TW424100B - Polymerisation catalyst - Google Patents

Abstract

A catalyst composition suitable for use in the polymerisation of olefins comprises a discrete metal complex having chelating ligands comprising at least one atom from O, S, N and P bound directly to the metal. The complexes are used in the presence of Lewis acids and may be exemplified by bis(cyclopentadienyl) zirconium complexs. Typical chelating ligands include acetylacetonate and the complexes have the particular advantage of not requiring traditional activators such as MAO.

Description

Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs 4 2 4 1 η Α7 _______ Β7_ V. Description of the Invention (1) The present invention relates to a novel discontinuous metal complex, its preparation method and its application to polymerized olefins Use of catalyst composition. In particular, the present invention relates to a catalyst composition comprising a discontinuous complex and an active agent. The use of transition metals to polymerize 1-olefins, such as ethylene, is known in the prior art. The use of Ziegler-Nattta catalysts made by activating titanium halides with organometallic compounds (such as triethylammonium) is essential for many commercial methods of making smoke. In the past two decades or three decades, further technologies have been developed which have such high activity that olefin polymers and copolymers containing very low residual concentrations can be directly produced commercially. The amount of catalyst remaining in the resulting polymer is so small that it is not necessary to separate and remove it for most commercial applications. Such a method can be performed by polymerizing monomers in the gas phase, or in a solution or suspension of a diluent of a hydrocarbon. The monomers can be in the gas phase ("gas phase method," for example, by fluidizing a bed including the target polyolefin powder and desired catalyst particles using a fluidized gas stream including gaseous monomers under polymerization conditions). Polymerization is carried out. In the so-called "solution method", (co) polymerization is the introduction of monomers into a catalyst solution or suspension in a hydrocarbon diluent under conditions of temperature and pressure at which the obtained polyolefin forms a hydrocarbon dilute solution. Perform "In the" mud method ", the temperature, pressure and release solution are selected so that the resulting polyolefins form a diluted hydrocarbon suspension. These methods are usually performed at relatively low pressures (e.g. 10-50 bar) and low temperatures (e.g. 5 〇-15〇.〇 operation. Commercially produce a variety of different types and grades of commercial polyethylene. Use a transition metal as the substrate for the high polymerization of ethylene to produce the so-called `` high density, grade of poly Ethylene "These polymers have a very high hardness (please read the precautions on the back before filling this page) -Packing ·-Thread J— This paper size applies to China National Standard (CNS) a4 specifications (210 X 297 mm) 4 424100, 424100, printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, this paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (2IO × 2? 7 mm) A7 B7 V. Description of the invention ( 2) " and can be used to make objects that require inherent rigidity β Commercially use the copolymerization of dilute and high carbon number 1-dilute hydrocarbons (such as dilute, dilute or dilute) to obtain a variety of different densities and Other copolymers with different important physical properties. Particularly important copolymers obtained by copolymerizing ethylene with high carbon number olefins using a catalyst with a transition metal as the substrate are copolymers having a density of 0 91 0 93. These Copolymers commonly referred to in the art as "linear low-density polyethylene" are, in many respects, similar to the so-called "low-density" polyethylene produced by the high-pressure free radical polymerization of ethylene. Such polymers and Copolymers are widely used in the manufacture of kneadable blown films. An important feature of the microstructure of ethylene and high carbon number 1-olefin copolymers is that the polymerized comonomer units are along the polymerized ethylene units. "Stem, chain distribution. Traditional Ziegler-Natta catalysts have always produced copolymers in which polymerized comonomer units are clustered along chains." In order to obtain particularly desirable film properties from such copolymers, each The comonomer units in the copolymer molecule are preferably not clustered together, but are arranged separately along the length of the linear polyethylene chain. In recent years, the use of discontinuous metal complexes with transition metals as substrates has been provided. The possible high activity of the catalyst can improve the distribution of comonomer units. Such complexes are known as metallocenes and can be exemplified by dicyclopentadienyl transition metal complexes. These are discontinuous metal complexes. The use of olefins as catalysts for olefin polymerization catalysts is now widely known. Examples of such complexes can be found in EP 129368, EP 206794 and EP 260130. Metallocene complexes traditionally include bis (cyclopentadienyl) zirconium complexes such as gasified bis (cyclopentadienyl) hammer or bis (tetramethylcyclopentadienyl) zirconium dichloride. * · — ≪ Please read the notes on the back before filling this page). Packing:, ιτ 线 24100 Printed by the Central Procurement Bureau of the Ministry of Economic Affairs, Consumer Cooperatives A7 Β7 V. Description of the invention (3) In such a catalyst In the system, the discontinuous metal complex is used in the presence of a suitable active agent. Most of the active agents suitable for use with such metallocene complexes are oxyxane, the most suitable is methylalumoxane or ΜΑΟ . Other suitable active agents are perfluorinated boron compounds. In more recent years, transition metal complexes with suppressed geometric structures have been used as a component of the hydrocarbon polymerization catalyst. Such complexes are described in EP 420436 and EP 415815. Such a complex is also used in the presence of an active agent such as alumina. However, 'the advantage is to improve the effectiveness of the catalyst for the polymerization of fluorene with a discontinuous complex as the matrix. It is also advantageous to use a simpler and less expensive active agent with a discontinuous complex, or to use a lower Active agent concentration. EP 519746 describes the catalyst system used in the polymerization of olefins, including bis (cyclopentadienyl) transition metal complexes with alkyl flavate ligands and organic oxygen compounds. Such a system requires the use of alumoxane as the active agent. EP 591756 describes a polymerization catalyst system comprising a polycationic complex of a metallocene complex and an ionic compound. The polycation complex may be, for example, bis (cyclopentadienyl) zirconium ditriflate. EP 598134 describes titanium complexes with chelate-forming ligands, such as acetoacetone esters, which can be used as catalysts for polymerizing olefins and compounds capable of forming ionic complexes with titanium complexes. . This reference also explicitly states that acetocyclopentadienyl compounds containing chelate-forming ligands, such as acetoacetone ester groups, can be combined with metallocenes to form ionic complexes at various paper sizes. Use Chinese National Standard (CNS) Α4 specification (210X297 fat) (Please read the precautions on the back before filling out this page)-? Ding Central Bureau of Standards of the Ministry of Economic Affairs-Industrial Consumer Cooperatives printed 2. 4 Q-A7 B7 5. Description of the invention (4) together as a catalyst "The obtained catalyst system is used in the presence of a base aluminum compound. EP 472741 describes an olefin polymerization catalyst, which includes a coordinating ligand (such as second brewing I ) And gas-fired. The complexes described herein do not contain cyclopentadiene ligands and the valence of the metal typically satisfies the digaside ligand β. Many complexes containing similar diketone ligands are prepared. Method has been described in the prior art β

Angew. Chem Int. Ed. Engl. (1996), 35 (1), 80-2 describes the use of preformed cyclopentadiene-betaine cations to prepare ethylacetonyl zirconium cyclopentadiene. Method of enoborate. Organometallics (1994), 13 (10), 3897-902 describe the preparation of (ethanylacetone) η-1- (° Λazole-N) cyclopentadiene tetraphenylborate.

Bull. Soc. Chim. Fr. (1984), (3-4, Pt 1), 113-14; Z. Naturforsch., B: Anorg. Chem. Org. Chem. (1984), 39B (5), 604 -6; Synth. React. Inorg. Met.-Org. Chem. (1983), 13 (8), 1059-65; Synth. React. Inorg. Met.-Org. Chem. (1983), 13 (3) , 357-66 and Monatsh. Chem. (1983), 114 (4), 399-405 describe methods for preparing metallocene 6 alkenylacetonate flavates and carbamates.

Izv. Akad. Nauk. SSSr, Ser. Khim. (1978), (11), 2645-7 describe a method for preparing Cp2Zr (PhCOCHCOPh) (Cl). It has been found that the use of discontinuous metal complexes including certain heteroatom-containing ligands as substrates is suitable for catalyst systems for polymerizing olefins. In addition, these catalyst systems have the particular advantage that they can be used in the absence of traditional alumoxane active agents. This paper size is applicable to China National Standard for Ladder (CNS) A4 (210X297 mm) (please read the precautions on the back before filling out this page). Packing. Order 424100 ΓΤ Α7 Β7 Ministry of Economics and Trade Central Cooperative Consumer Cooperative Preparation 5. Description of the invention (5 Therefore, the present invention provides a catalyst composition suitable for polymerizing women's cigarettes, the composition includes: (A) a neutral discontinuous metal complex, and its general formula is: (l ) p MYnXmZq where L is a ligand that does not remain bonded to ... under olefin polymerization conditions M is a group IIIA element or a transition metal of IIB, IVB, VB, VIB, or VIII (CAS version of the periodic table, cotton & Wilkinson fifth Version), Y is a chelating ligand including at least one atom selected from 0, S, N, and P and directly bonded to M, and X is the same as Υ or selected from the group consisting of hydride, Hydroxyl, substituted hydroxyl, dentate, peroxyacid, substituted sulfonate, trifluoromethyl sulfonate, methyl sulfonate, fluorosulfonate, aryl sulfonate, bis (trifluoro Methylsulfo) methyl, bis (trifluoromethylsulfo) benzyl, bis (trifluoromethylsulfo) ) Amines, alkoxides, aryl oxides, tetraalkylborates, tetraarylates, tetraphenylborates, substituted tetraphenylborates, tetrakis (pentafluorophenyl) Borates, Tetra [bis (3, 5-ditrifluoromethyl) phenyl] borates, Tetrafluoroborate, Hexafluorophosphate or Pentafluorotellurate groups ， Η > or = 1. Ρ > or = 1 m > or =, 〇 and q > or = 0, this paper standard is free of Chinese national standards (CNS> Α4 condition grid (2i0x297):-)- --------- J · 'install ------ order ----- 10% (please read the notes on the back to write this page) A7 B7 4 24100 V. Description of the invention u) But With the proviso that n, m, p, and q are integers or zeros that satisfy the valence of the metal; and (B) —or several Lewis acids. Suitable discontinuous metals used in the catalyst composition of the present invention to illustrate, but not to limit. Examples of complexes are metal complexes having the following Y groups in the above general formula: acetoacetate β-diketonate, β-ketoester, β-ketoaldehyde, dithioacetamidate Ketoester, HC (S02CF3) 2-, Carboxylate, Carbamate, Thio Acid ester, dithiocarboxylic acid ester, thiocarbamate, dithiocarbamate, flavonic acid, thioflavanate, hypophosphonate, thiophosphite, di Thiophosphite, dialkyl dithiophosphate, this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)-* ------- {-装 ----- --- Order ----- f Suspect (please read the notes on the back before filling out this page) Ministry of Economic Affairs Central Laboratories and 5 Industrial Consumers Cooperation System 9 04 4 Central Standards Bureau of Ministry of Economic Affairs Printed Λ Α7 Β7 V. Description of the invention (7) Lung acid (amidinate), bishnidazolate, phosphate ester, thiodiimidate, pyridoxate, geranone, grass Acid salt, oxalate, nitrate, nitrite, carbonate, squarate, ketoester, sulfinate, sulfate, sulfite, fluorosulfonate, hydroxy fatty acid Ester, thiohydroxy fatty acid ester, dithiohydroxy fatty acid ester. A preferred complex is a complex in which the Y group includes at least one 0 atom directly bonded to a metal. Particularly suitable complexes are those in which the Y group is a β-diketoester or β-ketoester, such as acetoacetone or substituted acetoacetone, such as fluorine. This paper is suitable for China. National Standard (CNS) A4 specification (210X 297 mm) (Please read the notes on the back before filling out this page)-Pack · 10 A7 B7 V. Description of the invention (Chemical derivatives. A particularly suitable complex is Where P is 1 or 2 and M is a group P / B metal, such as hammer or titanium. Particularly suitable complexes are those in which X is a hydroxyl group, a dentate or a triflate. Suitable for the present invention The discontinuous metal complexes used include metallocene complexes containing a dicyclopentadienyl ligand, such as disclosed in EP 129368 or EP 206794. Particularly suitable metallocene complexes are those having the following general formula Complex: (L) pMYnXmZq — IL ------ 4: 4-- (I read the notes on the back first and then fill out this page) L means unsubstituted or substituted cyclopentadienyl ligand M is a group IVB, VB, VIB or VIII transition metal (CAS version Periodic Table, Cotton & Wilkinson 5th Edition), Y is at least one chelating ligand selected from 0, S, N, and P directly bonded to M, and X is the same as Υ or selected from the group: Hydride, hydroxy, substituted acyl group, dentate, peroxyacid salt, substituted continuous acid salt, continuous acid trifluoromethyl vinegar, acetic acid methyl vinegar, fluoroacetic acid vinegar, dichloride, Bis (trifluoromethylsulfo) methyl, bis (trifluoromethylsulfo) benzyl, bis (trifluoromethylsulfo) fermented amine, burnt oxide, aryl oxide, tetrakistriol vinegar , Tetraaryl lutein acid vinegar, tetraphenyl butterfly acid vinegar, substituted tetraphenyl butterfly acid ester, four (five paper sizes common Chinese National Standard (CNS) A4 specifications (2 10x297 mm) 11 04 2 Α7 Β7 Central Standards of the Ministry of Economic Affairs and Consumers' Cooperative Work only. V. Description of the invention (9 fluorophenyl) borate, tetra [bis (3,5-ditrifluorofluorenyl) benzyl] borate, four Fluoroborate, hexafluorene phosphate or pentafluorotellurate, Z is a commanding Lewis base, η > or = 1 ρ > or = 1 m > or = 〇 and q > or = 0 , But conditionally η, m, p And q are integers or zeros satisfying the valence of the metal. The di% pentadienyl ligand may be an alkyl group, an aryl group, a dilute group, an aralkyl group or an alkaryl group, or two substituents may be combined. Together to form a bonded ring 'like a benzyl group. The preferred cyclopentadienyl system is substituted by a methyl group. When P is 2', that is, when two dicyclopentadienyl groups are present, they can pass through a bridging group ' For example, they are combined by the group of the chemical formula (R2Z) p, where Z is Shi Xi, germanium or carbon, p is 1-8 and R is hydrogen or selected from a hydrocarbon group or a combination thereof. The preferred complexes are those where 10M is wrong, or given, p is 2 and 11 is 1 or 2. Also suitable for use in the present invention are complexes having a suppressed geometric structure, such as those disclosed by EP 416815 or EP 420436. For example, a complex having the following general formula can be applied: Z — p / /

Cp *-μ / \ cn, (xl where

Cp * is a single η5-cyclopentadienyl or η5-substituted cyclopentadiene basic paper size, using China National Standard (CNS) A4 specification (2! 0X297 mm) ·. ~~ Ί --- --- f 4 丨-ί Please read the precautions on the back first, and then take this page j-order- 12 Α7 Β7 Printed by Zhengong Consumer Cooperative, Central Bureau of the Ministry of Economic Affairs 5. Description of invention (10) Cp * is single η5-cyclopentadienyl or η5-substituted cyclopentadienyl, which is optionally covalently bonded to M via Z-P and conforms to the following formula * RRR where each R is hydrogen or is selected from halogen, Alkyl, aryl, haloalkyl, alkoxy'aryloxy, silyl, and combinations of up to 20 non-argon atoms, or two or more R groups together form a combined ring system. M is a bond of η5 bonding mode to a cyclopentadienyl group or a substituted cyclopentadienyl group, and the valence is +3 or +4. Z is a partial metal including oxygen, boron and other metals or a group of elements of the group IVA of the periodic table (CAS version of the periodic table, Cotton & Wilkinson 5th Edition) 〇 P is a covalent bonding group with a metal, including gas , Broken, oxygen or sulfur, or Z and P together as needed to form a ring system, and X, Y, XI and m as defined above, to satisfy the valence of M. Preferred complexes are those where the metal M is titanium, P is nitrogen and Z is silicon. Other suitable complexes that can provide the L ligands of the present invention are the complexes described by EP 672676 and EP 757996. Such a complex includes a cyclooctatetraenyl (or COT) ligand, and thus when L is a cyclooctatetraenyl group, it represents the above chemical formula. An example of a suitable Lewis acid suitable for use in the present invention is, for example, trimethylaluminum

(Please read the precautions on the back before filling this page) The size of the paper used for this edition applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 13 424100 / ^ V. Description of the invention (11 > Printed by the Industrial and Commercial Cooperatives, such as A7, B7, etc .: He: 'Triisobutyl Shao', for example, aryl compounds such as ginseng (pentabenzene, etc.), such as tri-argonated compounds, such as hydrogenated diisobutyl, monofluorobenzyl The diisobutyl group is mixed with a halogenated compound, and the aryl / alkyl group is combined with, for example, a gasified di-base compound, or a base, such as a gasified di-base compound, or a bi-gasified base. Bidentate. Also suitable for use as Lewis acid are alkynyl or aryl butterfly, dentate and hydride, such as Qingzhuang_macrocyclic compound, alkynyl or edge town is also suitable. (Pentafluorophenyl) Triisobutyl Butyl O "such as (2'7-dimethyl], 8-diphenylene dioxy) bis (diiso · butylming) and other aryloxy IS compounds" and for example Also suitable are aryloxy-collar compounds such as carbamide, etc.-The ratio of the Lewis acid to the discontinuous metal complex of the present invention is 0.2: 10, _ 'is preferably 0.2: 5000. The catalyst composition of the present invention can be appropriately loaded. For example, discontinuous metal complexes can be recorded on catalyst carriers such as oxygen cutting and oxidizing degassing locks. The supported catalyst can be prepared by conventional techniques. The catalyst composition of the present invention may also include other catalyst components, such as

Ziegler catalyst or other metal complex β. For example, a reset catalyst composition including the supported metal complex and active agent of the present invention and ziegler catalyst (such as a titanium, magnesium and dentine) composition can be used. Thing. Such a reset catalyst can be prepared by a conventional route. The complex of the present invention can also be used in traditional active agents if necessary (for example, aluminum paper size using Chinese National Standard (CNS) A4 specifications (210x2S > 7 feet)) (Please read the precautions on the back before filling out this page )

14-π Produced by Shellfish Consumer Cooperation of the Central Bureau of Standards of the Ministry of Light Industry A7 B7 V. Description of the invention (12)-Appearance, especially methyl sintered oxygen). The complex of the present invention can also be used in the presence of an ionized ionic compound such as trityl tetrakis (pentafluorophenyl) borate monomethylaluminum tetrakis (pentaphenyl) borate, Lithium tetrakis (pentafluorophenyl) borate—benzyltetraphenylphosphonic acid®, tetrafluoroIL acid and the like. The present invention also provides a method for producing a polyolefin, especially a polymer of ethylene and a copolymer of ethylene and a smaller amount of at least one species of cyanine, preferably a C3 C8 alpha dilute hydrocarbon. The method includes contacting a monomer or monomers with the catalyst composition of the present invention in the presence of hydrogen if necessary at a temperature and pressure sufficient to initiate the polymerization reaction. A suitable alpha-olefin may be propylene, propylene-1, Hexene-1,4-fluorenylpentene-1 and octene q. The olefin polymerization catalyst composition of the present invention can be used to produce a polymer using a solution polymerization method's slurry polymerization method or a gas phase polymerization method. Methods and apparatus for conducting such polymerizations are well known and described in, for example, John

Encyclopedia of Polymer Science and Engineering, published by Willey & Sons, vol. 7, pp. 580-488, and 1988, p. 504-541. The catalyst of the present invention can be used under similar amounts and conditions of known olefin polymerization catalysts. The polymerization reaction can be carried out optionally in the presence of argon. Hydrogen and other suitable chain transfer agents can be used to control the molecular weight of the polyolefin produced. Another aspect of the present invention is to provide a novel metal complex having the following general formula:

(L) 2 μ YX The size of this paper is applicable to China National Standards (CNS) A4 (2〗 〖〇Χ 297mm) ^^ 1-1 ^ 1 m--I--i I. — ^ 1 {Please first Read the note f on the back and fill in this page) -15-A7 B7 Printed by the Central Bureau of Quasi-Ministry of the Ministry of Economic Affairs, Consumption Cooperation Du V. Invention Description (13)

Z-P / /

L——MXY where L represents an unsubstituted or substituted dicyclopentadienyl ligand, and Z is a part of a metal including a bivalent molecule such as oxygen 'boron or a group of elements of Group IVa of the periodic table (CAS version of the periodic table , Cotton & Wilkinson 5th Edition). P is a linker covalently bonded to a metal, including nitrogen, phosphorus, oxygen or sulfur 'or optionally Z and P together to form a combined ring system, and M is Zr, Ti or Hf, X is S03CF3 or Hydrocarbyl, Y is RCOCHCOR, where R can be the same or different, and is a hydrocarbyl or substituted nicotyl ', such as CH3, C2HS or CF3, c (ch3) 3 or och2ch3. In particular, a complex with the following chemical formula is disclosed: (1,3- (CH3) 2CjH3) 2Zr (CH3C0CHC0CH3) S03CF3 (l > 3- (CH3) 2CiH3) IZr (CF3COCHCOCF3) S〇3CF3 (IKCHAC ^ ZKCHjCOCHCOOCHjCHOSOSOCFj

CCHJ) 2Si ((CH3), C5) (NC ((CHs) 3) Ti (CFiCOCHCOCF3) SOJCFJ (U- (CH3) 2C5H3) 2Zr (CH3) 3CC0CHC0CH3) 3) S03CF3 (CJHJ) iZr (CH3COCHCOCH3) CH3 Another aspect of the present invention is to provide a method for preparing a novel complex, which comprises replacing at least one hydrocarbon group connected to a metal with a paper standard of Chinese national standard (CNS > A4 specification (2 丨 0X297 mm)) Please read the notes on the back before filling in this page) Order 16 Printed by the Central Samples Bureau of the Ministry of Economic Affairs, Mζ Industrial Consumer Cooperative Λ2 ά] Ο 〇ϊ; Λ Α7 _____ Β7__ 5. The precursors of the invention description (14) are mismatched (Such as Cp2Zr (CH3) (S03CF3) and appropriate dione in an appropriate solvent (such as toluene or pentane) and recover the complex by filtering or removing the solvent.) Therefore, a preparation formula Cp2-MXY is provided The method of the complex is by reacting the complex of the chemical formula Cp2M (hydrocarbyl) X with a diketone of the chemical formula RCOCH2COR in a suitable solvent, where M = Zr, Ti or Hf, Y = RCOCHCOR, X = S03CF3 , R = hydrocarbyl "t if the precursor complex contains more than one hydrocarbyl substitution And the complex needs to contain a hydrocarbyl substituent, it is best to add the diketone dropwise to the stirred solution of the precursor complex. Therefore, a chemical formula Cp2M (hydrocarbyl group) is also provided. ) A method of a complex of Y by treating a complex solution of the chemical formula Cp2M (hydrocarbyl) 2 with the two rims of the chemical formula RCOCH2COR, where M = Zr, Ti, Hf Y = RCOCHCOR, and R = nicotyl. The present invention will now be further exemplified with reference to the following examples. Example 1 H ^ (1,3- (CH〇X, H, VZrrCHXOCHCOCH,) SO, CF. ——— w £, this paper size applies China National Standard (CNS > Α4 Specification (210X297mm) (Please read the notes on the back of the repair before filling out this page) Order 17 Printed by the Sheller Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs «A7 B7 V. Invention Description (15) 88 microliters (1 mole) of trifluoromethanesulfonic acid was added to 307 mg (1 mmol) of dimethylated bis (1,3-dimethylcyclopentadienyl) benzene in 20 ml of toluene The mixture was stirred for one hour, and then 102 microliters (1 mole) of 2,4 pentanedione was added in one portion. The solvent was evaporated to Dry and recrystallize the residue from acetamidine / hexane to give 247 mg of (l, 3- (CH3) 2C5H3) 2Zr (CH3COCHCOCH3) S03CF3 as pale yellow crystals (47% yield). The characteristics obtained by NMR are as follows: W-NMR: (d8-toluene, ambient temperature) δ-5.63 (4Η, m, Cp-CH), 5.56 (2H, m, Cp-CH), 4.98 (1Η, s , Acac CH), 1.85 (12H, br s, Cp-CH3), 1.67 (6H, br s, acac Me) e 13C-NMR: (d8- toluene, ambient temperature) 5 = 14.7 (CHrCp), 26.5 ( £ Hracac), 102.3 (£ H-acac), 120.7, 129.4 (CH-Cp) »19F-NMR · (d8-toluene, ambient temperature) 6 = -79.4» Example 2 Disk preparation (1, SJCHACmZrfCFXOCHCOCIMSOXF, 1 One — * — · — One hundred and eight microliters (1 mole) of trifluoromethanesulfonic acid was added to 20 ml of methylbenzyl 307 mg (1 mmol) of dimethylated bis (1,3 · dimethyl formaldehyde) Cyclopentadienyl) fluorene. The mixture was stirred for one hour, and then 141 microliters (1 mole) of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione was added in one portion. The solvent was evaporated to dryness, and the residue was recrystallized from 1/10 of diethyl ether / hexane to produce 442 mg (丨, 3_ (CH3) 2C5H3) 2Zr (CF3C0CHC0CF3) S03CF3 of light yellow crystals (70%). Garden Standard (CNS) A4 (210 X297 mm) (Please read the precautions on the back before filling out this page) Clothing · Printed in the Ministry of Economic Affairs of the Zhuhai Bureau of Zhuhai Bureau of Carpenter Consumer Cooperative Co., Ltd. 4241 ㈣, λ: B7 V. Description of the invention (16) Yield) The characteristics obtained by NMR are as follows: W-NMR: (d8-toluene, ambient temperature ) 5 = 5.99 (1H, s, hfacac), 5.72 (2H, s, Cp-CH), 5.45 (1H, s, Cp-CH), 1.86 (6H, s, Cp-CH3), 1.65 (6H, s , Cp-CH3) o i3C-NMR: (d8-toluene, ambient temperature) 5 = 13.83, 14.02 (CH3-Cp), 92.31 (£ H3-hfacac), 116.286, 117.154, 123.081 (CH-Cp). 19F- NMR: (d8- toluene, ambient temperature) 5 = -77,10, -77.39, -79.41. Tube Example 3 Toilet (UVCHAqHAZrfCI ^ COCHCOOCt ^ CHpsO.r ^ 88 microliters (1 mole) of trifluoro Methanesulfonic acid was added to 307 mg (1 mmol) of bis (1,3-dimethylcyclopentadienyl) zirconium in 20 ml of toluene. The mixture was stirred for one hour, and then 127 μl ( 1 mole) ethylacetamidine acetate was added in one portion. The solvent was evaporated to dryness and the residue was recrystallized from 1/10 of ether / hexane to give 442 mg of (l, 3- (CH3) 2C5H3) 2Zr (CH3COCHCOOCH2CH3) S03CF3 as colorless crystals (76% yield). The characteristics obtained by NMR are as follows: lH-NMR: (d8-benzene, ambient temperature) δ = 5.76 (2Η, s br, Cp-CH), 5.63 (2H, s br, Cp-CH), 5. · 51 (2Η, s br, Cp-CH), 4.82 (1H, s, acac-CH), 4.46 (2H, s br, OCil2CH3), 190 (6H 's br' Cp-CH3) '18.5 (6H, s br 'Cp-CH3) The paper scale is applicable to China's National Slope (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling this page) Order 19 Consumption by the Ministry of Economic Affairs Cooperative cooperative seal 424 1 0 0; " A7 B7 V. Description of the invention (17), 1_52 (3H, s, br acac-CH3), 1.09 (3Η, s br, OCH2CH3) o 19F-NMR: (d8 -Toluene, ambient temperature 5 = -78.98-Example 4 Congratulations (CHASiaCHACjNCaCHAVTidCOCHCOCDSCKCF, one by one-instrument-ring · «· _ Apply the method of Example 2 to (CH3) 2Si ((CH3) 4C5) (NC ((CH3) 3) Ti (CH3) 2 was used as starting material to obtain (CH3) 2Si ((CH3) 4Cs) (NC ((CH3) 3) Ti (CF3C0CHC0CF3) S03CF3. The characteristics obtained by NMR are as follows: W-NMR : (d8-methylben, ambient temperature) δ = 6.15 (1Η, s, acac-CH), 2.23,1.91,1.82,1.09 (12Η, 4s, Cp-CH3), 0.99 (9Η, s, NC (CH3) 3, 0.48, 0.39 (6Η, 2s, Si-CH3). l9F-NMR: (d8-methylbenzyl, ambient temperature) 5 = -76.4 > -76.7 > -79.2 〇Example 5 Preparation of (l, 3- (CH,), CJiAZr (CHACCOCHCOCH, ysnTT?) 88 microliters (1 mole) of trifluoromethanesulfonic acid was added to 20 ml of methylbenzyl 307 mg (1 millimolar) difluorenyl Bis (1,3 · dimethylcyclopentadienyl) hammer. Stir the mixture for one hour and then 208 microliters (1 mole) of 2,2,6,6-w methyl-3,5-pentane Dione was added in one portion. The solvent was evaporated to dryness and the residue was recrystallized from diethyl ether / hexane 1/20 to yield 531 mg (1,3_ (CH3) 2C5H3) 2Zr (CH3) 3CCOCHCOCH3) 3) Ben & Le Standards: China National Standard for Ladder (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)-20 424106 A7 B7 Explanation (18) S03CF3 # color crystal (87% yield). The characteristics obtained by NMR are as follows: H-NMR: (d8-toluene, ambient temperature) δ = 5.67 (4Η, m, CP-CH), 5.63 (2H, m, Cp-CH), 5.8 (bs, acac CH) , 2.03 (12H, br s, Cp-CH3), 1.0 (18H, br s, acac'Bu) ° lC-NMR: (d8-toluene, ambient temperature) 5 = 14.6 (CH3-Cp), 27.8, 28.3 ( tBu-acac) '92.2 (CH-acac), 116.3, 117.0, 122.9 (CH-CP) e Example 6 Preparation (aHAZKCHXOCHCOCtUCH, 370 microliters (3.6 moles) of 2,4-pentamin was dropped dropwise Add 920 mg (3.6 millimoles) of dimethylated bis (1,3-dimethylcyclopentadienyl) fluorene in 100 ml of -78 ° C oxane. Stir the mixture before warming to ambient temperature. Hours. Isolated by filtration and rinsed with cold pentane (2X50 ml) to form a white precipitate. (C5H5) 2Zr (CH3COCHCOCH3) CH, yield 630 mg (52% yield). The characteristics obtained by NMR are as follows: M-NMR: (d6-benzene, ambient temperature) δ = 5.79 (10Η, s, CP), 5.08 (1H, s, acac CH), 1.61 (6H, s, acac CH3), 0.61 (3H, s, CH3 ). Polymerization Examples 7-12 were performed in a 1-liter autoclave using isobutane as the reaction medium. Reactor Heat to 85 ° C and clean thoroughly with nitrogen (2 liters / minute) for 90 minutes. Then lower the temperature to 50t and introduce the selected alkylaluminum reagent and isobutane (500ml) into the reactor . At 75. <: Mix the paper ruler under the paper with the Chinese national standard (&^; 5) 8 4 size (210 father 297 male shame) HI n ^ i ^^ 1 »I ^ i--I ^ -i 1 ^ 1 n ^ i ^ fi— (Please read the notes on the back before filling out this page) 21 A7 B7 V. Description of the invention (19) Compound (200 rpm) for at least 120 minutes, and then 10 bar super Pressurized ethylene is added. Metal complexes and other Lewis acids (if useful) are added to the reactor. Ethylene is added to keep the reactor pressure constant while the reaction is in progress. To quickly vent the reactor and cool to 2 ° C. ° C to stop the reaction. The solid polymer product was washed with methane-like gasified argon, rinsed with ethanol aqueous solution and dried (50 ° C 'vacuum, 16 hours). The complexes and Lewis acids used are as follows * * Example 7 Combine triisobutylaluminum (3 ml of 1 M in toluene; Aldrich) and trimethylamine (1 ml of 2 M in hexane; Aldrich). (1,3 · (CH3) 2C5H3) 2Zr (CH3COCHCOCH3) SO3CF3 (0-95 micromolar; prepared as in Example 1) was introduced into the reactor. The reaction time was 66 minutes. The yield of the beta polymer was 10.22 g, and the catalytic activity was 978 g of polymer per millimolar Zr.b.he. Example 8 Triisobutylsauric acid (4 ml of a 1 M solution in toluene; Aldrich) , Followed by (l, 3- (CH3) 2CsH3) 2Zr Printed by the Central Ministry of Economic Affairs and the Cooperative Consumer Cooperative (Please read the precautions on the back before filling this page) (CH3COCHCOCH3) SO3CF3 (1.0 micromolar; if implemented Example ⑽ Preparation) and a mixture of triisobutylaluminum (10 micromolar) was introduced into the reactor. The reaction time was 60 minutes. The polymer yield was 23.47 g, and the catalytic activity was 2347 g polymer / mmole Zr.bh Example 9 Triisobutyl succinate (4 ml of a 1 M solution in toluene; Aldrich), followed by (l, 3- (CH3) 2C5H3) 2Zr (CH3COCHCOCH3) SO3CF3 (0.95 micromolar) as in Example 1 Prepared) and B (C6F5) 3 (Boulder Scientific; 1.425 paper standard in use® National Standard (CNS) A4 specification (210X 297 male)) 22 424100 A7 B7 20 V. Description of the invention (micromolar) "Introduction to the reactor" The reaction time is 60 minutes. The polymer yield is 15.61 g, and the catalyst activity is 1643 g polymer / mmol. Zr.bh Put it into practice 丨] 0 Triisobutylaluminum (5 ml of 1 μL in benzene; Aldrich), then (1,3- (CH3) 2C5H3) 2Zr (CF3C0CHC0CF3) S03CF3 (0.95 micromolar : As prepared in Example 2) and B (C6F5) 3 (Boulder Scientific; 0.95 micromolar) were introduced into the reactor. The reaction time was 60 minutes. The polymer yield was 21 · 61 g, and the catalyst activity was 2275 g of polymer / Millimoles Zr.bh. Example 11 Triisobutylaluminum (4 ml of a 1 M solution in toluene; Aldrich) followed by (1,3- (CH3) 2C5H3) 2Zr (CH3COCHCOCH3) S03CF3 (0.95 micromoles As prepared in Example 3) and B (C6F5) 3 (Boulder Scientific; 0.95 micromolar) were introduced into the reactor. The reaction time was 60 minutes. The polymer yield was 12.19 g, and the catalyst activity was 1283 g polymer / mmol. Ear Zr.bh. Example 12 Triisobutylaluminum (4 ml of a 1 M solution in toluene; Aldrich) followed by (1,3- (CH3) 2CsH3) 2Zr (CF3C0CHC0CF3) S03CF3 (1.0 micromolar; as (Prepared in Example 2) and MAO (A1 · · Z1 * ratio of 6000: 1) were introduced into the reactor. The reaction time was 60 minutes. The polymer yield was 48.8 g and the catalyst activity was 4880 g polymer / mmol Zr.b * h.

Example U Triisobutyl Ming (4 ml of a 1 M solution in toluene; Aldrich), followed by (l, 3- (CH3) 2C5H3) 2Zr (CH3C0CHC0CH3) S03CF3 (0.95 micromole CNS) Cong Mi (2iQX297 male thin) 11 ^-II-_ — ^^^ 1 n Ε (Please read the precautions on the back before filling out this page) Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 23 A7 ____ £ 5. Description of the invention (21) ear; prepared as in Example 3) and [CPh3] [B (C6F5) 4] (Boulder Scientific; 1.43 micromoles) were introduced into the reactor. The reaction time is 60 minutes. The polymer yield was 37.8 g and the catalytic activity was 3979 g polymer / mmol Zr.b.h. Example 14 Triisobutylaluminum in 40 ml of toluene (2.5 ml of a 1 M solution in toluene; Aldrich) was added to (C5H5) 2Zr (CH3COCHCOCH3) Me (17.5 mg, 0-5 mol; as in the example 6)) and B (C6F5) 3 (25.6 mg, 0.05 micromolar). The solution was degassed under reduced pressure and backfilled with ethylene atmosphere. During the 60 minutes, the solution was opened to stand to supply ethylene at atmospheric pressure and stirred vigorously. The polymerization was terminated by adding diluted HC1 (approximately 40 ml) and stirred for 30 minutes to dissolve the alkyl residue. The solid polyethylene was filtered from the reaction, rinsed with acidified methanol and dried under reduced pressure of 40 t. Overnight 〇 The yield of polyethylene is 8.94 grams "(please read the precautions on the back before filling this page).

Claims (1)

Announcement Λ8 B8 CS Π8 / year 1 η Revision i Supplement si Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Behr Consumer Cooperatives 6. Application for Patent Scope No. 80113216 Patent Reexamination Case Application for Amendment of Patent Scope Amendment Date: November 1, 89 A catalyst composition suitable for polymerizing olefins, the composition includes: (A) a neutral discontinuous metal complex, the general formula of which is: (L) P MYnVq where L represents that River-bonded ligands, M is a group IIIA element or a group IIIB, IVB, VB, VIB, or VIII transition metal (CAS version of the periodic table 'c〇tt〇n & Wilkinson fifth edition) j Y includes at least A chelating ligand for an atom selected from 0, S, N, and P directly bonded to M, X is the same as fluorene or selected from the group consisting of argon, radical, substituted hydroxyl, Compound, peroxy acid salt, substituted sulfonate, trifluorofluorenyl sulfonate, methyl sulfonate, fluorosulfonate, aryl sulfonate, bis (trifluoromethylsulfo) methyl , Bis (trifluoromethylsulfo) benzyl, bis (trifluoromethylsulfo) fluorenamine, alkoxide, aromatic Compounds, tetrakisylborate, tetraarylsulfonate, tetrabenzylborate, substituted tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3, 5-Ditrifluoromethyl) phenyl] borate, tetrafluoroborate, hexafluorophosphate or pentafluorotellurate, Z is a neutral Lewis base, η > or = 1 ρ > or = 1 m > or = 〇, and this paper size applies the national standard (CNS) A4 specification (210x297 public love) ---------------------- Order --------- β, (Please read the meaning of item ii on the back before filling in this page) A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application q > or = 0, provided that η, m, p, and q are integers or zeros that satisfy the valence of the metal; and (B) —or multiple Lewis acids, where the ratio of the Lewis acid to the metal beneficial compound is 0.2 : 10.0,00. 2. The catalyst composition according to item 1 of the patent application scope, wherein the ligand γ includes at least one O atom directly connected to M. 3 'The catalyst composition according to item 1 or 2 of the scope of patent application, wherein the ligand Υ is selected from the group consisting of β-diketonate, β-ketoester or β · ketoaldehyde. The catalyst composition of item 3, wherein the ligand γ is acetoacetone or a substituted acetoacetone. 5. The catalyst composition according to item 丨 of the application, wherein the X coordination system is a hydrocarbon group, a dentate or a trifluoromethyl sulfonate. 6_ The catalyst complex of item 1 in the scope of the patent application, wherein the Lewis acid is a base or aryl | g compound or a pit or aryl collar compound. 7. The catalyst composition according to the scope of application for item < 5, wherein the Lewis acid is triisobutylaluminum or gins (pentafluorophenyl) boron. 8. The catalyst composition according to item 1 of the patent application scope, wherein the neutral discontinuous metal complex has the following chemical formula: (L) p MYnXmZq where L represents an unsubstituted or substituted cyclopentadienyl group Ligand »M is a group IVB, VB, VIB or VIII transition metal (CAS version of the periodic table, Cotton & Wilkinson 5th Edition), -2 * ------------ "- ------ 1 Order --------- Line 6 i < Please read the precautions on the back before filling this page) The K degree of this paper is applicable to China National Standard (CNS) A4 (210 X Published in 297) 8 88¾ ARCD Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumer Cooperative, printed patent application scope γ is an integrated ligand including at least one atom selected from 0, s, N and p and directly bonded to Μ , X is the same as hydrazone or selected from the group consisting of hydride, hydroxy 'substituted radical, dentate, peroxyacid salt, substituted sulfonate, difluorofluorenyl sulfonate, methyl methyl Esters, fluoroesters, aryl esters, bis (trifluoromethylsulfo) methyl, bis (trifluoromethylsulfo) benzyl, bis (difluoromethylhexyl) fluorenamine Alkoxide 'aryl oxides, tetraarylates, tetraphenylborates, substituted tetrabenzylborates, tetrakis (pentafluorophenyl) borates, tetra [bis (3,5 -Ditrifluoromethyl) phenyl] borate, tetrafluoroborate, hexafluorophosphate or pentafluorotellurate, Z is a neutral Lewis base, η > or = 1 Ρ > or = 1 m > or = 〇, and q > or = 〇, with the proviso that n, m, p, and q are integers or zeros that satisfy the metal valence. A composition in which M is a Group IVB metal, p is 2 and η is 1 or 2. 10. For example, the catalyst composition in the scope of patent application No. 8 wherein M is 鍅. 11. The catalyst composition according to item 8 of the scope of patent application, wherein the ligand γ is selected from the group consisting of β-di snapperate, β_ketoester, or β_rimaldehyde β 12. According to the scope of patent application 11 The catalyst composition of the item, wherein the ligand is acetoacetone or substituted acetoacetate. ----------- I 1 i — * ----- II «II ---- 1 (Please read the notes on the back before filling in this I) Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printing AS BS CS D8 6. Application scope of patent 13. If the catalyst composition of the first scope of patent application, the neutral non-interlinked metal complex has the following chemical formula: Z —- p / / CP- Μ / \ ⑺. · (¾ where Cp * is a single η5-cyclopentadienyl or η5 · substituted cyclopentadienyl 'which is optionally covalently bonded to Μ via Z-P and conforms to the following chemical formula : R wherein each R is hydrogen or selected from the group consisting of halogen, alkyl, aryl, haloalkyl, alkoxy, aryloxy, silyl and combinations of up to 20 non-hydrogen atoms' or two or two More than R groups together form a combined ring system; M is a η5 bond modal, cyclopentadienyl or substituted cyclopentadienyl-bonded hammer, titanium, or hafnium and the valence is +3 or + 4; Z is a bivalent molecular part of oxygen or boron, or an element of Group IVA of the periodic table (CAS version of the periodic table, Cotton & Wilkinson 5th Edition); P is covalently bonded to the metal, and includes Linking group of nitrogen, phosphorus, oxygen or sulfur, or Z and P as needed to form a combined ring system -4-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- ---------- 1 Pack .----- (I Order -------- I ((Please read the notes on the back before filling this page) AS B8 CS m 、 Application The scope of the patent, and X, Υ, η, and m are as defined above, whereby η and m satisfy the valence of M. 14. The catalyst composition as claimed in item 13 of the patent scope, wherein the metal M is Qin 'P is Nitrogen and z is 15. If the catalyst composition according to item 1 of the patent application scope, wherein the discontinuous metal complex is loaded. 16. If the catalyst composition according to item 15 of the patent application scope, wherein the carrier is oxide stone Xi. 17. — A discontinuous metal complex with the following chemical formula: (Lh Μ Υ X ------------ · (， 装 -------- (Please read first Note on the back, please fill in this page again.) Order 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 L--M XY where L represents unsubstituted or substituted cyclopentadienyl ligands, Z is One includes the divalent molecular part of oxygen and boron or an element of group IVA of the periodic table (CAS version of the periodic table, Cotton & Wilkinson 5th edition); P is covalently bonded to the metal, including nitrogen, disk, Oxygen or sulfur linker 'or Z and P together as needed to form a combined ring system, and M is Zr, Ti or Hf, X is SO3CF3 or Fe group, -5-This paper is applicable to national standards ( CNS) A4 specification (210 X 297 public love) 424 10 AS B8 C8 DS 6. The scope of patent application Y is RCOCHCOR, where R can be the same or In the same place, it is a hydrocarbon group or a substituted hydrocarbon group. 18. The discontinuous metal complex according to item 17 of the scope of patent application, which has the following chemical formula: (l, 3- (CH3) 2C5H3) 2Zr (CH3C0CHC0CH3) S03CF3 ( 1,3- (CH3) 2C5H3) 2Zr (CF3C0CHC0CF3) S03CF3 (l, 3- (CH3) 2C5H3) 2Zr (CH3COCHCO0CH2CH3) SO3CF3 (CH3) 2Si ((CH3) 4C5) (NC ((CH3) 3) Ti (CF3C0CH0) ) S03CF3 (l, 3- (CH3) 2C5H3) 2Zr (CH3) 3CCOCHCOCH3) 3) S03CF3 (C5H5) 2Zr (CH3COCHCOCH3) CH3. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs III --- II i III ^ ^ --- I-— II ^ 11111111 ^ It — — — — — — — — — — — — — — IJ. (Please first Read the notes on the reverse side and fill out this page} This paper size applies the Chinese National Standard (CNS) A4 (210 x 297 mm) A7 B7 V. Description of the invention (Chemical derivatives. Particularly suitable complexes are among them P is 1 or 2 and M is a group P / B metal, such as hammer or titanium. Particularly suitable complexes are those in which X is a hydroxyl group, a dentate or a triflate. Suitable for use in the present invention The discontinuous metal complexes include metallocene complexes containing a dicyclopentadienyl ligand, such as those disclosed in EP 129368 or EP 206794. Particularly suitable metallocene complexes are those having the following general formula Complex: (L) pMYnXmZq — IL ------ 4: 4-- (谙 Please read the notes on the back before filling out this page) Booked by the central central laborer's consumer cooperation Sugiyoshi? Water where L Indicates that the unsubstituted or substituted cyclopentadienyl ligand M is a group IVB, VB, VIB or VIII Metal (CAS version of the Periodic Table, Cotton & Wilkinson 5th Edition), Y is at least one chelating ligand selected from 0, S, N and P directly bonded to M, X is the same as 是 or selected From the group: hydride, hydroxyl, substituted mesogen, dentate, peroxyacid salt, substituted dibasic acid salt, dibasic acid trifluoromethyl vinegar, acetic acid methyl vinegar, fluoroacetic acid vinegar, Diaryl vinegar, bis (trifluoromethylsulfo) methyl, bis (trifluoromethylsulfo) benzyl, bis (trifluoromethylsulfo) amine, calcined oxide, aryl oxide, Burning base vinegar acid, tetraaryl lutein acid vinegar, tetraphenyl butterfly acid vinegar, substituted tetraphenyl butterfly acid ester, four (five paper sizes common Chinese National Standards (CNS) A4 specifications (2 l0x297) PCT) 11 04 2 Α7 Β7 Central standard of the Ministry of Economic Affairs and only consumer cooperation cooperation. V. Description of the invention (9 fluorophenyl) borate, tetra [bis (3,5-ditrifluorofluorenyl) benzyl] A group of a borate, a tetrafluoroborate, a hexafluorene phosphate, or a pentafluorotellurate, Z is a commanding Lewis base, η > or = 1 ρ > or = 1 m > or = 〇 and q > or = 0, with the proviso that η, m, p, and q are integers or zeros that satisfy the valence of the metal. The bis% pentadienyl ligand can be an alkyl, aryl, dilute, aralkyl, or alkaryl The radical is substituted or two substituents can be combined together to form a bonded ring 'like a benzyl group. The preferred cyclopentadienyl system is substituted with a methyl group. When P is 2', that is, when two dicyclopentadienes When an alkenyl group is present, it can be bonded together via a bridging group, such as by a group of the formula (R2Z) p, where Z is Shi Xi, germanium or carbon, p is 1-8 and R is hydrogen or selected from a hydrocarbon group or a combination thereof . The preferred complexes are those where 10M is wrong, or given, p is 2 and 11 is 1 or 2. Also suitable for use in the present invention are complexes having a suppressed geometric structure, such as those disclosed by EP 416815 or EP 420436. For example, a complex having the following general formula may be applicable: Z — p / / Cp *-μ / \ cn, (xl where Cp * is a single η5-cyclopentadienyl or η5-substituted ring The basic paper size of pentadiene (CNS) A4 size (2! 0X297 mm) ·. ~~） ------ f 4 丨-ί Please read the precautions on the back first This page j -Order-12 T ------------------------- Second.--..._____ ~ „4 2 4 1 Ο 0 I " ^ ΐ-·;: !! '" Ή! ----- 1 Α5-^ __ _Β5_ IV. Abstract of Zhongyou Invention (Invention M claims: Polymerization catalyst is a catalyst composition suitable for polymerizing olefins, It includes a discontinuous metal complex containing at least one chelating ligand of an atom selected from O ′S, N and P and directly bonded to M. The complex is in the Lewis acid It is used in the presence and can be exemplified by bis (cyclopentadienyl) complexes. Typical chelating ligands include acetoacetate and complexes do not require traditional activators (e.g. MAO ). I In * ^ 1 ^^^ 1 n ^ i ^^^ 1 I--· m. In (Please read the precautions on the back before it-it writes each page in the English abstract of the invention (the name of the invention: POLYMERISATION CATALYST Order printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs) A catalyst composition suitable for use in the polymerisation of olefins includes a discrete metal complex having chelating ligands comprising at least one atom from 0, S, N and P bound directly to the metal. The complexes are used in the presence of Lewis acids and may be exemplified by bis (cyclopentadienyl) zirconium complexs. Typical chelating ligands include acetylacetonate and the complexes have the particular advantage of not requiring traditional activators such as MAO. L This paper size is commonly used in China ## (CNS) A4 Grid (2 丨 0 X 297 mm) Notice Λ8 B8 CS Π8 / year 1 η amendment i supplement si Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Behr Consumer Cooperative Co., Ltd. VI. Application for Patent Scope No. 80113216 Patent Reexamination Case Application for Amendment of Scope of Patent Amendment Date: November 89 1. One Application For polymerizing olefins Media composition comprising: (A) a neutral discontinuous metal complex, the general formula of which is: (L) P MYnVq where L represents a ligand that remains bonded to the river under olefin polymerization conditions, M is a group IIIA element or IIIB, IVB, VB, VIB or VIII transition metal (CAS version of the periodic table 'c〇tt〇n & Wilkinson fifth edition) j Y includes at least one selected from 0, S, N The chelating ligand of the atom in P and directly bonded to M, X is the same as hydrazone or is selected from the group consisting of argon, radical, substituted hydroxy, sulfide, peroxyacid, Substituted sulfonates, trifluorofluorenyl sulfonate, methyl sulfonate, fluorosulfonate, aryl sulfonate, bis (trifluoromethylsulfo) methyl, bis (trifluoromethylsulfonate) Group) benzyl, bis (trifluoromethylsulfo) phosphonium amine, alkoxides, aryl oxides, tetrakisylborate, tetraarylsulfonate, tetrabenzylborate, substituted tetra Phenyl borate, tetra (pentafluorophenyl) borate, tetra [bis (3, 5-ditrifluoromethyl) phenyl] borate, tetrafluoroborate, hexafluorophosphate or penta Fluorotellurate, Z is a neutral Lewis base, η > or = 1 ρ > or = 1 m > or = 〇, and this paper size applies the national standard (CNS) A4 specification (210x297 public love) ---- ------------------ Order --------- β, (Please read the ii meaning on the back before filling this page)