TW518344B - Metallocene catalyst for preparing olefin polymer - Google Patents

Abstract

A metallocene complex in which the cyclopentadienyl group is substituted with an alkanediyl silyl group. The yield of the metallocene complex is high, and it can be used as the catalyst for preparing high molecular weight olefin polymers.

Description

518344 * Case No. 89112708 Amended on May. 5, V. Description of the invention (1) The present invention relates to a novel aromatic metal complex __ (metallocene complex), and particularly to an aromatic metal complex The bad 戍 Ermuji was replaced by the alkanediyl si 1 y 1. This aromatic cycloolefin metal complex is suitable for preparing olefin polymers ° -------- ----- olefin-based polymers have been widely used for a long time. One of the most common olefin-based polymers is polyolefin (ρ 〇 1 y 〇 1 e f i n s), that is, a monomer or copolymer of olefin. These polyolefin plastics are generally used in blow molding, injection molding, extrusion coating, films, blanks, pipes, wires, and cables. An example of a polyolefin is an ethylene-propylene elastomer (ethylene-propylene rubber, EP R). Because of its good weather resistance, good heat aging properties, and can be mixed with a large amount of fillers and plasticizers, it is widely used in industry. Typical applications in the automotive industry, such as radiators, heating tubes, vacuum tubes, weather stripping,> sponge doorseals, and so on. Another common olefin-based polymer is terpolymer of ethylene, propylene, and a non-conjugated ed diene, commonly known as EPDM elastomer or EPDM. E P D M elastomer has excellent weather resistance, acidity, and high and low temperature performance. Such properties make EPDM particularly suitable for use as hoses, loops, belts, bumpers, as a blend of plastics and as tire sidewalls in vehicles. In addition, because of its insulation, EPDM is particularly suitable for the insulation of wires and cables. Many catalyst systems have been developed so far for the "polymerization of ene-fume"

518344 J_ Case—No. 89112708__Year Month Day Amendment __— One. Five, the description of the invention (2) can be divided into two categories: Zieg 1 er-Na ΐ ta catalyst system, and aromatic and fine metals Compound catalyst system.

Ziegler et al., In US Patent No. 3, 113, 115, used a TiCl / AlEtCl catalyst system to prepare EPR. Natta et al. In U.S. Patent Nos. 3,3 0,4,5-9, use Yang (: 13 / Aug 1 ((: 61113)) catalyst system to produce general EPR °

Floyd and Ho el. In U.S. Patent Nos. 5,00,205, 4,871,705, and 5,2,9,4,78, 'use, for example, dicyclopentadienyl compounds Aromatic metal compounds to prepare olefin polymers. Dow Chemical Company has developed monocyclopentadienyl compounds in WO 9,308,221 and European Patent No. 0,416,815 A2, in which the cyclopentadienyl group is subjected to a constraint-inducing moiety (such as difluorene Silicon-based). However, the overall yield of this particular constrained geometry catalyst (CGC) is very low (about 30%). There is still a need to develop aromatic cycloolefin metal complexes with high yields and useful as catalysts for the polymerization of olefins. The object of the present invention is to provide an aromatic cycloolefin metal complex with a yield of up to 80%. Another object of the present invention is to provide an aromatic cycloolefin metal complex, which can prepare an olefin polymer with a high molecular weight and high catalytic activity. In order to achieve the above object, the present invention provides an aromatic cycloolefin metal complex having a chemical formula represented by the formula (I) ...

518344 Case No. 89112708 A_Ά said Amendment V. Description of Invention (3) I2

R2 i3) 〇 (I) where M is the group I VB transition metal of oxidation state + 4; Z is the group I VA element; R 1 is a divalent unsubstituted or substituted C 3_ crazy diyl group ( a 1 kanediy 1), a ring-opening system with Z, wherein the substituent is composed of a selective C η alkyl group, a C η alkenyl group, a C 6_2 aryl group, a C 7_2 alkaryl group, and a C 7_2 aralkyl group In the same group; R may be the same or different and are H, C η linear, branched, or cyclic hydrocarbon group, or silane group, or two adjacent R are connected together to form C 4 with the carbon to which they are attached _ Ring system; X is independently an -1 or -2 anionic ligand; and ρ = 2 or 1; Υ is the VA or VI element A; when Y is the VA element, q is 1, When Y is the VI A element, q is 0; and R is Η, or C _2 is a linear, branched, or cyclic hydrocarbon group.

Page 7 518344-^ Mi22〇8-^, Η V. Description of the invention (4)-

LI The present invention provides another aromatic cycloolefin metal complex, the chemical formula of which is shown in the formula ...

'R2 (Π) where: the steel group element, M is a group consisting of optional IIIB transition metals, the oxidation state is + 3; Z is a Group IVA element; R 1 is a divalent unsubstituted or Substituted C— "alkanediyl", which is separated from Z; a ring-forming system, in which the substituents are optionally C 2 alkyl, c 2 alkenyl, c 6_2 aryl, c 7_2 alkylaryl, And c in the group consisting of 70; R may be the same or different; and H '; C is a linear, knife, or cyclic hydrocarbon group, or a silane group, or adjacent R groups are connected together. And the slave to which it is connected forms a C 4-? System; X is independently an -1 or -2 anionic ligand; P = 2 or 1; Y is the VAth or VIA element; when Y is the VAth Element, q is 2, and when Y is the VI Ath element, q is

Page 8 518344 No. 1 89112708

5. Description of the invention (5) 1; and ~ R3 is ί, or Ch linear, branched, or cyclic hydrocarbon group. The figure is simple. Figure 1 shows the 1H NMR chart of the aromatic cycloene metal complex of the present invention. Figure 1— Figure 2 shows the single crystal Xie line mode f of the aromatic cycloene metal product. The invention provides two similar aromatic cycloolefin metal complexes ^ and (II). ， 人 @ In formula (I), M is a Group IVB transition of oxidation state +4, [generating metals 'such as Ding 1 (+4), 21' (+ 4), and 1 ^ (+ 4). 2 is a column of Group 11 ^ elements: carbon, silicon, and germanium. R may be a divalent unsubstituted or substituted C 3_alkanediyl. The substituent may be a C 2 phenyl group, a C 2 alkynyl group, a C 6-2 carbaryl group, a C 7_2 madaryl group, or a C 7_2 alkyl group. Preferably, R 1 is a divalent unsubstituted C 3 -alkanediyl group which forms a ring system with 2. Specific examples of R 1 include trimethylene, tetramethylene, pentamethylene, and hexamethylene. R may be the same or different, and are independently H, C2, bicyclic, branched, or cyclic hydrocarbon (hydrocarby 1), or silane (si ly 1). The silyl group may be an alkyl silyl group, an alkyl silyl group, a p-dimethylsilyl group, a trimethylsilyl group, and a methylethylsilyl group. Or ^ 'Two adjacent R rivers are connected together and form a system with the carbon to which they are connected, 0

Specifically, the C, C, and C 2 linear, branched, or cyclic hydrocarbon groups can be c, Ch, or (6_2 Suixiang, C7_2 aryl, 2 aralkyl. R lack of specific examples Including η ^ 5 methyl, ethyl, propyl isobutyl, pentyl, isopentyl, hexyl, ethyl hexyl

Page 9 518344 __Case No. 89112708 _ Year and month Amendment _ V. Description of the invention (6) Octyl, vinyl, dipropyl, isopropyl, phenyl, and fluorenyl. _ Specifically, when two adjacent Rs are linked together to form a C 4_ ring system with the carbon to which they are connected, R may form a saturated or unsaturated polycyclic ring with the cyclopentadienyl moiety connected to it. A pentadienyl ligand, such as indenyl, tetrahydroindenyl, fluorenyl, or octahydrofluoro. -One-

Examples of C 5 (R 2) include 5-cyclopentadienyl, 7? 5-methylcyclopentadienyl, 77 5-ethylcyclopentadienyl, 7? 5-tetramethylcyclopentyl Dienyl, 7? 5-pentamethylcyclopentadienyl, 77 5-n-butylcyclopentadienyl, indenyl, tetrahydrogenyl, fluorenyl, and octafluorene Fluoro. R is H, Ch alkyl, Ch alkenyl, C6_2 aryl, C7_2 alkaryl, or C 7-2 (P5 " carbon. X may be an anionic ligand of -1 or -2 valence. When X When it is an anionic ligand with a valence of -1, p = 2, and specific examples of X at this time include fluorene, C carbamoyl, halogen, alkoxy, aryloxy, and fluorenylamino. When X is -2 Valence anion S jijiji, p = 1, X may be dicarborane dianiono When Y is a Group VA element, specific examples are nitrogen, phosphorus, and arsenic. When Y is a Group VI Α element, specific examples For oxygen, sulfur, and bump.

When Y is a Group A element, Q is 1, and when Y is a Group A element, q is 0. Specific examples of Y (R3) 拗 include -NH-, N (CH3)-, N (t-butyl)-, -PH-, -P (CH3)-, -P (t-butyl)-, -0-, And -S-o Another aromatic cycloolefin metal complex provided by the present invention has a chemical formula represented by formula (II), and its structure is similar to that of formula (I), but the bonding between M and Y is different. And M in formula (II) is a transition metal of oxidation state +3.

Page 10 518344 ^ _ Case No. 89112708 _ Che Yue Yue Xiu _ V. Description of the invention (7) In formula (II), M may be a transition metal of group IIIB, such as samarium, -yttrium, lanthanide , Or titanium. The bond between M and rhenium is not a covalent bond, but a dative bonding in which rhenium supplies two electrons to M. The definitions of the symbols Z, R1, R2, X, Υ, and R 噚 in formula (II) are the same as those in formula (I). ○-X may be -1 or -2 anionic ligands. When X is an anionic ligand with a valence of -1, ρ = 2, and specific examples of X at this time include fluorene, C carbamoyl, halide, alkoxy, aryloxy, and fluorenylamino. When X is a -2 anionic ligand, p = 1, and X may be a dicarborane dianion. For formula (II), specific examples of Y (R3) include OH, 0CH3, SH, SCH3, NH2, N (CH3) 2, NH (CH3), NH (C6HU), N (C6Hn) 2, NH (tert- butyl), PH2, P (CH3) 2, PH (CH3), PH (C6Hn), and p (c6h ") 2. In the present invention, the aromatic cycloene metal complex can be combined with an activated co-catalyst to form a catalyst composition, and this catalyst composition can be used to prepare a high molecular weight olefin polymer. The activation catalyst may be aluminoxane, trisalyl I, a dialkyl aluminum halide, inert non-coordinating anionic salts, or a mixture thereof. _ A commonly used and commercial Shaoxing hospital is methyl aluminoxane (MAO). Trisalyl aluminum is selected from the group consisting of free trisyl group | Lu, triethyl group ‘tripropyl group’ triisopropyl group, tributyl group, and triisobutyl group group (TIBA). ^ The inert non-coordinating anion may be a monoborate. Borates suitable for the present invention include N, N-difluorenylbenzyl (pentafluorophenyl) borate

518344 __Case No. 89112708_year month_repair ____ V. Description of the invention (8) (N, N-dimethyl anilinium tetrakis (pentaf luorophenyl) borate) 'Triphenyl carbon rare earth (pentafluorobenzyl) (Tri phenyl carbenium tetrakis (pentafluorophenyl) borate), tri methy 1 ammonium (pentafluorophenyl) borate (tri methy 1 ammonium ------------ tetrakis (pentafluorophenyl) borate) , Ferrocenium (pentaphenyl) borate (ferrocenium tetrakis (pentaf luorophenyl) borate), dimethyl tetrakis (pentafluorophenyl) borate (dimethyl tetrakis (pentafluorophenyl) borate), and silver shop ( Pentafluorobenzyl) silver tetrakis (pentafluorophenyl) borate. The activated co-catalyst is preferably a mixture of fluorenyl aluminoxane salts or a mixture of triisobutylaluminum and alumoxane. Media), can be synthesized olefin polymers. In the presence of a catalyst effective amount of bright aromatic cycloolefin, which is a chemical catalyst, and under the conditions of polymerization, the olefin monomer can be polymerized (ie, homopolymerized) to obtain olefin monomer and other The monomers are polymerized (copolymerized) one. Wear "4: can be ethylene, or α-smoke. The water β-substance paid by the invention can be an ethylene homopolymer, an α-olefin, an α-olefin copolymer, and ethyl acetate. Hydrocarbons include co-products of olefins having a carbon number of 3 to 12. α-ene, buxene, bucinene ... such as buprofine, bubutene, bupentene, etc. The catalyst system of the present invention is particularly suitable for use To make B

Page 12 518344 __Case No. 89112708_Year Month Amendment __ V. Description of the Invention (9) Homopolymers of olefins, including high-density polymers with broad molecular weight distributions, multimodal lines, or bimodal line fractions + quantity distributions Ethylene (HDPE), which can be used in high molecular weight films and blow molding. In addition, in particular, the catalyst system of the present invention is particularly suitable for preparing a copolymer of ethy 1 ene-and propylene (EPR), and it is also suitable for preparing ethylene, a C3_12a-Copolymer of olefin and a non-conjugated diene. In particular, when the C 3-12 α-olefin is propylene, a copolymer of ethylene, propylene, and a non-conjugated diene can be obtained, which is called EPDM. A suitable non-conjugated diene may be 5-ethylidene-2-norbornene (ENB), 5-methylene-2-orbornene (5-methylene-2— norbornene), 5-vinyl idene-2-norbornene, 1,4-hexadiene (HD), or dicyclopentadiene DCPD). The present process is carried out under the present process. Under the gas phase and the solution temperature, the polymerization of the aromatic ring dilute gold that is part of the range of the following methods and features is also possible. Therefore, the obtained clear catalyst system is suitable for a liquid polymerization reaction state. At atmospheric pressure to 3, there are several embodiments and advantages, but it is not used to control the amount of the synthesizer which belongs to the attached patents, percentages, and proportions according to the required range. = Slurry reaction state. Hydration reaction is usually performed at 0 0 psi between 0 ° C and 250 ° C. = To further explain the method of the present invention t limit the date and month of the issue> 4Ar. ^ Ng range is it, the present invention $ Μ'quasi. Unless otherwise stated, all weights are based on weight. Example 1: Preparation of (C5Me4H) Li

518344: _Case No. 89112708_ Year Month Day Amendment V. Description of Invention (10)

Tetramethylcyclopentadiene (8.57 g, 70.2 mmole) was placed in a 300 ml round-bottomed flask and dissolved in 150 m 1 of ether. This clear solution was cooled to -78 ° C, and 1 equivalent of n-buty 1 lithium (n-BuLi) was injected through a syringe. The mixture immediately turned yellow and gradually disappeared in color. Allow the mixture to warm to room temperature (about 20-30 ° C) and stir overnight. Filtration gave 4.8 3 g of lithium salt. Example 2: Preparation of (C5Me4H) (C3H6) SiCl

Me

The lithium salt (4.8 g, 0.03 75 mole) obtained in Example 1 was suspended in a mixed solvent of toluene / THF (volume ratio 2: 1). This slurry was cooled to -78 ° C and an excess of trimethylenesilyl dichloride was injected with a syringe. The mixture was warmed to room temperature and stirred overnight. Then, it was vacuum-dried to remove the solvent and excess dichlorite. Pentamyl was added to remove L i C 1. The yellow filtrate was dried to obtain an oil.

Page 14 518344

Page 15

518344 __Case No. 89112708_Amendment of the Year and Month_ V. Description of the Invention (12) The ligand obtained in Example 3 (8 · 1 g, 3 0 · 7 8 mmo 1 e) is 2J 0 m 1 diethyl ether Dissolve. The solution was cooled to -7 ° C, and then 2 equivalents of η-B u L i was injected through a syringe. No significant change. The mixture was drained to reduce the amount of solvent to one-third of the original amount and stirred overnight. Filter to collect 7.5 g of a white solid. Example 5: Preparation of (C5Me4) (C3H6) Si (t-BuN) TiCl2 [trimethylenesi lylenecyclopentadienyl-t-butylamido d i ch 1 orot i tan i um]

The dilithium salt (2.07 g) and Ti Cl 3 (thf) 3 (including the tetrahydrofuran and T i C 1 surface adducts) obtained in Example 4 were respectively suspended in 2 5 m 1 of THF (tetrahydrofuran). ), And cooled to -30 ° (:. Mix the two solutions and stir. The mixture will turn black after 1 hour and a clear solution of dark blue after 3 hours. Then, place this clear solution of dark blue into In an aluminum foil-coated bottle, excess AgCl (2.1 g) was added and stirred overnight in the dark. The reaction mixture was a clear orange-red. Filtered to remove the Ag salt.

Page 16 518344 Case number 89112708

V. Description of the invention (13) The red filtrate is drained and the residue is dissolved in 40 ml of toluene.过 忧 # Removed Li C 1 and concentrated again to precipitate a yellow solid, which was filtered and collected as a yellow solid (2.2 g). The yield is about 80%, which is higher than the yield of the conventional 'constrained geometry catalyst' (CGC). The E NMR spectrum of the solid product is shown in Figure 1. Figure 2 is a single crystal X-ray model of an aromatic metal product. Example 6

SiMe3

LiCl + Me-Si-Cl Me Dissolve 1-9 g of cyclopentadienyllithium (CpLi) (26.8 mmol) in 50 ml of THF, stir, and cool to -30 ° C. 3 g of gasified trimethylsiiyi chloride (TMSC1) (27.6 mmol) was diluted with 10 ml of THF and cooled to -3 (TC. This diluted TMSC1 was added dropwise to the CpLi solution at room temperature. It was reacted for 24 hours. Then, it was vacuum-dried under vacuum to remove the solvent. Pentane was added to remove L i C 1. The filtrate was vacuum-dried to obtain 21 g of C 5H 5S i M e yellow liquid. Example 7

518344 Case No. 89112708 _η Revision V. Description of the invention (14)

SiMe,

SiMe,

KH ύ κΘ + η2 The C 5Η 5S i Μ e 3 (1.9 g) obtained in Example 6 was dissolved in 20 m 1 of TfF. 0. 65 g of K H was suspended in 30 m 1 of T H F. The two solutions were cooled to -30 ° C for 30 minutes. The C 5H 5S i M e solution was added to the K Η solution, and the mixture was allowed to warm to room temperature. The transition is to remove KK ′ after 5 and the filtrate is cooled to −30 ° C for use in Example 8. Example 8

SiMe,

SiMe,

K TMSCl Q SiMe 'The potassium salt filtrate obtained in Example 7 was diluted with THF and cooled to -30 ° C. Dilute 1.5 g of TMSC1 with 10 ml of THF and then cool to -30 ° C. The TMSC 1 solution was dropped into the mash salt solution, and the mixture was warmed to room temperature and stirred overnight. It was then dried under vacuum to remove THF. Ethyl alcohol was added to remove K C 1. The filtrate was pumped to dryness to obtain 2.1 5 g of C 5H 4 (S i M e 3) 2. Example 9

Page 18 518344 Case No. 89112708 Month, Day Amendment V. Description of Invention (15)

SiMe3

KH

'SiMe3

+ ¾ SiMe3

C 5H 4 (SiMe 3) 2 (2.15 g) and 0.42 g of KH obtained in Example 8 were each diluted with 30 ml of THF, and then cooled to -30 ° C. C 5H 4 (S i M e 3) pain solution was dripped into the KΗ solution, and the mixture was allowed to warm to room temperature and stirred overnight. Then, it was filtered to remove KH. The filtrate was dried under vacuum to obtain 2. 4 5 7 g of tream salt. Example 1 0

THF / pentane

SiMe3 ♦ κΘ

SiMe3

The potassium salt (2.445 g) obtained in Example 9 was dissolved in 50 ml of a THF / pentane mixed solvent (volume ratio 1: 1). This slurry was cooled to -78 ° C, and then an excess of trimethylene silicon dichloride (2.8 g) was injected through a syringe. The mixture was warmed to room temperature and stirred overnight. Then, it was vacuum-dried under vacuum to remove the solvent, filtered, and washed with pentamidine. The filtrate was dried to obtain a yellow liquid (2.3 8 g, yield = 77%).

Page 19 518344 __Case No. 89112708_ Year Month Date _ Amendment V. Description of the Invention (16) Example 1 1

The yellow liquid (C 5H 3) (Si Me 3) 2 (C 3H 6) Si C 1 (2.38 g) and NMe2Li (0.38 5 g) obtained in Example 10 were dissolved in 20 ml of toluene, respectively. Medium, cool to -3 ° C for 2 hours. Add the (C 5H 3) (S i Me 3) 2 (C 3H 6) S i C 1 solution to the NMe 2L i solution dropwise, warm the mixture to room temperature, and stir overnight. The reaction mixture was filtered, dried under vacuum and washed with pentane. The filtrate was evaporated under vacuum at 80 ° C. 0.74 g of the distilled liquid was recovered as a yellow clear liquid (yield = 60 · 5%). Example 1 2

The amines (0.74 g) and KH (0.1 g) obtained in Example 11 were separately dissolved in 20 ml of THF, and cooled to -30 ° C for 30 minutes. The amine solution was added dropwise to the KH solution, and the mixture was warmed to room temperature and stirred overnight. The reaction mixture was filtered, suction-dried, and washed with ethyl alcohol. Recovered 0.69 g of steam

Page 20 518344 _Case No. 89112708_ Year Month and Day_ «V. Description of the invention (17) German liquid is a light yellow liquid. Example 1 3

The potassium salt (0.69 g) and T i C 1 3 (t h f) 3 (0.70 7 g) obtained in Example 12 were separately dissolved in THF and cooled to -30 ° C. The potassium salt was added dropwise to the T i C 1 3 (t h f) mash, the mixture was allowed to warm to room temperature, and stirred for 3 hours. The reaction mixture was filtered, suction dried, washed with toluene, and filtered. The filtrate was drained and recrystallized from toluene / pentane to obtain a green solid. Synthesis of polymers Example 14 4: Synthesis of ethylene-propylene rubber (EPM)

The reaction tank was heated to 105 ° C and nitrogen was injected for 5 minutes to remove oxygen from the reactor. The reaction tank was then evacuated for 2 hours to ensure complete removal of moisture and oxygen. The temperature of the reaction tank was adjusted to 80 ° C, and toluene of 500 m 1 was injected. After the temperature has stabilized, add 8 ml (1.2 x 10_2mol) of MAO (methyl aluminum oxide) and mix. After 5 minutes, 2 m 1 (4x 1 0 -6mo 1) of the aromatic cycloolefin metal catalyst obtained in Example 5 dissolved in toluene was added and stirred. After stirring at 80 ° C for 1 minute, 100 ps i of ethylene and propylene gas (volume

Page 21 518344 Case No. 89112708 Five. Description of the invention (18) Ratio: 40/50) Injected into the reactor After the polymerization reaction is complete, the solution is deposited; Filter the product, dry it, and make each 籀, 咚 to make the house settle. Just try. The results are shown in Table 1. Examples 15 and 16 are as described in Example 14, but the reaction temperature is changed. The results are shown in Table \. UU 1 7 · To synthesize ethylene propylene diene rubber (epdm), the tank should be heated to 105 ° C, and nitrogen should be injected for 5 minutes to remove oxygen from the reactor. The reaction tank was then evacuated for 2 hours to ensure complete removal of moisture and oxygen. The temperature of the reaction tank was adjusted to 800 ° C, and toluene was injected at 5000 m. After the temperature was stabilized, 8 m 1 (1.2 x 1 0, 0 1) of μ A 0 (methylaluminoxane) was added and stirred. After 5 minutes, 2 m 1 (4x 10 to 6 mo 1) of the aromatic cycloolefin metal catalyst obtained in Example 5 dissolved in toluene was added and stirred. After stirring at 80 ° C for 5 minutes, 10 m 1 of 5-ethylidene-2-norbornene (ENB) was added and stirred. After 1 minute, 100 psi of ethylene and propylene gas (volume ratio: 40/50) was injected into the reactor. After the polymerization reaction was completed, the solution was cooled and methanol was added to precipitate the product. The product was filtered, dried, and subjected to various tests. The results are shown in Table 1. The procedure of Example 18 was the same as that of Example 17 except that the ethylene / propylene feed ratio was changed to 50/40 (volume ratio). The results are shown in Table 1.

Page 22 518344 1-Case No. 89112708_year a_ amendment V. Description of the invention (19) Table 1 Example reaction strip with activity _ Product property temperature ENB (xlO5 g / g-metal-hr) Tg E / P Mw MWD (° C) (ml) Molar ratio 14 80 0 3.97 -39.4 43/57 368,320 3.3 15 95 0 4.8 -39 41/59 157,787 2.9 ^ 16 110 0 3.2 -42.4 47/53 117,209 2.6 17 80 10 0.8- 43 68/32 18 80 10 0.8 -43 68/32

E / P feed ratio = 40/50 (Examples 14-17) E / P remote feed ratio = 50/40 (Example 18) Pressure = 100 psi Comparative Examples 1-3 The procedure is the same as that of Example 14 but the used The aromatic cycloolefin metal catalyst is C5Me4 (Me2Si-N-tert-Bu) TiCl2 [dimethylsilylcyclopentadienyl-1 -butylamidino titanium dichloride; dimethylsilylcyclopentadienyl-t-butylamidodichlorochloro, Is a constrained geometry catalyst (CGC)], and the reaction volume is changed, and the feed volume ratio of ethylene and propylene gas is changed to 50/50. The results are shown in Table 2.

Page 23 518344 _ Case No. 89112708_ Year Month Day _ Amendment V. Description of the invention (20) Table 2 Comparative Example Reaction Temperature CC) Activity (xlO5 g / g-metal-hr) Product i Biomass Tg rc) E / P Morwbee Mw MWD 1 80 1.2 -43.9 63/37 334,544 2.5 2 100 0.51 -47.3 67/33 203,518 2.36 3 120 0.49 -47.44 67/33 247,183 3.14

E / P feed ratio = 50/50 Lean force = 1 00 psi From the results of Table 1 and Table 2, it can be seen that the catalyst of the present invention has higher catalytic activity than the conventional CGC. Moreover, the olefin polymer obtained from the catalyst of the present invention has a relatively high molecular weight. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make changes and retouching without departing from the spirit and scope of the present invention. The scope of protection shall be determined by the scope of the attached patent application.

Page 24 518344 _Case No. 89112708_ Year Month Day _ Amendment

Page 25

Claims (1)

518344 _Case No. 89112708_ Year and Month Amendment_ 6. Scope of Patent Application R is H, or Ch is linear, branched, or cyclic carbofluorenyl. — 2. The aromatic cycloolefin metal complex as described in item 1 of the scope of the patent application, wherein R 1 is a divalent unsubstituted C 3_alkanediyl group forming a ring system with Z. 3. The aromatic cycloene metal complex as described in item 2 of the scope of the patent application, wherein R1 is trimethylene. --------------- 4. The aromatic cycloolefin metal complex as described in item 1 of the scope of patent application, wherein Z is Si. 5. The aromatic ring dilute metal complex as described in item 1 of the scope of the patent application, wherein R stands for selenium, C 2 alkyl, C 2 alkyl, C 6_2 aromatic, C 7_2 alkyl Group, C 7_2 aralkyl group, and silyl group. 6. The aromatic cycloolefin metal complex as described in item 5 of the scope of patent application, wherein RI Shu Li is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, pentyl, and isopentyl. Group, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, and tolyl. 7. The aromatic ring sulfonium metal complex as described in item 5 of the scope of patent application, wherein R stands for methylsilyl, dimethylsilyl, trimethyl In the group consisting of alkyl and methyl ethyl. 8. The aromatic cycloene metal complex as described in item 1 of the scope of patent application, wherein two adjacent Rs are linked together to form a C 4-pole system with the carbon to which they are linked. 9. The aromatic ring dilute metal complex as described in item 8 of the scope of the patent application, wherein R is more saturated or unsaturated than the cyclopentadienyl moiety to which it is attached. Page 27 518344 _ case number 89112708 _ year month__ Sixth, the scope of patent application Cyclopentadienyl ligands of the ring. _ 1. The aromatic cycloolefin metal complex as described in item 9 of the scope of the patent application, wherein R and its cyclopentadienyl moiety form indenyl, tetrahydroindenyl, fluorenyl, or octahydrofluoro base. 11. The aromatic ring dilute-gold repeated complex I described in item 1 of the scope of the patent application, where X is an anionic ligand of -1 valence, p = 2, and X is selected from fluorene, C hydrocarbon, and halogen , Alkoxy, aryloxy, and amido groups. 12. The aromatic cycloolefin metal complex as described in item 1 of the scope of patent application, wherein q is 1, and Y is a Group VA element. 13. The aromatic cycloolefin metal complex as described in item 1 of the scope of the patent application, wherein q is 0 and Y is a Group VI A A element. 14. The arylcycloolefin metal complex as described in item 1 of the scope of the patent application, wherein R is optional H, C 1-2 alkyl, C 1-2 cupyl, C 6-2 (5 ^ , C 7-2 Zhu aryl, C 7_2 threonyl group. 1 5. —An aromatic cycloolefin metal complex catalyst composition for the preparation of olefin polymers, including: '(a) if applied The aromatic cycloolefin metal complex as described in the first item of the patent scope; and (b) —activation promoter, selected from aluminoxane, three-burner base, and dialkyl dihalide aluminum halide), salts of inert and non-coordinating anions, and mixtures thereof, in which the aromatic ring dilute metal complex of (a) is used in an amount of 0. 0 (Π ~ 0. 0 0 0 0 1 times, wherein the amount of the (b) activating catalyst used is 200 to 6 0 000 times of (a) the aromatic cycloolefin metal complex. Page 28 518344 _Case No. 89112708_ Year & Month> Name ___ VI. Patent Application Range 16 · The catalyst composition according to item 15 of the patent application range, where _ the trialkyl aluminum is optional Methyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, and triisobutyl aluminum (TIBA). 17. The catalyst composition as described in item 15 of the scope of patent application, wherein the inert and non-coordinating anion is a borate. 1 8 · The catalyst composition as described in item 17 of the scope of the patent application, wherein the borate is N-N-dimethylaniline (pentafluorophenyl) borate (N, Nd i me thy 1 anilinium tetrakis (pentafluorophenyl) borate), triphenyl carbenium tetrakis (pentafluorophenyl) borate, trimethyl ammonium tetrakis (pentafluorophenyl) borate ), Ferrocenium (pentafluorophenyl) borate (ferrocenium tetrakis (pentafluorophenyl) borate), dimethyl (pentafluorophenyl) borate (dimethyl tetrakis (pentafluorophenyl) borate), and silver tetrakis (pentafluorophenyl) petrate (si lver tetrakis (pentafluorophenyl) b o r a t e) in the family of monarch sheep. 19. The catalyst composition as described in item 15 of the scope of patent application, wherein the activating co-catalyst is fluorenyl aluminoxane. 20. The catalyst composition according to item 15 of the scope of the patent application, wherein the activating co-catalyst is a mixture of trialkylaluminum and borate. Page 29 518344 _ Case No. 89112708 _ year month and month amendment _ 6. Patent application scope 2 1. A method for preparing an olefin polymer, including the catalyst composition described in the patent application _ scope item 15 In the presence of an effective catalyst amount and polymerization conditions, (1) polymerize an olefin, or (2) polymerize an olefin and another monomer. 2 2. The method according to item 21 of the scope of patent application, wherein the method comprises polymerizing an olefin, and the olefin is ethylene. 2 3. The method according to item 21 of the scope of patent application, wherein the method comprises polymerizing at least one olefin and another monomer, wherein the olefin is ethylene, and the other monomer is at least one carbon number of 3 to 1 2 alpha-olefins. 24. The method of claim 23, wherein the method comprises polymerizing at least one olefin and at least another monomer, wherein the olefin is ethylene and the other monomer is propylene. 25. The method according to item 21 of the scope of patent application, wherein the method comprises polymerizing a monohydrocarbon, wherein the olefin is an α-olefin having 3 to 12 carbon atoms. 26. The method according to item 21 of the scope of patent application, wherein the method comprises polymerizing an olefin and another monomer, wherein the olefin and the other monomer are both α-dilute carbons having 3 to 12 carbons. hydrocarbon. 27. The method of claim 21, wherein the method comprises polymerizing at least one olefin and another monomer, wherein the olefin includes ethylene and an α-olefin having a carbon number of 3 to 12, and the other The monomer is a non-conjugated diene. 28. The method as described in item 27 of the scope of the patent application, wherein the non-conjugated diene is 5-ethylidene-2-norbornene (ENEB), 5 -5-methylene-2-norbornene, 5-methylene-2-norbornene 518344 Case No. 89112708 Amended on the Month of the Sixth, Patent Application Range (5-viny 1 idene-2-nor bor ne ne), 1,4-hexadiene (HD), and Dicyclopentadiene (DCPD). 29. The method according to item 21 of the scope of patent application, wherein the polymerization reaction is performed in the presence of hydrogen. ____________ 30.—Aromatic ring dilute metal complex with the chemical formula of formula (II): R2 (Q) Among them: M is a group consisting of transition group I I I B transition metals, lanthanides, and titanium, and the oxidation state is +3; Z is an element of Group I VA; R 1 is a divalent unsubstituted or substituted C 3_ kanediy 1 (a 1 kanediy 1), and Z; a ring-forming system, wherein the substituent is a free C Base, C-base, C 6_2 aryl, C 7_2 aryl, and C 7-2 aryl Page 31 518344 _Case No. 89112708 _ Year and month amendments_ VI. In the group of patent application bases; _ R can be the same or different and H, C Η linear, branched, or cyclic hydrocarbon Group, or silane group, or two adjacent R are connected together to form a C 4_ ring system with the carbon to which they are attached; X is independently an -1 or -2 anionic ligand; 2 or 1;- ------- Υ is the VA or VIAA element; when Y is the VA element, q is 2; when Y is the VIA element, q is 1; and R 3 is Η, or C 2 Linear, branched, or cyclic hydrocarbon. 31. The aromatic cycloolefin metal complex as described in item 30 of the scope of patent application, wherein R 1 is a divalent unsubstituted C 3 -alkanediyl group forming a ring system with Z. 32. The aromatic cycloolefin metal complex according to item 31 of the scope of patent application, wherein R1 is a trimethylene group. 3 3. The aromatic cycloolefin metal complex as described in item 30 of the scope of patent application, wherein Z is Si. 3 4. The arylcycloolefin metal complex as described in item 30 of the scope of the patent application, wherein R stands on the ground is selenium, C 2 2, C 2 2, C 6_20 aromatic, C 7_2 Among the group consisting of alkaryl, C 7_2 aralkyl, and silyl groups, the arylcycloolefin metal complex as described in the scope of application for patent No. 34, wherein R stands for selective free Η, 曱Base, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, And tolyl. Page 32 518344 _Case No. 89112708 _ Month and Day __ VI. Application for patent scope 36. The aromatic cycloolefin metal complex as described in the scope of patent application No. 34, in which R stands on the ground. Group consisting of methylsilyl, dimethylsilyl ^ trimethylsilyl, and methylethylsilyl. 37. The aromatic cycloolefin metal complex as described in item 30 of the scope of patent application, wherein two adjacent R are connected together to form a C 4-ring system with the carbon to which they are connected. 38. The aromatic cycloolefin metal complex as described in item 37 of the scope of the patent application, wherein R and its attached cyclopentadienyl moiety form a saturated or unsaturated polycyclic cyclopentadienyl Ligand. 39. The aromatic cycloolefin metal complex as described in item 38 of the scope of patent application, wherein R and the cyclopentadienyl moiety connected to it form indenyl, tetrahydroindenyl, fluorenyl, or octahydrofluoro base. 40. The aromatic cycloolefin metal complex as described in item 30 of the scope of the patent application, wherein X is an anionic ligand with a valence of -1, p = 2, and X is selected from Η, C 1-2 f carbon In the group consisting of nitrogen group, tooth element, alkoxy group, aryloxy group, and amino group. 4 1. The aromatic cycloolefin metal complex as described in item 30 of the scope of patent application, wherein q is 2, and Y is a Group VA element. 4 2. The aromatic cycloolefin metal complex as described in item 30 of the scope of the patent application, wherein q is 1, and Y is a Group VI A A element. 4 3. The aromatic cycloolefin metal complex as described in item 30 of the scope of the patent application, wherein R is selective H, C η alkyl, C η alkenyl, C 6_2 aryl, C 7_2 alkaryl, C 7_2 threonyl group. 4 4. An aromatic cycloolefin metal complex for the preparation of olefin polymers Page 33 518344 _Case No. 89112708_Year_Month__ VI. Patent application media composition, including: _ (a) the aromatic cycloene metal complex as described in item 30 of the patent application scope; and ( b) —Activation promoter, which is selected from the group consisting of free aluminoxane, trialkylaluminum, dialkyl halides, inert and non-coordinating anions, and mixtures thereof. ) Of the aromatic cycloolefin metal complex, the amount of use of which is 0. 0 (Π ~ 0 0 0 0 0 0 times the product, wherein the amount of (b) activating catalyst is (a) aromatic 200 to 600 times of the cycloolefin metal complex. 45. The catalyst composition as described in item 44 of the scope of patent application, wherein the trialkylaluminum is a selective trifluorenyl aluminum, triethyl Aluminium, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum (TIBA) in the group consisting of 406 The inert and non-coordinating anions are borates. 4 7. The catalyst composition according to item 46 of the patent application scope, wherein the borates are optional N, N -Dimethylaniline (pentafluorophenyl) borate, triphenylcarbene (pentafluorophenyl) shed, tris (trifluoroammonium) (pentafluorophenyl) shed, ferrocene (Pentafluorophenyl) acid salt, difluorenyl (pentafluorophenyl) borate salt, and silver (pentafluorophenyl) borate salt group. 48. As described in item 44 of the scope of patent application The catalyst composition, wherein the activation co-catalyst is methylalumoxane. 4 9. The catalyst composition according to item 44 of the scope of application for a patent, wherein the activation co-catalyst is a trialkyl group | g and A mixture of acid salts. 5 0. A method for preparing olefin polymers, including 518344 _Case No. 89112708_ Modification of the month of the year _ 6. In the presence of an effective catalyst amount of the catalyst composition described in item 4 and scope of the patent application, and under the conditions of Cuihe, (1) polymerize an olefin, or (2 ) Polymerizing one olefin with another monomer. 5 1. The method as described in claim 50 of the scope of patent application, wherein the method comprises polymerizing a residual hydrocarbon, and the olefin is ethylene. ________________ 5 2. The method according to item 50 of the scope of patent application, wherein the method comprises polymerizing at least one olefin with another monomer, wherein the olefin is ethylene, and the other monomer is at least one carbon number of 3 to 1 2 α-olefins. 53. The method of claim 52, wherein the method comprises polymerizing at least one olefin and at least another monomer, wherein the olefin is ethylene and the other monomer is propylene. 5 4. The method as described in item 50 of the scope of patent application, wherein the method comprises polymerizing an olefin, wherein the olefin is an α-olefin having 3 to 12 carbon atoms. 5 5. The method as described in claim 50 of the scope of patent application, wherein the method comprises polymerizing an olefin and another monomer, wherein the olefin and the other monomer are both α-olefins having a carbon number of 3 to 12 . 56. The method of claim 50 in the scope of patent application, wherein the method comprises polymerizing at least one olefin and another monomer, wherein the olefin includes ethylene and an alpha-olefin having a carbon number of 3 to 12, and the other The monomer is a non-conjugated diene. 5 7. The method as described in item 56 of the scope of patent application, wherein the non-co-chemic dilute is selective free 5-ethylidene-2 -orbornyl, 5 -methylene-2 -orbornylene , 5-vinylidene-2-orbornene, 1,4-hexadiene, and dicyclopentadiene. 58. The method as described in claim 50 of the scope of patent application, wherein the polymerization Page 35 518344 Case No. 89112708_Year_Month_ Amendment VI. The scope of patent application reaction is performed in the presence of hydrogen lie Page 36 Order if No .: 89112708 f. Amendment-rr _ Invention Patent Specification 518344, Invention Name in Chinese Aromatic metal catalysts used to prepare olefin compounds. Metallocene Uatalyst for Preparing Olefin Polymer Name (Chinese) 2. Cai Jingcheng 3. Chen Yijun 4. Tong Shousong Inventor Applicant Nationality Residence and Residence Yin Ming 4f] Name 3 (Name) (Clip) (Four spears period representative surname (中 #) l. Ching Ting 2 · Jing-Cherng Tsai 3. Yi-Chun Chen 4 · Sung-Song Hua i · Republic of China 2. Republic of China 3. Republic of China 4. Republic of China 1. 堑 Ιίΐ Kaofu Road, Section 2, No. 303, 6th Floor 2. Xiangxiong + No. 56, Jinzhou Street, Ermin District 3. Hsinchu City, 4th Floor, No. 63, Lushui Road 4 4th Floor, No. 3, Lane 8, Lane 35, Lane 35, Chongqing Road 1. Industrial Technology Research Institute 1. Republic of China _____ Γ Section 4, Jinxing Road, Zhudong Town, Hsinchu County-No. 95 1. Sun Zhen Representative (English 3) Page 1 518344 89112708 1 · An aromatic cycloene metal complex having the formula (I): ⑴ Among them: M is the group I VB transition metal of oxidation state + 4; Z is the group I VA element; R 1 is a divalent unsubstituted or substituted C 3_ probedyl (a 1 kanediy 1) , And Z form a ring system, wherein the substituent is selected from the group consisting of C 1-2 phenyl, C η diaryl, C 6_2 aromatic, C 7-2 antiaryl, and C ^ consisting of groups; 7'2 Your ring is the same or different size, and is H, C 2 linear, branched, hydrocarbon group, or silane group, or two adjacent r connected together and 1 connected carbon Form a C 4_ ring system; ^ X is independently an anion ligand of -1 or ~ 2 valence; and Y is the VAth or VIA element; ash When Y is the VAth element, _ 丨, when γ is Vu element 0; and f 5