TWI245775B - Catalyst composition for preparing olefin polymers - Google Patents

Abstract

A catalyst composition for preparing olefin polymers. The catalyst composition includes a metallocene compound and an activating cocatalyst. In the metallocene compound, two cyclopentadienyl groups are bridged by X (C, Si, Ge, or Sn) in a ring structure. The bite angle formed by the two cyclopentadienyl rings and X is equal to or greater than 100 degrees. The obtained olefin polymer has high cycloolefin conversion and a high glass transition temperature. In addition, the catalyst composition can still maintain relatively high activity at high temperature reaction conditions.

Description

V. Description of the invention (1) — Less-— 1 —- Background of the invention: The present invention relates to a catalyst composition for preparing olefin polymers. This composition is particularly suitable for the preparation of high cyclic olefin conversion and An olefin polymer with a high glass transition temperature and can maintain a relatively high polymerization activity under high temperature reaction conditions. Olefin-based polymers have been widely used for a long time. Among them, the most common olefin-based polymers are polyolefins, that is, monomers or copolymers of olefin L. These polyolefin plastics are generally used for blow molding, injection molding, extrusion coating, films, die-cutting, pipe fittings, electrical wires, and electrical viewing. An example of a polyolefin is an ethylene-propylene elastomer (ethylene-propylene rubber ' EPR). Due to its good weather resistance, good heat aging properties, and its ability to be mixed with fillers and plasticizers, it is widely used in industry. Typical uses in the automotive industry, such as radiators, heating tubes, vacuum tubes, weather stripping, sponge door doorsea 1s) and so on. Another olefin-based polymer is a cycloolefin copolymer (COC). One of them is a copolymer of cycloolefin and ethylene, which has excellent transparency. Moreover, it also has heat resistance, heat aging resistance, chemical resistance, solvent resistance, low dielectric properties, and high rigidity. Therefore, ethylene / cycloolefin copolymers are very suitable for use as optical materials, such as optical memory discs and optical fibers. Ethylene / cycloolefin copolymers are usually in the presence of a metallocene / aluminoxane catalyst system

Page 5 1245775 Case No. 89112711 Revision V. Description of Invention (2) " ~~~ As described in National Patent No. 5,602,219 (Aulbachetal ·). Abe et al. Revealed that the aromatic cycloolefin metal was isopropylidene (cyclopentadienylmethylcyclopenta-dinyl) zirconium dichloride ° Aulbach et al. The exposed aromatic cycloolefin metal is dimethyllithium- (1-benzyl) -cyclopentadienyl zirconium dichloride [dimethyl si 1 ^ 1 ~ ^ 1'1ndeny1) -Cyc1 opentadieny 1 zirconi um dichloride] 〇 丘 n 二 二 is willing to pass the f side to prepare the ethene / cyclodilute hydrocarbon copolymer has the following: Diene conversion (-) is too low. Because of its high conversion rate of ethylene, it has a high transition temperature (Tg). hand. In order to improve the conversion of cycloolefins, the temperature of the olefin copolymer is too low. The temperature or lower the reaction pressure of ethylene is used early. The method used is to increase the reactivity of the reaction polymer, such as us 1, and this will make the ring Olefins and Us Patent N. · 5,559,199 2 2 N. 5,602,21 9 techniques will reduce the commercial viability of COC aggregation. Reveal the way. Obviously, this technology is very hopeful that the COC polymerization process can increase the conversion of cycloolefins in industrial applications. + Reactivity to increase the purpose and summary of the invention: The purpose of the present invention is to solve the above-mentioned problem of the catalyst composition for preparing olefin polymers, and to provide a cyclic copolymer for olefin copolymers, For the preparation of ethylene / ring—achieve ^^, ::: 2 high Tg.

SiiiSSiS—Hydrocarbon polymer page 6 0424-4548TWF3.ptc 1245775 Case No. 89112711 V. Description of the invention (3) Media composition, including ... (a) — an aromatic cycloolefin metal compound represented by the chemical formula (1) , (R3R4C) n lur2 (I) R2

Rh wherein R1 may be the same or different, and is selected from the group consisting of hydrogen, halogen, and alkyl, alkenyl, aromatic, alkaryl, or aralkyl groups having 1 to 20 slave atoms, or two Adjacent and connected to different carbon atoms, R1 can be connected to form a saturated or unsaturated ring system with 4 to 20 carbon atoms with the carbon to which it is attached; R2 can be the same or different, and its definition is the same as R1 x is C, Si, Ge, or Sn; n is 2, 3, or 4; R and R4 may be the same or different, and are alkyl, alkenyl, aromatic, and alkylaryl groups selected from free carbon and halogen 7 carbon atoms; In the group consisting of: For Group IVB transition metals having an oxidation value + 4, and, and having 1 or aralkyl group 0424-4548TWF3.ptc page 7 1245775 ^ amendment

And independently anionic coordination of -1 valence_Case No. 89112711 V. Description of the invention (4) Y may be the same or different, and the angle formed by 0 is equal to or greater than two cyclopentadienyl rings and X 1 0 0 degrees; and (b) — activating co-catalyst, selected from a mixture of A1RUR 丨 2Ri3 and borate ^ A1D} figures, and (3) A1RnR12R13 and alumoxane The catalyst composition of the present invention can be used to prepare Olefin polymer. Using this catalyst composition to prepare cyclic olefin copolymers can increase the conversion of cyclic olefins = = = The obtained copolymer has a high glass transition temperature, which is in the range of 60 to 35. A simple illustration of the diagram: Figure 1 is X-ray crystal structure of the aromatic cycloolefin metal compound prepared by the catalyst example 5 of the present invention. Fig. 2 is an X-ray crystal structure of the aromatic cycloolefin metal compound prepared in Catalyst Example 6 of the present invention. Figure 3 is the X-ray crystal structure of the aromatic cycloolefin metal compound prepared in Example 7 of the catalyst of the present invention. Figure 4 is the X-r a y crystal structure of the aromatic ring dilute metal compound prepared in Comparative Catalyst Example 8 of the present invention. Figure 5 is the X-r a y crystal structure of the aromatic ring dilute metal compound prepared in Comparative Catalyst Example 9 of the present invention. Fig. 6 shows the light transmittance of the ethylene / orbornene copolymer obtained by the polymerization example 1 of the present invention at different wavelengths.

〇424-4548TWF3.ptc Page 8 1245775 μ Case No. 89112711 V. Description of the invention (5) Detailed description of the invention: The present invention provides a catalyst composition for preparing an olefin polymer, which comprises a catalyst composition as described in formula (I) Shown are aromatic metal compounds and an activating catalyst. One feature of the present invention is that χ (Group IVA element such as C, Si, Ge, or Sn) and-(CR3R4) n- (η is 2, 3, or 4) in the chemical formula (I) form a two-membered ring The ring structure of four-member ring or five-member ring constitutes a bridge. Please refer to the conventional aromatic cycloolefin metals used in the preparation of cycloolefin copolymers in the aforementioned U.S. Patent Nos. 5,559, 1 99 (US '199) and 5,602, 2 1 9 (U · S ·' 219), For example, isopropylidene (cyclopentadienylmethylcyclopentadienyl) digasification [isopropyl idene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride] and dimethyllithium- (1- 萌 基) -cyclopentyl Diluted zirconium dichloride [dimethylsilyl- (l-indenyl) -cyclopentadienylzirconium dichloride]. It can be found that the carbon or second atom on the dilute aromatic metal is bonded to two fluorenyl groups. For ease of understanding, Table 1 depicts a partial structure of an aromatic cycloolefin metal, where Cp represents an unsubstituted or substituted cyclopentadienyl group, h, 02, and h represent Cp, a Group IVA element, and another Cp The angle formed (Cp_IVA-Cp) is called the bite angle.

〇424-4548TWF3.ptc Page 9 Case No. 89112711

1245775 V. Description of the invention (6) Table 1 US tf199 (bite angle's X-ray data, ^ Journal 〇f Organometailic Chemistry 1995, 497, 105). US ^ 219 (bite angle's X-ray data, see Organometailic 1994, 13, 964 and Journal of Organometailic Chemistry 1989, 369, 359). The present invention is shown in Figure 1 and Table 2) 'CH3 Cp > 0 4 CH3' Cp CH3 .Cp 0j = 98.4o 02 = 94.3-94.8 ° = 100.8 ° In contrast to U.S. Patent Nos. 5, 5 5 9, 1 9 9 and 5, 602, 2 1 9, in the present invention, the Group IVA element such as carbon is the same as-(CR3R4) n- (n = 2 , 3 or 4) constitute a bridge, and form a ring structure of three-member ring, four-member ring or five-member ring. With such a bridging method, the angle between Cp_IVA_Cp can be increased. That is, the angular center is greater than & and 02. It is worth noting that up to ^ ', there have been no reports in the literature of aromatic metal catalysts having a bite angle greater than 100 degrees. When traditional aromatic cycloolefin metal compounds are used as catalysts to prepare copolymers of cyclic olefins and non-cyclic olefins (such as ethylene), because the bite angle is small, it is difficult for the thinner fumes larger than ethylene to contact the aromatic olefins. Active position

0424-4548TWF3.ptc Page 10 1245775 V. Description of the invention Case number (7) 19112711

site). As a result, the cyclic olefin conversion (conversion; incorpration am0Unt) of the obtained copolymer was not good. As a catalyst, when the dicyclic dicyclic metal compound is removed as a catalyst, "the angle may be V = square% of the active site of the olefinic metal has a larger space. By this, the size of the cyclic olefin has a greater chance of contacting the reaction site." The copolymer obtained by the catalyst composition tends to have a higher cyclic olefin conversion rate on the polymerization = backbone, so the glass transition temperature (Tg; giass transition temperature) is greatly increased. In the bridged ring rare metal of the present invention, when the Bite AngU sandwiched by the two Cp rings on it is opened, the active center of the metal will move outward. This will cause the production of olefins or non-cyclic olefins. The rate θ of the coordination between the monomer and the active center of the catalyst is obviously & rise, the higher the proportion of the cyclic olefin or non-cyclic olefin monomer in the copolymer, of course, the glass transition temperature (Tg) of the copolymer is also The higher it is, the higher the reactivity will also increase. It is worth mentioning that in the aromatic ring of the bridging system; in metal catalysts, the Bite Angle formed by Carbon-Bridge is significantly larger than that of Silcon-Br ^ id. Due to the atomic radius of carbon ) Is smaller than the atomic radius (1 · 11 angstroms) of silicon, and the anion (2 · 5) of carbon is larger than silicon (1.8), making the carbon-carbon bond bond energy much larger than that of silicon-carbon bonds. Therefore, When Cp and the IVA private element form a bridge, Silcoon-Bridge has a larger deformation space than carbon, and therefore has a smaller Bite Angle. In Chemical Formula (I), when Ri and r2 are In the case of an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, or an arylalkyl group, it is preferably 丨 to "

0424-4548TWF3.ptc Case number 89112711 1245775

5. Description of the invention (8) Alkenyl, C6_1Q aryl, C7, alkaryl, and k◦aralkyl. Specific examples of RMOR2 include hydrogen, methyl, ethyl, propyl butanyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl 'heptyl, octyl, vinyl, and alkenyl. Propyl, isopropyl, phenyl, and tolyl When two adjacent R1 (or R2) are joined together to form a cyclic system with 4 to 20 carbon atoms to the carbon to which they are attached, 4 to 6 carbon atoms, the cyclic soil system may be a saturated or unsaturated polycyclic cyclic fluorenyl dibasic ligand, such as a benzyl, tetrahydrogenyl, fluorenyl, or octachlorodiyl . Specific examples of the ligand include cyclopentadienyl, methylcyclopentadienyl, 7? 5-tetramethylcyclopentadienyl, 775-pentamethylcyclopentadienyl, 々5-n- Butylcyclopentadienyl, indenyl, tetrahydroindenyl, thienyl, octaarginyl. , Υ can be hydrogen, hydrocarbon, halogen, c6_2 aryl, c7_2Q aralkyl or alkaryl, Chq alkoxy, Chq aryloxy (aryiox), nh2, NHR7, NR7R8,-(C = 0) NH2,-(〇〇) NHR9,-(C = 0) NR9R1G, each of R, R8, R9 and R1G is a Cu alkyl group. Suitable gammas include fluorenyl, ethyl, phenyl, chlorine, bromine, methoxy, ethoxy, mono-NH2, -NH (CH3), -N (CH3) 2, -N (C2H5) 2, -N (C3H7) 2. According to the present invention, the aromatic cycloolefin metal compound represented by the chemical formula (I) can be combined with an activating co-catalyst to form a catalyst composition, and the catalyst composition can be used for preparing an olefin polymer. Suitable activating catalysts for use in the present invention may be in the group consisting of (丨) aluminoxane, (2) a mixture of A1RUR12R13 and shed salt, and (3) a mixture of A1RUR12R13 and alumoxane. R11, R12 and R13 are an aliphatic group or a c6_1 () aromatic group. The preferred aluminoxane is methyl aluminoxane (MAO) ° AlRnR12R13

0424-4548TWF3.ptc Page 12 1245775 Case No. 89112711 Amended 5. Description of Invention (9) (Trialkylaluminum) Specific examples include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropyl Aluminum, tributyl aluminum, and triisobutyl aluminum (TIBA). Deletable acid salts suitable for the present invention include N, N-dimethyl anilinium tetrakis (pentaf1uoropheny1) borate, triphenylcarbons (pentabenzene Triphenyl carbenium tetrakis (pentafluorophenyl) borate), trimethyl ammonium tetrakis (pentafluorophenyl) borate, ferrocene (pentafluorophenyl) Ferrocenium tetrakis (pentafluorophenyl) borate, dimethyi tetrakis (pentafluorophenyl) borate, and silver tetr ak is (pentafluorophenyl) borate), etc. Using the catalyst composition of the present invention, an olefin polymer can be synthesized. In the presence of an effective catalyst amount of the above-mentioned catalyst composition of the present invention and polymerization conditions, one olefin monomer can be polymerized (ie, homopolymerized), or at least one olefin monomer can be polymerized with at least one other monomer Action (Co-, according to the present invention, the preferred olefin is a cyclic olefin. The present invention: It is better to carry out the homopolymerization of cyclic olefins or the copolymerization of cyclic olefins. Applicable = The cyclic olefins of the present invention may be bicyclic Heptenes, rare hydrocarbon polymerization parties and acyclic

ϊ, ΐϊ: one carbohydrazone, four-ring dodecane carbohydrate, pentacyclic, pentafluorene + 'carbadiene, it hexadecanoate, susceptible, six

〇424-4548TWF3.ptc Page 13 1245775

Type, heptacyclic eicosene, heptacyclic twenty-one carbonene, octacyclic twenty-two carbonene, nine-ring fifteen carbonene, and nine-ring twenty-six carbonene. Specific examples are norbornalene, tetracyclododecene, dicyclopentadiene, vinyl norbornene, and ethylidene norbornene. Acyclic olefins suitable for use in the present invention may be ethylene, or alpha-olefins having 3 to 12 breaks. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, and [-octene, etc.]. The catalyst composition of the present invention is particularly suitable for preparing an acyclic olefin / cycloolefin smoke copolymer 'such as an ethylene / cycloolefin copolymer. The ethylene / cycloolefin copolymer obtained by this special catalyst composition has high cycloolefin conversion rate and high Tg. With the special catalyst composition of the present invention, the glass transition temperature of the obtained olefin polymer can be within 6 Between 0-35 (rc, preferably between 120-35 () t, more preferably between 250-350 ° C. Therefore, the inventive catalyst composition is suitable for sludge Slurry reaction state, gas-phase reaction state, and solution polymerization reaction state. According to the experimental results of the present invention, it can be proved that the special catalyst composition of the present invention has an excellent reaction at a higher reaction temperature " Γ, = Activity, which is an undisclosed phenomenon that cannot be achieved by similar catalysts. This excellent reactivity can not only increase the conversion of cycloolefin smoke, but also synthesize cycloolefin copolymers with extremely high Tg. This high Tg material is also unattainable by similar catalyst systems in the past. According to the present invention, specific examples of the aromatic cycloolefin metal compound of formula (I) include the following chemical formulas:

〇424-4548TWF3.ptc Page 15

〇424-4548TWF3.ptc Page 16

〇424-4548TWF3.ptc Page 17

Where A is halogen. In the following, the methods, features, and advantages of several embodiments are used, but the scope of what is not used should be further explained by the attached patent application rules, all parts, percentages, ratios, etc. The invention limits the scope of the invention The present invention shall prevail. Unless otherwise specified, no is based on weight. Synthetic catalyst example of aromatic cycloolefin metal catalysts Example 1: Bucyclopentadienyl- 丨 -indenylcyclobutane (1-(^ 〇1〇1 ^ 1 ^ & (141 ^ 1-1-; 111 (^ 1171 (: ^ 1〇1311 "1 ^) (a type of bridged cyclopentadiene) Synthesis 5.8 g (50 mmole) indene (Indene) was placed in a 25 ml round bottom flask '50 ml of four gas Tetrahydrofuran (THF), under ice bath conditions, slowly add 40 m 1 (1.6 M, 64 mmo 1 e) nButyl lithium, during which the solution appeared orange-red, and then removed Bingluo 'continue to stir for 3 hours', drain off all solvents, and wash out excess n-butyllithium with 50 m 1 pentamene, filter, and take the precipitate.

0424-4548TWF3.ptc Page 18 1245775 Case No. 89112711 Amendment of the fifth and description of the invention (15) Re-add 5 0 m 1 tetrahydrofuran to dissolve the precipitate, and slowly add 5.9 g (50 mmole) 6 under ice bath conditions 6 , 6-trimethylenefulvene (6,6-trimethylenefulvene), continue stirring for 24 hours, then add 1 m 1 of water to stop the reaction, and drain all solvents. Then, it was dissolved in 1000 m 1 of hexane, the salts were filtered, and the filtrate was taken. This crude product was directly separated using 20 g of silica gel for column chromatography, and the conditions of the eluent were 100% hexane. The product layer was collected and concentrated to give a pale yellow liquid product 8.2 g (yie 1 d = 7 0 〇 / 〇) 〇Catalyst Example 2: Synthesis of 1-methylcyclopentadienyl-1 -indenylcyclobutane (1-methylcyclopentadienyl-1-indenylcyclobutane) 2.9 g ( 25 mmole) Indene was placed in a 250 ml round-bottomed flask, 30 ml of tetrahydrofuran (THF) was added, and 20 m 1 (1.6 M, 32 mmo 1 e) of n-butyl was slowly added in an ice bath. NButyl 1 i thium, during which the solution appeared orange-red, then removed the ice bath 'and continued stirring for 3 hours, drained all solvents, and washed out excess n-butyl lithium with 500 m 1 pentane, filtered, Take the precipitate. Add 30 m 1 of tetrahydrofuran to dissolve the precipitate, and slowly add 3.3 g (25 mmole) of 3-methyl-6,6-trimethylenefulvene (3-methyl-6,6-trimethylenefulvene) in an ice bath. ), Continue to mix for 24 hours

0424-4548TWF3.ptc Page 19 ’Then add 1 m 1 of water to stop the reaction and drain all solvents. It was then dissolved in 50 ml of hexane, the salts were filtered, and the filtrate was taken. 7 g This crude product was directly separated by column chromatography using 20 g of stone gum, and the conditions of the eluent were 100% hexane. The product layer was collected and concentrated to give a light yellow liquid product 4.7 g 1245775 Case No. 89112711 means the fifth amendment (16) (yie 1 d = 7 5 · 8%). Catalyst Example 3: Cyclobutylene (l-? 75-cyclopentadienyl) (1-π5-indenyl) bis (difluorenylamino) fluorene ([Cyclobutyl ideneU- 7? 5-cyclopentadienyl) ( Synthesis of l-々5-indenyl) bis (dimethylamino: zirconium)) 0.94 g (4 mmole) of 1-cyclopentadienyl-1-benzylcyclobutane (1-Cyclopentadienyl) obtained from Catalyst Example 1 -l-indenylcyclobutane) and 1 g (3.7 mmole) tetrakis (dimethylamino) zirconium; (Zr (NMe2) 4), put into a 100 ml round bottom flask, add 20 ml toluene, The reaction was carried out at room temperature for 15 hours, and then all solvents were drained off, and 50 ml of pentane was added to dissolve the solid, filtered, and the filtrate was taken. After concentration, a yellow solid product 1.45 g (yield = 95%) was obtained. Example 4: Cyclobutylene (1- 7? 5-methylcyclopentadienyl) (Bu 7? 5-Mengyl) bis (difluorenylamino) ([Cyclobutylidene (l- 7/5 -methylcyclopentadienyl) (l-a5-indenyl) bis (dimethylamino) zirconium)) was synthesized by taking 0.999 g (4 mmo 1 e) of 1-fluorenylcyclopentadienyl-1 obtained from Catalyst Example 2. -1-methylcyclopenta dienyl -1-indeny lcyclobutane) and 1 g (3.7 mmole) tetrakis (dimethylamino) zirconium; (Zr (NMe2) 4), put into a 100 ml round bottom flask, add 20 ml Toluene, reacted at room temperature for 15 hours, then drained off all solvents and re-added 〇.

0424-4548TWF3.ptc Page 20 1245775 Case No. 89112711 Amendment V. Description of the invention (17) ml of pentane to dissolve the solid, filter, take the filtrate, and concentrate to obtain a yellow solid product 1.54 g (yield 98%) . Catalyst Example 5: Cyclobutylene (1-W5-cyclopentadienyl) (1-π5-fluorenyl) dichloride [cyclobutylidene (l-β5-cyclopentadienyl) (1- ^ 5 ~ f1uoreny1) zirconium di chloride] Synthesis 1-cyclopentadienyl-1-fluorenylcyclobutane was prepared in a similar manner as described in Catalyst Example 1. In a 100 ml round bottom flask, the resulting material (1.14 g, 4 mmole) was mixed with Zr (NMe2) 4 (1 g, 3.7 mmole) in toluene. 20 ml of toluene was added to the flask, and the mixture was allowed to react at room temperature for 15 hours to obtain an amide complex of an aromatic olefin metal. Then, the resulting solution was treated with 1.05 ml of trimethylsilylchloride. The resulting solution was then reacted at room temperature for 6 hours to obtain cyc 1 〇buty 1 idene (1 -7? 5-cyclopentadienyl) (l-775-fluorenyl) zirconium dichloride (1.15 g, yield 62%) . The precipitated powder of the catalyst was recrystallized from toluene to form a single crystal catalyst of X-ray quality. X-ray crystal data and structural refinement were recorded with a Nonius Kappa ccd diffractometer at 2 9 5 K. The product cyclobutylidene (1- 7/5 -cyclopentadienyl) (1-τ? 5-fluorenyl) dicyclo hammer [cyclobutylidene (l- 7? 5-cyclopentadienyl) (l-775-fluorenyl)- zirconium dichloride) (labeled 1C 8359) and X-ray crystal data

〇424-4548TWF3.ptc Page 21

1245775 Case No. 89112711 A_ Amendment V. Description of the invention (19) Table 2. Crystal data and structure of IC8329

Identification code Diffractometer- used Empirical formula Formula weight Temperature Wavelength Crystal systein Space group Unit cell dimensions

Volume, Z

Derisity (calculated)

Absorption coefficient F (000)

Crystal size

Grange for data collection

Limiting indices

Reflections collected

Independent reflections

Absorption correction

Max. And rain, transmission

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2

Final R indices [Ι > 2σ (Ι)] R indices (all data)

Extinction coefficient Largest diff. Peak and hole ic8359

Nonius KappaCCD C ^ iHi ^ CliZr:

444.48 295 (2) K 0.71073 A Honoclinic P2i / C a = 9_49350 (10) A alpha = 900 b = 21.3760 (3) A beta = 104.2460 (10) 'c-9.34090 (10) A gamma = 900 1837.28 (4) A3, 4 1.607 Hg / m3 0.890 tcqxi'1 896 0.30 x 0.25 x 0.25 ram 2.21 to 25.00 ° -12 ^ /? ^ 12, -27 ^^ 27, -12ύΙύ \ 2 11705 3235 (Rint = 0.0225) int

Hulti-scan 0.915 and CL 865

Full-raatrix least-squares on F £ 3192/0/227 1.352 R1 = 0.0364, WR2 = 0,1053 R1 = 0.0421, wR2 = 0.1206 0.032 (2) 0.808 and -0.774 e A -3

Page 23 〇424-4548TWF3.ptc 1245775 ,,, η, π… s ⑽ 5. Description of the invention (20) Table 3. Bond length [person] and bond angle Zr (1) -C (10) 2.414 of 8359 ( 3) Sr (1) -Cl (1) 2.4204 (9) Sr (1) -Cl (2) 2.4274 (9) Sr (1) -C (5) 2.439 (3) Zr (1) -C (l) 2.446 (3) Sr (1) -C (4) 2.460 (3) Zr (1) -C (14) 2.519 (3) Zr (1) -C (11) 2 * 523 (3) Zr (1)- C (2) 2.535 (3) Zr (1) -C (3) 2.545 (3) Zr (1) -C (12) 2.650 (3) Zr (1) -CU3) 2.652 (3) C (l)- C (2) 1.403 (5) C ⑴-C (5) 1.420 (5) C (2) -C (3) 1.387 (5) C (3) -C (4) 1.414 (5) C (4)- C (5) 1.415 (5) C (5) -C (6) 1-521 (5) C (6) -C (10) 1.526 (5) C (6) -C (7) 1.547 (5) C (6) -C (9) 1.548 (5) C (7) -C (8) 1.549 (5) C (8) -C (9) 1.537 (5) C (10) -C (ll) 1.435 (5 ) C (10) -C (14) 1.438 (5) C (ll) -C (15) 1.423 (5) C (11) -C (12) 1.442 (5) C (12) -C (18) 1.419 (5) C (12) -C (13) 1.433 (5) C (13) -C (19) 1.412 (5) C (13) -C (14) 1.439 (5) C (14) -C (22 ) 1.413 (5) C (15) -C (16) 1.36 * 7 (5) C (16) -C (17) 1.408 (6) C (17) -C (18) 1.360 (5) C (19) -C (20) 1.368 (6) C (20) -C (21) 1.402 (6) C (21) -C (22) 1.373 ⑹ C (10) -Zr (1) -Cl (1) 125.58 (8 ) C (10) -Zr (1) -Cl (2) 126.19 (8) Cl (1) -Zr (1) -Cl (2) 96.90 (3) C (10) -Zr (1) -C (5) 57.87 (11) C1 (1) -Zr (l) -C (5) 124.92 (8) Cl (2) -Zr (1) -C (5) 125.23 (8) C (10) -Zr (1)- C (l) 78.75 (11) Cl (l) -Zr (1) -C (l) 91.40 (9) Cl (2) -Zr (1) -C (l) 137.27 (9) C (5) -Zr (1) -C (l) 33.79 (12) C (10) -Zr (1) -C (4) 79.97 (11) Cl (l) -Zr (l) -C (4) 135.49 (9) Cl ( 2) -Zr (1) -C (4) 92.13 (8) C (5) -Zr (1) -C (4) 33.57 (11) C (l) -Zr (l) -C (4) 55.18 ( 12) C (10) -Zr (1) -C (14) 33.81 (11) Cl (l) -Zr (1) -C (14) 136.92 (8) Cl (2) -Zr (l) -C ( 14) 92.92 (8) C (5) -Zr (l) -C (14) 79.91 (11) C (l) -Zr (1) -C (14) 109.01 (12) C (4) -Zr (1 ) -C (14) 85.60 (11) C (10) -Zr (1) -C (ll) 33.71 (11) Cl (1) -2r (1) -C (ll) 92.45 (8) Cl (2) -Zr (1) -C (ll) 137.19 (8) C (5) -Zr (1) -C (11) 79.89 (11) C (1) -Zr (l) -C (ll) 83.81 (11) C (4) -Zr (1) -C (ll) 109.73 (11) C (14) -Zr (1) -C (ll) 54.49 (11) C (10) -Zr (l) -C (2) 109.70 (12) Cl (1) -Zr (1) -C (2) 81.97 (9) Cl (2) * Zr (l) -C (2) 107.34 (9) C (5) -Zr (1)- C (2) 54.69 (12) C (l) -Zr (1) -C (2) 32.67 (12) C (4) -Zr (1) -C (2) 53.83 (12) C ( 14) -Zr (l) -C (2) 134.17 (11) C (ll) -Sr (1) -C (2) 115.33 (12) C (10) -2r (l) -C (3) 110.63 ( 11) Cl (l) -Zr (1) -C (3) 105.31 (9) Cl (2) -Zr (1) -C (3) 83.36 (9) C (5) -Zr (1) -C ( 3) 54.84 (11) C (l) -Zr (1) -C (3) 54.10 (12) C (4) -Zr (l) -C (3) 32.77 (12) C (14) -Zr (1 ) -C (3) 117.47 (12) C (ll) -Zr (1) -C (3) 133.80 (11) C (2) -Zr (l) -C (3) 31.70 (12) C (10) -Zr (1) -C (12) 54.80 (11) Cl (1) -Zr (1) -C (12) 83.86 (8) Cl (2) -Zr (1) -C (12) 107-56 ( 8) C (5) -Zr (1) -C (12) 110.28 (11) C (l) -Zr (1) -C (12) 114.99 (11) C (4) -Zr (1) -C ( 12) 134.13 (11) C (14) -Zr (1) -C (12) 53.26 (11) C (ll) -Zr (l) -C (12) 32.24 (10) C (2) -Zr (1 ) -C (12) 143.59 (12) C (3) -Zr (l) -C (12) 165.08 (11) C (10) -Zr (1) -C (13) 54 · 7 7 (11) Cl (l) -Zr (1) -C (13) 107.46 (8) Cl (2) -Zr (1) -C (13) 84.23 (8) C (5) -Zr (1) -C (13) 110.22 (11) C (l) -Zr (1) -C (13) 132.66 (12) C (4) -Zr (1) -C (13) 116.80 (11) C (14) -Zr (1) -C (13) 32.18 (11) C (11) -Zr (1) -C (13) 53.21 (11) C (2) -Zr (1) -C (13) 164.43 (12) C (3) -Sr ( 1) -C (13) 146.07 (12) C (12) -Zr (1) -C (13) 31.37 (11) C (2) -C (l) -C (5) 108.2. (3) C (2) -C (1) -Zr (1) 77.2 (2) C (5) -C (l) -Zr (l) 72.8 (2) C (3) -C (2) -C (l) 108.9 (3) C (3) -C (2) -Zr (l) 74.6 (2) C (l) -C (2) -Zr (l) 70.2 (2) C (2) -C (3) -C (4) 107.7 (3) C (2) -C (3) -Zr (l) 73.7 (2) C (4) -C (3) -Zr (l) 70.3 (2) C (3) -C (4) -C (5) 108.6 (3) C (3) -C (4) -Zr (1) 76.9 (2) C (5) -C (4)- Zr (1) 72.4 (2) I1 · I Page 24 0424-4548TWF3.ptc 1245775 _ Case No. 89112711_ year month day_ amendment V. Description of the invention (21) C (4) -C (5) -C (0J 106.6 (3) C (4) -C (5) -C (6) 126.0⑼ C (l) -C (5) -C (6) 123.3 (3) C (4) -C (5) -Zr ( l) 74,0 (2) C (l〉 -C (5) -Zr⑴ 73.4 (2) C (6) -C (5) -Zr (1) 100.2 (2) C (5) -C (6) -C (IO) 100.8 (3) C (5) -C (6) -C (7) 113.7 (3) C (10) -C (6) -C (7) 120.9 (3) C (5)- C (6) -C (9) 112.5 (3) C (10) -C (6) -C (9) 121.8 (3) C (7) -C (6) -C (9) 87.8 (3) C (6) -C (7) -C (8) 87.8 (3) C (9) -C (8) -C (7) 88.1 (3) C (8) -C (9) -C (6) 88.2 (3) C (ll) -C (10) -C (14) 106.9 (3) C (ll) -C (10) -C (6) 126.2 (3) C (14) -C (10) -C (6) 125.5 (3) C (ll) -C (10) -Zr (1) 77.3 (2) C (14) -C (10) -Sr (1) 77.1 (2) C (6) -C ( 10) -Zr (1) 101.1 (2) C (15) -C (ll ) -C (10) 132.2 (3) C (15) -C (ll) -C (12) 118.9 (3) C (10) -C (ll) -C (12) 108.9 (3) C (15) -C (ll) -Zr (1) 117.4 (2) C (10) -C (ll) -Zr (1) 69.0 (2) C (12) -C (ll) -Zr (1) 78.8 (2) C (18) -C (12) -C (13) 132.5 (3) C (18) -C (12) -C (ll) 119.9 (3) C (13) -C (12) -C (ll) 107.6 (3) C (18) -C (12) -Zr (1) 121.8 (2) C (13) -C (12) -Zr (1) 74.4 (2) C (11) -C (12)- Zr (1) 69.0 (2) C (19) -C (13) -C (12) 132.3 (3) C (19) -C (13) -C (14) 119.9 (3) C (12) -C (13) -C (14) 107 · 8 (3) C (19) -C (13) -Zr (1) 123.2 (3) C (12) -C (13) -Zr (1) 74.3 (2) C (14) -C (13) -Zr (1) 68.8 (2) C (22) -C (14) -C (10) 131.8 (3) C (22) -C (14) -C (13) 119.4 (3) C (10) -C (14) -C (13) 108.8 (3) C (22) -C (14) -Zr⑴ 117.0 (3) C (10) -C (14) -Zr (1 ) 69.1 (2) C (13) -C (14) -Zr (1) 79.0 (2) C (16) -C (15) -C (ll) 118.9 (3) C (15) -C (16) -C (17) 121.8 (4) C (18) -C (17) -C (16) 121.4 (3) C (17) -C (18) -C (12) 119.1 (3) C (20)- C (19) -C (13) 118.9 (4) C (19) -C (20) -C (21) 121.2 (4) C (22) -C (21) -C (20) 121.9 (4) C (21) -C (22) -C (14) 118.7 (3)

Symmetry transformations used to generate equivalent atoms: Catalyst Example 6: Synthesis of Cyclobutylene (I-775-Cyclopentadienyl) (1-? 75-Indenyl) Zirconium Dichloride (Catalyst A) [cyclobutylidene ( l-7? 5-cy c 1 open tad i eny 1) (1--indenyl) zirconium dichloride] (1) 6,6-三亚 曱 基基 稀稀 (6,6-trimethylenefulvene)

5 g of cyclobutanone (71 mmol) and 14.35 mL of cyclopentadiene (175 mmol) were placed in a 300 mL reaction flask, 70 mL of CH3OH was added as a solvent, and then slowly dropped into 8 75 mL D pyrrolidine (105 mmol), stir at room temperature; stir for 30 minutes, then slowly add 6.3 mL CH3C00H (105 mmol), stir for 10 minutes, add H20 and pentyl Extract each 200 mL of pentane, and collect the upper pentane layer. The lower aqueous layer was extracted three more times with pentagon, and all the pentane layers were collected, and MgS04 was added to stand for 30 minutes to remove water, and then filtered to remove MgS04.

0424-4548TWF3.ptc Page 25 1245775 Case No. 89112711 Amended 5. Description of the invention (22) The filtrate can be concentrated under reduced pressure to obtain a yellow liquid product 5.5 g, yield = 68 (2) 1-cyclopentane Dienyl-1-indenylcyclobutane [l-cyclopentadienyl-1-indenylcyclobutane] Put 5.8 g of indene (50 mmol) into a 250 mL round bottom flask, add 50 mL of THF as a solvent, In an ice bath, 34.3 mL / iBuLi (1.6 M, 55 mmol) was slowly added, during which the solution appeared orange-red, then the ice bath was removed, and after stirring for 3 hours, 5. 4 g 6, was slowly added. 6-trimethylenefulvene (46 mmol), followed by 24 hours, and then added 1 m L of water to stop the reaction, drained all solvents, washed with 100 mL pentane, and washed the salts Filter and take the filtrate. This crude product was directly separated by 20 g of si 1 icage 1 as column chromatography, and the condition of the dike solution was 100% ammonium bromide. The product layer was collected and light yellow after concentration. Liquid product 6.96 g, yield = 65%. (3) Cyclobutylene (1-7 / 5 -cyclopentadienyl) (1-Ty5 mono-indenyl) bis (difluorenylamino) [l-cyclobutylidene (l- 775-cy c 1 open t ad i eny 1) (1-^ 5_ indenyl) bis (dimethylamino) zirconium] take 1 g of 1-cyclopentadienyl-1-indenylcyclobutane [1-cyclopentadieny1-1-indenylcyclobutane] (4 · 3 mmol) and 1.06 g Zr (NMe2) 4 (4.0 mm〇i) were placed in a loo mL round bottom flask, 50 mL toluene was added as a solvent, and after 24 hours of reaction, the tears were drained and 20 mL After washing with alkanes and filtering, the precipitate can be dried to obtain orange.

0424-4548TWF3.ptc Page 26 1245775 Case No. 89112711 Modification 5. Description of the invention (23) 1.47 g of color solid product, yield = 89.3%. (4) Cyclobutylidene (1- 7y5 -cyclopentadienyl (1- 7/5 -mene) dichloride [cyclobutyl idene (l-7? 5-cy c 1 o pen t ad i eny 1 ) (1-η 5 -i ndeny1) -zi rcon i um dichloride] Take 0.5 g of cyclobutylene (1- 7? 5-cyclopentadienyl) (i — y —indenyl) bis (di Methylamino) 鍅 [1 -cyclobutyl i dene (1- π 5 -cyclopentadieny1) (1- ^ 5-indenyl) bis (dimethylamino) -zirconium] (1.2 mmol) was placed in a 100 mL round bottom flask, and 2 was added 〇mL toluene, at room temperature, slowly add 0.39 g (CH3) 3SiCl (3.6mmo 1), react for 24 hours, drain off all solvents, and wash several times with pentagon to 'excess (C Hs) 3 S i C 1 was washed out, and the precipitate was taken to dryness to obtain 0.4 g of light yellow product, yield = 83.5%. The product cyclobutylene (1- γ-cyclopentadienyl (1- 7? 5-molyl group) The X-ray crystal structure of [cyclobutylidene- (1- γ ~ cyclopentadienyl) (l- -indenyl) -zirconium di chi or ide]] is shown in Figure 2. The results clearly show that 'can be obtained with a very large Bi te ang 1 e (100.44.) A novel catalyst. Catalyst Example 7: Synthetic ring Amyl (1- π5-cyclopentadienyl) (1 indenyl) hafnium dichloride (catalyst B) [eye 1 openty 1 i dene (1-7y5-cyc 1 opentad i eny 1) (1 -indenyl ) -zirconium dichloride] (1) 6,6-tetramethylenefulvene Take cyclopentanone (71 mmol) and 14.35

1245775 Case No. 89112711 Yue Xiu_ V. Description of the invention (24) Cyclopentadiene (175 mmol) was placed in a 300 mL reaction flask, 70 mL of CH30H was added as a solvent, and then 875 mL of pyrrolidine ( pyrrolidine) (105 mmol), stir the reaction at room temperature for 30 minutes, and then slowly add 6.3 mL of CH3C00H (105 mmol). After ten minutes of incubation, add H20 and 20 mL of pentagon to extract and collect the upper layer. E courtyard floor. The lower aqueous layer was extracted three more times with pentagon, all pentane layers were collected, MgS04 was added to stand for 30 minutes to remove water, and then MgS04 was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a yellow liquid product 8 · 4 g, yield = 8 9 %. (2) 1-cyclopentadienyl-1-benzylcyclopentane (1-cyclopentadienyl-1-indenylcyclopentane) Put 5.8 g of Indene (50 mmol) into a 250 mL round bottom flask, and add 50 mL THF was used as a solvent. In an ice-bath condition, 3 4.3 mL nBuLi (1.6 M, 55 mmo 1) was slowly added, during which the solution appeared orange-red, then the ice bath was removed, and stirring was continued for 3 hours, and then 6.1 was slowly added. g of 6,6-tetramethylene rich (6,6-16 seven "& 1116111716116 {111 ¥ 6116) (46 mmol), continue stirring for 24 hours, then add 1 mL of water to stop the reaction, and drain all solvents , Wash with 100 mL of pentane, filter the salts, and take the filtrate. This crude product was directly separated by 20 g of si 1 icage 1 as column chromatography, and the conditions for flushing the bank liquid were 100% pentane. The product layer was collected and light yellow after concentration. Liquid product 7.6 g, yield = 67%. (3) Cyclopentylene (I- ;; 5-Cyclopentadienyl-indenyl) bis (difluorenylamino) group [eye 1 openty 1 i dene (1 ~ 575 ~ cyc 1 opentadi eny 1) (1-7? 5-

〇424-4548TWF3.ptc Page 28 1245775 Case No. 89112711 Amended 5. Description of the invention (25) indenyl) -bis (dimethylamino) zirconium] Take 1 g of 1-cyclopentadienylindenylcyclopentane (1 -cyclopentadienyl-1-indenylcyclopentane) (4.0 mmol) and 0.96g Zr (NMe2) 4 (3.6 mmol) were placed in a 100 mL round-bottomed flask, 50 ml of toluene was added as a solvent, and after reacting for 24 hours, pump The dried mash was washed with 20 mL of pentane and filtered. The precipitate was dried to obtain an orange-yellow solid product 1.4.1 g, yield = 90.2%. (4) Cyclopentylene (1- 775 -cyclopentadienyl) U-π5-indenyl) zirconium dichloride [eye 1 openty 1 i dene (1-775-cyc 1 opentadi eny 1) (1- 7? 5-i ndeny1) -zi rcon i um dichloride] Take 0.51 g of cyclopentylidene (1-775 -cyclopentadienyl) (bu; -indenyl) bis (difluorenylamino) (l-7? 5-cyclopentadieny1) (1- -indenyl) bis (dimethylamino) zirconium] (1.2 mmol) was placed in a 100 mL round bottom flask, 20 mL of toluene was added, and 0.39 was added slowly at room temperature. g (CH3) 3SiCl (3.6 mmo 1) 'Reaction for 24 hours, drain off all solvents, wash with pentagon, wash out excess (C H3) 3 S i C 1, and take the precipitate to dry Light yellow product 0.42 g, yield = 85.7%. Product cyclopentylidene (1-775 -cyclopentadienyl) (1- 7 / -indenyl) mono-gasification [cyclopentylidene (l_ 7 / 5-cyclopentadienyl) (l ~ 7? 5-indenyl) -zirconium d 1 chi or ide] X-ray crystal structure is shown in Figure 3. The results clearly show that a novel catalyst with a very large bite angle (1 0 1 · 0 °) can be obtained.

0424-4548TWF3.ptc Page 29 1245775 _Case No. 89112711_ Year and Month Revision _ V. Description of the Invention (26) Comparative Catalyst Example 8: Synthesis of Cycloheptylene (1- 7/1 2 3 4 -Ring Pentadienyl) (Bu 7? 4-indenyl) rhenium dichloride (catalyst C) [cyc1ohepty1idene (1-β4-cyc1 opentadieny 1) (1-η4 -indenyl) -zirconium dichloride] (1) 6, 6-hexamethylenefulvene Take 8 g of cycloheptanone (71 mmol) and 14.35 mL of cyclopentadiene (175 mmol) in a 300 mL reaction flask 70 mL of CH30H was added as a solvent, and then 8.75 mL of pyrrolidine (105 mmol) was slowly added dropwise, and the reaction was stirred at room temperature for 30 minutes, and then 6.3 mL of CH3C00H (105 mmol) was slowly added and mixed for ten minutes. After that, H20 and 200 mL of each pentamidine were added for extraction, and the upper pentamidine layer was collected. The lower aqueous layer was extracted three more times with pentane. All pentane layers were collected, MgS04 was added and left to stand for 30 minutes to remove water, and then MgS04 was filtered to remove the filtrate. The filtrate was concentrated under reduced pressure to obtain a yellow liquid product 10 · 6g, yield = 9 3%.

〇424-4548TWF3.ptc

Page 30 1-cyclopentadienyl-1-indenylcycloheptane 2 Take 5 · 8 g of Indene (50 mmol) into a 250 mL round bottom flask Add 50 mL of THF as the solvent, and slowly add 34.3 mL «BuLi (1.6 M, 55 mmol) under ice bath conditions, during which the solution appears orange-red, then remove the ice bath and continue stirring for 3 hours Add 7.4 g of 6, 6-hexamethylenefulvene (46 mmol) slowly, 4 continue to incubate for 24 hours, then add 1 mL of water to stop the reaction, drain off all solvents' to 100 m L was burned and washed, the salts were filtered, and the mash was taken. This crude yield 1245775

The product was directly separated by using 20 g second gel as column chromatography, and the conditions for flushing the bank liquid were 100%. The product layer was collected. After concentration, a pale yellow liquid product 8.6 g was obtained. Yield = 6 7. 7%. (3) cycloheptylidene (1-γ-cyclopentadienyl) (bu ^ indenyl) bis (difluorenylamino) zirconium [cycloheptyl idene (l-7? 5-cy c 1 open t ad i eny 1) (1-Vb ~ indenyl) -bis (dimethylamino) zirconium] Take 1 g of 1 J 1-pentanyl- 1-yl-cycloheptan (1-cyclopentadieny l * ~ l-indenylcycloheptane) (3. 6 mmol) and 0.86 g Zr (NMe2) 4 (3.2 mmol) were placed in a 100 mL round-bottomed flask, 50 mL of toluene was added as a solvent, and after 24 hours of reaction, the filtrate was drained, washed with 20 mL of pentane and filtered. The precipitate was dried to give 1.25 g of an orange-yellow solid product, yield = 86%. (4) Cycloheptylene (1-7? 5-cyclopentadienyl) (1-π5-spermyl) zirconium dichloride [cy c 1 ohep ty 1 i dene (1-5-cy c 1 open t ad i eny 1) (1-η5-indenyl) -zirconium dichloride] take 0.5 g of cycloheptylene (1- 7/5 -cyclopentadienyl) U-7? 5-indenyl) bis (dimethyl) (Aminoamino) [cycloheptylidene- (1-7 / 5 -cyclopentadienyl) (l-7? 5-indenyl) bis (dimethylamino) zirconium] (1.1 mmol) was placed in a 100 mL round bottom flask, and 20 mL was added Toluene, at room temperature, slowly add 0.36 g (cH3) 3SiCl (3.3 mM 1), react for 24 hours, 'dry all solvents' and wash several times with pentagon, and excess (CH3) 3SiCl was washed out, and the precipitate was taken out and dried to obtain a pale yellow color.

0424-4548TWF3.ptc Page 31 1245775 Case No. 89112711 Month Revision V. Description of the Invention (28) Product 0.41 g, yield = 85.2%. Product cycloheptylidene (1- 775 -cyclopentadienyl) (1- 775 -benzyl) dichloride [cycloheptylidene (l-7/5 -cyclopentadienyl) (l-τ / 5-indenyl) -zirconium X-ray crystal structure of dich 1 oride] is shown in Fig. 4. The results show that the bite ang1e is 99.8. Comparative catalyst Example 9: Synthesis of cyclohexylene (1-τ? 5-cyclopentane Alkenyl) (Ια5-indyl) dichloride [eye 1 ohexy 1 i dene (1-7? 5-cy c 1 open tad i eny 1) (1-rjb -indenyl) zirconium dichloride] (catalyst E ) (1) 6, 6-pentamethylenefulvene (6, 6-pentamethylenefulvene) Take 7g of cyclohexanone (71 mmol) and 14.35 mL of cyclopen ta diene (175 mmol) In a 300 mL reaction flask, add 70 mL of CH30H as a solvent, then slowly drop 8.75 mL of pyrrolidine (105 mmol), stir the reaction at room temperature for 30 minutes, and then slowly add 6.3 mL of CH3C00H (105 mmol). After stirring for ten minutes, add 200 mL of H20 and pentane each for extraction, and collect the upper pentane layer. The lower aqueous layer was extracted three times with glutamate, collected all pentamed layers, added MgS04 and left to stand for 30 minutes to remove water, then filtered to remove MgS04, and the filtrate was concentrated under reduced pressure to obtain a yellow liquid product 8.7 g, yield = 83 . 3%. (2) 1-cyclopentadienyl-1-indenylcyclohexane (1-cyclopentadienyl-l-indenylcyclohexane) Put 5 · 8 g of indene (50 mmol) into a 250 mL round bottom flask, add 50 mL of THF was used as a solvent, and in an ice bath, slowly added 34.

〇424-4548TWF3.ptc Page 32 1245775 Case No. 89112711 Amended 5. Description of the invention (29) 3 mL nBuLi (1.6 M, 55 mmol), during which the solution appeared orange-red, then removed the ice bath and continued After stirring for 3 hours, slowly add 6.7g of 6,6-pentamethylenefulvene (46 mmol), continue stirring for 24 hours, then add 1 mL of water to stop the reaction, and drain off all solvents. Wash with 100 mL of pentane, filter the salts, and take the filtrate. This crude product was directly separated by 20 g of silica gel for column chromatography. The condition of the dike solution was 100% pentane. The product layer was collected and concentrated to give 8.3 g of a pale yellow liquid product. Yield = 69%. (3) cyclohexylene (1

V alkenyl) (1- 7? 5-indenyl) bis (dimethylamino) pyr [cyclohexylidene (l-775-cyclopentadienyl)-(1- 77 5-indenyl) bis (dimethylamino) zirconium] Take 1 g Dicyclopentadienyl-1-indenylcyclohexane (1-cyclopentadienyl-1-indenylcyclohexane) (3.8 mmol) and 0.91 g Zr (NMe2) 4 (3.4 mmol) were placed in a 100 mL round bottom flask 50 mL of toluene was added as a solvent, and after 24 hours of reaction, the filtrate was drained, washed with 20 mL of pentane and filtered, and the precipitate was dried to obtain an orange solid product 1.27 g, yield = 84 · 8 %. (4) Cyclohexylene (1-π5-cyclopentadienyl) (Bu 7? 5-indenyl) zirconium dichloride [eye 1 ohexy 1 i dene (1-775-eye 1 opentadi eny 1) (1 -η5-indenyl) -zirconium dichloride] Take 0.53 g of cyclohexylene (I-? / 5-cyclopentadienyl) U-7? 5-indenyl) bis (difluorenylamino) zirconium [ cyclohexylidene (1- π5-cyclopentadienyl) (l- Θ5-indenyl) bis (dimethylamino)

〇424-4548TWF3.ptc Page 33, 1245775 Revised in January-Case 89189111 V. Description of the invention (3〇) z ^ co ^ iium] (12 _〇1) Place in a 10 () mL round bottom flask, add Human μm, at room temperature, slowly add 0.39 g (CH3) 3SiCl • jmmol), react for 24 hours, drain off all solvents, and wash the human body with I (CHs, S 1 C 1 washing The precipitate was taken out and dried to obtain 42 g of pale yellow substance, yield = 82.5%. The X-ray crystal structure of the product is as shown in Figure 5. The results show that the bite angie is 97.3. Polymer Synthesis Example A: Synthesis of ethylene / orbornene copolymer. Toluene was heated to reflux with sodium to remove water. Its water content must be measured by an on-line moisture analyzer and less than 10 ppm before use. Polymerization monomer Orbornene (norbornene) solution is prepared by adding 500 g of norbornene to 88 g of dry toluene under nitrogen to prepare an 85 wt% solution. The 500 m 1 reactor is first heated To 丨 2 〇, evacuate for 1 hour, and then fill with nitrogen, and then repeatedly pump nitrogen 3 to 4 times to ensure that the water and oxygen are completely removed. Introduce ethylene into the reactor to replace nitrogen and vent. Repeat this step. Then, under nitrogen, 100 grams of 85% by weight norbornene solution was injected into the reactor, and the solution was stirred at 250 rpm. At the same time, 4 ml of 1.49 M MAO (methyl aluminoxane) was injected with a needle at the same time. The reaction temperature was adjusted to 100. After the temperature was stabilized, 1 mg of the aromatic cycloolefin metal complex obtained in Catalyst Example 3 was placed in a glove box. It is dissolved in 1 m 1 of toluene. Then, 3 m 1 MA0 is added to the aromatic cycloolefin metal solution for activation. After 5 minutes of activation, the aromatic cycloolefin metal solution is injected into the reactor to start polymerization, The mixture was stirred at a speed of 750 rpm. Finally, 1245775 Case No. 89112711 (Amendment V. Invention Description (31) 15 kg / cm2 pressure ethylene was introduced into the reactor, so that the concentration of ethylene in the solution was saturated, and the speed of the mixture was still maintained At 75 rpm. The reaction was carried out for 30 minutes. After the polymerization reaction was completed, the reaction solution was poured into an acetone solution to precipitate the product. The product was washed two or three times with acetone 'and filtered at 80 ° C for 1 2 hour The resulting copolymer is 43 · 2 g. The results are shown in Table 4.

Examples B to F Several cyclic olefin copolymers were prepared in the same manner as in Example A, except that the reaction temperature, the amount of the aromatic cycloolefin metal, and the amount of MAO were changed. The aromatic rings used are the same. The results are shown in Table 4. Table 4 Example Aromatic metal compounds (mg) MAO (ml) Reaction temperature CC) Ethylene pressure (kg / cm2) Yield (g) Activity (g / gZr.hr) Tg CC) A 1.00 7 100 15 43.2 3.90 χ 105 173 B 0.24 1.3 80 15 10.9 2.07 χ 105 163 C 0.23 1.3 100 15 15.3 5.9 χ 105 176 D 0.22 1.3 120 15 20.4 8.23 χ 105 185 E 0.23 1.3 140 15 26.4 10.2 χ 105 195 F 0.24 1.3 155 15 11.1 4.22 χ 105 193

〇424-4548TWF3.ptc Page 35 1245775 Revised HM 89119711 V. Description of the Invention (32) Comparative Example G (Compared to Example a) Toluene is heated to reflux with sodium to remove water, and its water content must be passed online Moisture analyzer, use less than 10 ppm. The polymerization monomer norbornene solution is prepared by adding 5,000 g of norbornene to 88 g of dry toluene under nitrogen to prepare an 85 wt% solution. 0 First, 500 m 1 is reacted. The inside of the device was heated to 200, vacuumed for 1 hour, then filled with nitrogen, and then repeatedly pumped with nitrogen for 3 to 4 times to ensure complete removal of water and oxygen. Ethylene was introduced into the reactor to replace nitrogen and vented. Repeat this step. Then, under nitrogen, 1000 g of an 85% by weight norbornene solution was injected into the reactor, and the solution was stirred at 250 rpm while 4 ml of 1.49 M MA0 was injected through a syringe. The reaction temperature was adjusted to 100 t :. After the temperature stabilized, 1 mg of diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride was dissolved in 1 ml of toluene in a glove box. Then, 3 m 1 MA0 was added to the aromatic cycloolefin metal solution for activation. After 5 minutes of activation, the aromatic metal solution was injected into the reactor, and the initial polymerization 'mixture was stirred and stirred at a speed of 7500 r p m. Finally, ethylene at a pressure of 15 k g / cm 2 was introduced into the reactor to saturate the concentration of ethylene in the solution, and the speed of the mixture was still maintained at 750 rpm. The reaction was carried out for 30 minutes. After the polymerization was completed, the reaction solution was poured into an acetone solution to precipitate a product. The product was washed two or three times with acetone, filtered, and dried under vacuum at 80 ° C for 12 hours. The copolymer obtained was 26.9 grams. The results are shown in Table 5.

0424-4548TWF3.ptc Page 36 1245775 «89Π27Π. Year, month, fifth, description of the invention (33) Table 5 Example reaction temperature (. Ethylene pressure ㈣ cm2) MAO (ml) / 100 ml 85% Nb live i ± secret, hr)-Tg CC) G 100-15 7 '----- ^ 154- A 100 ^-15 ^ ---- 7 3.9〇 ^ qJ ^ 173

Nb = norbornene

Examples I to K were repeated the same steps as described in Example A to prepare several cyclic olefin copolymers with high τ. The same arylcyclic metal was used, but the reaction temperature was set to 120. (: 'The reaction time was extended from t to 1 hour, changing the ethylene pressure plate: changing the use of the aromatic ring metal and M A 0. The results are shown in Table 6. Table 6 Examples of aromatic ring olefin compounds (mg) MAO (ml) Reaction temperature (° C) Ethylene pressure (Kg / cm2) Production string (g) Activity (g / gZr.hr) Tg (° C) I 1.05 1.3 120 3 27.4 1.17 χ 105 292 J 0.52 1.3 120 5 24.4 2.14 χ 105 245 232 K 0.55 1.3 120 7 34.9 2.87 χ 105 Comparative Example L (compared to Example J) θ must be heated to reflux with sodium to remove water 'its water content

〇424-4548TWF3.ptc Page 37 1245775

It can be used only when it is less than 10 ppm, as determined by the dagger and the water slicing analyzer. The method of preparing the norborneene solution of polymerized monomers is to add 5,000 g of norbornene to 88 g of dry toluene under nitrogen to prepare 85 w1:% solution 0 First, 500 m 1 The reactor is heated to 200 ° C, evacuated for 1 hour, and then filled with nitrogen, and then repeatedly pumped with nitrogen 3 to 4 times to ensure complete removal of water and oxygen. Ethylene was introduced into the reactor to replace nitrogen and vented. Repeat this step. Then, under nitrogen, 1000 g of an 85% by weight norbornene solution was injected into the reactor, and the solution was stirred at a speed of 250 pm while 4 ml of 1.49 M MA0 was injected through a syringe. The reaction temperature was adjusted to 100 ° C. After the temperature stabilized, 1 mg of diphenylmethylidene (cyclopentadienyl) (9 ~ fluorenyl) zirconium dichloride was dissolved in 1 ml of toluene in a glove box. Then, 3 m 1 of M0 was added to the aromatic cycloolefin metal solution for activation. After 5 minutes of activation, the aromatic cycloolefin metal solution was injected into the reactor to initiate polymerization, and the mixture was stirred at a speed of MOPm. Finally, ethylene at a pressure of 15 k g / cm 2 was introduced into the reactor to saturate the concentration of ethylene in the solution, and the speed of the mixture was still maintained at 750 rpm. The reaction was carried out for 30 minutes. After the polymerization is completed ', the reaction solution is poured into an acetone solution to precipitate a product. The product was washed two or three times with Propylene I, transitioned, and dried under vacuum at 80 ° C for 12 hours. The obtained copolymer was 15 · 3 g. The results are shown in Table 7.

0424-4548TWF3.ptc Page 38 1245775 Case No. 89112711 Amended in five, the description of the invention (35) Table 7 Example of spores Aromatic cyclopentene compound (mg) MAO (ml) Reaction temperature (° C) Ethylene pressure (Kg / cm2) Yield (g) Activity (g / gZr.hr) Tg (° C) J 0.52 1.3 120 5 24.4 2.14x105 245 L 1.00 7 120 5 15.3 ^ 9.37x104 199 Example M ~ 0 Same as Example A This method prepares several cycloolefin copolymers and uses the same aromatic cycloolefin metal, but the conditions are that the reaction temperature is set at 120 ° C, the ethylene pressure, the amount of the aromatic cycloolefin metal and the amount of MAO are changed. Table 8 shows. Table 8 Example Aromatic metal compounds (mg) MAO (ml) Reaction temperature (° C) Dyneene pressure (Kg / cm2) Twinning activity (g) Activity (g / gZr.hr) Tg (° C) M 0.22 1.3 120 15 20.4 8.23χ105 185 'N 0.49 3.4 120 30 59.0 10.9χ105 147, 〇0.47 3.4 120 60 52.5 ΙΟ.ΟχΙΟ5 105 ^

Examples P to S Several cyclic olefin copolymers were prepared in the same manner as in Example A, and the same aromatic cyclic olefin metal was used, but the reaction temperature, ethylene pressure, and aromaticity were changed.

〇424-4548TWF3.ptc Page 39 1245775 Case No. 89Π2711 Amendment V. Description of the Invention (36) The amount of cycloolefin metal and the amount of MAO, and the use of different concentrations of original norbornene, Table 9 shows the polymerization results. Table 9 Examples Aromatic cycloenes (mg) MAO (ml) Protobornene concentration (70) Reaction temperature CC) Otomolysine cm2) Pyrene production (g) Activity (g / gZr.hr) Tg (° C) P 0.23 1.3 85 15 120 28.5 5.50 x 105 183 Q 0.22 1.3 50 15 120 30.8 12.4 x 105 156 R 0.46 5.2 85 60 100 70.6 1.36 x 105 103 S 0.47 5.2 50 60 100 33.0 6.30 x 105 66

Example T The same steps as described in Example A were performed, but the aromatic metal compound used was changed to the catalyst prepared in Example 5. The reaction temperature was 120 ° C, the reaction time was 10 minutes, and Al / The Zr Morse ratio is 3 000. The results are shown in Table 10.

Comparative Example U The same procedure as described in Example τ was performed, but the aromatic metal compound used was changed to the one used in US Patent No. 5,5 59,199 [dimethyl si lyl- (l-indenyl) -cyclopentadienyl zirconium dichloride] and US Patent No. 5,602,219 (isopropenylidene cyclopentadienyl fluorenyl zirconium dichloride). The results are shown in Table 10.

〇424-4548TWF3.ptc Page 40 1245775 Amendment No. 89112711 V. Description of the invention (37) Table 10 Catalyst ethylene pressure (kg / cm2) Reaction time (min) Tritium production (8) Tg (° C) Reactive g / g Zr-hr conversion rate of original ice moon woman e / 〇) USP 5,559,199 15 10 4.8 89.66 3.9E + 05 5.1 USP 5,602,219 15 10 23.6 159.96 1.92 E + 06 25.40 Catalyst 15 obtained in Example 5 of the catalyst of the present invention 15 10 32.0 186.15 2.59 E + 06 36.29 As can be seen from Table 10, compared with the conventional catalyst system, the cycloolefin copolymer obtained by using the catalyst composition of the present invention has a higher norbornene conversion rate (norbornene conversion), and has a significantly higher slope glass transition temperature (T g), while still maintaining a relatively high catalytic reaction activity. Polymerization Example 1: Synthesis of ethylene / orbornene copolymer. After 5000 m 1 of the reactor was repeatedly pumped with nitrogen 3 to 4 times, 100 ml (85 wt% of a toluene solution) was intubated with low-pressure nitrogen. The original borneol solution was pressed into the reaction tank, the mixer was turned on to adjust the rotation speed to 250 rpm, and the bake was replaced twice to heat to 60 ° C. 2ml of MAO (1.49M) was injected into the reactor with a syringe and taken from the glove box. 〇 · 〇12g Catalyst A (A: cyclobutyl idene (l-7 ~ 5 ~ cyc 1 open t ad i eny 1) (1-indenyl) -zirconium dichloride, prepared by catalyst example 6) 10 ml toluene Dissolve and take this dissolved catalyst 0.9g (2.74 χ

〇424-4548TWF3.ptc Page 41 1245775 Amendment No. 89112711 V. Description of the invention (38) 10, 〇1) Add 0.4 Π MA0U.49M) activation for 5 minutes, take out with a syringe = enter the reaction and then heat to the reaction temperature. # When the reaction temperature c is reached, the valve of Otomo is opened, the reaction pressure is 10 kg / cm2, and the reaction is started. At this time, the rotation speed of the mixer is 75 rpm and the reaction time is 30 minutes. After the reaction is completed, first close the ethylene feed valve and close the temperature controller. Pressurize the reactor to normal pressure, add 1000 m 1 of toluene to dilute the product, and then add the product to dilute hydrochloric acid in acetone solution to precipitate the product. The product was washed 2 to 3 times with an acetone solution, the product was filtered and dried for 12 hours, and the copolymer was weighed to obtain 2 6 · 3 g of copolymer. The results are shown in Table 11. FIG. 6 shows the light transmittance of the ethylene / orbornene copolymer prepared in Polymerization Example 1 at different wavelengths, indicating that the cycloolefin copolymer (coc) is 90% transparent at 400 to 1600 nm. Light. Polymerization Examples 2 to 3 The same method as in Polymerization Example 1 was used, except that the catalyst type was changed to Catalyst B: cyclopentylidene (l-7y5 -cyclopentadienylKl-775-indenyl) zirconium dichloride 0.95g ( 2.74 xl0-6mol) and catalyst C. The cycloheptylidene (l-7 / 5-cyclopentadienyl) (l 'τ? 5-indenyl)-zirconium dichloride 1.0g (2.74 χ ΙΟ-6) obtained from Catalyst Example 8 mOl), and the polymerization results are shown in Table 11. Comparative Polymerization Example 4 The same preparation method as Polymerization Example 1 was used, but the catalyst type was changed to D:

0424-4548TWF3.ptc Page 42 1245775 Case No. 89112711 Amendment V. Description of Invention (39) diphenylmethylidene (cyclopentadieny1) (9-fluoreny 1) zirconium dichloride 1.3g (2.74 x 106 mol) The results are shown in Table 11. Table 11 Polymerization Example Catalyst Product (g) Active Tg (° C) (ring formed by bridge) (g / gZr.hr) 1 A (four-membered ring) 26.3 2.1X105 289.1 2 B (five-membered ring) 26.3 2.1X105 288.3 3 C (seven-membered ring) 21.5 1.7X105 285.8 4 D (acyclic) 6.9 O.SxlO5 216.3 A cyclobutylidene (l ^ 5 -cyclopentadienyl) (l ^ 5-indenyl) zirconium dichloride B ^ cyclopentylidene (l- ^ -cyclopentadienyl) (l-^-indenyl) zirconium dichloride C-cycloheptylidene (l ^ 5 -cyclopentadienyl) (l-^-indenyl) zirconium dichloride D: diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride Polymerization Example 5 Polymerization Example 1 had the same preparation method, but the reaction temperature was changed to 120 ° C and the reaction pressure was 1.5 kg / cm2. The results are shown in Table 12. Polymerization Examples 6 to 8 The same preparation method as in Polymerization Example 5 was used, but the catalyst type was changed to Catalyst B 0.95 g (2.74 X 10-6 mol), Catalyst C 1.0 g (2.74 X 10-6 mol), and catalyst Media E 0.97 g (2.74 x 10-6 ml), polymerization

0424-4548TWF3.ptc Page 43 1245775 Case No. 89112711 Month, day, and amendment V. Description of the invention (40) The results are shown in Table 12. Table 12 Types of catalyst in the polymerization examples (rings formed by bridging) Product (g) Activity (g / gZr.hr) Tg (° C) 5 A (four-membered ring) 33.4 2.7X105 330.2 6 B (five-membered ring) 33.6 2.6xl05 317.1 7 c (seven-membered ring) 29.4 2.4X105 310.3 8 E (six-membered ring) 19.5 1.6X105 309.9 E cyclohexylidene (l ^ 5-cyclopentadieny 1) (1-η5-indenyl) zirconium dichloride Polymerization Example 9 with Polymerization Example 5 was the same preparation method, but the reaction time was changed to 20 minutes. The results are shown in Table 13 below. Example 1 0 ~ 11 The same preparation method as in Polymerization Example 9 was used, but the catalyst type was changed to 0.95 g (2.74 x 10-6 mol) of catalyst B and 1.0 g (2.74 X 10-6 mol) of catalyst C. The results of the polymerization are shown in Table 13.

0424-4548TWF3.ptc Page 44 1245775 89119711 V. Description of the invention (41) Table 13

Tg〇T 312 .: 307.1 305.7 Activity (g / gZr.hr) 3.1X105 3.1X105 ~ 3.1xl05 (Tables 11 to 1 above 3) are based on the results of the reaction of the media composition of the present invention to the production of polyhydrocarbons. Aromatic ring metal B), A), or five-shell structure without ring structure (catalyst = catalyst two to touch, the composition includes a bridge or seven-membered ring structure (catalyst C)) Ring structure (compared with traditional catalyst systems, using the catalyst of the present invention ^ Jiguo shows that it has a higher primary :: wide product, the obtained ring conversion) than the dilute hydrocarbon copolymer, and has a conversion rate ( n〇rb〇rnene can maintain a relatively high catalytic reaction H transfer temperature (Tg), while still limiting the invention's second exposure: on, but it is not used to: and range " can be changed; :::: invention The essence of the invention should be defined as the scope of the attached patent application; the scope of protection of the present invention is 0424-4548TWF3.ptc page 45

Claims (1)

The angle Θ formed by Xiuyi & ring and X is equal to or greater than the tongue promoter, and is selected from Π) alumoxane, (2) a mixture of old phosphonates, and (3) A 1 R11 R12R " and | g Oxygenation = In the group consisting of mouthpieces, R11, Rls and, aliphatic or C6-1G aromatic groups. 2. The catalyst composition for preparing an olefin polymer as described in item 1 of the scope of the patent application, wherein R1 and R2 are independently selected hydrogen, (ν1 () alkyl Cl_1Q 埽 group, Cm aryl group, c7_1G Alkaryl and C7_1G aralkyl groups. • The catalyst composition for preparing an olefin polymer as described in item 2 of the scope of the patent application, wherein R1 and R2 are independently selected from hydrogen, methyl, ethylpropyl, butyl, isobutyl, pentyl Group consisting of methyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, and fluorenyl. 4. The catalyst composition for preparing an olefin polymer as described in item 1 of the scope of the patent application, wherein two adjacent ones are connected together to form a ring having 4 to 20 carbon atoms with the carbon to which they are attached. system. 5. The catalyst composition for preparing an olefin polymer as described in item 4 of the scope of patent application, wherein two adjacent R1 are connected together to form a saturated or unsaturated saturated cyclopentadienyl moiety Polycyclic cyclopentadienyl ligand. 6. The catalyst composition for preparing an olefin polymer as described in item 5 of the scope of the patent application, wherein two adjacent R1 are connected together and connected to it. 0424-4548TWF3.ptc 1245775 said-case number 89112711_ Sixth, the scope of patent application. Contact 7 Π: ":;: used in the preparation of thin smoke polymer as described in item 1, two adjacent R2 are connected to one another as industrial carbon to form a ring with 4 to 20 carbon atoms The catalyst composition of the system (whereas it is connected with the catalyst as described in item γ of the claimed patent), wherein two adjacent R2 are connected to a cyclopentadienyl moiety to form a saturated or unsaturated polycyclic ring. No .: 2nd base. %% of pentadienyl in the coating. The catalyst composition for the preparation of dilute smoke polymer in item 8 of item 8 is used, in which two adjacent π are connected together with its cyclopentane. The dienyl moiety forms an indenyl, tetrahydroindenyl, thienyl, or octahydroyl group. Ι〇. A catalyst composition for the preparation of an olefin polymerization as described in item 丨 of the application, wherein Y is optional Hydrogen, Q, hydrocarbon, gas, c " aryl, C ?, aryl or aryl, xyloxy, aryloxy, question 2, NHR7, NR7R8,-(C = 〇) NH2, — ((: = 〇) Ν " ΗΚ9,-(C = 0) NR9R1Q, each r ?, R8, "" and alkyl groups. 11 · Used as described in item 丨 of the scope of patent application Preparation of olefin polymer Catalyst composition, in which γ is -N (CH3) 2. ° 12. "… polymerizes (a)-olefin in the presence of the catalyst composition as described in item 1 of the scope of patent application ^ Monomer (s) or (b) method for preparing olefin polymer (s) includes polymerizing (a) an olefin monomer under the conditions of polymerization of the left a τ β of a composition that touches a woman as described in the first paragraph of the effective catalyst blue patent range. With at least one other monomer, at least a dilute smoke monomer, and one less other monomer. 13. The method for preparing an olefin polymer as described in item 12 of the patent application scope, wherein the method comprises polymerizing (a) Ene II 丨 Foot and face pain, fine coffee hidden 丨: Other coffee " 0424-4548TWF3.ptc Page 48 Case No. 89112711 1245775 6. Scope of Patent Application Hydrocarbon. 14. The method of preparing olefins as described in item 12 of the scope of the patent application, wherein the method comprises polymerizing (b) at least one olefin and at least two monomers, wherein the olefin is a cyclic dilute hydrocarbon and the other monomers are Non-produced other15. Preparation of ene smoke H smoke as described in item 14 of the scope of patent application. Method, wherein the cyclic olefin is selected from the group consisting of free bicycloheptenes, tricyclic undecenes, tetracyclododecenes, pentacyclic octadecadienes, cyclopentadecanes Dienes, pentacyclic hexadecenes, hexacyclic seventeen dienes, pentacyclic eicosenes, heptacyclic twenty-one carbenes, octacyclic dienes, etc. Consisting of seven kinds, seven-two rings, twenty-five carbonenes, and nine-ring twenty-six carbons, == 2, 16 · The method for preparing olefins as described in item 14 of the scope of patent application, wherein the acyclic dilute Smoke is ethylene, or -olefin with = mouth. 17. The method of preparation as described in item 16 of the scope of patent application, wherein the -olefin is selected from the group consisting of propylene, butylene, and 1-octene. 1-Fang,: 8. :: Λ The method for preparing an olefin polymer as described in item 14 of the patent scope, wherein the method comprises polymerizing (b) a monocyclic olefin, a compound, and an isynene; I : The raw material is norbornene (olefin), and the olefin is ethylene. And the acyclic 1 9 · The preparation method described in item 4 of the scope of the application for patent, JL Φ, ancient, it compound 60 ° C to 3 5 0. (Between 3. The distance of transfer > the degree of phoenix is _2 0 · If the scope of application for patent is 14th 仏 a system ^ 1245775 Case No. 89112711_ 生 _ ^ _ Θ_ Amendment 6. Application Patent range method, wherein the glass transition temperature of the olefin polymer produced by the method is between 120 ° C and 350 ° C. 2 1. Preparation of olefin polymer as described in item 14 of the scope of patent application , Wherein the glass transition temperature of the olefin polymer produced by the method is between 2 50 T: and 3 50 T: 2 2. The method for preparing an olefin polymer as described in item 12 of the scope of patent application, The aromatic cycloolefin metal compound represented by the chemical formula (I) has the following structure: Where R is a hydrocarbon group. 2 3. The method for preparing an olefin polymer according to item 12 of the scope of the patent application, wherein the aromatic cycloolefin metal compound represented by the chemical formula (I) has the following structure: 〇424-4548TWF3.ptc Page 50 1245775 ^ _Case No. 89112711_ Year Month Date Amendment 6. Scope of Patent Application Where R is a Cp% hydrocarbon group. 24. The method for preparing an olefin polymer according to item 12 of the scope of the patent application, wherein the aromatic ring fluorene metal compound represented by the chemical formula (I) has the following structure: Where R is a hydrocarbon group. 25. The method for preparing an olefin polymer as described in item 12 of the scope of patent application, wherein the aromatic cycloolefin metal compound represented by the chemical formula (I) has the following structure: 〇424-4548TWF3.ptc Page 51 1245775 Case No. 89112711 Amendment VI. Scope of Patent Application The description of the preparation of polyalkylene compounds is described in item 2 is Fan Lizhuan. I would like to ask Su Shen if I have a chemical compound of aurene ring aromatics in 6 A 2 I I Γν formulate the structure, formulate the formula Where R is a hydrocarbon group. 2 7. The method for preparing an olefin polymer according to item 12 of the scope of the patent application, wherein the aromatic cycloolefin metal compound represented by the chemical formula (I) has the following 0424-4548TWF3.ptc Page 52 1245775 Case No. 89112711 Amendment VI. Structure of patent application scope: 〇424-4548TWF3.ptc Page 53 1245775 Case No. 89112711 Amendment VI. Method of Patent Application, where the structure of the pen ^ shown in the chemical formula (I): ^% ~ metal compounds have the following, Α where A is halogen. 30. A kind of cycloolefin smoke copolymer, which is a copolymer of which the glass transition temperature is 195. 〇 ~ 35〇 ^ 不 〜 状 状 烟 3 ^ The cyclic olefin θ as described in item 30 of the patent application range, the glass transition temperature is between 25 ° and 35 °. -32. The cyclic olefins total bicycloheptyl, tricyclodecane, tricyclic twelve seats jt Γ t, pentacyclopentadecenes, pentacyclic fifteen carbons as described in item 30 of the application Alkenes,, /, Slenes, Hexadecene 17-Carnes, 7-Cyclostadecenes, 7; Ethyl-11, Alkene, 8-Cyclosenes, 9-Cyclosines In the group consisting of carbene and nine-ring hexadecene. 233. The cyclic dilute hydrocarbon copolymer as described in item g 0 of the Shen Jing patent, wherein the acyclic olefin is ethylene, or an olefin having 3 to 12 breaks. 34. The cyclic olefin copolymer according to item 33 of the scope of patent application, which Page 54 1245775 Rev. 1-^ Day 1-‘Dilute 3 is selected from the group consisting of propene, buprene, buprene, 1-hexene, and pinene. 3 5 · The mounting olefin copolymer as described in item 30 of the strict and clear profit-seeking range in Shen Shizhu Kui ^, where is the original 'norbornene', and Cj 饰 〇3 6 · If you apply for a Straight / Yi-Cycloolefin copolymer, it is a transparent clothing division of the 30th monthly patent scope UC. W & month date · JU /, Case No .: 891 Cheek Fare · W Death Responsibility "L—— 丨.): .¾ \ η α ^ 1, The above valley sheds will be filled out by the inning of this 1-note, ------ -_________" m Ju ----- -Description of Invention Patent Chinese Catalyst Composition for Preparing Olefin Polymers Invention Name Catalyst Composition for Preparing Olefin Polymers English Name (Chinese) 1. Cai Jingcheng 2. Wu Mingyuan 3. Words 丨 East Reading 4. Wei Yuying Inventor Name (English ) • Jing-Cheng Tsai 2. Ming-Yuan Wu 3. Tung-Ying Hsieh 4. Yuh-Yuan Wei 1. Residence and residence nationality 1. Republic of China 2. Republic of China 3. Republic of China 4. Republic of China g 鹊 Lion II segment_ Applicant 1. INDUSTRIAL technology research institute Name of Representative (Chinese) Name of Representative (English) 0424-4548TWF3.ptc Page 1 1245775 _ Case No. 89112711 6. Scope of patent application 1 · A kind of olefin polymer used for the preparation of ⑻ -... shown in the formula ；; and J thing 'including ... one side & olefin metal Compound, day-modification. R1 (R3R4C; R1 XJQ. R2 R2: Choi 2 (I) R2-, R2 where R1 can be the same or different, and is selected from free hydrogen, halogen, and alkane having 1 to 20 carbon atoms Group, alkenyl group, aromatic group, alkaryl group, or aralkyl group) or two adjacent R1 connected to different carbon atoms can be connected together to form a carbon with 4 to A saturated or unsaturated cyclic system of 20 carbon atoms; R2 can be the same or different, and its definition is the same as Rl; X is C; η is 3 or 4; R3, P can be the same or different, and Η or _CH3 M is a Group IVB transition metal having an oxidation value + 4; and Υ may be the same or different, and is independently an anion ligand of valence; 0424-4548TWF3.ptc Page 46