TW438827B - Metallocenes, and the use thereof as catalysts - Google Patents

Abstract

The present invention relates to a stereorigid metallo-cene compound which contains, as ligands, at least two substituted or unsubstituted cyclopentadienyl groups which are bonded to one another via a monocyclic or polycyclic ring system, wherein at least one cyclopenta-dienyl group is fused to the monocyclic or polycyclic ring system. The metallocene compound can be used as a catalyst component in the preparation of polyolefins.

Description

438827 ΑΊ B7 V. Description of the invention (!) The present invention relates to a stereorigid metallocene compound whose ligands are bonded to each other in a specific manner. The compounds according to the invention can be advantageously used as catalyst components in the preparation of polyolefins. It is disclosed in the literature that the preparation of polyolefins can convert neutral metallocenes to cationic and stable metallocenes. Among them, the preparation of polyolefins is the use of soluble metallocene compounds in combination with aluminoxanes or other co-catalysts and is Because of its Lewis acidity. The use of soluble metallocene compounds based on bis (cyclopentadienyl) dialkyl zirconium or bis (cyclopentadienyl) dihalide as a base, combined with oligomeric indwelling Polymers are not of industrial importance because of their imbalance and insufficient product characteristics. Zirconocene dichloride derivatives can be used as catalysts for iso specific polymerization of olefins due to their consistent rigidity. Among them, two substituted cyclopentanes Dienyl groups are bonded to each other via a methyl, ethylene, or diraethylsilylene bridge. (Chera. Lett. 1989 I pp. 1853–1856, or European Patent Application No. 0 316 155). Metallocenes containing (replaced) indenyl as ligands are particularly important when preparing highly isotactic polymers with high crystallinity and high melting points (European Patent No. 4 8 5 8 2 3 and 5 3 0 6 4 7). However, i is quite noticeable for products with characteristic distributions between the two limits. The purpose of the present invention is to provide a catalyst system ’which enables a 3-438827 A7 R7

i'-f. iX- '. Call charge J V. Description of the invention (2) The preparation of polymers has a degree of brightness reduction and a low melting point at the processing temperature. Therefore, the present invention is a system which contains at least two kinds of cyclopentadienyl groups. Among them, at least one kind of cyclopentane is in a preferred monocyclic or polycyclic system to a monocyclic or polycyclic system. Monocyclic or polycyclic ring systems may or may have substituted ring atoms) 0 Low crystallinity, enhanced impact strength and permeability, high flowability, and low score are related to a stereo rigid metallocene compound The substituted or unsubstituted cyclopentadienyl groups are bonded to each other via a monocyclic or polycyclic ring system, and the dienyl group is fused to a monocyclic or polycyclic ring system. In one embodiment, one cyclopentadienyl group is a substituent, and the other cyclopentadienyl group is fused, which may be aromatic, aliphatic, or a mixture of aromatic and aliphatic. It preferably has at least six ring atoms (the molten cyclopentadienyl group is mono-fused (e.g., via the 1 '2 or 1' 3 position of the cyclopentadienyl ring) or more dense Fused (for example, 1 '2 > 3 or 1, 2, 3, 4-position of the cyclopentadienyl ring), preferably monofused. The preferred metallocene compound has the following Compound of Chemical Formula (1) (TNS) (210 X 297. >#) 4-. ¾ Printed by CK Industrial Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs ii A6 ______B6_ 5. Description of the Invention (3)

M1 is a metal selected from the periodic table, iVb, Vb or V I b group; M 2 is carbon or silicon:

R1 and R2 are the same or different and are hydrogen atoms, Ci — (: 10 alkyl, Ci—C :. alkoxy, Ce—Cx. Aryl, C6_C25 aryloxy, C2_Cl0 alkenyl, C4 0 aralkyl Group, C * — C4alkenyl group, 0H group or halogen atom, or R1 and R2 and the atoms linking them together to form a ring system: R3, R4, R5, R6, R7, R8 and R9 are the same also Or different and it is a hydrogen atom, a halogen atom, Cx-Ci. An alkyl group may be a halogenated alkyl group, C6-C2. An aryl group:-NR142, 10S i R14s, -Si 143 or a PR142 and other groups , Where R14 is a halogen atom: C a-C 10 alkyl or C6-C 10 aryl or two or more adjacent R3, R4, R5, R6, R7, R8 and R9 and other groups and The atoms connecting them together form a ring system: ... .... Edit, please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS 丨 A4 specifications (210X297); ¢ 1 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs " 4388 27 A6 B6 V. Description of the invention (4) 1 ~ 1 ° is a hydrogen atom, 〇1-(: 20 alkyl) (: 1-(: 10 alkoxy, Ce-C2. Aryl, Ce-C20 aryloxy 'C2-Cizyl, C7-C4. Aralkyl, C7-C40 alkaryl or C8-C40 Arylalkenyl; each of the above groups may have a group such as NR143, —SR142 or OS i R143, where R14 is a halogen atom, Cl—C10 alkyl or C 6 -C 10 aryl; R 11 is 5 Ϊ cl -

: I c I R Π

K > n R — umIR

R — C-'R

X 15lte R Ic · — R 5 I1 I 1 RICIR

5 RI C — R RICIR Π ........................... .. strike ... I, " {Please read the notes on the back before writing this page)

5 R I e 3 1 • M-p 5 Π

RI c I R 5 | * 13 1 R I M — R

5 RICIR 5 Γ 13 1 RIMIRr ~ R t c I R

o 5 RICIR 5 π ο

5 R— CII Π where η is an integer from 1 to 8; X is 0, = N3R14, = C0, = PR14, = P (0) Ri4, = s〇, two S〇2 or one S —, where R14 It is a halogen atom. The size of this paper is applicable to a Chinese standard (CNS) A4 specification (210X297 mm) ^ 38827 printed by the Economic and Central Bureau of Standards and Consumers ’Cooperatives A6 B6 _ V. Description of the invention (5), Ci — C1 . Academy base or C6 — Ci. Aryl: R1 5 and R1 6 are the same or different and are hydrogen atom, hafnium element atom, Cl — ClO alkyl group, Cl — Cio alkyl group, Ci — Cio oxygen group, Ce — Cio aryl group, C6 — Cio aryl, Ce—Cio aryl, C2—ClO aryl, C7—C40 aryl fluorenyl, C ·? — C40 aryl or C8—c40 aryl alkenyl or two R15 radicals, two R16 or R15 and R16 groups; in each case together form one or more rings with the atoms connecting them: M3 is silicon, germanium or tin: R12 and R13 are the same or different and are hydrogen atoms, Ci—Cu alkyl , Cl — Cl. Ethoxy, Ce-Cz. Aryl, C6-C20 aromatic, C2-Cl2, C7_C4. Arylamino group C7-C40 aryl or C8-C4Q arylalkenyl, each of the above groups may have -NR143, _3 feet 142 or -30; R143 and other groups, where R 14 is _ atom, Cl-C 10 Fluorenyl or C 6 —Cl. Aryl: various groups or may have a halogen atom: R23 is the same or different and is a hydrogen atom, Ci-C10 alkyl, C! — —ClO alkoxy group> Ce — ClO aryl group, C6 — C25 aryloxy group , C2 —Cl. Suspected, Ct-C4. Aryl 'C7—C40 aryl groups or dent atoms; or one or two R 23 groups bonded to one or two R 15 and R 16 groups: and m is an integer from 0 to 2 4 where R11 When it is CH2, at least one of R3, R4, R6, R7 and R9 is not hydrogen. For compounds with chemical formula (I), M1 is preferably a tapered paper size, using Chinese National Standard (CNS) A4 specifications (210X297): (Please read the precautions on the back first, and then read this page)-Installation d 438827 A6 B6 V. Description of the invention (6) or 绐, especially 锸. R.1 and R2 are the same and are Ci-Ca alkyl plugs or halogen atoms, especially chlorine; R3, R4, R5 , R6, R7, 5 ^ 8 are the same as or different from Chi 9 and are hydrogen atoms, C; 1-Ci. Alkyl or (: 6-C24 aryl; or two or more adjacent groups in common Forms a ring system of aromatic or aliphatic hydrocarbons with the atoms connecting them: R is a gas atom 'Ce — C24 or Ci — Ci. Academies, specifically C 1-C 4 academy R 1 1

R'6 (please read the precautions on the back before filling the nesting page). Installed by the Central Industrial and Commercial Standards Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperatives " where η is an integer from 1 to 8 *, especially an integer from 2 to 4; R 15 and R 16 are the same or different and are a hydrogen atom or a C 1-C 10 alkyl group, or two R15 groups, two R16 groups, or R15 and R1 6 together form a hydrocarbon ring system with the atom connecting them: M 2 is carbon; R12 and R13 are the same or different and are hydrogen atoms, Ci-C10 alkyl, especially CT-C4 alkyl or C6 "C10 aryl; and m is zero. Particularly preferred The compound of formula (I) means that M 1 is chromium: R 1 is the same as R 2 and is a fluorene atom, especially chlorine; R 3, R 4, R 5, R 6, R 7, R 8 and R 9 are the same or not. Applicable to Chinese national standard (CNS 丨 A4 specification (210X297mm) 438827) China National Standards Bureau, Ministry of Economic Affairs, only Industrial Cooperative Press 51 A6 __B6__ 5. Description of the invention (7) Same as hydrogen atom or Ci-C 4 alkyl: either R 8 and R 9 and R 3 and R 4 and / or R 5 and R 6 together with the atom linking them to form an aromatic hydrocarbon ring system, especially a nodular ring and It may be substituted by itself: Μ 2 is a carbon atom rule 1 ° is (: 1-0; 6 alkyl, especially methyl: R11 is-CH2-CH2: R12 is the same as or different from Ri 3 and is a Or phenyl: zero with m. Examples of metallocene compounds according to the present invention are: [4-((r? 5-cyclopentadienyl) -4,7,7-trimethyl ("5_4,5 , 6,7-tetramethyl group)] dichlorozin, [4- (75-cyclopentadienyl) -4,7,7-trimethyl (?? 5-4,5,6,7- Tetrahydropyridyl)] two-gas junction, [4- (775-cyclopentanediyl)-4 '7,7-trimethyl (τ? 5--4, 5, 6, 7-tetrahydropyridyl) ] Digasbell, [4_ (Vs-Cyclopentadienyl> -1,4,7,7-triphenyl (? 75-4,5,6,7-tetrahydro)) Digasin, [4 — (7? 5-Cyclopentadienyl) -4,7,7-triphenyl ("5-4,5,6,7-tetrahydropine group") ........................................ ................................................. Order .............. line (Please read the note on the back first Matters are refilled on this page) This paper size is applicable @ S 家 样 准 （CNS) f 4 specifications （210X297mm） 438827 Ministry of Economic Affairs t Central Bureau of Standards Staff Consumer Cooperatives A6 B6 5. Description of invention (8 ) [4-mono (π5-cyclopentadienyl) -4,7-dimethyl-7-phenyl ("5-4,5,6,7-tetrahydrofluorenyl)] titanium dichloride, [4 Mono (7? 5-cyclopentadienyl) -4,7-dimethyl-7-phenyl (π5- 4,5,6,7-tetrahydrofluorenyl)] dichlorofluorene, [4 一 ( 7/5 —cyclopentadienyl) —4,7—dimethyl—7—fluorenyl (π5—4,5,6,7—tetrahydrofluorenyl)] dichlorotitanium, [4 — (π5— Cyclopentadienyl) -4,7-dimethyl-7-some (? 75-4,5,6,7_tetrahydrofluorenyl)] dichlorozirconium, [4- (7? 5-cyclopentadienyl) -4,7-dimethyl-7-butyl (? / 5—4,5 »6 * 7—tetra MIL 5)] dichlorozine, [4-((75—cyclopentadienyl) —4, 7—dimethyl—7—butyl (—75— 4 ， 5,6,7-tetrahydropinyl]] two gas pins' 〔4-(? / 5-3 mono-tert-butylcyclopentadienyl)-4,7,7-trimethyl- (π5- 4,5,6,7-tetrahydrofluorenyl)] titanium dichloride 9 [4 — (»75-3 mono-tert-butylcyclopentadienyl)-4,7,7_trimethyl — (? 5 — 4, 5 '6, 7 — Siqi Pinji)] Erqi -10-This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) (Please read the precautions on the back before filling in this Page} 438827 A6 B6 Ministry of Economic Affairs, Central Bureau of Industry and Consumer Cooperation, Du Yinsi V. Description of the invention (9) »[4 — (π5— 3— _ tert-butylcyclopentadienyl) —4, 7, 7 — Triphenyl- (775-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium> [4 — (?? 5-3-_tert-butylcyclopentadienyl)-4, 7, 7 Triphenyl_ (?? 5-4,5,6,7-tetrahydrofluorenyl)] dichloro pin > [4-(π5-3--tert-butylcyclopentadienyl) -4,7_ di Methyl-7-phenyl (?? 5-4,5,6,7-tetrahydrofluorenyl)] dichlorozin, [4- (?? 5-tert-butylcyclopentadienyl) -4, 7-Dimethyl-7-phenyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichloro, [4 — (ί; 5-3 -tert-butylcyclopentadienyl) -4,7-dimethyl-7- (yl group (775-4,5,6,7-tetrahydrofluorenyl)] dioxan, [4-(7? 5-3 tert-butylcyclopentadienyl ) —4,7—dimethyl—7—a certain group (? 75-4,5,6,7-tetrahydrofluorenyl)] two (please read the “Precautions on the back side before filling out this page). Order. Line · This paper size applies to the Chinese national standard (CNS > A4 specification (210x297mm) Π 4 388 2 7 A 6 B6 V. Description of the invention (ίο) Gas pin, [4 — (τ? 5— 3, 1-tert-butylcyclopentadienyl) -4,7-dimethyl-7-butyl (? 75-4,5,6,7-tetrahydrofluorenyl)] dioxin, [4 — ( 75—3, one uncle Pentadienyl) _4,7-dimethyl-7-butyl (?? 5-4,5,6,7-tetrahydro; yl)] digas zirconium, [4-(π5-fluorenyl)- 4,7,7-trimethyl ("5-4,5,6,7_tetrahydrofluorenyl)] dichlorotitanium, [4-(π5 -fluorenyl) -4,7,7-trimethyl (? 75-4,5,6,7-tetrahydropinyl]] dichloride "[4-(ί? 5_Ι5 基)-4,7,7 -triphenyl (ϊ75-4, 5, 6,7_ Tetrahydropyridyl)] Titanium dichloride, printed by the Industrial and Commercial Bureau of the Ministry of Economic Affairs, China Industrial Cooperatives (please read the precautions on the back before filling out this page) [4-(ί / 5 — 15 based) -4 , 7,7-triphenyl (π5_4,5,6,7-tetrahydro15yl)] gas, [4 — (7? 5-fluorenyl) -4,7-dimethyl-7-benzene (Π5 -4,5,6,7 -tetrahydrofluorenyl)] titanium dichloride, this paper size is applicable to China A standard (CNS) T4 specification (210x297 mm) -12-438827 A6 B6 V. Invention Note (11) (Please read the precautions on the back before filling out this page) [4 I (ί 5 — 15 base) — 4, 7, 7 —dimethyl — 7 —phenyl (T75 — 4, 5, 6, 7-tetrahydrofluorenyl)] dichloride, [4 — (”5-fluorenyl) -4,7-dimethyl-7-some (7-5-4,5,6,7-tetrakis Radical)] dichlorozine, [4- — (π5 -fluorenyl) -4,7-dimethyl-7-fluorenyl (5? 4,5,6,7-tetrakisyl)) pin [4-((5 | fluorenyl) -4,7-dimethyl-7-butyl (π3 -4,5,6,7-tetrahydrofluorenyl)] titanium dichloride, [4-(π5- Fluorenyl) _4,7-dimethyl-7-butyl (? 75-4,5 > 6 »7_tetrakisyl group)]-chlorine pin, [4 — (π5 -cyclopentadienyl ) -4,7,7-trimethyl (π5-4,5,6,7_tetrahydrofuryl)] titanium dichloride, 4 4 5 6 bases printed by the Ministry of Economic Affairs Central Bureau of Labor and Consumers Cooperatives * νι-τ ene dipentane 4 7 7 methazolium 4 4 5 7 yl hydrogen tetrayl ene dipentane 4 chrome 7 7 benzene benzene tri 7 dimethyl tetrahydrogen tetratitanium chloride This paper applies the national standard of China (CMS) Form 4 specifications (210x297 mm) -13-438827 A6 B6 V. Description of the invention (12) 4 4 5 Alkenyl dipentane 4 7 7 Alkylbenzene W · 7 radicals 0 Hydrogen tetrazirconyl chloride di 4 radicals Alkenyl dipentyl 77 4 5 6 7 7 radical, matter 4 gas i tetra 1 titanium based chloroform di 7 benzene (please read the precautions on the back before filling out this page 1 4 alkenyl dipentyl 7 radical 77 4 6 7 groups, channeling 4 Μ one four one zirconyl chloromethane 7 benzene-packed 5 / fv I 4 group 4 7 radical, TltK 4 gas f tetra radical 7 to-ene, di 6 pentane, ring 5 _ titanium based chloroform VII strips, 4 alkene dipentyl radical " 5 6 7 7 radical, channel 4 Gas_tetra-zirconyl chloromethane 7 ί strip. Line. 4 radical 77 4 7 radical, 4 0 I tetra \ 1 / I radical 7 ene, di 6 pentane, ring 5 ί titanium-based chloromethyl 7 7 ¾ Printed by the Central Ministry of Standards and Technology, Machining and Consumer Cooperatives, 4 radicals, 4 7 radicals, tttN 4 hydrogen-tetra \] / I radicals 7 olefins, 2 6 pentane, ring 5-zirconium based gas methyl 7 4 radicals C A 3 5- Based on the four-dipentyl 7 ring, A 6 7 7 trititanium chloride paper standard applicable to China Standards (CNS) A 4 specifications (210x297 mm) -14 Ministry of Economic Affairs Printed by the cooperative 438827 A6 _B6_ V. Description of the invention (13) [4 — (? 75_3 —methylcyclopentadiazyl) _4 '7' 7 -trimethyl (75-4, 5, 6, 7-tetrahydrofluorene Group)] dichlorozirconium, [4- (775-3 3-methylcyclopentadienyl) -4,7,7-triphenyl ("5-4,5,6,7-tetrahydrofluorenyl) ] Titanium dichloride, [4 — (?? 5-3 methylcyclopentadienyl)-4, 7 7-triphenyl (V5-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4 — (?? 5-3, monomethylcyclopentadienyl)-4, 7-di Methyl-7-phenyl (T; 5-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [4 — ("5_3-methylcyclopentadienyl) -4,7- Dimethyl-7-phenyl (π5-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4 — (7? 5-3 > —methylcyclopentadienyl) — 4 , 7-dimethyl-7- (a group (τ? 5-4, 5, 6, 7, 7-tetrahydro; group)] titanium dichloride, [4 — (?? 5-3 a methylcyclopentadiene A) (4,7-dimethyl-7) -a group (π5-4,5,6,7-tetrahydrofluorenyl)] dichloro ...... ........................................ ............................................... ............. line < Please read the notes on the back before filling out this page) The paper size is applicable in 1S home standard (CNS) A4 specification (210x297mm) 15 4 3882 7 A6 B6 Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Masonry and Consumer Cooperatives V. Description of the Invention (14) Zirconium, [4-( 5-3, monomethylcyclopentadienyl) -4,7-dimethyl-7-butyl ("5-4,5,6,7-tetrayl)] dichlorozin, [4-(? 75- 3 methylcyclopentadienyl) -4,7-dimethyl-7-butyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4 one (π5-ring Pentadienyl) -4,7,7-trimethyl (π5 2 -methyl-4,5,6,7-tetrahydrofluorenyl)] titanium dichloride, [4-(J? 5-cyclopentyl Dienyl) -4,7,7-trimethyl (? 75 -2 -methyl- 4,5,6,7 -tetrahydrofluorenyl)] dichlorozirconium, [4-(π5 -cyclopentadienyl)-4, 7, 7 -triphenyl (? 5-2-methyl-4,5,6,7-tetrahydro15yl)] titanium dichloride, [4 — (π5 -cyclopentadienyl) _4,7,7-triphenyl (π5 -2 —Methyl-1,4,5,6,7-tetrahydrofluorenyl>] dichlorozirconium, [4 — (π5-cyclopentadienyl) -4, 7-dimethyl-7-phenyl (τ? 5-2 —Methyl-4,5,6,7—Tetrahydrofluorenyl)] Two paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 public love) ~ -1〇- (Please read the back first Please fill in this page for the matters needing attention) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 4388 27 A6 B6 V. Description of the Invention (15) Titanium chloride 7-Dimethyl-7-phenyl (? / 5-2—methyl-4,5,6,7-tetrahydrofluorenyl)] dichloro, [4-mono (π5-cyclopentadienyl) A 4,7-dimethyl-7-group (? 75-2-methyl-4,5,6,7-tetrahydropinyl)] diazin, [4 一 (7 ? 5-Cyclopentadienyl) -4,7-dimethyl-7-group (? 5-2-methyl-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4- — (π5-cyclopentadienyl) -4,7-dimethyl-1-7-butyl (7-5—2-methyl-4,5,6,7_tetrahydrofluorenyl)] di Chlorocin, [4- (π5-Cyclopentadienyl) _4,7-dimethyl_7-butyl (ί-5-2 -methyl-4,5,6,7-tetrahydropine) 〕 Dichloro pin, [4 — (7? 5--3 mono-methylcyclopentadienyl)-4, 7, 7, 7-trimethyl (τ? 5-2-methyl-4, 5, 6, 6, 7 —Siqi Pinji)] -17-This paper size applies to the Chinese national standard (CiNS 丨 A4 specification (210x297 mm) ........... ........................................ ............ Installing …………………… Order ……………… line {Please read the precautions on the back before filling out this page} The Ministry of Economic Affairs, China Standard Bureau only works Printed by the Consumer Cooperative ^ 827827 A6 B6 V. Description of the invention (16) Titanium dichloride, [4-(?? 5-3-methylcyclopentadienyl)-4, 7, 7-3 Methyl (? 75-2 —methyl-4,5,6,7-tetrahydrofluorenyl)] Chromium dichloro, [4-(π5-3 -methylcyclopentadienyl)-4, 7, 7-triphenyl (5? -Methyl-4,5,6,7-tetrahydrofluorenyl)]-chloroqin '[4-(π5-3 -methylcyclopentadienyl)- 4,7,7-triphenyl ("5-2-methyl-4,5,6,7-tetrahydrofluorenyl)] dichlorofluorene, [4-(7? 5-3, monomethylcyclopentane Dienyl) -4,7-dimethyl-7-phenyl (? ? 5-2-methyl-1,4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [4— (τ? 5-3 methylcyclopentadienyl) -4,7-dimethyl-1 7-phenyl (? 75-2 -methyl-4,5,6,7-tetrahydropine)] dichlorochromium, [4-a (π5-3 -methylcyclopentadienyl) -4, 7-Dimethyl-7-fluorenyl (?? 5--2-methyl-4,5'6,7-tetrahydrofluorene-18-This paper is applicable to 13 national standards (CNS) A4 specifications (210x297) Mm > .............................. ....... Install ... ……………… 'Order ......... line (please read the precautions on the back before filling in On this page j 4388 2 7 A6 B6 Employees' Cooperatives of the Central Lengzhun Bureau of the Ministry of Economic Affairs of the People's Republic of China 5. Inventory (17) basis) Titanium dichloride, [4 — (? 75— 3 " " —Mecyclopentane Carbo) -4,7-dimethyl-7-fluorenyl (?; 5-2_methyl-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4 1 (? 5-3—methylcyclopentadienyl) -4,7-dimethyl-7-butyl ("5-2-methyl-4,5,6" 7-tetrahydrofluorenyl)] titanium dichloride, (4- (77 5-3 -methylcyclopentadienyl)-4, 7-dimethyl-7-butyl (τ? 5-2-methyl -4,5,6,7-tetrahydrofluorenyl)] chromium dichloride, [4-(? 75- diyl) -4,7,7 -trimethyl (?? 5-4, 5,6, 7-tetrahydrofluorenyl)] dichlorotitanium, [4 — (?? 5-fluoro radical)-4, 7, 7-trimethyl (?? 5-4, 5, 6, 7-tetrahydrofluorenyl )] Zirconium dichloride, [4- — (π5--manganyl) -4,7,7-triphenyl (π5--4,5,6,7-tetrahydrofluorenyl)] titanium dichloride, [4-a ( π5 -manganyl) -4,7,7-triphenyl (π5-4, -19-this paper method is applicable to the Chinese National Standard Half (CXS) A4 specification (210X297 mm) ... ........................................ ................................................... ..... (Please read the notes on the back before filling out this page) Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Printed by the Industrial and Commercial Cooperatives 438827 A6 B6 V. Description of the Invention (18) 5, 6, 7-Siqi Pinji.)] Dichloride pin, [4-(π5 —Ferky)-4, 7- Methyl-7-phenyl (π5-4,5,6,7-tetrahydropinyl)] Diazepine '[4-(π5 -Feryl) -4,7-dimethyl-7-phenyl (75-4,5,6,7-tetrahydro 15 radicals)] Chromium dichloro, [4-(?? 5-Mizyl) -4, 7-dimethyl-7-fluorenyl (π5 -4, 5,6,7-tetrahydrofluorenyl)] titanium dichloride, [4 ( 75—manganyl) —4,7—dimethyl—7—a certain group (? 5—4, 5, 6, 6, 7—tetrahydrofluorenyl)] dichlorozirconium, [4 1 (—5—Eph. Radical) -4,7-dimethyl-7-butyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [4-(π5 -furthyl) -4,7 -Dimethyl- 7-butyl (7.5-5,4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [4-(π5 -cyclopentadienyl) -4,7,7 -Trimethyl-4,5,6,7,10,11,12,13-Octaaza-5,6-benzobenzoyl)] Chromium dichloride, this paper standard applies to China National Standard (CNS) A4 specifications (210X297 male cage) ................ ................................................. ……………… .4 (Please read the notes on the back before filling in this page) -20-438827 Printed by A6 B6, Central Consumers ’Cooperative Bureau, Ministry of Economic Affairs, Fifth, 5. Description of invention (19) [5 — (7 ? 5-Cyclopentadienyl) _4,7,7-trimethyl (7? 5-4,5,6,7-tetrahydropine)] Dioxin :, [5 — (7? 5- ring Dienyl) -4,7,7-trimethyl (π5-4,5,6 * 7-tetrakispinyl)]-gas pin, [5-("5_cyclopentadienyl) -4 , 7,7-triphenyl (π5--4,5,6,7-tetrapinyl)]-chloroqin, [5-(π5-cyclopentadienyl) -4,7,7-triphenyl (7-5-5,4,5,6,7-tetramethylimidyl)] dichloride, [5 — (7? 5-cyclopentadienyl) -4,7-dimethyl-7-benzene (5-5,5,6,7-tetrahydrofluorenyl)] titanium dichloride, [5 — (7-5 —cyclopentadienyl) — 4,7-dimethyl-7 —benzene (T 5-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium, [5 — (π5 —cyclopentadienyl) -4,7-dimethyl-7 —calyl ( π5-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [5 — (π5-cyclopentadienyl) -4,7-dimethyl-7-fluorenyl (?; 5— 4,5,6,7-tetrahydrofluorenyl)] Zirconium dichloride, {Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 21 438827 A6 B6 V. Description of the invention (20) [5- (π5-Cyclopentadienyl) -4,7-dimethyl-7-butyl (7-5-4,5,6,7-tetrahydrofluorenyl)] titanium dichloride , [5 — (π5-Cyclopentadienyl) -4, 7-dimethyl-7-butyl (^ 5-4, 5,6, 7-tetrahydrofluorenyl)] chromium dichloride, [5 — (? 75-3 mono-tert-butylcyclopentadienyl) _4,7,7-trimethyl (π5-4,5,6,7-tetraargonyl)] dichlorotitanium, [5 — ( ? 75-3 mono-tert-butylcyclopentadienyl) -4,7,7-trimethyl (? ? 5-4,5,6,7-tetrahydroruthyl)] dichlorochromium, [5 — (7 / 5-3 tert-butylcyclopentadienyl) -4, 7, 7-triphenyl (? 75 — 4,5,6,7 —Tetrapinyl)] — Qiqin, [5 — 3 —tert-Butylcyclopentadienyl) _4, · 7 '7 —triphenyl (?? 5-4, 5 , 6,7 -tetrahydrofluorenyl)] dichlorozirconium, ... ........................................ Assembling ............ Ordering ............ line (please read the notes on the back before copying Page) Central Consumers Association of the Ministry of Economic Affairs, Machining and Consumer Cooperatives, India Bismuth 5 Titanium Chloride 5 7 7 5 Group 77 Benzene 3 Tertiary 4 Group 7 * ΐρ · Pour, 2 6 Pentam, 5 5 Hydrogen Tetramethylene 3 / 1 \ 5_yl β benzene tertyl ene dipentane 4 7 hydrogen tetra 7 radical, 10 .PP A paper size applicable to national standard iCNS) A4 specification (210x297 male dragon) -22-438827 A6 B6 Hyunji Printed by the Ministry of Standards of the People's Republic of China, Co., Ltd., and F. Cooperatives. V. Description of the invention (21) Zirconium chloride, [5 — (“5-3 > —tert-butylcyclopentadienyl) — 4, 7 —dimethyl — 7 — 棻 基 (?????? 5 4,5,6,7-tetrahydrofluorenyl)] dichlorozin, [5 — ("5-3--tert-butylcyclopentadienyl) -4,7 -dimethyl-7 -fluorenyl ( 5-4,5,6,7-tetrahydrofluorenyl)] chromium dichloro, [5 — (7? 5 — 3 > —t-butcyclopentadienyl) _4, 7 —dimethyl-1 7-butyl (775-4,5,6,7-tetrahydrofluorenyl)] dichlorozin, [5 — (τ? 5-3 > —tert-butylcyclopentadienyl) -4,7 — Dimethyl-7-butyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichlorochromium, [5-(? 75 -fluorenyl) -4,7,7-trimethyl ("5-4,5,6,7-tetrahydropyridyl)] titanium dichloride, [5-(" 5-fluorenyl)-4, 7, 7, 7-trimethyl ("5-4, 5, 6,7-tetrahydrofluorenyl)] Zirconium dichloride, .................. ................... Order ......... Order ... ....... line (please read the notes on the back before writing this page) This paper size applies to the Chinese national standard (CNSj A4 specification (210x297 mm) -23-4 3 882 7 Ministry of Economic Affairs Printed by the Central Bureau of Standards, Sealed Consumer Cooperatives A6 B6 V. Description of the Invention (22) [5 — (π5—fluorenyl) —4,7,7—triphenyl (ί? 5—4,5,6,7— Siqipinji>] Dichlorozine, [5 — (No 5 — in 5 groups) a 4,7,7 —diphenyl (ί? 5 4 '5, 6,7 — tetrakinuyl)]] Zirconium dichloride, [5- — (i? 5 —yl) -4,7-dimethyl-7-phenyl (5,5,4,5,6,7-tetraarginyl)] dichlorozin, [ 5 — (?? 5-fluorenyl)-4, 7, 7-dimethyl-7-phenyl (π5-4, 5, 6, 7-tetrahydrofluorenyl)] dichlorochromium, [5-(π5 — Fluorenyl) -4,7-dimethyl-7-fluorenyl (7 / 5-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [5 — (π5 -fluorenyl) -4 , 7-dimethyl-7-fluorenyl (π5-4,5,6,7-tetrahydropinyl)] chromium dichloride, [5-(π5-fluorenyl) -4,7-dimethyl-1 7-butyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium, [5-(? 75-fluorenyl) -4,7-dimethyl-7-butyl ( π5 a 4,5,6,7_four Product base)] Zirconium dichloride, ............... ........................................................ .... Order ......... (Please read the notes on the back before filling out this page) The paper size of the table is applicable to the Chinese National Standard (CNS; A4 Specifications (210X297mm) -24-438827 A6 B6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Cooperative Consumers Co., Ltd. Printing 5. Description of Inventions (23) [5 — ("5-cyclopentadienyl)-4, 7 , 7-trimethyl (π5 _4,5,6,7-tetrahydrocarbyl)] dioxin, [5- (775-cyclopentadienyl) -4,7,7-trimethyl (7 ? 5-4,5,6,7-tetrahydrofluorenyl)] dichloride, [5- (es-cyclopentadienyl) -4,7,7-triphenyl ("5-4,5 , 6,7-tetrahydromanthyl)] titanium dichloride, [5- — (π5-cyclopentadienyl) -4,7,7-triphenyl (7-5 — 4,5,6,7- Tetrahydrofluorenyl)] Cobalt dichloride, [5 — (?? 5-Cyclopentadienyl) -4,7-dimethyl-7-phenyl (75-4, 5,6,7-tetrahydro Mangyl)] titanium dichloride, [5 — (β5 —cyclopentadienyl) __ 4 7-Dimethyl-7-phenyl (7 / 5-4, 5, 6, 7, 7-tetrakisyl)] 2 gas sales "[5-(7? 5-cyclopentadienyl)-4, 7-Dimethyl-7-fruityl (7-5-4,5,6,7-tetrahydromanganyl)] titanium dichloride, [5 — (π5 —cyclopentylsuccinyl) — 4, 7 — Dimethyl-7-a certain group (? 75-4,5,6,7-tetrahydrofluorenyl)] dichlorohydrazone, installed ............ order ... ............. line. (Please read the notes on the back before filling out this page) This paper is again applicable to National Standard (CNS) A4 specifications (210 乂 297 mm) Shiyang Standard Bureau of the Ministry of Economic Affairs, MX Consumer Cooperative Association, India 4351 2 7 A6 B6 V. Description of Invention (24) [5 — (π5 —cyclopentadienyl) — 4, 7 — dimethyl — 7 —butyl (π5 — 4,5,6,7-tetrahydrofuryl)] titanium dichloride, [5 — (π5 —cyclopentadienyl) — 4, 7 —dimethyl — 7 —butyl (τ? 5-4 , 5,6,7-tetrahydrophenanthryl)] dichlorozirconium, [5 — (?? 5 -manganyl)-4 '7,7 -trimethyl (?? 5-4, 5, 6, 6, 7 _Tetrazyl group]] dikisin * [5 — (? / 5 — fenky)-4, 7, 7-trimethyl (? 5-4, 5, 6, 7_tetrakisinyl)]] Dichloro pin, [5- (π5 -manganyl) -4,7,7-triphenyl (775-4,5,6 * 7-tetrahydrofluorenyl)] titanium dichloride, [5-(? 75 -Fluorenyl) -4,7,7_triphenyl (7-5-4,5,6,7_tetra Pinyl)] two gas pins, [5 — (π5 — Jiang Ji) — 4, 7 — dimethyl_7_phenyl (? 5-4, 5, 6, 7_ tetrahydropinyl)] dichloride Titanium, [5- (π5-Ferky) -4,7-dimethyl-7-phenyl (π5-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium. ........................................ ........................................ Install ............ Order ........ line {Please read first Note on the back, write this page again) This paper size is applicable to China Standards (CNS) 4 specifications (210x297K: -26-Central Standards Bureau of the Ministry of Economic Affairs, China Industrial Standards Cooperative Society, Cooperative Press, 4388 2 / Α6 Β6__ V. Description of the invention (25) The nomenclature of the above-mentioned compounds according to the present invention is referred to [4-(? 75-cyclopentadienyl) -4,7,7-trimethyl (and 5--4,5, 6, 7-tetrakisyl)]] dichloride compound for illustration:

The compounds mentioned below are named according to the IUPAC nomenclature [775-9 — (7? 5 —cyclopentadienyl) tricyclic (6. 1.. 1. 0 2'6] dec-2, 5 — 2 Alkenyl] titanium dichloride, ["5-9-(7? 5-cyclopentadienyl) tricyclo [6. 1 1. 02 * 6] decyl-2, 5-dienyl] chromium dichloride, [Π5_7 —methyl-1 9 — (τ? 5 —cyclopentadienyl) tricyclic [6, 1.1.1.0, 2] decyl 2,5 —dienyl] titanium dichloride, methyl — 9_ (ί? 5_cyclopentadienyl) tricyclic [6 1. 1. 〇 2 '6] decyl 2,5 -dienyl] zirconium dichloride, this paper size applies Chinese National Standard (CNS) f 4 Specifications (210x297 mm) Packing ............ Order ... .. line (please read the precautions on the back before filling this page) -27-438827 Ministry of Economic Affairs t Central Standards Bureau 工 工 ## Cooperation Du printed A6 B6 V. Description of the invention (26) [? 75-9 1A A 9- (cyclopentadienyl) tricyclo [6. 1.. 1. 02 · 6] dec-2,5-dienyl] titanium dichloride, [75-9-methyl-1 9 one (7? 5-cyclopentadienyl) tricyclic [6. 1.. 1. 02'6] decyl 2, 5 — Diphenyl group] Dioxin pin, [7? 5-10 — (? 75 —Cyclopentadienyl) tricyclic [5. 2.. 1. 〇2,6] decyl 2,5 —dienyl] di Titanium chloride, [τ? 5—ΙΟ— (π5—cyclopentadienyl) tricyclo [5. 2. 1. 02'6] dec_2, 5-dienyl] dichloride, {V 5 ~ \ 0 —methyl-1 0 — (7? 5 —cyclopentadienyl) tricyclic [5. 2. 1. 02 > 6] dec-2,5_dienyl] titanium dichloride, {V 5- I 0 —methyl-1 0 — (π5 —cyclopentadienyl) tricyclic [5. 2. 1. 02'6] dec-2,5-dienyl] dichloride, [? 75-9 — (Π5 —cyclopentadienyl) tricyclo [5.2.2.2.0,6] undecyl-2,5-dienyl] titanium dichloride, [”5-9- (775-cyclopentyl Dienyl) tricyclic [5. 2. 2. 0 2-6 1 hafnium --- 2, 5-dienyl] dichlorozirconium, ... ........................................ ......... ^ ...: —....... IT ................... ..Line (please read the notes on the back before filling this page) This paper size applies to Chinese national standard (CNS 丨 A4 specification (210X297mm 丨 -28)-Central standard of the Ministry of Economic Affairs 8 f cooperative work eliminate wrinkling 438827 A6 B6 five printing described (27) invention [? 75-9 monomethyl-9 mono (cyclopentadienyl) tricyclo [5. 2. 2. 0 2 '6] Η --- 2,5-dienyl] diammonium titanium, [? 75-9-methyl-1 9- (π5-cyclopentadienyl) tricyclic [5 · 2.. 2. 0 2 · 6 3 Η --- 2,5-dienyl] dichlorozirconium, {η 5- I 0 — ("5-3 methylcyclopentadienyl) tricyclic [5. 2. 1. 02, 6] dec-2, 5-dienyl] titanium dichloride, [7? 5-1 0 — ("5-3 -methylcyclopentadienyl) tricyclic [5 '2. 1. 02 · 6] decyl 2,5 -dienyl] zirconium dichloride, t η 5 ~ I 0 — Methyl-1 0 — (? 5_3 -methylcyclopentadienyl) tricyclic [5. 2. 1. 02, 6] dec-2, 5-dienyl] digas titanium, {η 5 ~ 1 0 —methyl-1 10-(? 75-3 mono-methylcyclopentadienyl) tricyclic [5, 2. 1. 02_6] decyl-2, 5-dienyl] dioxo, [" 5-4 monomethyl 〇— (;? 5- 3-—methylcyclopentadienyl) tricyclic (5. 2. 1. 02, 6] decyl 2,5_ dienyl] dichlorozin,. ........................................ ........ ίί ………………… Order .............. line {Please read the notes on the back before filling Nest page} This paper size applies to China National Standards (CNS 丨 A 4 觇 Grid (210x297mm 丨- 29-43 88 27 5i A6 B6 printed by the Ministry of Economy, the Central Government, the Apple Bureau, and the Consumers ’Cooperative 5. V. Description of the invention (28) Tricyclic [5. 2. 1. 02'6] Deca-2,5-dienyl] zirconium dichloride, (77 5- 4, 10-dimethyl-1 1 0 — (r / s-3 a Monomethylcyclopentadienyl) tricyclic [5,2. 1. 02,6] deca-2,5-dienyl] titanium dichloride, [7-5-4, 1 0-dimethyl-1 ο-(775- 3 -methylcyclopentadienyl) tricyclic [5, 2. 1. 02,6] decyl 2,5-dienyl] chromium dichloride, [7? 5-5 -methyl -1 ο-(775- 3 -methylcyclopentadienyl) tricyclic [5. 2. 1. 02, 6] dec-2,5 -dienyl] dichlorozin, [τ? 5 — 5 —methyl-1 10 — (?? 5_3 -methylcyclopentadienyl) tricyclic [5. 2. 1. 02, 6] dec-2, 5-dienyl] dichlorozirconium, [" 5-5, 10-dimethyl-1 10- (π5--3-methylcyclopentadienyl) tricyclic [5. 2. 1. 02, 6] dec-2, 5-dienyl] di Titanium chloride, ............... ........................ .... install ......... order ......... line {Please read the back Note: Please fill in this page again.) This paper uses China National Standard (CNS) A4 specifications (210 > < 297 mm 丨 -30-438827 A6 B6. V. Description of the invention (29) [5-5, 1 0 —dimethyl-1 0 — (“5-3 monomethylcyclopentadienyl) tricyclic [5, 2, 1.02, 6] decyl 2,5-dienyl] dichlorozirconium . The preparation of metallocenes according to the present invention is illustrated by the following reaction scheme and reference is made to metallocenes of formula I, where m is zero and M4 is a metal of the main group Ia, IIa or IIIa.

II. Printed by the Central Industry Standards Bureau, Ministry of Economic Affairs, M Industrial Consumer Cooperatives

(III) + HjO

Loading ......... Order ... Note on the back, please fill in this page again.) The paper flavor standard is applicable to China National Standard (CNS) A4 specification (210 > < 297 gong)

........................................ ............................................... ....... Order ... I ...... line (please read the precautions on the back before filling in this page) Indun has bisfuenes with chemical formula II. They are composed of diketones (Chem. Page 3426 (1976): Ibid., No. 107, Page 2 453 (1974)) or the literature on the use of keto acids (J. Org. Chem. No. 57 (1929), page 2504: Ibid., No. 49 (1984), pp. 189: Chimia, No. 46 (1992), pp. 37-7). This paper is applicable to China National Standards (CNS) A4 specifications (210x297 male «) ΓΤ. ¾ Central Government Bureau of Standards M Industrial Consumers Cooperative Cooperative Printing si 438827 A6 _B6_ 5. Description of the invention (31) Double fulene II The ligand system converted to structure III is carried out by reaction with an organic gold compound (such as methyl lithium, butyl lithium, or phenyl lithium) or Grignard reagents. The salts of structure II can be directly converted into related di anion compounds of structure V by using deprotonat ion >, such as using butyl. Hydrolysis of compound III causes dicyclopentadiene Formation of the base compound IV, which is used as a structural isomer mixture and can be purified by chromatography. It is produced using, for example, double deprotonation of butyl lithium Dianionic compounds of structure V. The transition of the bridged metallocene of chemical formula VI and the isolation of the desired complex are basically well known. For this purpose, the anionic compounds of structure V are related Metal halide (metal halide) is reacted in an inert solvent. The metal halide can be, for example, a metallocene of tetrachloride structure VI or can be synthesized directly from bisfulnes of structure II without the need for intermediate isolation. Suitable solvents are aliphatic or aromatic solvents such as hexane or toluene, ether solvents, which are, for example, tetrahydrofuran or diethyl ether, or Are halogenated hydrocarbons, such as methylene chloride, or halogenated aromatic hydrocarbons, such as o-dichlorobenzene. A dicyclopentadienyl compound of formula IV and wherein R 3 to R 6 or at least one of R7 to R9 is a hydrogen atom, which is well known in the literature ... ........................................ ................ Order ... < Please read the precautions on the reverse side of this page before using this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 male *) 438827 V fulvene. This can be expressed by the following reaction

A6 B6 V. The method of invention description (32) was transformed into a structure diagram for explanation.

The reaction of fulvene I Va with an organometallic compound of the formula R19MS (where Ri9 = R 13 is the same or different: M5 = M4 and is the same or different) results in two equal R19M4 of the monoanionic compound III a The use of it directly leads to the formation of the dianionic compound v & ... ........ line (please read the precautions on the back before filling out this page) Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and Industrial Consumer Cooperatives 31 (fVo) Μ R *

ί Μ5] ί +) This paper is a standard of the National Park in China 4 specifications (210X297 mm) -34 _ A7 4 3 882 7 B7 V. Description of the invention (33 (Ilia) butyl lithium

2 [lithium] c R, 7 (V.) Salts of the structure IIa can be directly converted into related anion compounds of the structure Va by the deprotonation of butyllithium, for example, "bridged metallocene of formula I The conversion is a reaction corresponding to the transition from structure V to structure V1. Another method for forming a compound according to the present invention includes a monocyclic or polycyclic system reaction such as a cyclopentadienyl compound or a fluorenyl lithium compound, wherein, Cyclopentadienyl is fused and monocyclic or polycyclic ring systems may have functional groups that can act as leaving groups (such as bromide or tosylate) in substitution reactions. . The present invention also relates to a method for preparing an olefin polymer. This method is the polymerization or copolymerization of at least one olefin with the participation of a catalyst. * Among them, the catalyst contains at least one sterically rigid metallocene compound. Metal compounds with at least one cocatalyst: Stereo rigid metallocene compounds contain at least two substituted or unsubstituted cyclopentadienyl groups that act as ligands and the cyclopentadienyl group is via a monocyclic or polycyclic system Whereas, at least one of the cyclopentadienyl groups is fused to form a monocyclic or polycyclic ring system. Wood paper iMUii Sichuan small mMUMM (_ns) Λ < ι specifications uiouw public 筇) " -35-43882 7 .¾¾. Shao Central quasi bureau Η 工 工 f co-operative print ¾ A6 B6 5. Description of the invention (34) has the chemical formula R The olefins of a — CH = C Η-R b are preferably polymerized or copolymerized, wherein, 尺 1 and 111) are the same or different and are hydrogen atoms or have 1 to 20 carbon atoms, especially Is an alkenyl group having 1 to 10 carbon atoms, or 1 ^ & and rule 1 > together with the atom connecting them may form one or more rings. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl- 1-pentene and 1-octene. In particular, propylene or ethylene is polymerized. The polymerization or copolymerization is preferably carried out at a temperature of 60 to 200 ° C, particularly preferably 30 to 80 ° C. The pressure is preferably from 0.5 to 100 bar (bar), especially from 5 to 64 bar. The polymerization can be carried out in successive or batch processes in one or more steps and in solution, suspension or gas phase. The goldlocene drawer according to the present invention is a highly active catalyst component for the polymerization of olefins. The metallocene of the present invention can form a kind of isomeric mixture depending on the substituted form of the ligand. The metallocene is preferably in isomerically pure form. In most cases, the use of racemates is sufficient. However, it is also possible to use pure enantiomers in the (+) or (-) form. Optically active polymers can be prepared using pure specular isomers. However, metallocenes that are configured as isomeric forms should be isolated because the active centers (metal atoms) that polymerize in such compounds produce polymers with different characteristics. In some applications, such as soft moldings, this may be desirable. This paper size applies to Chinese national standard (CNS 丨 A4 specification (210X297 male: ¢) ~ '** 36-.............. ........................................ ..................................................... ..... Practice {«Read the notes on the back before filling out this page) 438827 A6 B6 V. Description of the invention (35) It is also possible to use a mixture of two or more metallocenes. This makes it possible to obtain polyolefins having a broad or multi-modal molecular weight fender. The method according to the present invention is preferably carried out using a goldlocene and a co-catalyst. The co-catalyst is preferably aluminoxane and preferably has a linear chemical formula Vila and / or a cyclic chemical formula Vllb, 20 > < Please read the notes on the back before filling this page} 20 0-A I -0. 20 -0p + 2 20 20 (Vllb)

Vila) ® The Central Standards Bureau of the Ministry of Economic Affairs only prints the consumer cooperatives in the chemical formulas V II a and V II b. The feet 2 ° are the same or different and are alkyl, C6-C18 aryl, fluorenyl or hydrogen; p is an integer from 2 to 50 and preferably an integer from 10 to 35. The R2 ° group is preferably the same and is preferably methyl, isobutyl, phenyl or benzyl, particularly preferably methyl. If the R 2 ° groups are not the same, they are preferably methyl and hydrogen or methyl and isobutyl, and the content of hydrogen or isobutyl is preferably from 0.01 to 40% (R 2Q Base number). Aluminoxane can be prepared by a variety of well-known methods-one of which can be, for example, an alurainum hydrocarbon compound and / or a hydrido-aluminun hydrocarbon compound in an inert solvent (this paper standard applies to Chinese standards) (CNS) A4 specifications (210X 297mm > -37-438827 A6 B6 Cooperative production of the Central Bureau of Standards, Ministry of Economic Affairs, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, etc. V. Description of invention (36) Such as toluene , Solid, liquid or bound form (such as crystal water) reaction. In order to prepare alkanes such as aluminum D containing different R 2e groups, two different trialkylaluminum compounds can be reacted with water according to the desired composition. Regardless of the preparation method, all aluminoxane solutions have different unreacted aluminum original compound contents, which are free forms or adducts. Before use in the polymerization reaction, use a co-catalyst, especially aluminum It is possible to pre-activate the metallocene with P-alkane. This greatly increases the activity of polymerization and improves grain morphology. The pre-activation of transition metal compounds is In solution. Goldlocene is preferably dissolved in an aluminoxane solution and in an emotional solvent. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferred. The aluminoxane concentration in the solution It is between about 1% by weight to the saturation limit, preferably 5 to 30% by weight and in each case based on the total content of the solution. Metallocenes can be used at the same concentration, but in each mole of aluminum The content of hafnium is preferably from 10 to 1 mole. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The temperature is from 78 to 100. ° C, preferably 0 to 70 ° C. Metallocene can be used for prepolymerization, and it is preferred to use olefins (or olefins) in the polymerization process. ° Metallocenes can also be applied to carriers ( support). A suitable carrier material may be, for example, silicone < si ca i ca ge s), alumina, solid aluminoxane or other inorganic carrier materials, such as magnesium chloride. Another suitable load (please read the “Notes on the back side before filling out this page”) • Order · This paper size is suitable for China Standard A (CNS) A4 specification (210X297 mm) -38-4388 2 7 The Central Bureau of Standards of the Ministry of Economic Affairs only prints A6 and B6 of the cooperative. V. Description of the invention (37) The body material is a finely divided polyolefin powder. Use a co-catalyst such as aluminoxane to the carrier, and then mix it with the catalyst. The gold shoulder reaction is relatively sloppy. Among them, the carrier can be silicone, alumina, solid aluminoxane, other inorganic carrier materials, or finely divided polyolefin powder. A suitable inorganic carrier can use flame pyrolysis (flame Pyrolysis) oxides prepared by the combustion of halide elements in an oxygen flame, or can be prepared similar to silicone with a certain size distribution and particle shape. The preparation of co-catalysts with a carrier can be carried out in For example, the method described in European Patent No. 92 107 331. 8 is carried out in an explosion-proof stainless steel reactor with a 60 bar onion system, an inert gas supply and a pump system. The heat exchanger uses water jacket cooling (jacket cce ling) and the temperature control of the second cooling circuit. The pump system draws out the contents of the reactor through the connecting tube at the bottom of the reactor and makes it enter the mixer and pass through the heat exchanger. It is returned to the reactor through the rising line. The mixture must have a narrow pipe cross section to increase the flow rate and a narrow axial flow must be established in the turbulence zone. The tube (feed line) is opposite to the direction of flow, and in each case a certain amount of water can be fed in a pulse-like manner under 40 bar of argon. The reaction is monitored via samples in the pump circuit. However, Basically, other reactors can also be used. Among the above-mentioned reactors with 16 dm 3 hip volume, the 5 dm 3 guiyuan was introduced into the reactor under inert conditions and 0.5 · d dm3 was added at 2 5 ° C. ........................................ ................................................. ......... Order .............. line {Please read the notes on the back before filling in a paper size on this page Applicable Family Sample Standard (CNS) A4 Specification (210x297 mm) -39-Made by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4388 2 7 A6 _______B6 V. Description of the Invention (38) (= 5.2 Moore) 2 Methyl aluminum. 250g of SD3216-30 (Grace AG) silicone is metered into the reactor through a solid funnel and uniformly distributed with the help of a stirrer and pump system. Among them, the silicone is first fluidised in the argon flow layer. bed) at 120 ° C. The total amount of water added to the reactor was 76.5 g and 0.1 cm3 was added every 15 seconds for a total period of 3.25 hours. The pressure caused by argon and the released gas was maintained at 10 bar fixed pressure. When all the water is introduced into the reactor, turn off the pump system and stir for another 5 hours at 25 ° C. The carrier co-catalyst prepared in this way is a 10% strength suspension in n-decane. 06 milmol of aluminum per cm 3 of aluminum suspension. The isolated solids contained 31% by weight of aluminum and the suspension medium contained 0.1% by weight of aluminum. In addition, the method for preparing the carrier co-catalyst is described in European Patent No. 92 1 0 7 3 3 1. 8 ^ 〇 The metallocene according to the present invention is then applied to the carrier co-catalyst and stirred with the carrier co-catalyst. After the solvent is removed, it is replaced with a hydrocarbon solvent, in which both the co-catalyst and the metallocene are insoluble. The reaction to form the carrier catalyst system is carried out at a temperature of -20 to +120 ° C, preferably 0 to 100 ° C, and particularly preferably 15 to 40 eC. The metallocene is a co-catalyst reaction with the carrier. The reaction is a co-catalyst combined with a metallocene solution in an inert solvent or a finely honing metallocene solid. Among them, the co-catalyst is 1 to 40% by weight strength. Suspensions, preferably suspensions with a strength of 5 to 20% by weight and the co-catalyst is aliphatic inert .............. ........................................ ........................... Order ......... ..... Feng < Please read the precautions on the back before digging this page} This paper size applies to China National Standard (CNS) Y 4 (210X297 mm 1 438827) Innu A6 B6_ 5. Description of the invention (39) In a suspension medium such as n-decane, hexane, heptane or diesel oil, the inert solvent in the metallocene solution may be toluene, hexane, heptane or Dichloromethane. Conversely, a co-catalyst reaction of the metallocene solution with the solid state is also possible. The reaction is carried out in an intensive mixing, which, for example, reduces the Αί / Μ1 molar ratio to 100 / 1 to 1 0, 0 0 0/1, It is preferably agitated at a ratio of 1 0/1 to 3, 0 0 0/1 and the reaction time is 5 to 120 minutes, preferably 10 to 60 minutes. In the reaction process for preparing the catalyst system for the carrier In particular, when using the metallocene having an absorption peak in the visible region of the present invention, the color change of the reaction mixture can be used to monitor the progress of the reaction. When the reaction is over, the upper solution is separated, which can be, for example, by filtration or decantation. (Decanting) is achieved. The remaining solution is washed 1 to 5 times with an inert suspension medium to remove the soluble components in the formed catalyst, especially to remove unreacted and therefore soluble metallocene. The inert suspension medium may be, for example, It is toluene, n-decane, hexane, diesel, or dichloromethane. The carrier catalyst system prepared in this way can either be dried in the air like a powder or still adhere to the solvent and can be suspended in any of the above as a suspension. Resuspension in an inert suspension medium and metering to the polymerization system. According to the present invention, in addition to aluminoxane, it has the chemical formula R 2; ικΝ H 4-xB R 224. R 21κΡ H 4-xB R 2 2 4 »R213c B R224 with B The compound of R223 can be used as a suitable co-catalyst or can replace algargane. In this kind of chemical formula, X is an integer of 1 to 4, preferably 3: R21 groups are the same or different, preferably the same And Ci ............... ............................................................ ........... Order ......: ... line. TPlease read the precautions on the back before reading this page)

This paper size applies to the Chinese National Standard (CNS) Yin 4 specifications (210x297 mm I —41-printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4388 2 7 A6 B6 V. Description of the invention (40) 1 C 1. Burning base * C 6 — C 18 aryl or two R 21 groups together form a ring with the atom connecting them: R 22 groups are the same or different, preferably the same and are C 6-C: 8 aryl groups, which can be substituted Alkyl, haloalkyl or fluoro. Specifically, R21 is ethyl, Ryl or phenyl, R22 is phenyl, perfluorophenyl, 3,5-bistrifluoromethylphenyl ( bis triftuoromethylphenyl), mesityl, xylyl or toly 丨 (see European Patent No. 2 7 7 033,277 004 »426638 ||) 〇 When using the above co-catalyst, The actual (living) polymerization catalyst includes one of the reaction product of the metallocene and the compound. For this reason, it is preferred that this reaction product is first prepared in a separate step outside the polymerization reactor. A suitable solvent is used. Basically, according to the present invention, the co-catalyst can be any compound Because of its Lewis acidity, it can convert a neutral metallocene into a cation and establish this cation (labile coordination). In addition, the co-catalyst or anion formed should not react with The formed goldlocene cation undergoes any additional reaction (see European Patent No. 4 2 7 6 9 7). In order to remove catalyst toxins present in olefins, for example, trimethylaluminum or triethylaluminum is used The purification of alkyl aluminum compounds is advantageous. Such purification can be carried out in the polymerization system itself, or the olefin can be contacted with the aluminum compound and then removed before the polymerization system is introduced. If necessary, it can be added Hydrogen is used as a molecular weight regulator and / or to increase activity. The total pressure in the polymerization system is 0.5 to ......... ..................................... ... fitting ........... ordering ......... line (please first M Read the notes on the reverse side and rewrite this page.) This paper size is applicable to a standard (CNS) A4 size (210x297 mm) -4 2-438827 Printed by A6 ____B6__ of the Central Industry Standards Bureau of the Ministry of Economic Affairs ____B6__ 5. Description of the invention (41) 1 0 0 bar. The polymerization is carried out at a pressure range of 5 to 64 bar which is of particular interest in the industry. The pressure range is particularly good. of. The concentration of the metallocene used in the polymerization is based on the transition metal as a solvent per dm3 or a reactor volume per dm3 containing 10-30 to 10-8 moles, preferably 10-4 to 1 mole. Transition golden urn. The aluminum bromide has a bromine content of 10 to 10 mol, preferably 10 1 to 12 mol. The other co-catalysts mentioned are roughly equal to the molar amount of the metallocene. However, basically, higher concentrations are also feasible. If the polymerization is carried out like suspension or solution polymerization, an inert solvent commonly used in the Ziegler low pressure method is used. For example, the polymerization is carried out on aliphatic or cycloaliphatic hydrocarbons, examples of which are propane, butane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. Furthermore, it is also possible to use benzine or hydrogenated diesel fractions. Toluene can also be used. The polymerization is preferably carried out in a liquid monomer. If an inert solvent is used, the monomers are metered in the gas or liquid phase. The polymerization can be carried out at any desired period, because the catalyst system to be used according to the invention exhibits only a slight reduction in the time effect on Polymerization activity. Before the catalyst is added, especially the carrier catalyst system (including the co-catalyst of the metallocene of the present invention and the carrier or the metallocene of the present invention and the organoaluminum compound in the finely divided polyolefin powder), another kind of Aluminium compounds can be additionally added to the reactor to make the polymerization system in an inert state (for example, to remove catalyst toxins present in olefins). Such alkylaluminum compounds ... ........................................ ............................................. Order ... ........ line (please read the precautions on the back before filling in this purchase) This paper size is applicable to 0 Chinese standards (CNS 丨 A4 specifications ( 210 parent 297 mm) 43-438827 ® Printed by A6 _B6, Masonry Consumer Cooperative of the Central Bureau of Standards of the Ministry of Education of the People's Republic of China 5. Description of the invention (42) The material can be, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Trioctyl or isoprenyl aluminum. The compound Ao degree added to the polymerization system is 100 to 0.01 millimoles of aluminum per kilogram of reactor capacity. Preferably in every male The reactor capacity contains 1Q to 0.1 millimolar aluminum triisobutylaluminum and triethylaluminum. In the synthesis of the carrier catalyst system, this can allow for the choice of A]? / Μ 1 mole ratio However, basically, it is not necessary to use another substance to promote the catalysis of the polymerization reaction, that is, the system of the present invention can be used as the sole catalyst for the polymerization of olefins. According to the present invention Metallocene is suitable for the preparation of polymers. Such polymer technologies have reduced crystallinity, enhanced impact resistance, increased transparency at processing temperatures (preferably 50 ~ 100X), High fluidity and low molecular weight and reduced melting point. The low molecular weight polymer (preferably 100-800 g / mole) of the present invention preferably has vinylyend-endgroups. This The main applications of polymer-like polymers are plasticizers, lubricant formulations, hot melt adhesives (h ot-meit: adhesive) applications, coatings, seals, insulation, and embedded Flush-molding composition, sound insulation Materials, waxes or fatty alcohols and fatty acid precursors. The following examples are provided to illustrate the invention in detail. General introduction. Organometallic compounds are in the blanket of argDn, which is free of air and moisture. ) (Schlenk technology) and the preparation and i paper size ^ 7 using the Chinese national standard (CNS 丨 A 4 specifications (210X297 public 隹 _) --- -44 a ......... .............................................! ί .. .............................................. Order .. ......... line · (Please read the precautions on the back before filling in this page) 4388 2 7 Printed by the 8th Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs ^ A6 ___B6_ 5. Description of the Invention (43) Treatment. All required solvents must be water-free before use. This can be achieved by boiling with a suitable desiccant for several hours and then distilling under argon. The diketones and ketoaldehydes used as starting compounds can be prepared by methods well known in the literature. Cyclopentadiene and methylcyclopentadiene are obtained from cracked dimers and stored at _ 3 5 ° C. The A / CΗ3 ratio in aluminoxane is determined by using sulfuric acid to decompose the sample and determining the volume of the hydrolyzed gas generated under standard conditions, and detecting the content in the sample using a complex titration method (corap lexometric titration). The inscription was dissolved by the Schwarzenbach method. The properties of the compounds were obtained by 1H-NMR, 13C-NMR and infrared spectroscopy. A. Preparation of bisfulvene II Example 12 Synthesis of 2,5-bis (2,4-cyclopentadienyl-1) hexane According to an improved reaction procedure [a], 11. 〇g (96. 3 mmol) of 2,5 —hexanedione and 1 2. 7 g (193 mmol) of freshly cracked cyclopentadiene were dissolved in 60 ml of methanol, the solution was cooled to 0 ° C and added 8.60 g (121 mmol) of pyrrolidine. After the mixture was stirred at 0 ° C for 90 minutes, the reaction solution was hydrolyzed with 5 ml of glacial acetic acid and 50 ml of water and extracted twice with 70 ml of diethyl ether each; the combined organic phases were saturated with The chloride solution was rinsed and dried with magnesium sulfate. When the solvent was removed in the air, 18.0 was produced. This paper size is applicable to China S Jiaquan (CNS) A 4 specifications 210x297 mm)--45-{Please Read the notes on the back before filling this page) ¾ Printed by Jiqi t Central Standards Bureau, M Industrial Consumer Cooperative, 5ί 4388 2 7 A6 __________B6____ 5. Description of the invention (44) g (8 9%) orange red, oily residue double Fullene. [A] = M.S. Erickson, J.M., Kerlon, J.G. Insia, M.L. McLaughlin, J. Chem, 57 (1992), 2504-2503. K. J. Shi Dong (S t ο ne), R'D. Li Tou (L i 111 e), J. Org. Chera. 49 (1984), pp. 1849—1853 0 * B. Bridge Synthetic Example 2 of Dicyclopentadienyl Anion Compound V: [4 — (?? 5-cyclopentadienyl) -4,7,7-trimethyl (? 75-4,5,6, 7_Tetrakis)] Synthesis of dilithium 62.4 ml (99. 8 mmol) of a 1.60M methyl lithium solution of ether was slowly added to 150 ml of diethyl at 0 ° C A solution of 10.0 g (47.5 millimoles) of 2,5-bis (2,4-cyclopentadienyl-1) in hexane in ether and stirred vigorously. The mixture was allowed to warm to room temperature and a beige precipitate was formed after 24 hours of stirring. After filtration and repeated washing with pentane, 13.2 g (89%) of a lithium powdered dilithium salt was formed, which was coordinated with one mole equivalent of diethyl ether. Example 3: I ............ tr ................... 1 line · {Please read the precautions on the back before filling in this page.) This paper method applies tg S home sample standard (CNS1 A4 size (210X297 mm) -46-Central Industry Standards Bureau, Ministry of Economic Affairs, M Industrial Consumer Cooperatives, India, Si 4388 2 7 A6 B6 V. Description of the invention (45) (4_ (π5-cyclopentadienyl) -4,7-dimethyl-7 ~ phenyl (?? 5-4,5,6,7_tetra Hydrogen S5 group)] dilithium synthesis of an ether phenyllithium solution (8.3.4 ml, 7 3.4 mol, 0.8 9 M diethyl ether solution) was added dropwise to the next 0 oC 7.10 g (33.7 millimoles) of bisfulvene (Example 1> solution in 100 ml of diethyl ether). After about 5 minutes, a beige precipitate began to settle. The mixture was allowed to Warm to room temperature, and then stir for an additional 12 hours at 25 ° C. After filtration and repeated washing with pentane and drying in the air with an oil pump, a powdery lithium salt which is very sensitive to hydrolysis is formed. The yield was 82% (10. 3 g). Example 4 [4-((?-Cyclopentadienyl)-4,7-dimethyl —7-Butyl (π5-4,5,6,7-tetrahydrofluorenyl)] dilithium synthesis Dissolved in 100 ml of diethyl ether 15.0 g (7 1. 3 mmol) ) Solution of bisfulvene (Example 1) was cooled to a temperature of 30 ° C and 94 ml (150 mmol) of 1.60M n-butyl lithium solution in hexane was slowly added and vigorously stirred to form 0g (91%) The precipitate of lemon yellow. The mixture was allowed to warm to room temperature and stirred for an additional 24 hours to complete the reaction. The precipitate was filtered off and washed several times with pentane and dried in the air with an oil pump to produce 23.0 g (91% ) Is the lithium salt, which is beige and is a powder that is very sensitive to hydrolysis, and it is also coordinated with one mole of diethyl ether. This paper uses the Chinese Standard (CNS) A 4Specifications (210X297 public ......... Order ... (Please read the precautions on the back before filling in this page) -47-Α3 %% 2 鼙 鼙 83101176 Patent Application Chinese Specification 傪 正 IT 民 β 84 12 12 ΛCounty Α7 Β7 Alkenyl-4,7 6 Printed by the Staff of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 5. Production Description (46). L __ ^ '' C. Synthesis of Bridged Cyclopentadiene IV ..............-Example 5: 7-Cyclopentadiene-4'4,7-Trimethyl-4,5,6,7 —Tetra nitrogen—1 Η — Synthesis of ερ 50 ml of degassed water at 0 ° C Next drop-by-drop was added to 7.35g (23.5 mmol) in 50 ml of diethyl ether A suspension of two lithium salts (Example 2). During this process, the beige suspension quickly disappeared and a clear and orange diethyl ether phase was obtained. This phase was then separated in a separatory funnel, and then the aqueous phase was extracted twice with 25 ml of diethyl ether each. The combined organic phase was washed with 20 ml of a saturated sodium chloride solution and dried over magnesium sulfate. After the solvent is removed in vacuum, isolation is used to generate 5.1 g (9 6%) of a orange-red oily hydrolysate. Example Preparation of Methyl-7-Phenyl-4 7-Tetrahydro-1H-Tor 3.36 g (9.72 mmol) of the dilithium salt in 50 ml of diethyl ether (Example 3) The yellow suspension was hydrolyzed by slowly adding 20 ml of degassed water under cooling to 0 ° C. During this process, the suspension disappeared and a clear and yellowish reaction solution was obtained. After the mixture was extracted twice with 20 ml of diethyl ether each, the combined organic phases were washed several times with a saturated aqueous sodium chloride solution and dried over magnesium sulfate. Then, when the solvent was removed in vacuum, the paper was produced in a yellow oily form through segregation. According to the standard of CNS > A4 (210 X 297 cm) ^^^ 1-m HI n ^ i af am— ml an— ai (please read the precautions on the back before filling out this page)-48-Printed by the Ministry of Economic Affairs, China Industrial Standards Bureau, Consumers Cooperatives 51 51 438827 A6 B6 V. Description of the invention (47) Hydrolysate, Its yield was 9.4% (2.6 2 g). Example 7 7—Cyclopentadienyl-4,7-dimethyl-7-butyl-4,5,6,7-tetrahydro— Preparation of 1H-tritium 3.64 g (9.72 mmol) of a yellow suspension of the dilithium salt (Example 3) in 50 ml of diethyl ether was cooled to 0 ° C by slow addition of 2 0 ml of degassed water for hydrolysis. In the process, the suspended hips disappeared to give a clear and yellowish reaction solution. After the mixture was extracted twice with 20 ml of diethyl ether each, the combined organic phases were saturated The aqueous solution of sodium chloride was washed several times and dried over magnesium sulfate. Then, after the solvent was removed in the air, a yellow color was formed by separation. The yield of the hydrolyzed product was 96% (4.59 g). D. Synthesis of the bridged cyclopentadiene-fulvene ligand IV a via a substituent introduced later Example 8 7- ( 70 — (34.0) Synthesis of 3-isopropylidenecyclopentadienyl_1,4) -4,4,7-trimethyl-4 »5 '6,7-tetragas-1H Mol) of cyclopentadienyltetrahydrofluorenyl (Example 5) was dissolved in 70 ml of methanol and cooled to 0 ° C. 2. 9 g (51.0 mmol) of acetone and 4. 83 g (68.0 mmol) of pyrrolidine was added to the orange-red reaction solution successively. After the mixture was stirred at G ° C for 5 hours, it was stirred at room temperature for 2 ^ ..... ....... ίτ ........................ Please read the precautions on the back Write this page) This paper uses the Chinese national standard (CNSI A4 size (210x297 mm > -49-4388 2 7 A7 B7____ V. Description of the invention (48)) (Please read the notes on the back before filling in This page) hours to complete the reaction and 4 ml of glacial acetic acid was added before the reaction was completed. The clear and reddish reaction solution was hydrolyzed by 200 ml of water The yellow suspensions were each extracted 3 times with 50 ml of diethyl ether. The combined organic phases were washed several times with a saturated aqueous solution of sodium chloride and dried in magnesium sulfate to produce orange-red and rich waxy residue. Yield, its yield is 88% (8.0 g) ° E. Synthesis Example of Dianion Complex V a 4-[3-tert-butyl (7? 5-cyclopentadienyl)-4 , 7,7_ Trimethyl () 75-tetrahydrofluorenyl)] dilithium synthesis Tetrahydrofluorenylfulvene (Example 8) and methyl lithium solution of ether (2 equivalents) react at 0 ° C and After only a few seconds, a precipitate of intense yellow was formed. The mixture was stirred at room temperature for 12 hours and filtered and washed with pentane. When dried in an oil pump vacuum, a dilithium salt was formed, which was a direct reaction without additional treatment. Central Samples Bureau, Ministry of Economic Affairs, Shellfish Consumption Cooperation, Du Printed F. Synthesis of Metallocenes of Chemical Formula I Example 10 [4-((?? 5-cyclopentadienyl) -4,7,7-trimethyl (J? 5.4, 5'6, 7-tetrahydrofluorenyl)] Synthesis of zirconium dichloride 7.50 g (32. 2 millimoles) of zirconium tetrachloride in time intervals of 1 ◦ minutes Add to 9.58g cooled to -78 ° C (This paper is suitable for China @ 家 橾 准 （CNS） 八四 秘 （210X297mm） -50-438827 Printed by A6 __B 6 V. Description of the invention (49) 30.7 millimoles) A suspension of the dilithium compound (Example 2) in 2.0 ml of toluene. After the mixture was stirred at room temperature for 50 hours, the precipitate was filtered off and the orange filtrate was evaporated to dryness in the air. After washing several times with pentamidine, 4.38 g of orange-yellow powdered zirconocene dichloride was produced, and its crude yield was 37%. For purification, orange-yellow powder is extracted with pentane in a circulating filter for several days. After the solvent is removed in the air by an oil pump, 1.70 g (14%) of yellow powdery chromium dichlorocene is formed. , Its melting point is 2 2 3 ° C (decomposition type of DSC). Example 1 1 [Synthesis of 4- (7? 5-cyclopentadienyl) -4,7,7-trimethyl ("5_4,5,6,7-tetrahydropine)] 5 4 6 g (17.5 mmol)> The etherified dilithium suspension in 200 ml of toluene was cooled to 78 ° C and 3.3 g (17.5 mmol) of tetrachloride was added. Titanium. The reaction solution quickly turned dark red. The mixture was stirred at room temperature for 30 hours. The insoluble components were filtered through a filter. The dark red toluene phase was evaporated and dried in the air by an oil pump. 1. 8 g of brown-beige powdery titanocene dichloride. The crude product was then extracted with pentane in a circulating filter for several days. After the solvent was removed, a brown solid was formed. Titanocene chloride has a yield of 13% (780 mg) and a melting point of 259 ° C (decomposition type of DSC). (Please read the "Cautions on the back side" before filling out this page >. Binding and binding · This paper size is in accordance with China National Standard (CNS) A4 specification (210 > < 297g *) -51-Central Industry Standards Bureau, Ministry of Economic Affairs, 3 Industrial Consumer Cooperative, India 438827 A6 B6 V. Description of the invention (50) Example 12 2: Derived from 2,5-bis (2,4-cyclopentadienyl-1) hexamethylene [4- (75-cyclopentadienyl) A 4,7,7-trimethyl ("5_4,5,6,7_tetrahydropinyl)] a gaspable synthesis

62.4 ml (99.8 mmol) of ether in a 1.60M methyllithium solution was slowly added at 0 ° C to 1 ° S (47. 5 mmol) in 150 ml of toluene. A solution of 2,5-bis (2,4-cyclopentadienyl-1) hexane (Example 1) was stirred vigorously. When the addition is complete, the mixture is stirred at room temperature for 2 to 4 hours and then cooled to a temperature of 30 ° C and 9.32 g (40 mmol) of thallium tetrachloride is added. After the mixture was stirred at room temperature for 30 hours, Li CiZ was filtered off and the filtrate was evaporated in the air and dried and then washed several times with pentane to produce 4.02 g (26%) of zirconocene dichloride. Example 1 3: Two kinds of [4-((5-? Cyclopentadienyl) _4,7-dimethyl-7-phenyl (7? S-4,5,6,7-tetrahydrofluorenyl) )] Synthesis of dia-stereomers of dichlorozirconium (dia-stereomers) 2. 7 2 g (11.7 millimolar) of chromium tetrachloride was gradually added to cool to 78 t: 4.3 A suspension of 7 g (11.7 millimoles) of dilithium salt (Example 3) in 200 ml of toluene. The mixture was warmed to room temperature and the yellow suspension was stirred at 20 ° C for another 20 hours. After filtration, the solvent was removed from the filtrate in an oil pump and the orange-red powdery oily residue was vigorously stirred in 20 ml of pentane to make a powder. Pick up

This paper size is applicable to China Solid B Standard (CNS 丨 T4 is now standard (210X297 male: SH installed ......... Order ...) ...... line (please read the notes on the back before filling in this page) • 52 Printed by the Central Standards Bureau of the Ministry of Economic Affairs S Industrial Consumers Cooperative Society 438827 A6 B6 Description of the invention (51): After the pentane is removed in the air, it can produce 2. 6 4 ^ (50%) orange yellow powdered dichloromethylene chloride. The 1H-NMR spectrum of the crude product shows diastereomerism. The ratio of isomers is about 8: 1. Example 14: Two kinds of [4- — (”5-cyclopentadienyl) — 4, 7 —dimethyl — 7 monobutyl (? 75-4, 5,6,7-tetrakisyl)] Synthesis of diastereomeric diastereoisomers 7.8 g (22. 0 mmol) dilithium salt in 200 ml toluene (Example 4) The suspension was cooled to 78 ° C and 5.10 g (22.0 mmol) of zirconium tetrachloride was gradually added. The mixture was heated to room temperature and the orange suspension was stirred for an additional 4 8 hours. Insoluble The ingredients are decanted through a filter and the solvent is removed in the air by an oil pump. The orange-red oil is vigorously stirred in pentane to make a powder, which produces The crude yield of zirconocene dichloride was 30% (2.72 g). Purification was performed by extracting the crude product in a circulating filter with pentane for several days. IH-NMR of the yellow fine precipitate Contains two signal groups with a ratio of 15: 1. The filtrate through a siphon is stored at 30 ° C to isolate a few crystals. This type of pure zirconocene dichloride crystals with diastereoisomeric properties (PR, 4R , 7R-4-(T? 5-cyclopentadienyl) -4, 7-dimethyl-7-butyl (?? 5-4, 5, 6, 7-tetrahydrofluorenyl)] dichloro锸) 1H-NMR can indicate each signal group. The crystals crystallized from the pentane solution are equivalent to the minimum limit. (Paper size 4 is applicable to National Standards (CNS) Grade A 210 × 297 mm) ~ — -53 _ .............................. ............................................................ ........... Order .............. line (please read the precautions on the back first and then use this page) Ministry of Economic Affairs 35gPrinted by the Central Bureau of Standards, M, G, and F Cooperatives 438827 A6 B6 Fifth, the description of the invention (52) degree of diastereomers. Crystals can also be 1.35g (14%) was obtained by the isolation of a yellow fine powder, which was a solution of approximately 1000 mg of powder in a small amount of methylene chloride and allowing methane to diffuse into the solution to crystallize very slowly. The main product is another diastereomer. Example 1 5: 4- (J75-cyclopentadienyl) -4,7-dimethyl-7-butyl ("5-4,5,6,7-tetrahydrofluorenyl)] dichloro Synthesis of lead 1.81 g (5.5 65 mol) of zirconium tetrachloride was added to 2. 0 g (5.64 mol) cooled to a 78 eC> two in 150 ml of toluene Lithium salt (Example 4) suspension. The yellow suspension was heated to room temperature and stirred for another 2 days to complete the reaction. Insoluble ingredients were filtered through a purifier: the orange filtrate was dried in an oil pump by evaporation. 30 ml of pentane was added to the orange-red residue and the mixture was stirred vigorously overnight. After the solvent was removed in the air, a beige powder of hafnocene dichloride was formed, with a crude yield of 7 0 0 Mg (24%). The 1H-NMR spectrum of the crude product shows only one diastereomer. Example 16: Two 4— (π5—cyclopentadienyl) -4,7-dimethyl groups _7 —Butyl ("5-4,5,6,7-tetrahydrofluorenyl)] Synthesis of diastereomers of titanium dichloride 5.9 5 g (16. 8 mmol) Dilithium salt (Example 4 ϋ scale applicable National Standard i CNS) A 4 ^ grid (210X centimeters) ~ -54-............ ........................................ ... installation ............ order ......... line { (First read the meaning on the back of the page and then fill in this page) 438827 Printed by A6 B6 of the Ministry of Economic Affairs, Central Bureau of Standards, M Industry and Consumer Cooperatives V. Description of the invention (53) When g (16.8 mmol) of titanium tetrachloride was added to the suspension at -78 ° C, the beige suspension immediately turned dark red. The suspension was stirred at room temperature for another 3 to 6 hours. After the precipitate was filtered off, the dark red filtrate was dried by evaporation in the air of an oil pump. This resulted in two diastereoisomers of titanium dichloride, which was a brown-red powder and had a crude yield of 1.54 g (24%). The 1H-NMR spectrum of the crude product showed the signals of two diastereomers in a ratio of 8: 1. The brown-red powder was extracted with pentane in a circulating filter for several angels to obtain a brown precipitate which was allowed to settle in the filtrate. 1H — NMR spectrum showed that the pentane solution contained 1: 1 isomers (150 mg, 2.3%), while the brown powder (720 mg, 11%) was pure non-paired Enantiomers. Example 17: {4_ [3 > _ tert-butyl (J75 —cyclopentadienyl)]-4,7,7-trimethyl (7s-tetrahydroruthyl)] synthesis of dichloro pin 2.8 A suspension of 4 g (7.71 mmol) of a lithium salt (Example 9) was suspended in 150 ml of toluene and cooled to -78 ° C. After 1.79 g (7.71 mmol) of chromium tetrachloride was gradually added, the mixture was warmed to room temperature and carried for 4 8 hours. Next, the insoluble components are filtered out and the orange toluene phase is evaporated to dryness in the air of an oil pump. The orange-red oil is vigorously stirred in pentane to make a powder and thus an orange-yellow powdered zirconium chloride is formed. The crude yield was 23% (787 mg). The 1H-NMR spectrum of the crude product shows two ratios of 1: 1. The paper size is applicable to China National Standard (CNS) A4 specification [210x297 mm 1 " -55-.......... ........................................ .......... ^ ...................... " ............... ...... ^ (Please read the precautions on the back before filling in this page) 438827 A6 B6 Printed by the Economic and Central Bureau of Standards, Bureau of Industrial and Commercial Cooperatives V. Description of Invention (54) Diastereomers The signal. The orange powder was extracted with pentane in a circulating filter to produce 370 mg (11%) of zirconocene chloride at a ratio of 1: 1. Synthesis of G-Dialkylene Metallocene Complexes Example 18: 4-(π5 -cyclopentadienyl) -4,7,7-trimethyl, 5,6,7 -tetrahydropine)] Synthesis of dimethyl zirconium According to the step [b] in the literature * 3. 30 ml (5. 33 mmol, 1. 60 M) of a methyl lithium solution of ether at -7 ° C. was slowly added to 1 A suspension of 03 g (2.66 mmol) of chromium dichlorochloride (Example 10) in 50 ml of diethyl ether. The mixture was slowly warmed to room temperature in a cooling tank and stirred at room temperature for 5 hours. The solvent was removed in the air and the colorless residues were each extracted 3 times with 50 ml of pentane. The combined pentane solution is evaporated and stored at-2 5 ° C for crystallization. The solvent was removed via a siphon and dried in the air with an oil pump to produce 700 mg (7 6%) of dimethylchromocene as a colorless crystalline powder. [B] E. Samuel, M.D. Rausch, J. Am, Chem. Soc. 95 (1973) p. 6263.聚合. Polymerization Example General Inspection Steps Copolymerization of methylaluminoxane into 5 G 0 ml polymerization reaction This paper size applies Chinese National Standard (CNS > 肀 4 Specification (210x297) ... ........................................ ............................................................. .. Order .............. line (please read the precautions on the back before digging into this page > A7 438827 _______B7_ 5. Description of the invention (55) (Please read the precautions on the back before filling out this page) The solution is dissolved in 250 ml of toluene in the device, and the solution is cooled to -50 ° C. Propylene passes through the solution through the gas-inlet tube and thus For condensation, excess propylene can be discharged through the bubble meter. When the desired amount of liquid propylene is reached (approximately 30_35 ml), the intake pipe is closed. When the temperature reaches a level, add a little toluene Catalyst solution. After an appropriate reaction time, the reaction is ended in hydrochloric acid by adding 5 ◦ 0 ml of methanol. When the solution boils violently, excess propylene is discharged. Polymer Isolate by separating the toluene phase and extract the water / methanol phase with diethyl ether. The combined toluene and diethyl ether phases are then evaporated to dryness in vacuo. The experimental results achieved are shown in the table below: Using metallocene / Polymerization of propylene in methylaluminum pentane catalyst system, in which * the metallocene used is 4- (? 5-cyclopentadienyl) _4, 7, 7-trimethyl 4 * 5, 6, 7 — Tetrahydrofluorenyl)] Chromium dichloride (Example 10), 4-(?? 5-cyclopentadienyl) -4,7,7-trimethyl (? 75-4,5,6,7 —Tetrahydrofluorene-based]] Titanium dichloride (Example 11). The paper size printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (21〇 × 297); -57-Printed by the Consumers 'Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 438827 A7 B7 I ~.' .ΝΊ V. Description of the Invention (56) Polymer catalyst temperature [° c] Time [minutes] Catalyst [mg] Total contact Medium / catalyst ratio polypropylene [g] Active M 7 Example 11 0 120 22 500 11.2 1300 9000 10 Example 10 -5 240 20 320 29.5 1500 2100 12 Example 10 70 60 10.6 2200 1000 13300 300 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CMS) A4 specification (2 丨 OX 297mm) -58-438827 A7 e 2 ';

_I 1 M V. Description of the invention (57) In all examples, a 10.6% strength methylaluminosin solution in toluene was used as a cocatalyst. Activity is calculated according to the following formula: Activity = PP / ((Μ) _ t _ P) PP = content of polypropylene, unit is g, [M] = content of transition metal in catalyst, t = period, unit is Hours, P = pressure in bar. An oligomer having a Mn of 100 to 800 g / mole. 1 ^^^ 1 ^^^ 1 In mt-----i-i V 1 " -5 (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size is applicable to China National Ladle Soap (CNS) A4 (210 X 297 mm > 438827

Attachment 1㈤: Patent Application No. 83101176 Chinese Example of Preparation of Chinese Metallocene Amended in December, 1984

Example I a) Synthesis of 2,7-dimethyl-5- (1-cyclopenta-2,4-diazyl) -4,5,6,7-tetramushroom: 'will 1. as (25 5 mol) solution of cyclopentadienyl lithium in 20 ml of tetrahydrofuran was added to 2.58 at -20 ° 〇: 1.0-1.0 mol) 5-bromo-2,7-dimethyl-4,5, In a solution of 6,7-tetrahydropine in 50 ml of tetrahydrofuran, the mixture was stirred at 0 C for 6 hours, and then hydrolyzed with 50 ml of ice water. The product was taken up with pentane, and the organic layer was washed with 80 ml of ice water It was dried 4 times with sodium sulfate and the solvent was removed under vacuum. The crude product was decanted by decantation method (SiO2, Wuyuan / Erqijiayuan, 20/1). Yield 0.46s (20%) of 2,7-dimethyl-5- (1-cyclopentane-2,4-diazyl) -4,5,6,7-tetrahydrostation (double bond isomerism Mixture of things) 〇

b) Synthesis of [2.7-dimethyl-5- (1-cyclopentyl-2,4-diazyl) -4,5,6,7-tetrakis 15-yl] -dioxo Volume solution of butyl lithium (1.6M in the hospital; 4.9 mils) ^ 38827 was added to 0.9 g (2.4 mmol) of 2,7-dimethyl-5- (Cl- Cyclopentyl-2 · 4-diaphthyl) -4, 5,6,7-tetrahydropine in 30 ml of diethyl ether solution, and then slowly add 0.6 g (2.6 mmol) of tetrakis to 20 Add millilitres of diethyl ether, and take an hour to form an orange suspension. Remove the solvent under low pressure, extract the residue with hot heat and overfill it, and prepare ochre yellow crystals in your own tincture. Yield: 0,39s (1.1 millimoles; 44¾) of [2,7-dimethyl-5- (1-pentamyl-2,4-diazyl) -4,5,6,7-tetrakis Hydrogen radical] two gas junction.

Example II a) Synthesis of 5- [3-ethyl- (1-cyclopent-1,3-dialkyl)]-7.7-dimethylbicyclo [5.3.0] deca-1,3-diene : 4.0S (40 ml mole) of ethylcyclopentadiodiyl lithium in 40 ml of tetragas n-furan solution was added at 6.20 (24.9 millimoles) 5- Mo-7 , 7-Dimethylbicyclo [5.3.0] deca-1,3-diamine in 200 ml of solution, the temperature does not exceed, mix the quinqueline compound for 4 hours, then add 200 ml of ice water to hydrolyze It was extracted with pentane, and the orange tincture was washed three times with 100 ml of ice water. It was dried with sodium sulfate, the solvent was removed under reduced pressure, and the crude product was purified by chromatography (Si02 · pentan / ethyl acetate, 40/1). Yield: 3.4s (54%) of 5- [3-ethyl- (1-cyclopent-1,3-diazyl)]-7,7-dimethylbicyclo [5.3.0] deca- 1,3-dilute (mixture of double bond isomers). 2- 438827

b) Synthesis of [5- [3-ethyl- (1-cyclopent-1,3-diakyl) -7,7-dimethylbicyclo [5.3.0] deca-1,3-dilutel ] Two gas wrong: 15 ml of n-butyllithium (1.6M in the hospital; 24 millimoles) was added to 3.0g (11.8 millimoles) 5- [3-ethyl- (1 -Cyclopentyl-1.3-dioxo)] 7, 7-dimethyl-bicyclo [5.3 · 0] deca-1,3-dioxane in a solution of 60 ml of diethyl and 10 ml of tetrahydrofuran, 30 A yellow solution was formed within minutes, followed by stirring for 2 hours, and a solid 2. (12 mil) tetrahydrojunction was added. The orange slurry was stirred at room temperature for 2 hours, and then the solvent was evaporated under reduced pressure. Yellow crystals were prepared in the alkane solution. Yield: 2.0 g (4.8 millimoles; 41¾) of [5- [3-ethyl- (1-cyclopent-1,3-dioxyl)]-7,7-dimethylbicyclo [5.3 .0] ten-1,3-diphenyl] = gas pin.

Example III a) Synthesis of 5- (1-cyclopentyl-1,3-diaphthyl) tricyclo [8.3.0.07,12] Thirteen lime-1,3, dilute: fill·lg (15 millimoles ) A solution of cyclopentadienyl lithium in tetragas furan was added to 3.0 g (10 · 0 mmol) 5-iodine-triamidine at 3- 438827 -60 ° C [8.3.0.07.12] ten Tricarbon-1,3-diamine was dissolved in a solution of 50 ml of diethyl _ and 20 ml of tetrahydrofuran, and the temperature rose to or within 1 h when the mixture was stirred, and the solution was hydrolyzed with 50 ml of water. The mixture was then slaughtered with Wuyuan, and the orange layer was washed 4 times with 50 ml of water, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The crude product was purified by chromatography (Si02, E House / Er Qi Jia Yuan, 18/1). Yield: 0.67s (28%) of 5- (1-cyclopentan-1,3-diflammyl) tricyclo [8.3.0.07,12] tridecyl-1,3-diene (double bond isomerism) A mixture of things).

b) Synthesis of [5- (1-cyclopentyl-1,3-diluted) tricyclic [8 · 3.0.07,12] Thirteen Stones and -1,3-dialkyl] Dioxo: 2.8 A solution of n-butyllithium (1.6M in the courtyard; 4.5 millimolar) at 0.5 ° C was added to 0.5s (2.1 millimolar) 5- (1-cyclopenta-1,3-di Dilute group) Tricyclic [8.3.0 · 07,12 Thirteen positions-1,3-Diamine in a solution of 30 ml of diethyl acid and 3 ml of tetrahydrofuran, stir the light yellow solution at room temperature for 2 hours , And then reacted with 0.51s (2.2 millimolar) four gas junction (solid) to form a yellow suspension, and searched for 2 hours, then, the solvent was removed under reduced pressure, the residue was extracted with diethyl ether and cleaned. In other words, the crude product was crystallized several times with diethyl ether to obtain yellow crystals from diethyl ether. Yield: 92 mg (0.23 mmol) of [5- (1-cyclopenta-1,3-dienyl) tricyclo [8.3 · 0.07,12] tridecyl-1,3-diaperyl] di气 ία 〇4— .4 3 BB 2 7

438827 Annex 2 (¾: Patent No. 8310117 (3) Chinese Polymerization Example

In December of the Republic of China, the revised examples A-M: General experimental steps: Add a methyl laxinoxane co-catalyst to a 500 ml reactor, dissolve in 250 ml toluene and cool to -50 * 0, C Suspected to flow through the solution through the inlet pipe and condense, excess propylene leaked out through the bubble meter, as long as the amount of liquid propylene has reached the required amount (about 30 to 35 ml), close the inlet pipe, and then adjust the required polymerization temperature Then, the catalyst was added in a small amount of toluene solution. After an appropriate reaction time, 500 ml of methanol in hydrogen acid solution was added to terminate the reaction. When the solution was boiled violently, too much propylene was released, and the polymer was separated by separating the toluene phase • The water / methanol phase is extracted with diethyl acid, and the mixed toluene and diethyl ether are evaporated to dryness under vacuum. The experimental results obtained are shown in the following table: Using the ansa ergometall / methyl-Mingqiyuan catalyst system, the erro metal is used as 4- (r? 5-cyclomacrolein) -4,7,7-trimethyl (η 5_4,5,6,7-tetraarginyl) digas (a) · 4- (ϊ7% cyclomethylenedioxanyl) -4,7,7- Trimethyl (7? S-4,5,6,7-tetrahydrofluorenyl) digas junction (b) and 4- (77 5-cyclocenedienyl) -4,7-dimethyl-7 -Phenyl (r? S_4,5,6,7-tetrahydrazone anvil base) 4 3 88 2 7 mm T Pci lion mD Cat- ㈣ C «« afcr / d4t. Tula ft 【• J Mil λ 蠹 1 m aa ·. »4 aj n-ft o -10 HD 1 * 110 4 · 7 3B4 f · 丨 fl〇4 ΰ -44“ A 1 «S.» m noaoo fi 4} oo Δ4Α 1 »… C« 0 aiovftft -40 ΛΜ 1A 9 »i £ ft〇at -H u〇11 ftia 11.1 me U0D0 4 4) fl 130 11 (00 nee ^ J * ft« t hi * 10 3 & 0 IQ »» 1A atooo 1 hi «A £ no £ .1 m llftOO A) 10 aao 3, .C 1SO0 ai «e X h} u uo 34 caa l« 'l-L%) 1Λ «0 10.« Aloe 100A moe-U ok Oft 34 «1« m 1 '· In all cases, the total catalyst concentration used was 10.6% by weight Solution), the calculation of activity is based on the following equation: Activity = gPP / g [M] * t * P) where gpp = polypropylene (g) gtrih amount of transition metal in the catalyst t = residence time (Hours) P = calendar power (bar)

Example N a) Preparation of the catalyst component [4- (r? S-cyclocenelocene dialkyl) -4,7,7-trimethyl (n s-4,5,6,7-tetra 438827 counterfeit Based) Dichloride junction (such as EP567,952—supported on SiOz) b) Gas phase polymerization of ethylene in a steel autoclave with a bright wall of 2 dm3, the polymerization of ethylene in a gaseous state, by The shape of the mixer suitable for the wall of the autoclave helps to form a fluidized bed. Start by adding 10 g of polyethylene powder as a seed bed. Use a burette to count the total amount of catalyst (2 millimeters). Mol triisobutyl aluminum in 2cm3 isoprene), Is catalyst mixture (25.8 micromole Zr) was added, and the polymerization reaction was carried out at 80 ° C and ethylene for 8 bar for 1 hour, and then the autoclave was released. The M force in the device terminated the reaction. A 36 s polyethylene glycol having a VN of 70 ml / g was obtained, corresponding to the activity of a PE / s metallocene of 3.6 ks. Example ο-τ Clean the 1.5dm3 reactor at 20 ° C to remove the aromatic compounds in the reactor, add gasoline with a boiling point of 100 to 1201, and inject 2 barium and release the calendar power, so heavy Cover 4 times to remove the remaining nitrogen in the gas phase space of the reactor, and then add the toluene solution of 3.75dm3 methyl group gas courtyard. The reactor is heated to 30 ° C and the mixture is stirred (search speed 500rpm). Prepare to add monomers (JE and 5-ethylene-2-raw ice M (see table)). In parallel, 0.125 mg of diocenyl 4- (rj s-3 methyl-cyclopentanediyl) -4,7,7-trimethyl (η 5-2-methyl-4,5,6, 7-tetrahydrozhuangji) dichloride pin was dissolved in 1.25cm3 methyl bromide compound (1.67 mils A, n = 18) in toluene to dissolve 4388 2 7 liquid, and left for 15 minutes for complete reaction, and then the solution Add to the reactor, and heat the polymerization reaction to 5010, and properly cool to maintain the temperature at 50 ° C, add 2 ml of isopropanol to stop the reaction, pour the reactor contents to acetone and Dry under vacuum at ° C to precipitate the polymer (stabilized with Irganox 1010, 0.1 wt%, stabilized). The polymerization results are shown in the table below. Table: Copolymers and Terpolymers terpoiTMire 2-BftKilDXMM EiW) tIbu tHg VN: · fa mm ZM kr w ^ ti «V» {% hjf 〇a. A os-»i M. -1S ^ Ϊ.3 '— ί W 12 41 -S5- »35.D-0 u 3L.D i.as m; n • 45 JL box-· as 1.» 24-n -SU B X.9 1.0 19! si -4C.5 * · -2, • Rui L. # 3 ... > 0.0 _ SB -IX. »You · 13-3 Implement a 600cm3 solution of 180cm3 styrene (distilled under reduced calendar) in toluene to 1.5dm3 The autoclave (washed with Ar in advance), through continuous injection (1 bar) to make the solution contain saturated Ar, 10cm3 of methyl ether gas toluene toluene solution (concentration of 10.1% by weight of methyl group gas hospital solution, According to the freezing point reduction method, its molecular weight was 1300 g / mol). It was placed in the reactor in the reverse direction, and after pre-activation for 15 minutes ^^ 27, 10 mg of 4- (η 5 -isopropylcyclocene dimethanyl) -4,7.7_ Trimethyl (η 5-4,5,6,7-tetrakisyl) digas is added to the toluene solution of 10cm3 methyl bromide compound (to adjust the molecular weight with argon, Inject hydrogen at this time.) Search: Stir for 2 hours to polymerize the mixture, and the temperature is maintained at 70 = 0. When the reaction is complete At this time, pour the polymerization mixture into a container, and immediately add 5dm3 of ethanol, stir the mixture for 10 minutes, filter the precipitated product, and wash the cake with 3% thoronic acid and ethanol 3 times, then wash with water until it becomes neutral, and the residue The product was searched and mixed in ethanol and then filtered, and the purified product was dried under vacuum (0.2 bar) and 80 ° C for 1.5 hours. The 5.2 g of polymer obtained after drying had a glass transition temperature of 102 ° C. Implementation 111: Add a solution of 180cm3 cage of hoof (evaporated and retained under reduced temperature) in a solution of 600cm3 in toluene to a 1.5cin3iS heater (washed with ethyl acetate beforehand). Saturated ethyl acetate, 10cm3 toluene solution of methyl coke gas house (concentration of 10.1% by weight of methyl aluminum oxygen house solution, with a molecular weight of 1300g / mol according to the freezing point reduction method) was added to the reactor in a reverse metering manner, and after 15 minutes of preactivation In 10ms, 4- (π 5-isopropylcyclopentadienyl_4,7,7-trimethyl (r? 5-4,5,6,7-tetramethyl group) is formed in a gas. Add to the 10cm3 toluene solution of Kejin Gas Institute (to adjust the molecular weight with hydrogen, you can inject hydrogen at this time). For 1 hour (750 rpm), the injection pressure is too acetate acetic too kept at 1 bar and the reaction temperature was maintained ordered rows polymerization reaction mixture under conditions of 70 ° C by the performance. ^ 827827 The mixture was polymerized for 2 hours, at which time the temperature was maintained at 701. When the degree should be completed, pour the polymerization mixture into a container, and immediately add 5dm3 ethanol, stir the mixture for 10 minutes, filter the sanitized product, and wash the filter cake 3 times with 10% hydrogen acid and ethanol alternately, and then wash with water until It became neutral. The residue was stirred in ethanol and filtered again. The product purified in this way was dried for 15 hours under vacuum (0.2 bar) and 8 CTC. After drying, 21 g of a colorless polymer was obtained, which had a glass transition temperature of -24T: and a viscosity of 30 cm3 / s. Example V: To prepare a catalyst solution, 10 mg of metallocene A was dissolved in 10 ml of MA. In the solution, the mixture was stirred for 15 minutes. In parallel, 900 ml of diesel oil (boiling point 100 to 1200 was charged into a 1.5dm3 reactor with a stirrer, the temperature was adjusted to 70 ° C, the catalyst solution was added, and the mixture was polymerized at 750 rpm and a pressure of 7 bar for 1 hour. Then release the pressure in the reactor, filter it to separate the polymer from the suspension, wash it with acetone, and dry it in a vacuum drying box for 12 hours to obtain 39.2 g of polypropylene with a VN of 72 m i / s. Examples W to EA:

5 巴 ， 此 使 氢 历。 Repeated Example A using a specified amount of two metallocenes 1 to 5, the polymerization temperature of Example BA and DA were 50 and 85, and the hydrogen calendar power in Example X and EA is 0.5 bar, so that the hydrogen calendar The sum of the force and the suspected pressure is 7 bar. 1: [4- (r? S-Chenmobienyl) -4,7,7-trimethyl (η 5-4,5,6,7-tetrahydropinyl)] digas. 2: [4- (r > cyclocenedioxo) -4,7-dimethyl-7-butyl ((η 5-4, 5.6.7-tetrahydropinyl)] dichlorotriol. 3: [4 ~ (Γ7 5-Badecenedienyl) -4,7-dimethyl-7-phenyl C (n s-4, 5.6.7-tetrahydro 15yl)] two gas junction. 4: [ 4- (715-3-methylcyclocene dienyl) -4,7,7-trimethyl (775-4, 5.6.7-tetrahydrozinyl)] dichloride. 5: [4- ( η 5-3-methylcyclocenedienyl) -4,7,7-trimethyls-4, 5.6.7-tetrahydrozinyl)] dichloro junction. SMIJ ZiS6 «2 [Bar] 1 See kg / g ^ νκ t * c | [Bar], t« N ¥ 1 1% ϊ # 1 0 a.41 Ϊ% 1 19 τ «es 1.1 a T 1 1« 79 7 0 11.1 10 1 3 Ϊ 1 0 2 T from 4 ί Τ 0 3Τ 11 UL S 7 0 4, 3 n CA «* 7β 7 β 3» 20 U 1 4 II ϊ »f« »4 T« Α * Τ4 I.A 4 438827 Example FA: Add 500 ml of diesel oil (boiling point 100 to 1200 and 20 ml of methyl alcohol and 10% by weight of methyl bromide gas solution in toluene to 10 ml of autoclave for laboratory use) (The strips are filled with air, the temperature is 70.0, and the machine speed is 700 rpm). In parallel, 10 mg of the metallocene 5i is dissolved in a solution of 10% by weight of MAO in toluene. The metallocene / MAO solution and 4 bar of ethyl acetate were injected so that the polymerization degree should start. After 15 minutes, the polymerization reaction was terminated using CO2. The reactor contents were poured into 200 ml of HC1 methanol solution, and the mixture was stirred for 5 hours. After the brocade was removed, the polymer was excessively removed and washed with water, and dried under vacuum at 80 C for 12 hours to calculate the yield. A 4.8 s ethyl 1-hexene copolymer having a VN of 70 ms / g was prepared as Remove residual co The sample of Is was decomposed with hot diesel oil (boiling point 100 to 1200, sinking, filtering, washing with acetone and vacuum drying at 80T :, DSC boiling point was 110.5 ° C, and 13C-NMR showed that 4.6mol%. Example GA: Using 10 rcg metallocene 6 ([4- (τι 5-3-isopropylcyclocenediakyl) -4 · 7,7-dimethyl (r? 5- 4,5,6,7-tetrahydro G group)] Digaso) Repeated as Example J, 4S copolymer with a VN of 22 mg / g was prepared. After purification, the DSC boiling point was 102 ° C, and According to 13C-NMR, the content has been 7.1 mol%. 438827 Comparative Example 1 Except that the difference is 0.5 mg CpaZrC β 2 as the diocene gold tincture, Example FA was repeated to obtain a boiling point of 122π 4.5 g of ethylene-1-hexene copolymer. The amount of 1-hexane contained in the copolymer was about 2.1 mole%.

Claims (1)

§ 8 3 4 Male-Jl · One 22-port A8B8C8D8 / ^ J. · 1 I, | ·-· ^ · f / 六 、 Scope of patent application, f ............ Annex 1 ( a): * Patent Application No. 8 3 1 0 1 1 7 6 ^ Chinese Patent Application Scope Amendment 1949 1 February Amendment 1. A stereo rigid metallocene compound of formula I, < Please read the idea on the back of the page first, and then go to the homepage) ^ -------- Order --------- Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Is titanium 1 1 zirconium, hafnium; M 2 is carbon or silicon; R 1 and R 2 are the same or different and are hydrogen atoms TC 1 —C 1 0 alkyl ′ C 1-C x. Oxygen, C Θ ~ Ci 〇 aryl, C β-C 2 5 aryl, C 2 ~ C x. Alkenyl, C 7--C 4 0 aroyl, C 7 _ C 40 aryl alkenyl, OH or halogen atom, or R 1 and R. 2 and the atoms connecting them together to form a ring system; R 3, R 4 -R 5, R β, R 7, R 8 and R 9 are the same or not and are hydrogen atoms' c 1-C ac, alkyl and may be a dented alkyl, C β — This paper size applies to the Chinese National Standard < CNS) A4 specification (210 X 297 mm> 2 8 8 3 4 rib 880808 6. Application for patent scope c20 aryl; -NR142,-OS i R1 or one S i R base, Where R " is a halogen atom; Ci-C10 alkyl or Ce_C10 aryl or two or more adjacent R3, R4, R5, R6, RT 'R 8 and R 9 groups and the atoms connecting them The ring system R1Q is a hydrogen atom, Ca-C 2. Alkyl, C, C 2 -C: l. Oxygen 3C 1 2 aryl · C6-C 2. Aryloxy, C 7-C 4. Alkylaryl or C 8- c 4. Aryl JS i R Ct—C40 Aromatyl-: The above various groups may have one NR143, or 10 where '14 is a _ atom, Ci — Ci. Alkyl Or ce-c10〒 14 < 谞 read the back first Hyun precautions to fill out this page) η RIS 'I ------ *-II ----- * 5 ^ I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Γ r'H 1 —u —- 1 η R " Rn R ,; 1 I , 1 -C——UJ—c- or R '* R' I c—u odV n is an integer from 1 to 8: x is 0 ′ = NR14, where r " is a halogen atom and Cl — C ID Or C e — C i. Aryl; R 15 is the same as or different from Rie and is a hydrogen atom, halogen element atom This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 male cage) 4388 2 7 A8 B8 C8 D8 6. Apply for a patent Range 'Cl — C !. Alkyl, Cx-Ci. Fluoroalkyl 'C ^ -Cx. Alkoxy 'cs-Ci. Aryl, Ce—Ci. Fluoroaryl, Ce-Cio aryloxy 'c2-Ci. Alkenyl, C7-C4. Aralkyl, C7-C4. Alkaryl or 0-8-c4. Arylalkenyl or two kinds of R15 groups; two kinds of R16 or R15 and R 16 groups; in each case together with the atom connecting them to form one or more rings; M3 is silicon, germanium or tin; R12 and R13 are the same Or different and is a hydrogen atom, Ci-C2. Alkyl, C!-C1 () alkoxy, Ce-C2. Aryl 'Ce-0: 2 (? Aryloxy, C2-C12 alkenyl, C7-C4. Aralkyl' 匚 7- (: 40 alkylaryl or C8-C40 arylalkenyl, the above various groups may be Has -N R143 • or a S 0 i R143 and other groups, where R14 is a halogen atom, Ci-Ci. Alkyl or Ce-Ci. Aryl: various groups or may have a halogen atom P R23 is the same or Different and is a hydrogen atom * Cl—C :. Alkyl, Ci—Cl. Hydroxy 'C6 — Cl. Square group' Ce ~ " C25 aryloxy 'C2 — c10 alkenyl, c7-c4. Arane Group, c7-c40 arylalkenyl or halogen atom; or one or two R2 3 groups bonded to one or two R15 and R 1β groups; and m is an integer of 0 to 4, where R11 is CH2, At least one of R3, R4, Re, R7 and R9 is not hydrogen "2-a catalyst component containing at least one stereo rigid metallocene compound as described in the scope of patent application No. 1 (which is supported and / Or pre-polymerization) and carrier, where the carrier is silicone, alumina, solid aluminum, or its paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---------- -Clothing --- ----- Order -------- '(谙 W read the precautions on the back and fill out this page first >> Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. -3-438827 A8B8C8D8 VI. Application The scope of the patent is that it is an inorganic carrier material or a finely divided polyolefin powder. 3. A method for preparing an olefin polymer, which is characterized by polymerization or copolymerization with at least one olefin and the participation of a catalyst The catalyst contains at least one sterically rigid metallocene compound of at least one transition metal rhenium compound and at least one co-catalyst, wherein the steric rigid metallocene compound is a compound having the formula II in n ί n I— n < n. ^ 1 I nn 1 ^ 1 * —IP K K. I, {Please read the notes on the back before filling in this page) Shellfish Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed M 1 is a HI br] selected from the Periodic Table] [V b • V b or V] [Metal of Group b 1 M 2 is carbon or silicon:-R is the same as or different from R 2 and is hydrogen Atom, C α-c 1 0 Yuan, 'C 1 _ Cl. Ethoxy, Ce-ci0 aryl, C β-C 2 5 aryloxy 'c 2 — 〇1. ^ 〇7— [4〇arylfluorenyl, C 7 —C 4 0 arylalkenyl, fluorenyl or halogen atom, or R1 and R 2 and the atoms connecting them together to form a ring system; this paper size applies Chinese storehouse standard (CNS > A4 specification (210 X 297 males). -4-438827 A8B8C8D8 6. Application for patents: R3, R4, R5, R6, R7, R7, R8 and R9 are the same or different and are hydrogen Atom, Ci — Ci. Alkyl and may be halogenated alkyl, Cs — C2. Aryl:-NR142,-OS i R143, or a Si R143 group, where R14 is a halogen atom; Ci-Ci. Alkane Or Ce-C1 (J aryl or two or more adjacent R3, R4, R5, Re, R7, R8 and R9 and other atoms and the atoms connecting them together form a ring system t R1. Is hydrogen Atom 1 Ci-Cz. Alkyl, Ci-C :. Alkoxyphosphonium, ce-c2. Aryl, Ce-C2. Aryloxy, C2-Ci2 alkenyl, c7-c4. Aralkyl, c7-c4 .Alkylaryl or ce-c4.aralkenyl; the above various groups may have -NR143, or an OS i R1% group, where R14 is a halogen atom 'Cl-c10 alkyl or Ce-Ci. Aryl: R " Yes RIC — * R RI c · _ R 丨 ^ RIX Is111 ηκ H ^ —ν ίκκ an. — C — * .I 11------ [t — '衣' I _ I < Please read the note i on the back before filling this page ) Order --------- line. Printed by R-w R 3 # 1 in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on-cw-Wei J,] 1 f I * 1 c ,,! Ον HL · OR: I c IR RluIR RI w 1 R ,, .— CI-Number 8 to Tx is η This paper size applies Chinese National Standard (CNS) A4 (2W x 297 public love) 2 8 8 3 i ^ · A8B8C8D8 Printed by Shellfish Consumer Cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Patent application scope X is 0 '= NR14, where RH is a halogen atom and Cl-Ci. Yuan or cs—C1 (J aryl: R15 and R16 are the same or different and are hydrogen atom, halogen element atom 'Ci-Cio alkyl, c ^ -Ci. Fluoroalkyl, Ci-C :. alkoxy 'Ce-Ci. Aryl' Ce-ci0 fluoroaryl, Ce-Cio aryloxy. Cz-Ci. Alkenyl 'c7_c4. Aralkyl, C7_C4. Alkylaryl or C8-C4. Arylalkenyl or Two kinds of R1S groups, two kinds of Rie or R1S and R1 6 groups; in each case together with the atoms connecting them to form one or more rings; M 3 is silicon, germanium or tin: RU and R13 are the same or different and Is a hydrogen atom, Ci-C2. Alkyl, 010-010 alkoxy, Ce-C2. Aryl, Ce-C20 aryloxy 'C2-C12 alkenyl, C7-c4. Aralkyl, c7 ** c4. Alkylaryl or c8-C4. Aralkenyl, each of the above groups may have -NR1% 'or -S 0 i R143 and other groups * wherein R " is a halogen atom, Cl — C i. C: .aryl: various groups or may have a halogen atom 1 R23 is the same or different and is a hydrogen atom, Cl-Ci. Alkyl, (^ a c10 alkoxy, Ce-Ci. Aryl, ce- c25 aryloxy, c2-c10 alkenyl, —c40 aralkyl, c7 — c40 aryl Or halogen atom: or one or two R23 groups are bonded to one or two R15 and R16 groups: and m is an integer of 0 to 4 where * when R11 is CH2, R3, R4 * R6 'R7 and At least one of R 9 is not hydrogen. This paper size is in accordance with Chinese Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back of Jing before writing this page) * nn I n I n ^ SIH 1 n ϋ It line--6-4 3 88 2 7, C8 D8 6. Application for patent scope 4. For the method of application for scope item 3, in which the stereo rigid metallocene compound is supported and / Or pre-polymerization. 5. The method according to item 3 of the patent application, wherein the co-catalyst is an aluminoxane. 6. The method according to item 4 of the patent application, wherein the co-catalyst is an aluminoxane. ------------ 'Machine -------- Order—— un B— I 1 (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Cooperative Press 5 ^ This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -7-.JL Application Date No. Annex 3: Article 83101 Chinese patent application No. 6 page manual correction Republic of China was 83,101,176 Class 83 February 15 87 Oct (J, (The above columns are filled by this bureau.) Int. · Cl6f 433S2! Haze | Patent said · The name of the invention invented the new name Chinese metallocene and its use as a bracelet medium. Metal 1ocenes. And the use thereof as catalysts Name Guode (1) Michael * Aulbach, Michael 0, Ende Bachman, Bachmarm, Be, nd (3) Gerhard Erk, E, Ker, Ge, Harci (3) German creative living, Residence (1) Germany0 Germany (1) RheingaustraBe 61, Hofheiro / Taunus, Germany (2! Epstein / Taunus 6 5 8 1 7 Kreifzheck 4, 0 ^ 65817 Eppstein / Taunus, Germany (3) Adolf-Reichwein-Str. 50, Munster, Germany Binding Name (Name) il) Printed by Hoechst Aktiengesellschaft, Hoechst Aktiengesellschaft, Central Consumers ’Cooperative Bureau, Ministry of Economic Affairs, Consumer Cooperatives III. Applicant Line State Clamped 'Home (Office)' Name of Representative⑴ Germany (1) Frankfurt am Main, Germany Main, Federal Republic of Gerraank- (1) Han Jin Zhuoner Zauner, Hans Qiao Jie Lu H Lutz, Jurgen This paper size applies to the Chinese National Standard (cns) A4 size (2 丨 ㈣9) 438827 88. i. P (by this bureau ) Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperatives, Printing Co-operative Codes, Major Category A6, B6 1 PC Classification This case has been applied for a patent to: (country), application date: : December 21, 1993, P 43 43 566.1 0 No claim priority fl Hosting date: Hosting number: --- --- ------------------- order line (please read the first Note: Please fill in each phase on this page) This paper size is applicable to Chinese National Standard {CNS) A4 specification (210X297 mm) 2-1 438827 ΑΊ Β7 V. Description of the invention (! The present invention relates to a stereorigid metallocene compound whose ligands are bonded to each other in a specific manner. The compounds according to the invention can be advantageously used as catalyst components in the preparation of polyolefins. It is disclosed in the literature that the preparation of polyolefins can convert neutral metallocenes to cationic and stable metallocenes. Among them, the preparation of polyolefins is the use of soluble metallocene compounds in combination with aluminoxanes or other co-catalysts and is Because of its Lewis acidity. The use of soluble metallocene compounds based on bis (cyclopentadienyl) dialkyl zirconium or bis (cyclopentadienyl) dihalide as a base, combined with oligomeric indwelling Polymers are not of industrial importance because of their imbalance and insufficient product characteristics. Zirconocene dichloride derivatives can be used as catalysts for iso specific polymerization of olefins due to their consistent rigidity. Among them, two substituted cyclopentanes Dienyl groups are bonded to each other via a methyl, ethylene, or diraethylsilylene bridge. (Chera. Lett. 1989 I pp. 1853–1856, or European Patent Application No. 0 316 155). Metallocenes containing (replaced) indenyl as ligands are particularly important when preparing highly isotactic polymers with high crystallinity and high melting points (European Patent No. 4 8 5 8 2 3 and 5 3 0 6 4 7). However, i is quite noticeable for products with characteristic distributions between the two limits. The purpose of the present invention is to provide a catalyst system 'which can make a 3-438827 A7 R7 i'-f.iX-'. Call charge J V. Description of the invention (2) The polymer preparation has a reduced brightness and Processing temperature sub-quantity and reduced melting point. Therefore, the present invention is a system which contains at least two kinds of cyclopentadienyl groups. Among them, at least one kind of cyclopentane is in a preferred monocyclic or polycyclic system to a monocyclic or polycyclic system. Monocyclic or polycyclic ring systems may or may have substituted ring atoms) 0 Low crystallinity, enhanced impact strength and permeability, high flowability, and low score are related to a stereo rigid metallocene compound The substituted or unsubstituted cyclopentadienyl groups are bonded to each other via a monocyclic or polycyclic ring system, and the dienyl group is fused to a monocyclic or polycyclic ring system. In one embodiment, one cyclopentadienyl group is a substituent, and the other cyclopentadienyl group is fused, which may be aromatic, aliphatic, or a mixture of aromatic and aliphatic. It preferably has at least six ring atoms (the molten cyclopentadienyl group is mono-fused (e.g., via the 1 '2 or 1' 3 position of the cyclopentadienyl ring) or more dense Fused (for example, 1 '2 > 3 or 1, 2, 3, 4-position of the cyclopentadienyl ring), preferably monofused. The preferred metallocene compound has the following Compound (TNS) of chemical formula (1) (210 X 297. >#) 4-A7 4 3 882 7 B7 V. Description of the invention (33 (Ilia) butyl lithium 2 [lithium] c R, 7 (V.) Salts of the structure IIa can be directly converted into related anion compounds of the structure Va by the deprotonation of butyllithium, for example, "bridged metallocene of chemical formula I" The conversion is a reaction corresponding to the transition from structure V to structure V1. Another method for forming a compound according to the present invention includes a monocyclic or polycyclic system reaction such as a cyclopentadienyl compound or a fluorenyl lithium compound, wherein, Cyclopentadienyl is fused and monocyclic or polycyclic ring systems may have functional groups that can act as leaving groups (such as bromide or tosylate) in substitution reactions. . The present invention also relates to a method for preparing an olefin polymer. This method is the polymerization or copolymerization of at least one olefin with the participation of a catalyst. * Among them, the catalyst contains at least one sterically rigid metallocene compound. Metal compounds with at least one cocatalyst: Stereo rigid metallocene compounds contain at least two substituted or unsubstituted cyclopentadienyl groups that act as ligands and the cyclopentadienyl group is via a monocyclic or polycyclic system Whereas, at least one of the cyclopentadienyl groups is fused to form a monocyclic or polycyclic ring system. Wood paper iMUii 川 小 mMUMM (_ns) Λ < ι specifications uiouw 公 筇) " -35-Α3 %% 2Ύ 鼙 83101176 patent claim Chinese specification 傪 zheng IT people β 12 12 years Λ County Α7 Β7 alkenyl —4, 7 6 Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed five. Description of the invention (46). L __ ^ '' C. Synthesis of bridged cyclopentadiene IV ~ ........- · Implementation Example 5: Synthesis of 7-Cyclopentadienyl-4'4,7-Trimethyl-4,5,6,7-Tetrazine-1 Η-ερ 50 ml of degassed water in 0 ° C was added dropwise to a suspension of 7.35 g (23.5 mmol) of the dilithium salt (Example 2) in 50 ml of diethyl ether. During this process, the beige suspension quickly disappeared and a clear and orange diethyl ether phase was obtained. This phase was then separated in a separatory funnel, and then the aqueous phase was extracted twice with 25 ml of diethyl ether each. The combined organic phase was washed with 20 ml of a saturated sodium chloride solution and dried over magnesium sulfate. After the solvent is removed in vacuum, isolation is used to generate 5.1 g (9 6%) of a orange-red oily hydrolysate. Example Preparation of Methyl-7-Phenyl-4 7-Tetrahydro-1H-Tor 3.36 g (9.72 mmol) of the dilithium salt in 50 ml of diethyl ether (Example 3) The yellow suspension was hydrolyzed by slowly adding 20 ml of degassed water under cooling to 0 ° C. During this process, the suspension disappeared and a clear and yellowish reaction solution was obtained. After the mixture was extracted twice with 20 ml of diethyl ether each, the combined organic phases were washed several times with a saturated aqueous sodium chloride solution and dried over magnesium sulfate. Then, when the solvent was removed in vacuum, the paper was produced in a yellow oily form through segregation. According to the standard of CNS > A4 (210 X 297 cm) ^^^ 1-m HI n ^ i af am— ml an— yi (please read the precautions on the back before filling this page)-48-A7 438827 _______B7_ 5. Description of the invention (55) (please read the precautions on the back before filling this page) in the device and Dissolve in 250 ml of toluene, and the solution is cooled to -50 ° C. Propylene passes through the solution through a gas-inlet tube and thus undergoes condensation. Excess propylene can be discharged through a bubble meter. When When the desired amount of liquid propylene is reached (approximately 30 to 35 ml), the air inlet pipe is closed. When the temperature reaches a flat level, the catalyst solution in a little toluene is added. After an appropriate reaction time, the reaction is performed in hydrochloric acid The process was completed by adding 5 ◦ 0 ml of methanol. When the solution boiled violently, excess propylene was discharged. The polymer was isolated by separating the toluene phase and the water / methanol phase was extracted with diethyl ether. Then, the combined toluene and The ethyl ether phase was evaporated to dryness in vacuum. The experimental results achieved are shown in the following table: Propylene polymerization using a metallocene / methylaluminum-methane catalyst system, where * the metallocene used is 4 1 (? 5-Cyclopentadienyl) 4,7,7-trimethyl 4 * 5,6,7-tetrahydrofluorenyl)] Chromium dichloride (Example 10), 4- (?? Dienyl) -4,7,7-trimethyl (? 75-4,5,6,7-tetrahydrofluorenyl)] titanium dichloride (Example 11). The paper size of the printed papers of the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard of Ladder (CNS) A4 (21 × 297); «Η -57-Printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs 438827 A7 B7 I ~. '.ΝΊ V. Description of the invention (56) Polymer catalyst temperature [° c] Time [minutes] Catalyst [mg] Co-catalyst / catalyst ratio polypropylene [gram] Activity M 7 Example 11 0 120 22 500 11.2 1300 9000 10 Example 10 -5 240 20 320 29.5 1500 2100 12 Example 10 70 60 10.6 2200 1000 13300 300 (Please read the precautions on the back before filling out this page) This paper size applies to China National Standards (CMS ) A4 specification (2 丨 OX 297 mm) -58-438827 A7 e 2 '; _I 1 M 5. Description of the invention (57) In all examples, 10.6% strength methyl aluminum in toluene The krypton solution is used as a co-catalyst. The activity is calculated according to the following formula: Activity = PP / ((Μ) _ t _ P) PP = content of polypropylene, the unit is g, 〔M〕 = of the catalyst Transition metal content, t = period, unit is hour, P = pressure, unit is bar. Oligomer with Mη between 100 and 800 g / mole. 1 ^^^ 1 ^^^ 1 In mt-----i-i V 1 " -5 (please listen first Read the notes on the reverse side and fill out this page) The printed paper size of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies to the Chinese National Ladder Soap (CNS) A4 specification (210 X 297 mm > 438827 Attachment 1㈤: Patent Application No. 83101176 Chinese Example of Preparation of Dimetallocene Chinese Revised Example I in Dec. 84 a) Synthesis of 2,7-dimethyl-5- (1-cyclopentane-2,4-dioxin Base) -4,5,6,7-tetramushroom: 'Add a solution of (such as (25 mmol 5 mol) cyclopentadienyl lithium in 20 ml of tetrahydrofuran at 2.50 ° C to 2.58: 0. _1.0 millimolar) 5-bromo-2,7-dimethyl-4,5,6,7-tetrahydropine in 50 ml of tetrahydrofuran solution, the mixture was stirred at 0 C for 6 hours, then 50 ml It was hydrolyzed with ice water, and the product was taken up with pentane. The organic layer was washed 4 times with 80 ml of ice water, dried over sodium sulfate, and the solvent was removed under vacuum. The crude product was decanted by decantation method (SiO2, Wuyuan / Erqijiayuan, 20/1). Yield 0.46s (20%) of 2,7-dimethyl-5- (1-cyclopentane-2,4-diazyl) -4,5,6,7-tetrahydrostation (double bond isomerism Mixture of things) 〇 b) Synthesis of [2.7-dimethyl-5- (1-cyclopentyl-2,4-diazyl) -4,5,6,7-tetrakis 15-yl] -dioxo Butyllithium (1.6M in own hospital; 4.9 mils)-Volume 438827 Annex 2 (¾: No. 8310117 (Chinese Patent Application No. 3 Patent Application Example 3) In December of the Republic of China, the revised examples A-M: General experimental steps: Add a methyl laxinoxane co-catalyst to a 500 ml reactor, dissolve in 250 ml toluene and cool to -50 * 0, C Suspected to flow through the solution through the inlet pipe and condense, excess propylene leaked out through the bubble meter, as long as the amount of liquid propylene has reached the required amount (about 30 to 35 ml), close the inlet pipe, and then adjust the required polymerization temperature Then, the catalyst was added in a small amount of toluene solution. After an appropriate reaction time, 500 ml of methanol in hydrogen acid solution was added to terminate the reaction. When the solution was boiled violently, too much propylene was released, and the polymer was separated by separating the toluene phase. • The water / methanol phase is extracted with diethyl acid, and the mixed toluene and diethyl ether are evaporated to dryness under vacuum. The experimental results obtained are shown in the following table: Using the ansa ergometall / methyl-Mingqiyuan catalyst system, the erro metal is used as 4- (r? 5-cyclomacrolein) -4,7,7-trimethyl (η 5_4,5,6,7-tetraarginyl) digas (a) · 4- (ϊ7% cyclomethylenedioxanyl) -4,7,7- Trimethyl (7? S-4,5,6,7-tetrahydrofluorenyl) digas junction (b) and 4- (77 5-cyclocenedienyl) -4,7-dimethyl-7 -Phenyl (r? S_4,5,6,7-tetrapyrene anvil base) No. 83101176 Patent Application Chinese Specification Revision Page January, 1st year of the Republic of China amended the way to pass through the oligoene to the second class with pentane-like content This ring is suspected to be a kind of species, two-touch, the base one in 1 ^: is the olefin and few things 1. As a combination of two to 88. The use of pentamyl, the genus of the ring: and the gold of its gold to Mao. , Mao attributes take the knot. . King Kong's unbonded system uses molybdenum or relatives to make 4: stand for each other ^ in multiple groups ^ related systems or media ^ there is a ring contact ^ the position ring alone as m Ming match up to full seizures Maybe ^ This is a thick and thick medium, and the species is prepared in English. The abstract of the invention in English (the name of the invention: ABSTRACT OF THE DISCLOSURE Metallocenes / and the use thereof) as catalysts The present disclosure relates to a stereorigid metallocene compound which contains, as ligands, at least two substituted or unsubstituted eye1op en tadi eny1 groups which are bonded, to one another via a monocyclic or polycyclic ring system, except at least one cyclopenta-dienyl group is fused to the monocyclic or polycyclic ring system · The metallocene compound can be used as a catalyst component in the preparation of polyolefins. ----------- 餐 ------ ir ---- --Φ (Please read the notes on the back before filling in the -h columns) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) _ 2-§ 8 3 4 Male-Jl · One 22-port A8B8C8D8 / ^ J. · 1 I, | ·-· ^ · f / 六 、 Scope of patent application, f ............ Annex 1 (a): * Patent Application No. 8 3 1 0 1 1 7 6 ^ Chinese Patent Application Scope Amendment 1949 1 February Amendment 1. A stereo rigid metallocene compound of formula I, < Please read the idea on the back of the page first, and then go to the homepage) ^ -------- Order --------- Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Is titanium 1 1 zirconium, hafnium; M 2 is carbon or silicon; R 1 and R 2 are the same or different and are hydrogen atoms TC 1 —C 1 0 alkyl ′ C 1-C x. Oxygen, C Θ ~ Ci 〇 aryl, C β-C 2 5 aryl, C 2 ~ C x. Alkenyl, C 7--C 4 0 aroyl, C 7 _ C 40 aralkenyl, 0H group or halogen atom, or R 1 and R .2 and the atoms connecting them together to form a ring system; R 3, R 4 -R 5, R β, R 7, R 8 and R 9 are the same or not and are hydrogen atoms' c 1-C ac, alkyl and may be a dented alkyl, C β — This paper size applies to Chinese National Standard < CNS) A4 (210 X 297 mm)