TWI225073B - Catalyst composition for preparing olefin polymer having a broad molecular weight distribution - Google Patents

Abstract

The present invention relates to a catalyst composition comprising a bridged biscyclopentadienyl metallocene, a monocyclopentadienyl metallocene, and an activating cocatalyst. By using the catalyst composition, monomodal or bimodal olefin polymers having a broad molecular weight distribution can be prepared.

Description

1225073 Case No. 89112710 Λ_3 Β Modification 5 & Description of the Invention (1) The present invention relates to a catalyst composition for preparing an olefin polymer, and more particularly to a single-type or multi-type for preparing a wide molecular weight distribution. Catalyst composition of a dilute hydrocarbon polymer. Alumoxane-activated metal locene catalysts can effectively polymerize olefinic monomers to produce polymers with a relatively narrow molecular weight distribution. However, in many applications such as injection molding or molding processes, unimodal or multimodal (mu 11 i _ m 0da 1) ethylene polymers with a wide molecular weight distribution are extremely needed because of this type The polymer has very good handling properties (pr occessabi 1 ity). Therefore, a highly efficient aromatic cycloolefin metal catalyst system capable of providing a wide molecular distribution ethylene polymer will be urgently needed by related industries. The object of the present invention is to provide a novel catalyst composition which can be used to prepare single-type or multi-type dilute hydrocarbon polymers with a wide molecular weight distribution. In order to achieve the above object, the catalyst composition for preparing a wide molecular weight distribution olefin polymer according to the present invention includes: (a) a bridged biarylcycloolefin metal compound represented by the chemical formula (B),

MY, «(B)

Page 5 1225073 Case No. 89112710 Amended 5. Description of the invention (2) R1 may be the same or different, and is selected from the group consisting of hydrogen, halogen, and alkyl, dilute, aromatic, and 1 to 20 carbon atoms, In the group consisting of aryl or aryl, or two adjacent R1 can be connected together to form a saturated or unsaturated cyclic system with 4 to 20 carbon atoms; R2 It can be the same or different, and its definition is the same as R1; X is selected from the group consisting of free carbon, silicon, germanium, and tin; ¥ η is 2 to 12; R3 and R4 can be the same or different, and are free hydrogen , Halogen, and an alkyl group, alkenyl group, aromatic group, aromatic group, or aromatic group having 1 to 12 carbon atoms; M is a group IVB transition metal having an oxidation value + 4; and One can be the same or different, and is independently an -1 valent anionic ligand; '(b) — a monoaromatic metal compound, selected from a compound of free formula (A1), a compound of formula (A2), and In the group formed by its combination, _

Page 6 1225073 Case number 89112710 Description of the invention (3) Amendment

(A1

(A2) where M1 is a Group IVB transition metal with oxidation state +4; M2 is a group consisting of optional IIIB transition metals, lanthanides, and titanium; the oxidation state is + 3; Z may be The same or different, and is a Group IVA element; R21 may be the same or different, and is a divalent unsubstituted or substituted C3_6 alkanediyl, forming a ring system with Z, wherein the substituent is optional Cu group, Cu group, C6_2Q aromatic group, C7_2Q aromatic group, and C7_aralkyl group;

1225073 _ Case No. 89112710 Amendment V. Description of the Invention (4) R22 may be the same or different, and it is U, linear, branched, or cyclic, hydrogen, or sulphur, or two adjacent r22 may be Linked together to form a saturated or unsaturated ring 'system with 4 to 20 carbon atoms with the carbon to which they are connected; X21 may be the same or different and independently an -1 or _ 2 valent anionic complex Bit base ·, and p = 2 or 1; · Y1 and Y2 are VAth or VIA elements; when Y1 is the VAth element, q is 1, and when γι is the VIAth element, Q is 0; · ', '

When Y2 is the VAth element, q is 2, and when Y2 is the VIAth element, q is 1; and. R23 may be the same or different and H, or a linear, branched, or cyclic hydrocarbon group; and ^ (c) an activating catalyst, selected from the group consisting of (丨) alumoxane, (2) a mixture of AlRMRi2R13 and borate, and (3) a mixture of A1RnRi2R! 3 and alumoxane, in which Rn , Ri2 and 3 as a ^ aliphatic group or a C6_l () aromatic group. As described above, the catalyst composition of the present invention includes a bridged biscyclopentadienyl metallocene, an onocyclopentadienyl metallocene, and an activating catalyst. The bridged bisarylcycloolefin metal compound used in the present invention is represented by chemical formula (B). In chemical formula (B), osmium (Group VIII element, such as C, Si, Ge or Sn) and? CR3R4) n 崄 wells fry 硎 c to form a bridge.

1225073 Case number 89112710

j2_ ， «厂』 ό / L * vj \ uy In chemical formula (B), when silicon and!? 2 are an alkyl group, an alkenyl group, an aromatic group (aryi), When alkylaryl or arylalkyl is burned, it is preferably 1 to ^ carbon atoms, and R1 and R2 are preferably independently selected hydrogen, Ci, courtyard, alkenyl, C6_1 ( ) In the group consisting of aryl, C ?, alkaryl, and c? _1Garalkyl. Specific examples of R1 and R2 include hydrogen, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, and olefin Propyl, isopropenyl, phenyl, and tolyl. When two adjacent R1 (or R2) are connected together to form a saturated or unsaturated ring system with 4 to 20 carbon atoms, it is preferably / to 6 carbon atoms. The cyclic system may be a saturated or unsaturated polycyclic cycloalkenadienyl ligand, such as an ainyl group, a tetrahydroindenyl group, a fluorenyl group, or an octahydrodiyl group. Specific examples of ligands include; 75-cyclopentadienyl, 75 ~ methylcyclopentadienyl, -tetramethylcyclopentadienyl, "5 pentamethylcyclopentadienyl, ???? -n-Butyl $ yi 戍 ^ A diphenyl, indyl, tetrakisyl indyl, dimei, octahydrobuckyl. Soil '7 1Υ can be hydrogen, hydrocarbon, halogen, (6, aryl) , C7, aralkyl or alkaryl, (: Ί_2 {) alkoxy, (^ 2 () aryloxy (aryiox)), nh2, NHR7, NR7R8,-(C = 0) NH2,-( (C = 0) NHR9,-(C = 0) NR9Ri〇, each of R7, R8, Rlj and 1 ^ 1 {) are dagger, alkyl. Suitable γ includes methyl, ethyl, phenyl, gas, bromine , Methoxy, ethoxy, -NH2, -NH (CH3) and -n (ch3) 2 'The monoaromatic metal compound used in the present invention may be a compound represented by the chemical formula (A1), or a chemical formula ( The compound represented by A2) may be used in combination with a compound of formula (A 1) and a compound of formula (A 2). In formula (A1), 'Mi is a group IVB transition metal in oxidation state H, example

Page 9 1225073 — '. ... · Case No. _ Che Yue Hu _____ --- " V. Description of the Invention (6) Such as Ti (+4), Zr (+4), and Hi (+ 4) . z is a Group VA element such as carbon, silicon, and germanium. R21 may be a divalent unsubstituted or substituted C3-6 alkanediyl (a 1 kaned i y 1), and forms a ring system with Z. The substituent may be a Cu alkyl group, (:, _ fine group, C6_2 square group, C7_20 square group, or C7-2G square group. Preferably, R21 is a bivalent unsubstituted C3 ~ which forms a ring system with Z. 6 dialkyl. Specific examples of R21 include trimethylene, tetramethylene, pentamethylene, and hexamethylene. R22 may be the same or different, and are independently fluorene, linear, branched, Or cyclic hydrocarbyl, or siiyi. Silyl can be alkyl silyl, dialkyl silyl, trialkyl silyl, cycloalkyl silyl, etc. Specific examples include methylsilyl, = methylsilyl, trimethylsilyl, and methylethylsilyl, etc. Or two adjacent R22 can be linked together to form a carbon with 2 to 2 Saturated or unsaturated cyclic systems of 1 carbon atom. Specifically, the linear, branched, or cyclic carbon-nitrogen group of the above-mentioned L may be C, a ceryl group, a Cl group, a dilute group, a% aromatic group, or a aryl group. Specific examples of, or n-base / 22 include fluorene, methylHpropyl, butylamidine, pentyl, isopentyl, hexyl, 2'ethylhexyl, Heptyl, terpene, 2-propenyl, propyl, isopropenyl, benzyl, and tolyl. Form the ring "n adjacent to π linked together to the carbon ring attached to the diphenyl group I, two : 丨 ff saturated or unsaturated polycyclic group, or octanitrogen group. Examples of potential groups such as Indenyl, Tetraazainyl, (R22) 4 include h5

Round cyclopentadienyl, h5-methylcyclopentane Page 10 1225073

Modified dilute h ° ~ ethylcyclopentadienyl, h5-tetrafluorenylcyclopentadienyl, h5-pentamethylcyclopentadienyl, h5-n-butylcyclopentadienyl, indenyl ndenyl) , Tetrahydroinyl, fluorenyl, and octafluorofluoro. R is fluorene, C !, alkyl, alkenyl, C6, aryl, C7, alkyl, or C7-20 aralkyl. χ21 may be a -1 or -2 anionic ligand. When X2] is a valence anion = coordination group, ρ = 2, and specific examples of P at this time include η, a hydrocarbon :: functional element, an alkoxy group, an aryloxy group, and amidino group. When χ2ΐ is a -2 valence complex, P = 1 ’X21 may be a dicarborane dianion.

When Y1 is a group VA element, q is 丨, and specific examples of γ1 are nitrogen, ^, and kun. When γ1 is a group V 1 A element, q is 0, and specific examples of osmium 1 are oxygen, sulfur, and sulfur. Specific examples of ya1 () ^ \ include _ 关 _, n (CH3) _, N (t — butyl) —, —PH one, one P (CH3)-one p (Bubutyl) _ one 0_, and A monoaromatic metal compound represented by formula (A 2) has a structure similar to that of formula (A 1), but the bond between M2 and Y2 in formula (A2) and M1 and … The bond between them is different, and M2 in formula (A2) is a group 1118 transition metal (such as scandium, yttrium), lanthanide, or titanium in oxidation state + 3. In formula (A2), M2 The bond between Y2 and Y2 is not a covalent bond, but a dMlve bonding, in which γ2 supplies two electrons to ... When ^ is a VA family tl element, Q is 2, and Υ2 is VIA For family elements, (1 is 1. Formula U2) The definitions of the symbols z and R23 are the same as in formula (ai). · For the specific example of formula (A2) 'Y2 (R23)

1225073 Case No. 89112710 Month

B correction

V. Description of the invention (8) (tert-butyl), PH2, P (CH3) 2, PH (CH3), PHCQHh), and P (Cfi H 丨 1) 2 ° The activating catalyst suitable for the present invention may be (1) an alumoxane, (2) a mixture of AlRnRl2R13 and a borate, and (3) a mixture of AlRnR12R13 and alumoxane, wherein R11, R12 and R13 are Cu aliphatic or C6_1Q aromatic groups . (

The commonly used and commercial I-oxygen burner is methyl a 1 um i noxane (ΜA0). Specific examples of A 1R11 R12R13 (trialkyl) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum (TIBA). Borates suitable for the present invention include N, N-dimethylaniline (pentafluorophenyl) borate (N, Nd i me thy 1 an i 1 ini um te trak is (pent af 1 uoropheny 1) borate ), Triphenyl carbenium tetrakis (pentaf 1 uoropheny 1) borate), trimethyl ammonium (pentafluorophenyl) borate (trimethyl ammonium tetrakis

(pentaf 1 uoropheny 1) borate), ferrocene tetrakis (pentafluorophenyl) borate (ferrocenium tetraki s (pentafluorophenyl) borate), dimethyl tetrakis (pentafluorophenyl) borate (dimethyl tetraki s (pentafluorophenyl) borate), silver tetrakis (pentafluorophenyl) borate, etc. 0 The catalyst composition of the present invention can be used to synthesize a dilute hydrocarbon polymer. In the presence of an effective catalyst amount of the above-mentioned catalyst composition of the present invention and polymerization conditions, a monoolefin monomer can be polymerized (ie, homopolymerized), or

Page 12 I? 25073

Polymerize at least one olefin monomer). # Ｍmonomers are polymerized (ffl, alkene, 4, olefins, and specific examples include propene, 1 dilute, etc. 17 risk ten o'clock or acyclic olefins. Acyclic and two: m Hydrocarbons of up to 12 carbon numbers. Examples of a-dilute hydrocarbons include buprofen, butin, bupenten, buhex, and Η The catalyst composition of the present invention is particularly suitable for preparing linear low molecular weight distributions. Density olefin polymers, especially polyethylene.

The catalyst system of the present invention is suitable for slurry reaction state, gas phase and solution polymerization reaction conditions. The polymerization reaction is usually at a temperature of 0 to 25,000 ° C, and at an atmospheric pressure to 3,000 psi. Between. The method, features and advantages of the present invention will be further explained in the following through several embodiments, but it is not intended to limit the scope of the present invention. The scope of the present invention shall be based on the scope of the attached patent application. Synthesis of Cycloalkene Metals Example 1. Preparation of (C5Me4H) Li QMe4H2 (8.57 g, 70 · 2 mmol) was placed in a Schlenk flask filled with 150 ml of ether. Cool this flask to -78 ° C, and then inject an equivalent of n-butyllithium solution with a syringe. The mixture immediately turned yellow, and the color gradually disappeared. After dripping, warm to room temperature and stir overnight. The solution was filtered and washed several times with pentane, and finally a white solid salt (4.83 g) was obtained. Example 2. Preparation of (C5Me4H) (CH2) 3SiCl The lithium salt obtained in Example 1 ( 4 · 8 g) suspended in toluene / THF

Page 13 1225073

/ Cereal (volume ratio 2: 1) in Q, this slurry was cooled to -780 ° C, and the syringe was used as the main ethylene oxide trimethylenesilyl di chloride. The mixture was warmed to room temperature and stirred overnight. Vacuum dry to remove solvent and excess tris (fluorenyldiagas) silane. It was then extracted with pentane, filtered to remove the white L i C 1 salts, and the solvent was pumped to dryness to obtain a pale yellow liquid (8.50 g). Example 3. Preparation of C5Me4H-Si (CH2) 3-NHC (CH3) 3

The (: 51 ^ 411-5] ((: 112) 3 (: 1 (82) obtained in Example 2 was dissolved in 30 * ^ benzene, and the solution was cooled to -7 8 ° C, and then a syringe was used. Inject excess BuNH2 (2.1 equivalents). After dripping, warm to room temperature and stir overnight. Filter to remove white salts, and then draw off the pentane solution, and finally obtain a light yellow liquid (8.1 g). Example 4 Preparation of [C5Me4-Si (CH2) 3-NC (CH3) 3] Li2 The (: 5) ^ 411-51 ((:} 12) 3_question (: ((: 113) 3 (8.12) dissolved in 60 m 1 of ether, cooled the solution to -78 ° C, and then injected 2 equivalents of nBuLi with a syringe. After dripping, warmed to room temperature and stirred overnight. Transition to collect 7. 5 g of white solid.

Example 5. Preparation of [0 :, 64-81 ((:} 12) 31 (: ((:) 13) 3] 1 ^ (: 12 (Compound 1) The [C5Me4H-Si (CH2 ) 3-NHC (CH3) 3] Li2 (2.07 g) and TiCl3 (thf) 3 were suspended in 25 ml of THF and cooled to-30 ° C. After mixing the two solutions, stir for 3 hours. Add excess AgC 1 (2.1 g), stirred in the dark overnight. After filtering to remove the Ag salt, the filtrate was drained off. The product was extracted with toluene and recrystallized from benzene / pentanol. Finally, a pale yellow solid product was obtained. (80%). Example 6 Preparation of Cyclopapentadienyl-l-

Page 14 1225073 • »ί ^ __ Case No. 89112710 _ Revised this month. ____. 5. Description of the invention (11) indenylcyclobutane Put 5.8 g (50 mmol) Indene into a 250 ml round bottom flask, add 50 0 in 1 THF, under ice bath conditions, slowly add 40 m 1 (1.6 M, 64 mmol) nBuLi, during which the solution appears orange-red, then remove the ice bath, stir for 3 hours, drain all solvents, The excess nBuLi was washed out with 50 m 1 pentane, filtered, and the precipitate was taken. Add 50 m 1 of THF again to dissolve the precipitate. In an ice bath, slowly add 5.9 g (50 mmol) of 6,6-trimethylenefulvene, continue stirring for 24 hours, then add 1 m 1 of water to stop the reaction, and drain all solvents. . Then dissolve at 100 m 1 h e X a n e, filter the salts, and take the mash. # This crude product was directly separated by 20 g of silica gel for column chromatography. The extraction solution was 100% he X ane. The product layer was collected and concentrated to give 8.2 g (70%) of a light yellow liquid product. ). Example 7 Preparation of Cyclobutylidene (l-7 / 5-cyclopentadienyl) (7? 5-indenyl) bis (dimethylamino) Zirconium (Compound II) Take 0.94 g (4 mmol) of Cyclopentadienyr-1 obtained in Example 6 -indenylcyclobutane and 1 g (3.7 mmol) Zr (NMe2) 4, put into a 100 ml round bottom flask, add 20 ml of toluene, react at room temperature for 15 ^ small 4 'and then drain all solvents and add again 50 ml of pentane was used to dissolve the solid, and the filtrate was collected by filtration. After concentrating, a yellow solid product was obtained. 45 g (95%). Synthesis of polymer. Example 8-1 2 Synthetic polyethylene The reaction tank was heated to 11 ° C, vacuum for 2 hours, then fill with high purity

Page 15 1225073

Nitrogen. After repeated pumping of nitrogen for 3 to 4 times, use a double-ended needle to move a solvent (Toluene or isopar E; 5000ML) with a water content of less than 10 ppm into the reactor.

in. The temperature of the reaction tank was adjusted to the temperature to be reacted. After the temperature was stabilized, an appropriate amount of a catalyst MA0 was added to the syringe, and stirred evenly. Take the prepared solution of Catalyst I (obtained in Example 5) and Catalyst 11 (obtained in Example 7) with a syringe and immediately add it to the reactor according to the ratio. Stir for 3 minutes to start the reaction with ethylene at a constant pressure. . After 30 minutes, the reaction was completed, the temperature of the reaction tank was lowered to room temperature, and the pressure was reduced to normal pressure. The reactor was opened to take out the product, and an excess of mixed solvent (containing V / V = 1/10 hydrochloric acid / methanol) was added to precipitate the polymer and remove the metal salts in the product. After rinsing, rinse with methanol several times. The obtained polymer was dried in a vacuum oven (65 ° C) for 12 hours and then subjected to various tests. The results are shown in Table 1. Table 1 Example of polymerization results for a mixed catalyst system 1: 1 m (gTJ ^ Abi) Μν χία5 MWD • Number of ridges: 8 ο: ιω 290 < 1 (? 1Q8 285 1 9 25:75 3Jh \ (f 613 11.18 2 10 50 : 3) 5.39χ11ί 3.76 9.88 2 11 75:25 5.15x10s 211 850 2 12 100: 0 9.2 ^ 105 238 135 1

PC21M = 150 psig; Al / metal = 3000; Terap, = 120 ° C; Solvent = methylbenzyl. As can be seen in Table 1, under the same reaction conditions, catalyst 11 and catalyst were compared.

Page 16 1225073 Case No. 89112710 Month ‘Amendment V. Description of the Invention (13) The reaction of I monopolyethylene has a higher polymerization activity, but the molecular weight is lower than that of PE polymerized with Catalyst I. When we mixed Catalyst II and Catalyst I in different proportions for the polymerization reaction, two peaks can be seen on the GPC analysis chart of the obtained polymer. This result indicates that the polymer polymerized is Bi modal; When Media II accounts for 25%, the high molecular weight and low molecular weight GPC peaks of the polymer produced are almost equal. Its activity range is; between the activities exhibited by two single catalysts, as the catalyst I I ratio increases, the activity increases and the molecular weight decreases. 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 retouches 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 17 12250; Case No. 89112710 Amendment

Page 18

Claims (1)

1225073 Case No. 89112710 Amendment VI. Patent Application Scope 1. A catalyst composition for preparing an olefin polymer, including (a) a bridged biarylcycloolefin metal compound represented by chemical formula (B), (R; , R4C) n Wherein R1 may be the same or different, and are selected from hydrogen and an alkyl or aromatic group having 1 to 7 carbon atoms; R2 may be the same or different, and have the same definition as R1; X is composed of selected carbon and silicon In the group; η is 2 to 6; «R3, R4 may be the same or different, and is a group consisting of free hydrogen and an alkyl or aromatic group having 1 to 4 carbon atoms; M is the oxidation value + 4 Group IVB transition metals; and Υ may be the same or different, and are independently anionic valences of -1, and are selected from the group consisting of free hydrogen, (6 alkyl, NR7R8, each R7, R8 is q courtyard base, Page 19 1225073 • _ Case No. 89112710 _ month a___ Sixth, the scope of patent application (b)-monoaromatic metal compounds, select compounds of free chemical formula (A 1), compounds of chemical formula (A 2), and combinations thereof In the group of people, Where M1 is a group IVB transition metal with oxidation state + 4; M2 is a group consisting of optional group IIIB transition metals and titanium; the oxidation state is + 3; Z may be the same or different, and is C Or Si element; k R21 may be the same or different, and is a divalent unsubstituted or substituted C3_ _ mt 89112710 The scope of Shen Jing patent (revised f Glkanediyl), forming a ring system with z; may be the same or different, and Is H, Cu; can be the same or different, and independently are or _2 valence R22 Y2I position, which can be used as a back door% gate, and independently M or _2 valence anion coordination or 1 optional free Η In the group consisting of C, Cm, and halogen; and p = 2 Yi and Υ2 are the VA or VIA element; for the VA element, qg !, when γ] is the VIA element, ^ is when y2 ^ _ And 乂 are VA elements, q is 2, when γ2 is the Vja element, ^ is R23, σ is the same or different, and is jj, or (^ 8 linear, branched alkane, and AiR1H3 ~ activation aid Catalysts, choose (1) alumoxane, (2) Sihe RU and salt mixture, and (3) A1R! H! 3 and alumoxane ^ σ In the family group, wherein Rn, R] 2 and p are Ci 2g aliphatic group 6 heptaromatic group. And F 2 · The catalyst composition as described in item 1 of the scope of patent application, wherein Ri is independently selected Free hydrogen, methyl, ethyl, propyl, butyl, isobutylamyl, isoamyl, hexyl, 2-ethylhexyl group The catalyst composition 'wherein in the formula + formula (β), X is carbon. 4 · The catalyst composition as described in the scope of the application for patent, wherein η is 3 is hydrogen. Page 1225073 I... .. _ Case No. 89Π271Π_ Year Month-Japanese π_ 26. Patent application scope 5 · The catalyst composition described in item 1 of the patent application scope, where γ is -n ( ch3) 2. 6 · The catalyst composition according to item 1 in the scope of the patent application, where pi is trimethylene. 7 · The catalyst composition according to item 1 in the scope of patent application, where In the chemical formulae (A1) and (A2), Z is Si ° 8 The catalyst composition as described in item 1 of the scope of patent application, wherein R22 is independently selected from the group consisting of fluorene, methyl, Ethyl, propyl, butyl, isobutyl, fluorenyl, isopentyl, hexyl, 2-ethylhexyl group. 9 · Catalyst composition as described in item 1 of the scope of patent application, Among them, in formula (A1), 'Υ1 is a group va element, and q is 1. 1 0 · The catalyst composition as described in item 丨 of the patent application range, wherein in formula (A1), Y is the first Group VIA element, q is 0. 11. The catalyst composition according to item 1 of the scope of patent application, wherein in the formula (A2), Y2 is a group element and q is 2. 12. The catalyst composition according to item 1 of the scope of patent application, wherein in the formula (A2), Y2 is a vu group element and q is 1. 13. The catalyst composition as described in item 1 of the scope of patent application, wherein axan A1RU R ^ R13 is selected from trimethylammonium, triethylaluminum, tripropylaluminum, triisopropylaluminum, dibutyl Aluminium, and triisobutylaluminum (τ 丨 βΑ) in the group of 0 14. The catalyst composition according to item 1 of the scope of patent application, wherein the borate is selective N, N_dimethyl (N, N-dimethyl anilinium tetrakis) Page 22 1225073 Case No. 89112710 _'Year Month and Day Chromium ^ _ VI. Patent Application Range (pentafluorophenyl) borate) 'Triphenylphenoxide (pentafluorophenyl) borate (tr i pheny 1 carbenium tetraki s (pentafluorophenyl) borate ), Trimethyl ammonium tetrakis (pentaf 1 uoropheny 1) borate), ferrocene tetrakis (pentafluorophenyl) borate (ferrocenium tetraki s (pentafluorophenyl) borate), dimethyl tetrakis (pentafluorophenyl) borate (dimethyl tetraki s (pentaf 1 uoropheny 1) borate), and silver tetrakis (pentafluorophenyl) borate. 15 · The catalyst composition as described in item 1 of the scope of patent application, wherein the activation promoter is fluorenyl aluminoxane. 16. The catalyst composition according to item 1 of the scope of the patent application, wherein the activation promoter is a mixture of AlRnRi2Ri3 and a rotten acid drug. 17. · A method for preparing an olefin polymer, which comprises flushing h at a temperature between 100 ° C and 250 ° C in the presence of an effective catalyst amount as described in the catalyst composition described in item 1 of the patent application range) An olefin monomer, or (b) at least-a dilute hydrocarbon monomer and at least one other 18. The method according to item 7 of the scope of patent application, wherein the method comprises polymerizing an olefin, and the fluorene is ethylene. The date of this year: Application number: 89112710 (the above are filled by the Bureau) Chinese IPC classification invention patent specification 1225073 A catalyst composition for the preparation of a wide molecular weight distribution smoke polymer is the English name Catalyst Composition for Preparing Olefin Polymer having a Broad Molecular Weight Distribution Name (Chinese) Name (English) Inventor (total 4 people) Nationality (Chinese and English) 1. 王伯萍 2 · 丁晴 3. 时 国 诚 1. Bor-Ping Wang 2. Ching Ting 3. Kuo-Chen Shih 1. ROC 2. ROC 3. ROC Residence (Chinese: 1. No. 321, Section 2, Guangfu Road, Hsinchu City 2; No. 321, Section 2, Guangfu Road, Hsinchu City 3 · Hsinchu No. S, No. 321, Section 2, Guangfu Road, Shishi 1. Applicant (1 person) of the Industrial Technology Research Institute (namely, name 15) Country-lt) Residence Office) Residence 1 Office] Representative (Chinese) 1. industrial technology research institute l ROC 1 · No.195, Section 4, Zhongxing Road, Zhudong Town, Hsinchu County (this address is different from the previous applicant to your bureau) page 1