzene. The solvent may be treated with a small amount of alkylaluminum to eliminate a small amount of water and air which poison the catalyst composition, or a cocatalyst can further be used.
[0123] Examples of the olefin-based monomer which is polymerized using the metal complexes and the cocatalysts may include α-olefin and a cyclic olefin. A diene olefin-based monomer or a triene olefin-based monomer which have at least two double bonds may also be polymerized. Examples of the olefin-based monomer or triene olefin-based monomer may include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenylnorbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, divinylbenzene, and 3-chloromethyl styrene. More than two of the monomers may be mixed and copolymerized.
[0124] In particular, the catalyst composition according to an embodiment of the present invention is used to copolymerize ethylene and 1-octene having large steric hindrance at a high reaction temperature of 90 °C or higher to thereby obtain a copolymer having high molecular weight but having a very low density less than 0.910 g/cm3.
[0125] According to an embodiment of the present invention, there is provided an olefin polymer prepared using a method of synthesizing an olefm
[0126] The olefin polymer may be a homopolymer or a copolymer. When the olefin polymer is a copolymer of ethylene and a comonomer, the monomer may be at least one copolymer selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
[0127] The present invention will be described in greater detail with reference to the following examples.
[0129] Organic reagents and solvents were obtained from Aldrich Co., Inc. and Merck Co., Inc. and purified using a standard method. Each process for the synthesis was performed while isolated from air and moisture to improve reproducibility of experiments. The structure of compounds produced in the following examples was identified using a 400 MHz nuclear magnetic resonance (NMR) and an X-ray spectrometer.
[0132] 1.16 g (7.90 mmol) of 6-methyl-1,2,3,4-tetrahydroquinoline was dissolved in 4 ml of carbon tetrachloride and the solution was cooled to -20 °C. 1.41 g (7.90 mml) of solid-state N-bromosuccinimide was slowly added to the solution and the resultant mixture was reacted at room temperature for 5 hours. The product was filtered using a column chromatography with a MC/hexane (v:v = 1:1) solvent, and 0.71 g of pale yellow oil was obtained (40%).
[0133] 1 H NMR (C6D6): δ 1.42-1.52 (m, 2H, CH2), 2.00 (s, 3H, CH3), 2.39 (t, J = 6.4 Hz, 2H, CH2), 2.75 (dt, J = 2.8, 8.4 Hz, 2H, N-CH2), 4.04 (br s, 1H, NH), 6.51 (s, 1H, C6H2 ), 7.09 (s, 1H, C6H2) ppm. 13C{1H} NMR(C6D6): δ 20.06, 22.04, 27.60, 41.91, 108.84, 122.59, 126.16, 129.48, 130.67, 139.79 ppm. Anal. Calc. (C10H12BrN): C, 53.12; H, 5.35; N, 6.19 %. Found: C, 53.30; H, 5.13; N, 6.51 %.
[0136] 1.27 g (8.26 mmol) of 2-(dihydroxyboryl}-3,4-dimethyl-2-cyclopentene-1-one, 1.25 g (11.8 mmol) of Na 2CO3, 0.182 g (0.157 mmol) of Pd(PPh3)4, (Ph: phenyl group) and 7.87 mmol of 5-bromo-7-methyl-1,2,3,4-tetrahydroquinoline were mixed. 21 ml of degassed dimethylether (DME) and 7 ml of distilled water were added to the mixture. The resultant mixture was heated at 95 °C overnight. The reaction mixture was cooled to room temperature, and about twice extracted with 50 ml of ethylacetate. The product was filtered using a column chromatography with a hexane/ethylacetate (v:v =2:1) solvent, and a pale yellow solid product was obtained (90%).
[0137] 1H NMR (C6D6): δ 0.77 (d, J = 7.2 Hz, 3H, CH3), 1.59-1.70 (m, 2H, CH2CH 2CH2 ), 1.65 (s, 3H, CH3), 1.84 (dd, J = 2.4, 18.4 Hz, 1H, OCCH2), 2.21 (s, 3H, CH3), 2.20-2.30 (m, 1H, CH), 2.44 (dd, J = 6.4, 18.4 Hz, 1H, OCCH2), 2.60 (br t, J = 6 Hz, 2H, CH2), 2.97 (br t, J = 5.6 Hz, 2H, N-CH 2), 4.06 (s, 1H, NH), 6.66 (s, 1H, CH, C 6H2 ), 6.74 (s, 1H, C6H2) ppm. 13C{1H} NMR(C6D6): δ 15.83, 19.06, 20.58, 22.51, 27.92, 37.52, 42.48, 43.55 ppm. Anal. Calc. (C 17 H21 NO): C, 79.96; H, 8.29; N, 5.49 %. Found: C,80.17; H, 8.44; N, 5.75 %.
[0140] 21.4 mmol of anhydrous La(OTf)3, (Tf: triflate) was mixed with 24 ml of tetrahydrofuran (THF) and the mixture was cooled to -78 °C. 13.4 ml (21.4 mmol) of MeLi (Me: methyl) was added to the mixture and reacted for about 1 hour. 7.13 mmol of 5-(3,4-dimethyl-2-cyclopentene-1-one)-7-methyl-1,2,3,4-tetrahydroquinoline was added to the mixture and reacted at -78 °C for 2 hours. The resultant mixture was extracted using water and acetate. The obtained organic layer was added to 20 ml (2N) of HCl and the mixture was shaken for 2 minutes. The resultant mixture was neutralized with 20 ml of NaHCO3 water solution and dried with MgSO4. The product was filtered using a column chromatography with hexane/ethylacetate (v:v =10:1) solvent, and a pale yellow solid product was obtained (40%).
[0141] 1H NMR (C6D6): δ 1.66-1.71 (m, 2H, CH2 CH2 CH2), 1.80 (s, 3H, CH3), 1.89 (s, 3H, CH3), 1.90 (s, 3H, CH3), 2.24 (s, 3H, CH3), 2.64 (br t, J = 6.4 Hz, 2H, CH2), 2.74 (d, J = 2 Hz, 2H, CH2), 2.86-2.92 (m, 2H, N-CH2), 3.62 (br s, 1H, NH), 6.75 (s, 1H, C6 H2), 6.77 (s, 1H, C6H2) ppm. 13C{1H} NMR(C6D6): δ 11.85, 13.61, 14.39, 20.74, 22.86, 27.70, 42.20, 48.88, 120.81, 122.01, 124.78, 128.68, 129.36, 132.87, 136.36, 136.65, 140.75, 141.15 ppm.
[0143] ([(7-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl-eta5,kapa-N]titanium bis(dimethylamide)) compound
[0144] 0.696 mmol of 5-(2,3,5-trimethyl-1,3-cyclopentadienyl)-7-methyl-1,2,3,4-tetrahydroquinoline ligand and 0.156 g (0.696 mmol) of Ti(NMe2)4 were dissolved in 2 ml of toluene. The mixture was reacted at 80 °C for two days. After the solvents were eliminated, a red solid product was obtained (100%). The obtained titanium compound was identified through 1H-NMR spectroscope.
[0145] 1H NMR (C6D6): δ1.69-1.74 (m, 2H, CH2 CH2 CH2), 1.86 (s, 3H, CH3), 1.88 (s, 3H, CH3), 1.92 (s, 3H, CH3), 2.31 (s, 3H, CH3), 2.57 (t, J = 5.6 Hz, 2H, CH2), 2.95 (s, 6H, NCH3), 3.27 (s, 6H, NCH3), 4.02 (ddd, J = 5.2, 7.2, 12.0 Hz, 1H, NCH2), 4.24 (dt, J= 5.2, 12.4Hz, 1H, NCH2), 5.78 (s, 1H, Cp-H), 6.77 (s, 1H, C6H2), 6.91 (s, 1H, C6H2) ppm.
[0147] ([(7-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl-eta5,kapa-N]titanium dichloride) compound
[0148] 2 ml of toluene was added to the bis(dimethylamido)titanium compound that was obtained in Example 4. 0.269 g (2.09 mmol) of Me2SiCl2 was added to the mixture at room temperature and the mixture was reacted for about 4 hours. The obtained product was recrystallized in hexane at -30 °C and 0.183 g of a pure red solid product was obtained (66%).
[0149] 1H NMR (C6D6): δ1.36 - 1.44 (m, 2H, CH2 CH2 CH2), 1.76 (s, 3H, CH3), 1.85 (s, 3H, CH3), 2.07 (s, 3H, CH3), 2.18 (s, 3H, CH3), 2.12 (t, J = 4Hz, 2H, CH2), 4.50-4.70 (m, 2H, N-CH2), 6.02 (s, 1H, Cp-H), 6.59 (s, 1H, C6H2), 6.78 (s, 1H, C6H2) ppm. 13C{1 H} NMR (C6D6): 12.76, 14.87, 15.06, 21.14, 22.39, 26.32, 54.18, 117.49, 120.40, 126.98, 129.53, 130.96, 131.05, 133.19, 143.22, 143.60, 160.82 ppm. Anal. Calc. (C18 [150] H21Cl2NTi): C, 58.41; H, 5.72; N, 3.78%. Found: C, 58.19; H, 5.93; N, 3.89 %.
[0152] 957 mg (7.185 mmol) of 1,2,3,4-tetrahydroquinoline was dissolved in 10 ml of THF, and stirred at -78 °C for 30 minutes. 2.87ml (7.185mmol) of nBuLi was added thereto using a syringe under a nitrogen atmosphere (yellow suspension). The mixture was sufficiently stirred for 3 hours, and the temperature was increased to -20 °C to eliminate the gas. The temperature was cooled again to -78 °C and CO2 was injected to the mixture (The color of the mixture turned to colorless white). The temperature was increased to -20 °C and the remaining CO2 was eliminated in vacuum for 1 hour. Then, 5.07 ml (8.622 mmol) of tert-butyllitium (BuLi) was added to the mixture (The color of the mixture turned to red). While the temperature was maintained at -20 °C , the mixture was sufficiently stirred for 2 hours, and 26.1 ml (8.622 mmol) of 0.33 M CeCl3 2LiCl solution dissolved in THF and 1.182 g (8.622 mmol) of tetramethyl cyclopentenone were added to the mixture under a nitrogen atmosphere. While the temperature was gradually increased to room temperature, the solvents were eliminated by venting. Then, the mixture was titurated using pentane under a nitrogen atmosphere and filtered to obtain a white crystalline powder (41 %).
[0153] 1H NMR(C6D6):δ 1.00(d, J = 6.4 Hz, 3H, Cp-CH3), 1.66 - 1.74(m, 2H, quinoline-CH2), 2.64(t, J = 6.0 Hz, 2H, quinoline-CH2), 2.78-2.98(m, 2H, quinoline-CH), 3.05(br s, 1H, Cp-H), 3.76(br s, 1H, N-H), 6.76(t, J = 7.2 Hz, 1H, quinoline-CH), 6.91(d, J = 5.6 Hz, 1H, quinoline-CH), 6.93(d, J = 7.2 Hz, 1H, quinoline-CH)ppm
[0155] ([(1,2,3,4-Tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kapa-N] titanium dimethyl) compound
[0156] 220 mg (0.792 mmol) of 2.5 M n-butyllitium (n-BuLi) was gradually added to a cold (-30 °C) solution of 100 mg (0.396 mmol) of the obtained compound in Example 6 dissolved in ether while stirring. The temperature of the mixture was increased to room temperature. The resultant mixture was reacted for 6 hours, filtered, and washed several times with ether. Then the ether was evaporated in vacuum to obtain 90 mg of a pale yellow solid product (dilithium salt compound). It was identified that 0.43 equivalent of ether was coordinated (77%) through1H NMR and 13C NMR spectroscope.
[0157] 1H NMR(C6D6):δ 2.03(br s, 2H, Quinoline-CH2), 2.16(br s, 12H, Cp-CH3), 3.14(br s, 2H,Qnoline-CH2 ), 3.85(br s, 2H, Quinoline-CH2), 6.33(t, J= 6.4 Hz, 1H, Quinoline-CH), 6.95(d, J = 0.8 Hz, Quinoline-CH),7.32(br s, 1H, Quinoline-CH)ppm.
[0158] 66 mg (0.235 mmol) of TiCl4.DME was mixed with ether at -30 °C and the mixture was placed in a refrigerator for about 1 hour. Then, 3 ml (0.470 mmol) of 1.4 M methyllithium (MeLi) was gradually added to the mixture while stirring. After stirring for 15 minutes, 70 mg (0.235 mmol) of dilithium salt compound was added to the mixture. The mixture was reacted for 3 hours while stirring at room temperature. Then the solvent was evaporated in vacuum and the mixture was dissolved in pentane and filtered. The pentane in the resultant mixture was evaporated under a vacuum, and thus 52 mg of dark brown titanium complex was obtained (67%).
[0159] 1H NMR(C6D6):δ 7.00 (d, J = 7.6 Hz, 1H), 9.92 (d, J = 7.6 Hz, 1H), 6.83 (t, J = 7.6 Hz, 1H), 4.53 (m, 2H), 2.47 (t, J = 6.4 Hz, 2H), 2.05 (s, 6H), 1.66 (s, 6H), 1.76-1.65 (m, 2H), 0.58 (s, 6H).
[0162] Yellow oil was obtained in the same manner as in Example 6, except that indenone was used instead of tetramethyl cyclopentenone and the product was filtered using a column chromatography with a hexane/ethyl acetate (v:v = 20:1) solvent (Yield: 49%).
[0163] 1H NMR(C6D6) : δ 1.58-1.64 (m, 2H, quin-CH2), 2.63 (t, J = 6.8 Hz, 2H, quin-CH2) , 2.72-2.77 (m, 2H, quin-CH2), 3.17 (d, J = 2.4 Hz, 2H, indenyl-CH2), 3.85 (br s, 1H, N-H), 6.35 (t, J = 2.0 Hz, 1H, indenyl-CH), 6.76 (t, J = 7.6 Hz, 1H, quin-CH), 6.98 (d, J = 7.2 Hz, 1H, quin-CH), 7.17 (td, J = 1.6, 7.2 Hz, 1H, quin-CH), 7.20 (td, J = 1.6, 7.2 Hz, 2H, indenyl-CH), 7.34 (d, J = 7.2 Hz, 1H, indenyl-CH), 7.45 (dd, J = 1.2, 6.8 Hz, 1H, indenyl-CH)ppm. 13C NMR(C6D6) : δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm.
[0166] A dilithium salt compound was obtained in the same manner as in Example 7 using 5-indenyl-1,2,3,4-tetrahydroquinoline (Yield: 95%).
[0167] 1H NMR(C6D6) : δ 2.02 (t, J = 4.8 Hz, 2H, quin-CH2), 3.15 (t, J = 5.6 Hz, 2H, quin-CH2), 3.94 (br s, 2H, quin-CH2), 6.31 (t, J = 7.2 Hz, 1H, indenyl-CH), 6.76-6.83 (m, 2H, quin-CH), 6.99 (t, J =7.2, 2.0 Hz, 2H, quin-CH), 7.48 (d, J = 7.2 Hz, 2H, indenyl-CH), 8.02 (t, J = 8.0 Hz, 2H, indenyl-CH) ppm.
[0168] A titanium compound was prepared using the obtained dilithium salt compound in the same manner as in Example 7 (Yield: 47%).
[0169] 1H NMR(C6D6) : δ -0.01 (s, 3H, Ti-CH3), 0.85 (s, 3H, Ti-CH3), 1.56-1.68 (m, 2H, quin-CH2), 2.43 (t, J = 6.4 Hz, 2H, quin-CH2), 6.30 (d, J = 3.6 Hz, 1H, indenyl-CH), 6.61 (d, J = 3.6 Hz, 1H, indenyl-CH), 6.70 (ddd, J =0.8, 6.8, 8.4 Hz, 1H, indenyl-CH), 6.85 (t, J = 7.6 Hz, 1H, quin-CH), 6.95 (tt, J = 0.8, 6.8 Hz, 1H, quin-CH), 7.01 (tdd, J = 0.8, 6.8, 8.4 Hz, 2H, indenyl-CH), 7.13-7.17 (m, 1H, quin-CH), 7.48 (d, J= 8.4 Hz, 1H, indenyl-CH) ppm. 13C NMR(C6D6) : δ 22.83, 27.16,49.35, 55.12, 58.75, 103.36, 119.63, 120.30, 123.18, 125.26, 125.60, 127.18, 127.36, 127.83, 129.13, 129.56, 135.10, 161.74ppm.
[0172] A yellow solid compound was obtained in the same manner as in Example 6, except that fluorenone was used instead of tetramethyl cyclopentenone and the product was filtered using a column chromatography with a hexane/ethyl acetate (v:v = 20:1) solvent and recrystallized in diethyl ether (Yield: 56%).
[0173] 1H NMR(C6D6) : δ 1.20 (t, J = 7.6 Hz, 2H, quin-CH2), 1.71 (s, 1H, xx), 2.29 (s, 2H, quin-CH), 2.38(t, J = 6.0 Hz, 2H, quin-CH), 2.64 (s, 1H, quin-CH), 2.72 (s, 2H, quin-CH2), 2.30 (s, 1H, N-H), 3.82 (s, 0.5H, N-H), 4.81 (s, 1H, quin-CH), 6.42 (d, J = 7.2 Hz, 2H, quin-CH), 6.81 (t, J= 7.2 Hz, 1H, quin-CH), 6.94 (dd, J=1.2, 7.2 Hz, 1H, quin-CH), 7.10 (d, J = 7.6 Hz, 2H, fluorenyl-CH), 7.23 (t, J = 7.2 Hz, 2H, fluorenyl-CH), 7.32(d, J = 7.6 Hz, 2H, fluorenyl-CH), 7.42 (d, J = 6.8 Hz, 1H, quin-CH), 7.67 (d, J = 7.2 Hz, 2H, fluorenyl-CH)ppm.
[0176] A dilithium salt compound was obtained in the same manner as in Example 7 using 5-fluorenyl-1,2,3,4-tetrahydroquinoline (Yield: 94%).
[0177] 1H NMR(C6D6) : δ 2.17 (s, 2H, quin-CH2), 3.29-2.26 (m, 2H, quin-CH2), 4.11 (br s, 2H, quin-CH2), 6.31 (t, J = 7.2 Hz, 1H, quin-CH), 6.91 (t, J = 7.6 Hz, 2H, fluorenyl-CH), 6.99 (d, J = 7.2 Hz, 1H, quin-CH), 7.12 (t, J = 6.8 Hz, 2H, fluorenyl-CH), 7.58 (dd, J = 1.2, 7.6 Hz, 1H, quin-CH), 8.15 (d, J = 8.0 Hz, 2H, fluorenyl-CH), 8.57(d, J = 8.0 Hz, 2H, fluorenyl-CH)ppm.
[0178] A titanium compound was prepared using the obtained dilithium salt compound in the same manner as in Example 7 (Yield: 47%).
[0179] 1H NMR(C6D6) : δ 0.14 (s, 6H, Ti-CH3), 1.56-1.68 (m, 2H, quin-CH), 2.48 (t, J = 6.4 Hz, 2H, quin-CH2), 4.18-4.30 (m, 2H, quin-CH2), 6.88-6.96 (m, 3H, CH), 7.04 (d, J = 7.6 Hz, 1H, quin-CH), 7.10 (ddd, J = 1.2,6.8, 8.4 Hz, 2H, fluorenyl -CH), 7.17 (dd, J = 0.8, 8.4 Hz, 2H, fluorenyl-CH), 7.28 (d, J = 7.2 Hz, 1H, quin-CH), 7.94 (dd, J = 0.8, 8.4 Hz, 2H, fluorenyl-CH) ppm. 13C NMR(C6D6): δ 14.54, 22.76, 27.26, 48.58, 59.65, 111.21, 118.69, 118.98 120.17, 123.34, 123.67, 126.16, 126.42, 127.75, 129.29, 129.41, 137.28, 160.63ppm.
[0182] Yellow oil was obtained in the same manner as in Example 6, except that indoline was used instead of 1,2,3,4-tetrahydroquinoline and the product was filtered using a column chromatography with a hexane/ethyl acetate (v:v = 20:1) solvent (Yield: 15%).
[0183] 1H NMR(C6D6) : δ 0.99 (d, J = 7.6 Hz, 1H, Cp-CH), 1.82 (s, 3H, Cp-CH3), 1.87 (s, 6H, Cp-CH3), 2.68 - 2.88 (m, 2H, ind-CH2), 2.91 - 2.99 (m , 1H, Cp-CH), 3.07 - 3.16 (m, 3H, ind-CH2 N-H), 6.83 (t, J= 7.4 Hz, 1H, ind-CH), 6.97 (d, J = 7.6 Hz, 1H, ind-CH), 7.19 (d, J=6.8 Hz, 1H, ind-CH) ppm.
[0186] A titanium compound was prepared using 7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline in the same manner as in Example 7 (Yield: 71 %).
[0187] 1 H NMR(C6D6) : δ 0.69 (s, 6H, Ti-CH3), 1.71 (s, 6H, Cp-CH3), 2.04 (s, 6H, Cp-CH3), 2.73 (t, J = 8.0 Hz, 2H, ind-CH2), 4.67 (t, J = 8.0 Hz, 2H, ind-CH2), 6.82 (t, J = 7.2 Hz, 1H, ind-CH), 7.00 (t, J = 7.2 Hz, 2H, ind-CH) ppm. 13C NMR(C6D6) : δ 12.06, 12.15, 32.24, 54.98, 56.37, 120.57, 120.64, 121.54, 124.02, 126.52, 126.81, 136.75ppm.
[0190] 2-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline was obtained in the same manner as in Example 6, except that 5.02 g (34.1 mmol) of 1,2,3,4-tetrahydroquinaldine was used instead of 1,2,3,4-tetrahydroquinoline (Yield: 51%).
[0191] 1H NMR(CDCl3): δ 6.89(d, J=7.2Hz, 1H, CH), δ 6.74(d, J=7.2Hz, 1H, CH), δ 6.57(t, J=7.4Hz, 1H, CH), δ 3.76(br s, 1H, NH), δ 3.45(br s, 1H, Cp-CH), δ 3.32(m, 1H, quinoline-CH), δ 3.09-2.70(m, 2H, quinoline-CH2), δ 1.91(s, 3H, Cp-CH3), δ 1.87(s, 3H, Cp-CH3),δ 1.77(s, 3H, Cp-CH3),δ 1.67-1.50(m, 2H, quinoline-CH2), δ 1.17(d, J=6.4Hz, 3H, quinoline-CH6), δ 0.93(d, J=7.6Hz, 3H, Cp-CH3) ppm.
[0193] [(2-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopenta-dienyl-eta5, kapa-N]titanium dimethyl
[0194] 4.92 g of pale yellow solid (dilithium salt compound) to which 1.17 equivalent of diethyl ether was coordinated was obtained in the same manner as in Example 7 using 4.66 g (17.4 mmol) of 2-methyl-8-(2,3,4,5-tetramethyl- 1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (Yield: 77%).
[0195] 1H NMR(Pyridine-d8): δ 7.37(br s, 1H, CH), δ 7.05(d, J=6Hz, 1H, CH), δ 6.40(t, J=6.8Hz, 1H, CH), δ 3.93(br s, 1H, CH), δ 3.27(m, 1H, CH), δ 3.06(m, 1H, CH), δ 2.28-2.07(m, 12H, Cp-CH3), δ 1.99(m, 1H, CH), δ 1.78(m, 1H, CH), δ 1.18(d, J= 5.6Hz, quinoline-CH3) ppm.
[0196] 0.56 g of a titanium compound was prepared in the same manner as in Example 7using 1.00 g (2.73 mmol) of the obtained dilithium salt compound (Yield: 60%).
[0197] 1H NMR(CDCl3): δ 6.95(d, J=8Hz, 1H, CH), δ 6.91(d, J=8Hz, 1H, CH), δ 6.73(t, J=8Hz, 1H, CH), δ 5.57(m, 1H, CH), δ 2.83( m, 1H, CH), δ 2.55(m, 1H, CH), δ 2.24(s, 3H, Cp-CH3), δ 2.20(s, 3H, Cp-CH3), δ 1.94-1.89(m, 1H, CH), δ 1.83-1.75(m, 1H, CH), 81.70(s, 3H, Cp-CH3), δ 1.60(s, 3H, Cp-CH3), δ 1.22(d, J=6.8Hz, 3H, quinoline-CH3), δ 0.26(d, J=6.8Hz, 6H, TiMe2-CH3) ppm.
[0200] 6-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline was obtained in the same manner as in Example 6 except that 5.21 g (35.4 mmol) of 6-methyl-1,2,3,4-tetrahydroquinoline was used instead of 1,2,3,4-tetrahydroquinoline (Yield: 34%).
[0201] 1H NMR(CDCl3): δ 6.70(s, 1H, CH), δ 6.54(s, 1H, CH), δ 3.71(br s, 1H, NH), δ 3.25-3.05(m, 3H, Cp-CH, quinoline-CH2), δ 2.76(t, J=6.4Hz, 2H, quinoline-CH2), δ 2.19(s, 3H, CH3), δ 1.93-1.86(m, 2H, quinoline-CH2), δ 1.88(s, 3H, Cp-CH3), δ 1.84(s, 3H, Cp-CH3), δ 1.74(s, 3H, Cp-CH3), δ 0.94(br d, J=6.8Hz, 3H, Cp-CH3) ppm.
[0203] [(6-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopenta-dienyl-eta5, kapa-N]titanium dimethyl
[0204] 2.56 g of pale yellow solid (dilithium salt compound) to which 1.15 equivalent of diethyl ether was coordinated was obtained in the same manner as in Example 7 using 3.23 g (12.1 mmol) of 6 -methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (Yield: 58%).
[0205] 1H NMR(Pyridine-d8): δ 7.02(br s, 1H, CH), δ 6.81(s, 1H, CH), δ 3.94(m, 2H, CH2) , δ 3.19(m, 2H, CH2), δ 252-2.10(m, 17H, CH2, quinoline-CH3, Cp-CH3) ppm.
[0206] 0.817 g of a titanium compound (58%) was prepared in the same manner as in Example 7 using 1.50 g (4.12 mmol) of the obtained dilithium salt compound.
[0207] 1H NMR(C6D6): δ 6.87(s, 1H, CH), δ 6.72(s, 1H, CH), δ 4.57(m, 2H, CH2), δ 2.45(t, J=6.2Hz, 2H, CH2), δ 2.24(s, 3H, quinoline-CH3), δ 2.05(s, 6H, Cp-CH3), δ [208] 1.72-1.66(m, 2H, CH2), δ 1.69(s, 6H, Cp-CH3), δ 0.57(s, 6H, TiMe2-CH3) ppm.
[0210] 2-Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was obtained in the same manner as in Example 6, except that 6.23 g (46.8 mmol) of 2-methylindoline was used instead of 1,2,3,4-tetrahydroquinoline (Yield: 19%).
[0211] 1H NMR(CDCl3): δ 6.97(d, J=7.2Hz, 1H, CH), δ 6.78(d, J=8Hz, 1H, CH), δ 6.67(t, J=7.4Hz, 1H, CH), δ 3.94(m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24-3.08(m, 2H, quinoline-CH2, Cp-CH), δ 2.65 (m, 1H, quinoline-CH2), δ 1.89(s, 3H, Cp-CH3), δ 1.84(s, 3H, Cp-CH3), δ 1.82(s, 3H, Cp-CH3), δ 1.13(d, J=6Hz, 3H, [212] quinoline-CH3), δ 0.93(3H, Cp-CH3) ppm.
[0214] A dilithium salt compound to which 0.58 equivalent of diethyl ether was coordinated was obtained in the same manner as in Example 7 using 2.25 g (8.88 mmol) of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (1.37 g, Yield: 50%).
[0215] 1H NMR(Pyridine-d8): δ 7.22(br s, 1H, CH), δ 7.18(d, J=6Hz, 1H, CH), δ 6.32(t, 1H, CH), δ 4.61 (br s, 1H, CH), δ 3.54(m, 1H, CH), δ 3.00(m, 1H, CH), δ 2.35-2.12(m ,13H, CH, Cp-CH3), δ 1.39(d, indoline-CH3) ppm.
[0216] A titanium compound was prepared using 1.37 g (4.44 mmol) of the obtained dilithium salt compound in the same manner as in Example 7.
[0217] 1H NMR(C6D6): δ 7.01-6.96(m, 2H, CH), δ 6.82(t, J=7.4Hz, 1H, CH), δ 4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H, Cp-CH3), δ 2.01(s, 3H, Cp-CH3), δ 1.70(s, 3H, Cp-CH3),δ 1.69(s, 3H, Cp-CH3),δ 1.65(d, J=6.4Hz, 3H, indoline-CH3), δ 0.71(d, J=10Hz, 6H, TiMe2-CH3) ppm.
[0220] Dimethylsilyl(t-butylamido)(tetramethylcyclopentadienyl)titanium dichloride was purchased from Boulder Scientific, Inc. (U.S.A.) and directly used for the ethylene copolymerization.
[0223] 30 ml of toluene and 0.3 M 1-hexene was added to a 250 ml Endrew reactor, and the reactor was preheated to a temperature of 90°C. 0.5 m mol of titanium transition metal complex prepared in Example 5 treated with 200 m mol of triisobutylaluminum compound and 2 m mol of trityl tetrakis(pentafluorophenyl)borate cocatalyst were sequentially added to the reactor. Then copolymerization was performed for 5 minutes, and then 4 bar of ethylene pressure was added to the catalyst tank. The remaining ethylene was eliminated and the polymer solution was added to excess ethanol to induce a precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and the resultant was dried at 80 °C for over 12 hours in a conventional oven.
[0225] 1.0 L of hexane solvent and an appropriate amount of 1-butene comonomer was added to a 2 L autoclave reactor. The reactor was heated to 90 °C , and the reactor was filled with 20 bar of ethylene. 2 m mol of titanium transition metal complex prepared in Example 5 treated with 100 m mol of triisobutylaluminum compound and 10 m mol of dimethyl anilinium tetrakis(pentafluorophenyl)borate cocatalyst were sequentially added to a catalyst injecting cylinder and injected into the reactor. Polymerization was performed for 10 minutes by continuously injecting ethylene in order to maintain the pressure of the reactor between 19 bar to 20 bar. Heat generated from the reaction was removed through cooling coil installed in the reactor and the temperature was maintained as constant as possible. After the polymerization, the polymer solution was discharged to the lower portion of the reactor and cooled using excess ethanol. The obtained polymer was dried for over 12 hours in a conventional oven.
[0227] 1.0 L of hexane solvent and an appropriate amount of 1-octene was added to a 2 L autoclave reactor. The reactor was preheated to 160 °C , and was filled with ethylene at a pressure of 28 bar. 5.0 m mol of titanium transition metal complex prepared in Example 5 treated with 1.25 m mmol of triisobutylaluminum compound and 25 m mol of trityl tetrakis(pentafluorophenyl)borate cocatalyst were sequentially added to a 25 ml catalyst storing tank and filled. Polymerization was performed for 10 minutes while 40 bar of ethylene was added to the catalyst tank. The remaining ethylene was eliminated and the polymer solution was added to excess ethanol to induce a precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and the resultant was dried at 80 °C for over 12 hours in a conventional oven.
[0229] 1.0 L of hexane solvent and an appropriate amount of 1-butene comonomer was added to a 2 L autoclave reactor. The reactor was heated to 150 °C , and the reactor was filled with 35 bar of ethylene. 1.0 m mol (Al/Ti = 25) of titanium transition metal complex treated with an appropriate amount of triisobutylaluminum compound and dimethyl anilinium tetrakis(pentafluorophenyl)borate cocatalyst (B/Ti = 5) were sequentially added to a catalyst injecting cylinder and injected into the reactor. Polymerization was performed for 10 minutes by continuously injecting ethylene in order to maintain the pressure of the reactor between 34 bar to 35 bar. Heat generated from the reaction was removed through cooling coil installed in the reactor and the temperature was maintained as constant as possible. After the polymerization, the polymer solution was discharged to the lower portion of the reactor and cooled using excess ethanol. The obtained polymer was dried for over 12 hours in a conventional oven.
[0231] Polymerization was performed in the same manner as in Example 20, except that the transition metal complex prepared in Comparative Example 1 was used instead of the transition metal complex prepared in Example 5.
[0233] Polymerization was performed in the same manner as in Example 21, except that the transition metal complex prepared in Comparative Example 1 was used instead of the transition metal complex prepared in Example 5.
[0235] Polymerization was performed in the same manner as in Example 22, except that the transition metal complex prepared in Comparative Example 1 was used instead of the transition metal complex prepared in Example 5.
[0237] Polymerization was performed in the same manner as in Example 23, except that the transition metal complex prepared in Comparative Example 1 was used instead of the transition metal complex prepared in Example 5.
Density)
[0239] A Melt Index (MI) of the polymers produced in Examples 1-10 and Comparative Examples 1-4 was measured using a ASTM D-1238 (Conditions: E, 190 °C , 2.16 Kg load). A melting point (Tm) of the polymers was measured using a Differential Scanning Calorimeter (DSC) 2920 produced by TA Inc. That is, the temperature was increased to 200 °C, maintained at 200 °C for 5 minutes, and decreased to 30°C. Then the temperature was increased again and the summit of the DSC curve was measured as the melting point. The temperature was increased and decreased by 10 °C /min, and the melting point was obtained in a second temperature increase period.
[0240] In order to measure the density of the polymers, a sample that had been treated with 1,000 ppm of an antioxidant was formed into a sheet having a thickness of 3 mm and a radius of 2 cm by a 180 °C press mold, and then the prepared sheet was cooled by 10 °C/min. The cooled sheet was measured using a mettler scale.
[0242] The properties of the copolymers prepared in Example 20 and Comparative Example 2 respectively using the transition metal complexes prepared in Example 5 and Comparative Example 1 were measured according to the experimental methods described above. The results are presented in Table 1.
[0243]
Table 1: Results of copolymerization of ethylene and 1-hexene
| Catalyst | 1-hexene (M) | Activity (Kg / mmol-Ti hr) | Molecular weighta (g /10 min) | Branch content (mol%) | |
| Example 20 | Example 5 | 0.3 | 21 | 81,000 | 24 |
| Comparative Example 2 | Comparative Example 1 | 0.3 | 12 | 113,000 | 15 |
| a weight average molecular weight (Mw) |
[0244] As shown in Table 1, a degree of copolymerization activity of catalyst of Example 5 of the present invention was higher compared to Comparative Example 1. The molecular weight of the copolymer of Example 20 was relatively small; however, the Branch content was very high, and thus it shows that the reactivity of catalyst of Example 5 for the olefin monomer having large steric hindrance such as 1-hexene is excellent.
[0246] The properties of the copolymers prepared in Example 21 and Comparative Example 3 respectively using the transition metal complexes prepared in Example 5 and Comparative Example 1 were measured according to the experimental methods. The results are presented in Table 2. According to the content of 1-butene, Example 9 was divided to Examples 21A and 21B.
[0247]
Table 2: Results of copolymerization of ethylene and 1-butene
| Catalyst | 1-Butene (M) | Activity (Kg/ mmol-Ti hr) | Melt indexa (g /10min) | Melt index b(g/10min) | Density (g /cm3) | |
| Example 21A | Example 5 | 0.8 | 216.0 | 0 | 3.62 | 0.864 |
| Example 21B | Example 5 | 1.2 | 280.2 | 1 | 27 | 0.857 |
| Comparati ve Example 3 | Comparati ve Example 1 | 1.2 | 340.5 | 3.10 | ∞ | 0.878 |
| aI2 value, bI21,6 value |
[0248] As shown in Table 2, the catalyst of Example 5 of the present invention had a lower copolymerization activity than that of Comparative Example 1 when ethylene was copolymerized with 1-butene. However, the molecular weight of the copolymer of Examples 21A and 21B was higher than that of Comparative Example 3. According to an embodiment of the present invention , the reactivity of catalyst of Example 5 for the olefin monomer having large steric hindrance such as 1-butene was relatively excellent since the density of the copolymer was very low. In particular, in Example 21 A, even though a smaller amount of 1-butene (0.8 M) was used, a polymer having lower density than Comparative Example 3 using 1.2 M 1-butene was obtained. Therefore, the catalyst according to an embodiment of the present invention showed excellent copolymerization reactivity.
[0250] The properties of the copolymers prepared in Example 22 and Comparative Example 4 respectively using the transition metal complexes prepared in Example 5 and Comparative Example 1 were measured according to the experimental methods descried above. The results are presented in Table 3. According to the content of 1-octene, Example 22 was divided to Examples 22A and 22B.
[0251]
Table 3: Results of copolymerization of ethylene and 1-octene
| Catalyst | Temperature(°C) | 1-octene (M) | Activity (Kg / mol-Ti hr) | Melt indexa (g /10min) | Melting point(°C ) | Density (g/cm3) | |
| Example 22A | Example 5 | 160 | 0.6 | 48.0 | 6.4 | 58.6 | 0.869 |
| Example 22B | Example 5 | 160 | 0.8 | 55.6 | 5.3 | 49.8 | 0.864 |
| Comparative Example 4 | Comparative Example 1 | 160 | 0.8 | 30.4 | 5.1 | 98.2 | 0.904 |
| aI2 value |
[0252] As shown in Table 3, the catalyst of Example 5 of the present invention had a higher copolymerization activity than that of Comparative Example 1 when ethylene was copolymerized with 1-octene. The molecular weight of the copolymer of Examples 22A and 22B was similar to that of Comparative Example 4. The reactivity of the catalyst of Example 5 for the olefin monomer having large steric hindrance such as 1-octene was relatively excellent since the melting point and density of the copolymer was low. In particular, in the present invention, even though a smaller amount of 1-octene (0.6 M) was used, a polymer having lower density than Comparative Example 4 using 0.8 M 1-octene was obtained. Therefore, the catalyst composition according to an embodiment of the present invention showed excellent copolymerization reactivity at a high temperature such as 160 °C.
[0254] The properties of the copolymers prepared in Example 23 and Comparative Example 5 respectively using the transition metal complexes prepared in Examples 7, 9, 11, 13, 15, 17, 19 and 2 and Comparative Example 1 were measured according to the experimental methods. The results are presented in Table 4.
[0255]
Table 4: Results of copolymerization of ethylene and 1-butene
| 1-Butene (M) | Activity (kg/mmol-Ti) | Melt indexa (g/10min) | Melt index b (g/10min) | Density (g /cm3) | ||
| Example 23A | Example 7 | 1.6 | 43.7 | 3.5 | 28.8 | 0.859 |
| Example 23B | Example 9 | 1.6 | 3.4 | 0 | 0 | 0.870 |
| Example 23C | Example 11 | 1.6 | 16.6 | 0 | 0 | 0.860 |
| Example 23D | Example 13 | 1.6 | 15.3 | 0 | 0.66 | 0.873 |
| Example 23E | Example 15 | 1.6 | 36.0 | 15.4 | ∞ | 0.862 |
| Example 23F | Example 17 | 1.6 | 29.8 | 1.3 | 12.5 | 0.860 |
| Example 23G | Example 19 | 1.6 | 22.1 | 0 | 0.8 | 0.873 |
| Comparative Example 5A | Comparative Example 1 | 1.6 | 30.5 | 5.9 | 59 | 0.900 |
| Example 23H | Example 2c | 1.2 | 57.5 | 0 | 1.3 | 0.881 |
| Comparative Example 5B | Comparative Example 1c | 1.2 | 44.1 | 0 | 1.2 | 0.902 |
| aI 2 value, bI21.6 value, c 120 °C polymerization |
[0256] As shown in Table 4, the catalyst of the present invention had relatively enhanced reactivity for the olefin monomer having large steric hindrance such as 1-butene since the molecular weight of the copolymer of Example 23 (23A∼23H) was higher than that of Comparative Example 5 (5A∼5B) and the density of the copolymer was lower than that of Comparative Example 5 (5A∼5B) when 1-butene was applied. Particularly, the catalyst compounds obtained in Examples 7, 15, and 17 had a similar or higher polymerization activity compared to catalyst compounds obtained in Comparative Example 1, and even at 120 °C , the catalyst compounds obtained in Example 2 showed a higher polymerization activity, a higher molecular weight, and a lower copolymer density compared to catalyst compounds obtained in Comparative Example 1. Therefore, the catalyst according to the present invention showed excellent polymerization reactivity.
[0257] Accordingly, the transition metal complex and the catalyst composition of the present invention including the transition metal complex had improved copolymerization reactivity in α-olefin polymerization compared to a conventional catalyst composition. Therefore, when the catalyst composition of the present invention was used in α-olefin copolymerization, a copolymer having lower density can be obtained. Therefore, when the catalyst composition of the present invention is used, a copolymer with a higher amount of α-olefin than the conventional catalyst composition can be obtained.
[0258] A transition metal complex of the present invention has a pentagon ring structure having an amido group connected by a phenylene bridge in which a stable bond is formed in the vicinity of the metal site, and thus, a sterically hindered monomer can easily approach the transition metal complex. By using a catalyst composition including the transition metal complex according to the present invention, a linear low density polyolefin copolymer having a high molecular weight and a very low density polyolefin copolymer having a density of 0.910 g/cm3 or less can be produced in a polymerization of monomers having large steric hindrance. Further, the reactivity for the olefin monomer having large steric hindrance is excellent.
Industrial Applicability
[0259] By using a catalyst composition including the transition metal complex according to the present invention, a linear low density polyolefin copolymer having a high molecular weight and a very low density polyolefin copolymer having a density of 0.910 g/cm3 or less can be produced in a polymerization of monomers having large steric hindrance.
1. A transition metal complex represented by Formula 1 below:
where, R 1S and R 2S are each independently one selected from the group consisting of: a hydrogen atom; a C 1-20alkyl radical, a C 6-20aryl radical, a silyl radical; a C 2-20alkenyl radical, a C 7-20alkylaryl radical, a C 7-20arylalkyl radical; and a metalloid radical of Group 14 substituted with a C 1-20hydrocarbyl, wherein R 1and R 2can be connected to each other by an alkylidene radical containing a C 1-2oalkyl or aryl radical to form a ring; each of the R 3s are independently one selected from the group consisting of: a hydrogen atom; a halogen radical; a C1-20 alkyl radical, a C 6-20aryl radical, a C 1-20alkoxy radical, a C 6-20aryloxy radical, and an amido radical, wherein at least two R 3s can be connected to each other to form an aliphatic or aromatic ring; CY1 is a substituted or unsubstituted aliphatic or aromatic ring;
M is a Group 4 transition metal; and Q 1and Q 2are each independently one selected from the group consisting of: a halogen radical; a C 1-20alkylamido radical, a C 6-20arylamido radical; a C 1-20alkyl radical, a C 2-20alkenyl radical, a C6-20 aryl radical, a C 7-20alkylaryl radical, a C 7-20arylalkyl radical; and a C 1-20 alkylidene radical.
2. The transition metal complex of claim 1, represented by Formula 2 below:
where, R 4s and R 5s are each independently one selected from the group consisting of: a hydrogen atom; and a C 1-20alkyl, C 6-20aryl and silyl radical; each of the R 6s are independently one selected from the group consisting of a hydrogen atom; a C 1-20alkyl or C 6-20aryl radical; a C 2-20alkenyl radical, C 7-20 alkylaryl radical, a C 7-20arylalkyl radical; a C 1-20alkoxyl radical, a C 6-20aryloxyl radical, and an amido radical, wherein at least two R 6s can be connected to each other to form an aliphatic or aromatic ring;
Q 3and Q 4are each independently one selected from the group consisting of: a halogen radical; a C 1-20alkylamido radical, a C 6-20arylamido radical; and a C 1-20 alkyl radical; n is an integer of 0 or 1; and M is a Group 4 transition metal.
3. The transition metal complex of claim 1, selected from the group consisting of compounds
represented by the following Formulae:
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, a dimethylamido and a chloride radical.
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, a dimethylamido and a chloride radical.
4. An amine-based compound represented by Formulae 3 and 4 below:
where, R 1and R 2are each independently one selected from the group consisting of: a hydrogen atom; a C 1-20alkyl radical, a C 6-20aryl radical, a silyl radical; a C 2-20alkenyl radical, a C 7-20alkylaryl radical, a C 7-20arylalkyl radical; and a metalloid radical of Group 14 substituted with a C 1-20hydrocarbyl, wherein R ,and R 2can be connected to each other by an alkylidene radical containing a C 1-20alkyl or C 6-20aryl radical to form a ring; each of the R 3s are independently one selected from the group consisting of: a hydrogen atom; a halogen radical; a C 1-20alkyl radical, a C 6-20aryl radical, a C 1-20alkoxy radical, a C 6-20aryloxy radical, and an amido radical, wherein at least two R 3s can be connected to each other to form an aliphatic or aromatic ring; and n is a integer such as 0 or 1.
where, R 1and R 2are each independently one selected from the group consisting of: a hydrogen atom; a C 1-20alkyl radical, a C 6-20aryl radical, a silyl radical; a C 2-20alkenyl radical, a C 7-20alkylaryl radical, a C 7-20arylalkyl radical; and a metalloid radical of Group 14 substituted with a C 1-20hydrocarbyl, wherein R ,and R 2can be connected to each other by an alkylidene radical containing a C 1-20alkyl or C 6-20aryl radical to form a ring; each of the R 3s are independently one selected from the group consisting of: a hydrogen atom; a halogen radical; a C 1-20alkyl radical, a C 6-20aryl radical, a C 1-20alkoxy radical, a C 6-20aryloxy radical, and an amido radical, wherein at least two R 3s can be connected to each other to form an aliphatic or aromatic ring; and n is a integer such as 0 or 1.
5. A catalyst composition comprising: a transition metal complex represented by Formula
1 of claim 1; and at least one cocatalyst compound selected from the group consisting
of compounds represented by Formulae 5, 6, and 7 below:
-[Al(R8)-O]a - Formula 5
where, each of the R 8s are independently one selected from the group consisting of: a halogen radical; a C 1-20hydrocarbyl radical; and a C 1-20 hydrocarbyl radical substituted with a halogen atom; and
a is an integer of 2 or greater;
D(R8)3 Formula 6
where, D is aluminum or boron, and R 8is as described above; and
[L-H] +[Z(A)4]- or [L]+[Z(A)4]- Formula 7
where, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; and each of the As are independently a C 6-20aryl or C 1-20alkyl radical in which at least one hydrogen atom is substituted with a halogen atom, or a C1-20 hydrocarbyl radical, C 1-20alkoxy radical, or a phenoxy radical.
-[Al(R8)-O]a - Formula 5
where, each of the R 8s are independently one selected from the group consisting of: a halogen radical; a C 1-20hydrocarbyl radical; and a C 1-20 hydrocarbyl radical substituted with a halogen atom; and
a is an integer of 2 or greater;
D(R8)3 Formula 6
where, D is aluminum or boron, and R 8is as described above; and
[L-H] +[Z(A)4]- or [L]+[Z(A)4]- Formula 7
where, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; and each of the As are independently a C 6-20aryl or C 1-20alkyl radical in which at least one hydrogen atom is substituted with a halogen atom, or a C1-20 hydrocarbyl radical, C 1-20alkoxy radical, or a phenoxy radical.
6. The catalyst composition of claim 5, wherein the transition metal complex represented
by Formula 1 is selected from the group consisting of compounds represented by the
following Formulae:
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, dimethylamido and chloride radical.
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, dimethylamido and chloride radical.
7. A method of preparing a catalyst composition of claim 5, comprising:
bringing the transition metal complex represented by Formula 1 into contact with the cocatalyst compound represented by Formula 5 or 6 to obtain a mixture; and adding the cocatalyst compound represented by Formula 7 to the mixture.
8. The method of claim 7, wherein the transition metal complex represented by Formula
1 is selected from the group consisting of compounds represented by the following
Formulae:
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, a dimethylamido and a chloride radical.
where, each of the R 7s are independently a hydrogen atom or a methyl radical, and Q 5and Q 6are each independently one selected from the group consisting of: a methyl, a dimethylamido and a chloride radical.
9. The method of claim 7, wherein the molar ratio of the transition metal complex to
the compound represented by Formula 5 or 6 is in the range of 1:2 to 1:5000, and the
molar ratio of the transition metal complex to the compound represented by Formula
7 is in the range of 1:1 to 1:25.
10. A method of synthesizing an olefin polymer, wherein the catalyst composition of claim
5 is brought into contact with a monomer.
11. The method of claim 10, wherein the monomer is at least one selected from the group
consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene
and 1-eicosene.
12. An olefin polymer prepared using the method of claim 10.
13. The olefin polymer of claim 12, wherein the monomer comprises ethylene; and at least
one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene,
4-methyl-1-pentene, and 1-octene.
1. Übergangsmetallkomplex, dargestellt durch Formel 1 unten:
worin R1s und R2s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem Silylrest; einem C2-20-Alkenylrest, einem C7-20-Alkylarylrest, einem C7-20-Arylalkylrest; und einem Metalloidrest aus Gruppe 14, substituiert mit einem C1-20-Kohlenwasserstoffrest, wobei R1 und R2 miteinander durch einen Alkylidenrest verbunden sein können, der einen C1-20-Alkyl- oder Arylrest enthält, um einen Ring zu bilden; die R3s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem Halogenrest; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem C1-20-Alkoxyrest, einem C6-20-Aryloxyrest und einem Amidorest, wobei wenigstens zwei R3s miteinander verbunden sein können, um einen aliphatischen oder aromatischen Ring zu bilden; CY1 ein substituierter oder unsubstituierter aliphatischer oder aromatischer Ring ist;
M ein Gruppe 4-Übergangsmetall ist; und Q1 und Q2 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Halogenrest; einem C1-20-Alkylamidorest, einem C6-20-Arylamidorest; einem C1-20-Alkylrest, einem C2-20-Alkenylrest, eine C6-20-Arylrest, einem C7-20-Alkylarylrest, einem C7-20-Arylalkylrest; und einem C1-20-Alkylidenrest.
2. Übergangsmetallkomplex nach Anspruch 1, dargestellt durch Formel 2 unten:
worin R4s und R5s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; und einem C1-20-Alkyl-, C6-20-Aryl-und Silylrest; die R6s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus einem Wasserstoffatom; einem C1-20-Alkyl- oder C6-20-Arylrest; einem C2-20-Alkenylrest, C7-20-Alkylarylrest, einem C7-20-Arylalkylrest; einem C1-20-Alkoxylrest, einem C6-20-Aryloxylrest und einem Amidorest, wobei wenigstens zwei R6s miteinander verbunden sein können, um einen aliphatischen oder aromatischen Ring zu bilden;
Q3 und Q4 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Halogenrest; einem C1-20-Alkylamidorest, einem C6-20-Arylamidorest; einem C1-20-Alkylrest; n eine ganze Zahl von 0 bis 1 ist; und M ein Gruppe 4-Übergangsmetall ist.
3. Übergangsmetallkomplex nach Anspruch 1, ausgewählt aus der Gruppe, bestehend aus Verbindungen,
die dargestellt sind durch die folgenden Formeln:
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, einem Dimethylamido- und einem Chloridrest.
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, einem Dimethylamido- und einem Chloridrest.
4. Aminbasierte Verbindung, dargestellt durch Formeln 3 und 4 unten:
worin R1 und R2 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem Silylrest; einem C2-20-Alkenylrest, einem C7-20-Alkylarylrest, einem C7-20-Arylalkylrest; und einem Metalloidrest aus Gruppe 14, substituiert mit einem C1-20-Kohlenwasserstoffrest, wobei R1 und R2 miteinander durch einen Alkylidenrest verbunden sein können, der einen C1-20-Alkyl- oder C6-20-Arylrest enthält, um einen Ring zu bilden; die R3s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem Halogenrest; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem C1-20-Alkoxyrest, einem C6-20-Aryloxyrest und einem Amidorest, wobei wenigstens zwei R3s miteinander verbunden sein können, um einen aliphathischen oder aromatischen Ring zu bilden; und n eine ganze Zahl ist, wie etwa 0 oder 1.
worin R1 und R2 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem Silylrest; einem C2-20-Alkenylrest, einem C7-20-Alkylarylrest, einem C7-20-Arylalkylrest; und einem Metalloidrest aus Gruppe 14, substituiert mit einem C1-20-Kohlenwasserstoffrest, wobei R1 und R2 miteinander durch einen Alkylidenrest verbunden sein können, der einen C1-20-Alkyl- oder C6-20-Arylrest enthält, um einen Ring zu bilden; die R3s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Wasserstoffatom; einem Halogenrest; einem C1-20-Alkylrest, einem C6-20-Arylrest, einem C1-20-Alkoxyrest, einem C6-20-Aryloxyrest und einem Amidorest, wobei wenigstens zwei R3s miteinander verbunden sein können, um einen aliphathischen oder aromatischen Ring zu bilden; und n eine ganze Zahl ist, wie etwa 0 oder 1.
5. Katalysatorzusammensetzung umfassend: einen Übergangsmetallkomplex, dargestellt durch
Formel 1 von Anspruch 1; und wenigstens eine Cokatalysatorverbindung, ausgewählt aus
der Gruppe, bestehend aus Verbindungen, dargestellt durch Formeln 5, 6 und 7 unten:
-[A1(R8)-O]a- Formel 5,
worin die R8s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Halogenrest; einem C1-20-Kohlenwasserstoffrest; und einem C1-20-Kohlenwasserstoffrest, der mit einem Halogenatom substituiert ist; und a eine ganze Zahl von 2 oder mehr ist;
D(R8)3 Formel 6,
worin D Aluminium oder Bor ist und R8 ist, wie oben beschrieben; und
[L-H]+[Z(A)4]- oder [L]+[Z(A)4]- Formel 7,
worin L eine neutrale oder kationische Lewissäure ist; H ein Wasserstoffatom ist; Z ein Gruppe 13-Atom ist; und die As jeweils unabhängig ein C6-20-Aryl- oder C1-20-Alkylrest sind, in denen wenigstens ein Wasserstoffatom durch ein Halogenatom substituiert ist, oder ein C1-20-Kohlenwasserstoffrest, ein C1-20-Alkoxyrest oder ein Phenoxyrest.
-[A1(R8)-O]a- Formel 5,
worin die R8s jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Halogenrest; einem C1-20-Kohlenwasserstoffrest; und einem C1-20-Kohlenwasserstoffrest, der mit einem Halogenatom substituiert ist; und a eine ganze Zahl von 2 oder mehr ist;
D(R8)3 Formel 6,
worin D Aluminium oder Bor ist und R8 ist, wie oben beschrieben; und
[L-H]+[Z(A)4]- oder [L]+[Z(A)4]- Formel 7,
worin L eine neutrale oder kationische Lewissäure ist; H ein Wasserstoffatom ist; Z ein Gruppe 13-Atom ist; und die As jeweils unabhängig ein C6-20-Aryl- oder C1-20-Alkylrest sind, in denen wenigstens ein Wasserstoffatom durch ein Halogenatom substituiert ist, oder ein C1-20-Kohlenwasserstoffrest, ein C1-20-Alkoxyrest oder ein Phenoxyrest.
6. Katalysatorzusammensetzung nach Anspruch 5, wobei der Übergangsmetallkomplex, dargestellt
durch Formel 1, ausgewählt ist aus der Gruppe, bestehend aus Verbindungen, die dargestellt
sind durch die folgenden Formeln:
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, Dimethylamido- und Chloridrest.
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, Dimethylamido- und Chloridrest.
7. Verfahren zur Herstellung einer Katalysatorzusammensetzung nach Anspruch 5, welches
umfasst:
Inkontaktbringen des Übergangsmetallkomplexes, dargestellt durch Formel 1, mit der Cokatalysatorverbindung, dargestellt durch Formel 5 oder 6, um eine Mischung zu erhalten; und Zugeben der Cokatalysatorverbindung, dargestellt durch Formel 7 zur Mischung.
8. Verfahren nach Anspruch 7, wobei der Übergangsmetallkomplex, dargestellt durch Formel
1, ausgewählt ist aus der Gruppe, bestehend aus Verbindungen, die dargestellt sind
durch die folgenden Formeln:
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, einem Dimethylamido- und einem Chloridrest.
worin die R7s jeweils unabhängig ein Wasserstoffatom oder ein Methylrest sind und Q5 und Q6 jeweils unabhängig ein Rest sind, der ausgewählt ist aus der Gruppe, bestehend aus: einem Methyl-, einem Dimethylamido- und einem Chloridrest.
9. Verfahren nach Anspruch 7, wobei das Molverhältnis des Übergangsmetallkomplexes zur
Verbindung, dargestellt durch Formel 5 oder 6, im Bereich von 1:2 bis 1:5000 liegt
und das Molverhältnis des Übergangsmetallkomplexes zur Verbindung, dargestellt durch
Formel 7, im Bereich von 1:1 1 bis 1:25 liegt.
10. Verfahren zum Synthetisieren eines Olefinpolymers, wobei die Katalysatorzusammensetzung
von Anspruch 5 mit einem Monomer in Kontakt gebracht wird.
11. Verfahren nach Anspruch 10, wobei das Monomer wenigstens eines ist, das ausgewählt
ist aus der Gruppe, bestehend aus Ethylen, Propylen, 1-Buten, 1-Penten, 4-Methyl-1-penten,
1-Hexen, 1-Hepten, 1-Octen, 1-Decen, 1-Undecen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen
und 1-Eicosen.
12. Olefinpolymer, hergestellt unter Verwendung des Verfahrens von Anspruch 10.
13. Olefinpolymer nach Anspruch 12, wobei das Monomer Ethylen und wenigstens ein Comonomer
umfasst, das ausgewählt ist aus der Gruppe, bestehend aus Propylen, 1-Buten, 1-Hexen,
4-Methyl-1-penten und 1-Octen.
1. Complexe de métaux de transition représenté par la Formule 1 ci-dessous :
où R 1s et R 2s sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical silyle ; un radical alkényle en C 2-20, un radical alkylaryle en C 7-20, un radical arylalkyle en C 7-20 ; et un radical métalloïde du Groupe 14 substitué par un hydrocarbyle en C 1-20, dans lequel R 1 et R 2 peuvent être connectés l'un à l'autre par un radical alkylidène contenant un radical alkyle en C 1-20 ou un radical aryle afin de former un cycle ; chacun des groupes R 3s sont indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical halogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical alcoxy en C 1-20, un radical aryloxy en c 6-20, et un radical amino, dans lequel au moins deux R 3s peuvent être connectés l'un à l'autre pour former un cycle aliphatique ou aromatique ; CY1 est un cycle aliphatique ou aromatique substitué ou non substitué ;
M est un métal de transition du Groupe 4 ; et Q 1 et Q 2 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un radical halogène ; un radical alkylamido en C 1-20, un radical arylamido en C 6-20 ; un radical alkyle en C 1-20, un radical alkényle en C 2-220, un radical aryle en C 6-20, un radical alkylaryle en C 7-20, un radical arylalkyle en C 7-20 ; et un radical alkylidène en C 1-20.
2. Complexe de métaux de transition selon la revendication 1, représenté par la Formule
2 ci-dessous :
où R 4s et R 5s sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; et un alkyle en C 1-20, un aryle en C 6-20 et un radical silyle ; chacun des groupes R 6s sont indépendamment un groupe sélectionné parmi le groupe constitué d'un atome d'hydrogène ; un alkyle en C 1-20 ou un radical aryle en C 6-20 ; un radical alkényle en C 2-20, un radical alkylanyle en C 7-20, un radical arylalkyle en C 7-20 ; un radical alkoxyle en C 1-20, un radical aryloxyle en C 6-20 et un radical amino, dans lequel au moins deux groupes R 6s peuvent être connectés l'un à l'autre pour former un cycle aliphatique ou aromatique ;
Q 3 et Q 4 sont chacun un groupe sélectionné parmi le groupe constitué de : un radical halogène ; un radical alkylamido en C 1-20, un radical arylamido en C 6-20 ; et un radical alkyle en C 1-20 ; n représente un nombre entier valant 0 ou 1 ; et M représente un métal de transition du Groupe 4.
3. Complexe de métaux de transition selon la revendication 1, sélectionné parmi le groupe
constitué de composants représentés par les Formules suivantes :
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un méthyle, un diméthylamino et un radical chlorure.
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un méthyle, un diméthylamino et un radical chlorure.
4. Composant à base d'aminé représenté par les Formules 3 et 5 ci-dessous :
où R 1 et R 2 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical silyle ; un radical alkényle en C 2-20, un radical alkylaryle en C 7-20, un radical arylalkyle en C 7-20 ; et un radical métalloïde du Groupe 14 substitué par un hydrocarbyle en C 1-20, dans lequel R 1 et R 2 peuvent être connectés l'un à l'autre par un radical alkylidène contenant un alkyle en C 1-20 ou un radical aryle en C 6-20 afin de former un cycle ; chacun des groupes R 3s sont indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical halogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical alcoxy en C 1-20, un radical aryloxy en C 6-20 et un radical amido, dans lequel au moins deux groupes R 3s peuvent être connectés l'un à l'autre afin de former un cycle aliphatique ou aromatique ; et n est un nombre entier tel que 0 ou 1.
où R 1 et R 2 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical silyle ; un radical alkényle en C 2-20, un radical alkylaryle en C 7-20, un radical arylalkyle en C 7-20 ; et un radical métalloïde du Groupe 14 substitué par un hydrocarbyle en C 1-20, dans lequel R 1 et R 2 peuvent être connectés l'un à l'autre par un radical alkylidène contenant un alkyle en C 1-20 ou un radical aryle en C 6-20 afin de former un cycle ; chacun des groupes R 3s sont indépendamment un groupe sélectionné parmi le groupe constitué de : un atome d'hydrogène ; un radical halogène ; un radical alkyle en C 1-20, un radical aryle en C 6-20, un radical alcoxy en C 1-20, un radical aryloxy en C 6-20 et un radical amido, dans lequel au moins deux groupes R 3s peuvent être connectés l'un à l'autre afin de former un cycle aliphatique ou aromatique ; et n est un nombre entier tel que 0 ou 1.
5. Composition de catalyseur comprenant : un complexe de métaux de transition représenté
par la Formule 1 de la revendication 1 ; et au moins un composant cocatalyseur sélectionné
parmi le groupe constitué de composants représentés par les Formules 5, 6 et 7 ci-dessous
:
-[A1(R8)-O]a- Formule 5,
où chacun des groupes R 8s sont indépendamment un groupe sélectionné parmi le groupe constitué de : un radical halogène ; un radical hydrocarbyle en C 1-20 ; et un radical hydrocarbyle en C 1-20 substitué par un atome d'halogène ; et
a représente un nombre entier valant 2 ou supérieur ;
D(R8)3 Formule 6,
où D représente un aluminium ou un bore et R 8 est tel que décrit ci-dessus ; et
[L-H]+[Z(A)4]- oder [L]+[Z(A)4]- Formule 7,
où L représente un acide de Lewis neutre ou cationique ; H représente un atome d'hydrogène Z représente un Groupe de 13 atomes ; et chacun des As sont indépendamment un alryle en C 6-20 ou un radical alkyle en C 1-20 dans lequel au moins un atome d'hydrogène est substitué par un atome d'halogène ou un radical hydrocarbyle en C 1-20, un radical alcoxy en C 1-20 ou un radical phénoxy.
-[A1(R8)-O]a- Formule 5,
où chacun des groupes R 8s sont indépendamment un groupe sélectionné parmi le groupe constitué de : un radical halogène ; un radical hydrocarbyle en C 1-20 ; et un radical hydrocarbyle en C 1-20 substitué par un atome d'halogène ; et
a représente un nombre entier valant 2 ou supérieur ;
D(R8)3 Formule 6,
où D représente un aluminium ou un bore et R 8 est tel que décrit ci-dessus ; et
[L-H]+[Z(A)4]- oder [L]+[Z(A)4]- Formule 7,
où L représente un acide de Lewis neutre ou cationique ; H représente un atome d'hydrogène Z représente un Groupe de 13 atomes ; et chacun des As sont indépendamment un alryle en C 6-20 ou un radical alkyle en C 1-20 dans lequel au moins un atome d'hydrogène est substitué par un atome d'halogène ou un radical hydrocarbyle en C 1-20, un radical alcoxy en C 1-20 ou un radical phénoxy.
6. Composition de catalyseur selon la revendication 5, dans laquelle le complexe de métaux
de transition représenté par la Formule 1 est sélectionné parmi le groupe de composants
représenté par les formules suivantes :
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un méthyle, un diméthylamido et un radical chlorure.
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionné parmi le groupe constitué de : un méthyle, un diméthylamido et un radical chlorure.
7. Procédé de préparation d'une composition de catalyseur selon la revendication 5, comprenant
:
mettre le complexe de métaux de transition représenté par la Formule 1 en contact avec le composant catalyseur représenté par la Formule 5 ou 6 afin d'obtenir un mélange ; et ajouter le composant catalyseur représenté par la Formule 7 au mélange.
8. Procédé selon la revendication 7, dans lequel le complexe de métaux de transition
représenté par la Formule 1 est sélectionné parmi le groupe constitué de composants
représentés par les formules suivantes :
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionnée parmi le groupe constitué de : un méthyle, un diméthylamino et un radical chlorure.
où chacun des groupes R 7s sont indépendamment un atome d'hydrogène ou un radical méthyle et Q 5 et Q 6 sont chacun indépendamment un groupe sélectionnée parmi le groupe constitué de : un méthyle, un diméthylamino et un radical chlorure.
9. Procédé selon la revendication 7, dans lequel le rapport molaire entre le complexe
de métaux de transition et le composé représenté par la Formule 5 ou 6 se situe dans
la plage de 1:2 à 1:5000 et le rapport molaire entre le complexe de métaux de transition
et le composant représenté par la Formule 7 se situe dans la plage de 1:1 à 1:25.
10. Procédé de synthétisation d'un polymère à base d'oléfine, dans lequel la composition
de catalyseur selon la revendication 5 est mise en contact avec un monomère.
11. Procédé selon la revendication 10, dans lequel le monomère est au moins un groupe
sélectionné parmi le groupe constitué d'éthylène, 1-butène, propylène, 1-pentène,
4-méthyle-1-pentène, 1-hexène, 1-heptène, 1-octène, 1-décène, 1-undécène, 1-dodécène,
1-tétradécène, 1-hexadécène et 1-éicosène.
12. Polymère d'oléfine préparé en utilisant le procédé selon la revendication 10.
13. Polymère à base d'oléfine selon la revendication 12, dans lequel le monomère comprend
de l'éthylène ; et au moins un comonomère sélectionné parmi le groupe constitué de
propylène, 1-butène, 1-hexène, 4-méthyle-1-pentène et 1-octène.
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