TW490319B - Catalyst composition for preparing olefin polymers - Google Patents

Catalyst composition for preparing olefin polymers Download PDF

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TW490319B
TW490319B TW089115222A TW89115222A TW490319B TW 490319 B TW490319 B TW 490319B TW 089115222 A TW089115222 A TW 089115222A TW 89115222 A TW89115222 A TW 89115222A TW 490319 B TW490319 B TW 490319B
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catalyst composition
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Tung-Ying Hsieh
Jing-Cherng Tsai
Yeu-Ding Chen
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Ind Tech Res Inst
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A catalyst composition including a dicyclopentadienyl organometallic compound, a group IVB metal compound, and a cocatalyst. Both cyclopentadienyl groups are substituted with at least one group IIA or IIIA metal compound group. The catalyst composition can be used for preparing ethylene/cycloolefin copolymer with a high cycloolefin conversion and a high glass transition temperature.

Description

490319 案號 89115222 θ /年无月》I曰 修正 五、發明說明α) 本發明有關於一種用於製備烯烴聚合物之新穎觸媒組 合物,特別有關於可製備具有高環烯烴轉化率和高玻璃轉 移溫度之烯烴聚合物的新穎觸媒組合物。 烯烴系聚合物長久以來已被廣泛地應用。其中最常見 的一種烯烴系聚合物即是聚烯烴(ρ ο 1 y ο 1 e f i n s ),亦即, 烯烴的單聚物或共聚物。這些聚烯烴塑膠一般是用於吹模 成型、射出成型、擠壓塗佈、薄膜、壓料、管件、電線、 和電纟覽。490319 Case No. 89115222 θ / year without month "I. Amendment V. Description of the invention α) The present invention relates to a novel catalyst composition for the preparation of olefin polymers, and more particularly to the preparation of high cyclic olefin conversion and high Novel catalyst composition for olefin polymers with glass transition temperature. Olefin polymers have been widely used for a long time. One of the most common olefin-based polymers is polyolefin (ρ ο 1 y ο 1 e f i n s), that is, a monomer or copolymer of olefin. These polyolefin plastics are generally used for blow molding, injection molding, extrusion coating, film, die-cutting, pipe fittings, electrical wires, and electrical viewing.

聚烯烴的一個例子是乙烯-丙烯彈性體(乙烯-丙烯橡 膠,E P R )。由於其耐候性佳,熱老化性質良好,且可與大 量的填料及可塑劑混合,因此在工業上普遍被應用。在汽 車工業上典型的用途,例如散熱器、加熱管、真空管、防 風雨塞片(weather stripping)、〉每棉門封(sponge doorseals)等等。 另一種常見的烯烴系聚合物是環烯烴共聚物 (cyclo olefin copolymer; C0C)。其中之一是環稀烴和乙 烯之共聚物,其具有極佳之透明度。而且,亦具有耐熱 性、耐熱老化性、耐化學性、耐溶劑性、介電性質、及剛 性(r i g i d i t y )。因此,乙烯/環烯烴共聚物非常適合於用 作光學材料,例如光學記憶光碟和光纖。An example of a polyolefin is an ethylene-propylene elastomer (ethylene-propylene rubber, EPR). Because of its good weather resistance, good heat aging properties, and can be mixed with a large amount of fillers and plasticizers, it is widely used in industry. Typical applications in the automotive industry, such as radiators, heating tubes, vacuum tubes, weather stripping,> sponge doorseals, and so on. Another common olefin-based polymer is cyclo olefin copolymer (C0C). One of them is a copolymer of cyclic dilute hydrocarbon and ethylene, which has excellent transparency. Furthermore, it also has heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity (r i g i d i t y). Therefore, ethylene / cycloolefin copolymers are very suitable for use as optical materials, such as optical memory discs and optical fibers.

乙烯/環烯烴共聚物通常是在芳環烯金屬 (metallocene) / ί呂氧院(aluminoxane)觸媒系統的存在下 而製得的,如美國專利第5,559,199號(Abe et al.)和美 國專利第5, 6 0 2, 2 1 9號(Aulbach et al.)中所敘述。Abe et al.中揭露之芳環烯金屬為異亞丙基(環戊二烯基甲基Ethylene / cycloolefin copolymers are usually made in the presence of a metallocene / aluminoxane catalyst system, such as US Patent No. 5,559,199 (Abe et al. ) And U.S. Patent No. 5,602,219 (Aulbach et al.). The aromatic cycloolefin metal disclosed in Abe et al. Is isopropylidene (cyclopentadienylmethyl

第4頁 490319 ____案號 89115222_I 年 χ 月孓 I a__ 五、發明說明(2) 環戊二烯基)二氯化锆 [i sopropylidene(cyclopentadienylmethylcyclopenta-d ienyl)zirconium dichloride] oAulbach e t a 1 .中揭露 之芳環烯金屬則為二甲基矽烷基-(1 -茚基)-環戊二烯基二 氣化锆 [dimethylsilyl-(l-indenyl)-cyclopentadienylzirconi um dichloride]。 然而,以傳統方法來製備乙烯/環烯烴共聚物有以下 共同的問題。首先,環烯烴的轉化率(c〇n v e r s i〇η )太低。 其次,由於乙烯之轉化率高,使得共聚物有太低的玻璃轉 移溫度(T g ) ° 為了要增進環烯烴的轉化率,常用的方法是增加反應 溫度和壓力。然而’這樣會使得環烯烴和乙烯的轉化率都 增加。於是,共聚物的T g會降低。 本發明之目的在於解決上述之問題,而提供一種用於 製備烯烴聚合物之新穎觸媒組合物’特別是用於製備乙烯 /環烯烴共聚物,而具有高環烯烴轉化率和高T g。 為了達成上述之目的,本發明種用於烯烴聚合之觸媒 組合物,包括: (a) 如以下化學式(I )所示之有機金屬化合物:Page 4 490319 ____ Case No. 89115222_I χ Month 孓 I a__ 5. Description of the Invention (2) Cyclopentadienyl) Zirconium Dichloride [i sopropylidene (cyclopentadienylmethylcyclopenta-d ienyl) zirconium dichloride] oAulbach eta 1. The arylcycloolefin metal is dimethylsilyl- (l-indenyl) -cyclopentadienylzirconi um dichloride. However, the conventional method for preparing an ethylene / cycloolefin copolymer has the following problems in common. First, the conversion of cycloolefins (conn v er s ioη) is too low. Secondly, due to the high conversion of ethylene, the copolymer has too low a glass transition temperature (T g) ° In order to increase the conversion of cycloolefins, the commonly used methods are to increase the reaction temperature and pressure. However, this will increase the conversion of both cycloolefin and ethylene. As a result, the T g of the copolymer is reduced. The object of the present invention is to solve the above problems, and to provide a novel catalyst composition ' for preparing olefin polymers, especially for preparing ethylene / cycloolefin copolymers, with high cyclic olefin conversion and high Tg. In order to achieve the above object, a catalyst composition for olefin polymerization of the present invention includes: (a) an organometallic compound represented by the following chemical formula (I):

490319 _案號89115222_分,年么月3 1曰_ 五、發明說明(3)490319 _Case No. 89115222_ minutes, year 3 months, 1 month _ V. Description of the invention (3)

其中 .among them .

R1可為相同或不同,為擇自由氫、鹵素、具有1至20 個碳原子之烷基、烯基、芳香基、烷芳基、或芳烷基、和 MiR4n所組成之族群中,或者兩相鄰而連接於不同碳原子之 R1可連接在一起而與其所連接之碳形成一具有4至20個碳 原子之環狀系統; R2可為相同或不同,且其定義同R1 ; 至少一個R1為M1!^ ; 至少一個R2為Μ1!?4,; ML為第I ΙΑ族或第I I ΙΑ族之金屬元素; R4可為相同或不同,為擇自由氫、鹵素、和具有1至 20個碳原子之烷基、烯基、芳香基、烷芳基、或芳烷基所 組成之族群中; η為1或2 ;以及R1 may be the same or different, and is selected from the group consisting of hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl, aromatic, alkaryl, or aralkyl, and MiR4n, or two Adjacent R1 connected to different carbon atoms may be connected together to form a ring system with 4 to 20 carbon atoms with the carbon to which they are connected; R2 may be the same or different, and their definition is the same as R1; at least one R1 Is M1! ^; At least one R2 is M1 !? 4 ,; ML is a metal element of Group I IA or Group II IA; R4 may be the same or different, and is selected from free hydrogen, halogen, and has 1 to 20 A carbon atom of an alkyl, alkenyl, aromatic, alkaryl, or aralkyl group; η is 1 or 2; and

X分別連接於每個環戊二稀部分之一個R1和一個R2的位 置,藉此取代R1和R2,且X為擇自下列之族群中X is connected to one of R1 and one R2 of each cyclopentadienyl moiety, thereby replacing R1 and R2, and X is selected from the following groups

第6頁 490319 _案號 89115222_今/年天月列曰_ 五、發明說明(4) R11 I R11 R11 I I R11 R11 I I —M3—— I , 丨3 L ——Μ3——-I I , L 1 —Ivr—。— I | R12 R12 R12 R12 R12 R11 R11 I I R11 I R11 I 1 1 —C—C— 1 一c一 •3 —0—— I I ^ I , I R12 R12 R12 R12 —BR11 , , AIR11 -Ge—, ,—Sn—— , 〇 , S =S〇 :S〇2 , =ΝΡ.Π ,: =C〇, —PRU, P(0)Ru 其 中 R11 和R12 可為 相 同或 不同, 為擇自由氫、 鹵 素 、Chc 丨院 基 Ci- i。氣燒*基 、c( 3-10 方 香基、 C6_1()氟芳香基 、( ^1-10 烧氧 基、 :2-. μ烯基 、C, 7 - 4 0 方 烧 基、 Cs-40 方 稀基、C7_4Q烧芳基所 組成 之族 群 中 1 或 者 R11 和R12 可為 相 同或 不同, 為具有1至1 5個 碳原 子之 具 有 取 代 基 或 不具 取 代基 之烷二 基(alkanediy 1 gr 〇 up ) ,其 中Ru 和R12 和 碳原 子 或M3 相連接 形成一環狀系 統 5而 烷二 -基 上 之 取 代 基 為擇 白 由Ch 院基 、(^_2。卸基、C6_ -20 芳香 基、 C 7-20 院 基 C7_2Q烷芳基所組成之族群中,以及 M3 為 擇 自由 矽 、錯 、和錫 所組成之族群 中 j (b ) 如 化學 式(11) 所示之一金屬化合物 • M2R〔 ) 4 (I I) 其 中 Μ2 為 第】 :V B族金屬;Page 6 490319 _Case No. 89115222_ Today / Year Tianyue Lei _ V. Description of the invention (4) R11 I R11 R11 II R11 R11 II —M3—— I, 丨 3 L ——M3 ——- II, L 1 —Ivr—. — I | R12 R12 R12 R12 R12 R11 R11 II R11 I R11 I 1 1 —C—C— 1 —c— • 3 —0—— II ^ I, I R12 R12 R12 R12 —BR11,, AIR11 -Ge—, , —Sn——, 〇, S = S〇: S〇2, = NP.Π ,: = C〇, --PRU, P (0) Ru where R11 and R12 can be the same or different, and for free hydrogen, Halogen, Chc 丨 Yuan Ci-i. Gas burning group, c (3-10 square aryl group, C6_1 () fluoroaromatic group, (^ 1-10 alkoxy group, 2: 2-. Alkenyl group, C, 7-4 0 square alkynyl group, Cs-40 square 1 or R11 and R12 in the group consisting of a dilute group and a C7_4Q aryl group may be the same or different, and are alkanediy (alkanediy 1 gr 〇up) having 1 to 15 carbon atoms and having a substituent or no substituent. ), Where Ru and R12 are connected to a carbon atom or M3 to form a cyclic system 5 and the substituent on the alkanedi- group is selected from the group consisting of Ch, (^ _2. Unloading group, C6_-20 aromatic group, C 7-20 In the group consisting of C7_2Q alkylaryl groups, and in the group consisting of M3 selected from silicon, silicon, and tin, j (b) is one of the metal compounds represented by the formula (11) • M2R [) 4 (II) where M2 is the first]: Group VB metal;

第7頁Page 7

490319 _案號 89115222_今,年戈月3丨曰__ 五、發明說明(5) R5可為相同或不同,且為擇自由氫、鹵素、Ci-C2〇月旨 肪族基、C6-C1Q芳香族基、OH、OR6、NR72所組成之族群中, R6和R7獨立地為^-C2()脂肪族基或C6-C1()芳香族基;以及 (c ) 一活化助觸媒,擇自由(1 ) I呂氧烧,(2 ) A 1 R83和 硼酸鹽之混合物·,( 3 ) A 1 R83和鋁氧烷之混合物所組成之族 群中,其中R8為C i _ 2 Q脂肪族基或C 6 _ i Q芳香族基。 本發明提供一種新穎之觸媒組合物,包括如化學式 (I )所示之二環戊二烯基有機金屬化合物,如化學式(I I )490319 _Case No. 89115222_ Today, Niangeyue 3 丨 __ V. Description of the invention (5) R5 can be the same or different, and is selected from the group consisting of hydrogen, halogen, Ci-C2O aliphatic group, C6- In the group consisting of C1Q aromatic group, OH, OR6, and NR72, R6 and R7 are independently ^ -C2 () aliphatic group or C6-C1 () aromatic group; and (c) an activating catalyst, In the group consisting of (1) I Luoxian, (2) A 1 R83 and borate mixture, (3) A 1 R83 and alumoxane mixture, where R8 is C i _ 2 Q fat Group or C 6 _ i Q aromatic group. The present invention provides a novel catalyst composition including a dicyclopentadienyl organometallic compound represented by the chemical formula (I), such as the chemical formula (I I)

所示之第I V B族金屬化合物,和助觸媒。兩個環戊二稀基 上都有至少一個第I I A或第II I A族之金屬化合物基團MiR4n 之取代基,Μ1為IIA族或第IIIA族之金屬元素;R4可為相同 或不同,為擇自由氫、鹵素、和具有1至20個碳原子之烷 基、烯基、芳香基、烷芳基、或芳烷基所組成之族群中; 以及η為1或2。 較佳之Μ1為第ΙΙΙΑ族金屬。MiR4nt具體例子包括 A1(CH3)2,A1(C2H5)2,A1(C4H9)2,A1C12,GaCl2,Ga(CH3)2,Group I V B metal compounds shown, and promoters. Both cyclopentadienyl groups have at least one substituent of the metal compound group MiR4n of group IIA or IIIA, and M1 is a metal element of group IIA or IIIA; R4 may be the same or different, and is optional In the group consisting of free hydrogen, halogen, and alkyl, alkenyl, aromatic, alkaryl, or aralkyl group having 1 to 20 carbon atoms; and n is 1 or 2. Preferred M1 is a Group IIIA metal. Specific examples of MiR4nt include A1 (CH3) 2, A1 (C2H5) 2, A1 (C4H9) 2, A1C12, GaCl2, Ga (CH3) 2,

Ga(C2H5)2 及Ga(C4H9)2。Ga (C2H5) 2 and Ga (C4H9) 2.

如上所述,在化學式(I )中,至少一個R1為Μ1!?4,,至少 一個R2為Μ14η,其餘之Ri和1?2為氫、鹵素、具有1至20個碳 原子之院基、烯基(alkenyl)、芳香基(aryl)、烧芳基 (alkylaryl)、或芳烷基(arylalkyl),較佳為1至15個碳 原子者;或者兩相鄰而連接於不同碳原子之R1可連接在一 起而與其所連接之碳形成一具有4至2 0個碳原子之環狀系 統,較佳為4至6個碳原子之環狀系統。 除了至少一個R1為M1!^,至少一個R2為MiR4n之外,當其As described above, in the chemical formula (I), at least one R1 is M1!? 4, at least one R2 is M14η, and the remaining Ri and 1? 2 are hydrogen, halogen, a radical having 1 to 20 carbon atoms, Alkenyl, aryl, alkylaryl, or arylalkyl, preferably 1 to 15 carbon atoms; or two adjacent R1 connected to different carbon atoms It can be connected together to form a ring system with 4 to 20 carbon atoms, preferably a ring system with 4 to 6 carbon atoms. Except that at least one R1 is M1! ^ And at least one R2 is MiR4n, when its

第8頁 490319 ) _案號 89115222_年天月》1曰__ 五、發明說明(6) 餘之R1和R2為氫、鹵素、具有1至20個碳原子之烷基、烯 基、芳香基、烷芳基、或芳烷基時,R1和R2之具體例子包 括氫、甲基、乙基、丙基、丁基、異丁基、戊基、異戊 基、己基、2-乙基己基、庚基、辛基、乙烯基、稀丙基、 異丙烯基、苯基\和甲苯基等。Page 8 490319) _Case No. 89115222_Yantianyue "1__ V. Description of the invention (6) The remaining R1 and R2 are hydrogen, halogen, alkyl, alkenyl, aromatic with 1 to 20 carbon atoms In the case of alkyl, alkaryl, or aralkyl, specific examples of R1 and R2 include hydrogen, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethyl Hexyl, heptyl, octyl, vinyl, dipropyl, isopropenyl, phenyl \, and tolyl.

除了至少一個Ri為之外,當兩相鄰而連接於不同 碳原子之R1連接在一起而與其所連接之碳原子形成一具有 4至2 0個碳原子之環狀系統時,此環狀系統可為飽合或不 飽合之多環之環戊二烯基配位基,例如茚基、四氫茚基、 第基、或八氫第基。配位基的具體例子包括7?5 -環戊二烯 基,7/5-曱基環戊二烯基,7?5-四甲基環戊二烯基,7?5 -五曱基環戍二炼基’ 丁基環戍二稀基’印基’四氮 茚基,苐基,八氫第基。 除了至少一個R2為MiR4n之外,當兩相鄰而連接於不同 碳原子之R2連接在一起而與其所連接之碳原子形成一具有 4至2 0個碳原子之環狀系統時,此環狀系統可為飽合或不 飽合之多環之環戊二烯基配位基,例如茚基、四氫茚基、 荞基、或八氫苇基。配位基之具體例子如上所述。In addition to at least one Ri, when two adjacent R1 connected to different carbon atoms are connected together to form a ring system with 4 to 20 carbon atoms with the carbon atoms to which they are connected, the ring system It may be a saturated or unsaturated polycyclic cyclopentadienyl ligand, such as indenyl, tetrahydroindenyl, thienyl, or octahydrodenyl. Specific examples of the ligand include 7? 5-cyclopentadienyl, 7 / 5-fluorenylcyclopentadienyl, 7? 5-tetramethylcyclopentadienyl, 7? 5-pentafluorenyl ring Amidinyl 'butylcyclofluorenyl diindenyl'indenyl' tetrazindenyl, amidinyl, octahydrodiyl. Except that at least one R2 is MiR4n, when two adjacent R2 connected to different carbon atoms are connected together to form a ring system with 4 to 20 carbon atoms, the R2 The system may be a saturated or unsaturated polycyclic cyclopentadienyl ligand, such as indenyl, tetrahydroindenyl, buckwyl, or octahydrofluorenyl. Specific examples of the ligand are as described above.

化學式(I I )所示之金屬化合物M2R54中,M2為第I VB族金 屬;R5可為相同或不同,且為擇自由氫、氣、(:厂(:2{)脂肪 族基、C6-C1Q芳香族基、OH、OR6、NR72所組成之族群中,R6 和R7獨立地為Ci-Cw脂肪族基或C6-C1G芳香族基。M2R54之具體 例子包括Zr (N(CH3)2)4、ZrCl4、Z:r (0CH3)4、Z:r(0C2H5)4 和 Zr(0C4H9)4。 適用於本發明之活化助觸媒可為(1 ) 鋁氧烷,(2 )In the metal compound M2R54 represented by the chemical formula (II), M2 is a Group VB metal; R5 may be the same or different, and is selected from free hydrogen, gas, (: ((2 {) aliphatic group, C6-C1Q In the group consisting of aromatic group, OH, OR6, and NR72, R6 and R7 are independently Ci-Cw aliphatic group or C6-C1G aromatic group. Specific examples of M2R54 include Zr (N (CH3) 2) 4, ZrCl4, Z: r (0CH3) 4, Z: r (0C2H5) 4 and Zr (0C4H9) 4. The activating catalyst suitable for the present invention may be (1) alumoxane, (2)

第9頁 490319 _案號89115222_q /年孓眉」1日-^- 五、發明說明(7) A 1 R83和硼酸鹽之混合物,或(3 ) A 1 R83和鋁氧烷之混合物, 其中R8為^,脂肪族基或C6_1()芳香族基。 常用及商用之鋁氧烷為甲基鋁氧烷(methyl aluminoxane; MAO) °A1R83(三炫基铭)之具體例子包括三 甲基鋁,三乙基鋁,三丙基鋁,三異丙基鋁,三丁基鋁, 與三異丁基鋁(TIBA)。 適於本發明之硼酸鹽包括N,N -二甲基苯銨肆(五氟苯 基)硼酸鹽(N,N-dimethyl anilinium tetrakis (pentafluorophenyl) borate),三苯碳烯肆(五氟苯基) 石朋酸鹽(triphenyl carbenium tetrakis(pentaflu〇r〇phenyl)b〇rate),三甲基銨肆(五 氟苯基)石朋酸鹽(trimethyl ammonium tetrakis(pentafluorophenyl) borate),二茂鐵肆(五氟 笨基)酸鹽(ferrocenium tetrakis(pentaflu〇r〇phenyl)b〇rate),二甲基肆(五氟 笨基)硼酸鹽(dimethyl tetraki s(pentaf luorophenyl )borate),及銀肆(五氟苯 基)硼酸鹽(silver tetrakis(pentaflu〇rophenyl) borate)等。 使用本發明之觸媒組合物,可合成烯烴聚合物。在有 效催化劑量之本發明上述觸媒組合物的存在下及聚合條件 下,可使得一烯烴單體進行聚合作用(即均聚合),或者可 使得至少一烯烴單體與至少一其他單體進行聚合作用(共 聚合)。 依據本發明,較佳之稀烴為環稀烴。本發明之聚合方Page 9 490319 _Case No. 89115222_q / year frown "1st-^-V. Description of the invention (7) Mixture of A 1 R83 and borate, or (3) Mixture of A 1 R83 and alumoxane, where R8 Is ^, aliphatic or C6_1 () aromatic. The commonly used and commercial aluminoxane is methyl aluminoxane (MAO) ° A1R83 (trioxyl). Specific examples include trimethylaluminum, triethylaluminum, tripropylaluminum, and triisopropyl Aluminum, tributylaluminum, and triisobutylaluminum (TIBA). Borates suitable for the present invention include N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate, triphenylcarbene (pentafluorophenyl) ) Triphenyl carbenium tetrakis (pentafluorphenyl) borate), trimethyl ammonium tetrakis (pentafluorophenyl) borate), ferrocene (Pentafluorobenzyl) acid salt (ferrocenium tetrakis (pentafluorophenyl) borate), dimethyl tetrakis (pentafluorobenzyl) borate (dimethyl tetrakis (pentaf luorophenyl) borate), and silver ( Pentafluorophenyl) borate (silver tetrakis (pentaflurophenyl) borate) and the like. By using the catalyst composition of the present invention, an olefin polymer can be synthesized. In the presence of an effective catalyst amount of the above-mentioned catalyst composition of the present invention and polymerization conditions, one olefin monomer can be polymerized (ie, homopolymerized), or at least one olefin monomer can be made with at least one other monomer. Polymerization (copolymerization). According to the present invention, the preferred dilute hydrocarbon is a cyclic dilute hydrocarbon. Aggregate of the invention

第10頁 490319Page 10 490319

1 I _案號 89115222_q/年孓月M曰__ 五、發明說明(8) 法最好是進行環烯烴之均聚合,或者是進行環烯烴與非環 烯烴之共聚合。 適用於本發明之環烯烴可為二環庚烯類、三環癸烯 類、三環十一碳烯類、四環十二碳烯類、五環十五碳烯 類、五環十五碳二烯類、五環十六碳烯類、六環十七碳烯 類、七環二十碳稀類、七環二十一碳稀類、八環二十二碳 烯類、九環二十五碳烯類、和九環二十六碳烯類。具體的 例子為原冰片烯(norbornene) 、tetracycl〇dodecene 、及 dicyclopentadiene 〇 適用於本發明之非環狀烯烴可為乙烯,或具有3至12 個碳數的α -烯烴。α -烯烴之具體例子包括1 -丙烯,1 - 丁 烯,1-戊烯,1-己烯,和1-辛烯等。 本發明觸媒組合物特別適合於製備非環狀烯烴/環烯 烴共聚物,如乙稀/環稀烴共聚物。藉由此特殊觸媒組合 物,所得之乙烯/環烯烴共聚物具有高環烯烴轉化率以及 高Tg. 本發明之觸媒系統適用於汙漿狀(s 1 u r r y )反應狀態、 氣相與溶液聚合反應狀態。聚合反應通常在0 °C到2 5 0 °C的 溫度下,且於一大氣壓到3,0 0 0 p s i之間進行。 以下便藉由數個實施例以更進一步說明本發明之方 法、特徵及優點,但並非用來限制本發明之範圍,本發明 之範圍應以所附之申請專利範圍為準。除非特指明,否則 所有份數、百分比、比例等都是以重量為基準。 有機金屬化合物之合成 實施例1 : {二苯基[(二甲基鋁)環戊二烯基]-1 I _Case No. 89115222_q / year M__ V. Explanation of the invention (8) It is best to carry out homopolymerization of cyclic olefins or copolymerization of cyclic olefins and acyclic olefins. The cyclic olefins suitable for the present invention may be dicycloheptenes, tricyclodecenes, tricyclic undecenes, tetracyclododecenes, pentacyclopentadecenes, pentacyclic fifteen carbons Dienes, pentacyclic hexadecenes, hexacyclic heptadenes, hexacyclic twenty carbons, hexacyclic twenty-one carbons, octacyclic twenty-two carbons, nine ring twenty Five-carbonenes and nine-cyclo26-hexaenes. Specific examples are norbornene, tetracyclodedecene, and dicyclopentadiene. The acyclic olefin suitable for use in the present invention may be ethylene, or an α-olefin having 3 to 12 carbon numbers. Specific examples of the α-olefin include 1-propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene. The catalyst composition of the present invention is particularly suitable for preparing acyclic olefin / cycloolefin copolymers, such as ethylene / cycloolefin copolymers. With this special catalyst composition, the obtained ethylene / cycloolefin copolymer has a high cycloolefin conversion rate and a high Tg. The catalyst system of the present invention is suitable for a slurry state (s 1 urry) reaction state, a gas phase and a solution. Polymerization state. The polymerization reaction is usually carried out at a temperature of 0 ° C to 250 ° C, and at a pressure of one atmosphere to 3,000 p s i. In the following, the method, features and advantages of the present invention will be further explained through several embodiments, but it is not intended to limit the scope of the present invention. The scope of the present invention shall be based on the scope of the attached patent application. Unless otherwise specified, all parts, percentages, ratios, etc. are based on weight. Synthesis of Organometallic Compounds Example 1: {Diphenyl [(dimethyl aluminum) cyclopentadienyl]-

第11頁 490319 _餘89115222_7 /年i月ι /日 修正__ 五、發明說明(9) [(二曱基鋁)茚基]甲烷丨.4THF之合成 (Diphenyl[(Dimethylaluminum)cyclopentadienyl]-[(Dj methylaluminum)indenyl ]methane}· 4THF 之合成 取1 g (2.89 mmole)之二苯基(環戊二烯基)—茚基甲 烷[Diphenyl(cycl〇pentadienyl)-(indenyl)methane]置 入1 00 ml圓底燒瓶中,加入50 ml THF,在冰浴條件下, 緩慢加入5· 4 ml (1·6 Μ,8.67 mmole) 之正丁基鋰 (η B u L i ),期間溶液呈現橘紅色,然後移開冰浴,繼續攪 拌3小時,抽乾所有溶劑,並以1 〇〇 mi戊烷將過量nBuLi洗 出,過遽,取沉殿物。 重新加入5 0 m 1 乙醚將沉澱物溶解,緩慢加入8 . 7 m 1 (1·0 M,8_7 mmole)二曱基氯化 ί呂[dimethylaluminum c h 1 o r i d e ] ’繼續攪拌1 6小時,過濾,抽乾所有溶劑。接 著以2 0 m 1曱笨溶解,再次將鹽類過濾,取濾液經濃縮後 可得淡黃色固體產物1 · 8 2 g (產率=8 5 % )。 貫施例2 : [2-(二甲基ί呂)環戍二稀基-2- (二曱基鋁)茚基丙烷]- 4THF之合成 [2-(Dimethylaluminum)cyclopentadienyl~2-(Dimet hylaluminum) indenylpropane] ·4ΤΗΡ 之合成 取0·64 g (2·89 mmole)之2 -環戊二稀基-2 -萌基丙烧 [2-Cyclopentadienyl-2-indenylpropane]置入1〇〇 m1 圓 底燒瓶中,加入5 0 m 1 T H F,在冰浴條件下,緩慢加入5 . 4 m 1 ( 1 · 6 Μ,8 . 6 7 m m ο 1 e ) η B u L i ,期間溶液呈現橘紅色, 然後移開冰浴,繼續攪拌3小時,抽乾所有溶劑,並以1 〇 〇 m 1戊炫將過量η B u L i洗出,過渡,取沉激物。Page 11 490319 _ 余 89115222_7 / year i / month / day correction__ V. Description of the invention (9) [(Dimethylaluminum) indenyl] methane 丨. Synthesis of 4THF (Diphenyl [(Dimethylaluminum) cyclopentadienyl]-[ (Dj methylaluminum) indenyl] methane} · 4THF Synthesis Take 1 g (2.89 mmole) of diphenyl (cyclopentadienyl) -indenylmethane [Diphenyl (cycl〇pentadienyl)-(indenyl) methane] and put in 1 In a 00 ml round-bottomed flask, add 50 ml of THF, and slowly add 5.4 ml (1.6 M, 8.67 mmole) of n-butyl lithium (η B u L i) under ice bath conditions. Red, then remove the ice bath, continue to stir for 3 hours, drain all solvents, and wash out excess nBuLi with 1000 mi pentane, rinse, and take the sink. Re-add 50 m 1 ether to precipitate Dissolve, slowly add 8.7 m 1 (1.0 M, 8_7 mmole) dimethylaluminum ch [dimethylaluminum ch 1 oride] 'Continue stirring for 16 hours, filter, and dry all solvents. Then 20 m The solution was dissolved, and the salts were filtered again, and the filtrate was concentrated to obtain a light yellow solid product of 1.82 g (yield = 85%). Example 2: Synthesis of [2- (Dimethylaluminium) cyclopentadienyl-2- (dimethylaluminum) indenylpropane]-4THF [2- (Dimethylaluminum) cyclopentadienyl ~ 2- (Dimet hylaluminum) indenylpropane] · Synthesis of 4ΤΗΡ takes 0.64 g (2.889 mmole) of 2-cyclopentadienyl-2 -mene propane [2-Cyclopentadienyl-2-indenylpropane] and put it in a 100m1 round bottom flask 50 m 1 THF was added, and under ice-bath conditions, 5.4 m 1 (1.6 M, 8.67 mm ο 1 e) η B u L i was slowly added, during which the solution appeared orange-red, then Remove the ice bath, continue stirring for 3 hours, drain off all the solvents, and wash out the excess η B u L i with 100 m 1 pentamidine, transition, and take the exciter.

第12頁 490319 __棄號89115222_巧f年孓月予I曰__ 五、發明說明(10) 重新加入5 0 m 1 乙醚將沉澱物溶解,緩慢加入8 · 7 m 1 (1 · 〇 Μ,8 · 7 mmo 1 e )二曱基氣化鋁,繼續攪拌1 6小時,過 濾,抽乾所有溶劑。接著以2 0 m 1甲苯溶解,再次將鹽類 過濾,取濾液經濃縮後可得淡黃色液體產物1 . 3 g (產率 =73 ° 實施例3 : [ 1 -(二甲基鋁)環戊二烯基- 1 - (二甲基鋁)茚基環丁烷]之合成 [l-(Dimethylaluniinum)cycl〇pentadienyl-l -(Dimet hylaluminum)indenylcyclobutane]之合成 取0·94 g (4.0 mmole)之1-環戊二稀基-1-茚基環丁 l-Cyclopentadienyl-1-indenylcyclobutane]置入100 m 1圓底燒瓶中,加入5 0 m 1曱苯,緩慢加入〇 · 3 2 g ( 8 · 0 mmole) Κ Η,加熱迴流1 2小時,將溫度降至室溫,緩慢加 入8.8 ml (1·〇 Μ,8.8 mmole)二甲基氯化鋁,繼續擾拌 1 6小時,過濾,抽乾所有溶劑。便可得淡黃色液體產物!. 2 g (產率=87 %)。 #呂^[匕I才勿t予頁〉'舌^[匕 實施例4 取1 〇 rn g ( 〇 · 〇 1 3 4 m m ο 1 e )由實施例1所製得之鋁化合物 置於25 ml反應瓶中,加入3·58 mg(0 〇134 mm〇le) Z r ( N M e 2) 4,然後加入1 3 · 6 m 1之曱笨,於室溫下檀拌2 4小 時,將此溶液保存留待聚合反應時使用。 . 實施例5 取8· 33 mg(〇· 0 134 mmole)由實施例2所製得之鋁化合 物置於25 ml反應瓶中,加入3·58 mg(〇.〇i34 mmole)Page 12 490319 __Abandonment number 89115222_ 巧 年 年月 月 予 I__ V. Description of the invention (10) Add 50 m 1 of ether to dissolve the precipitate, and slowly add 8. 7 m 1 (1 · 〇 M, 8.7 mmo 1 e) difluorinated aluminum vaporized aluminum, continue to stir for 16 hours, filter, and dry all solvents. It was then dissolved in 20 ml of toluene, and the salts were filtered again. The filtrate was concentrated to obtain a light yellow liquid product 1.3 g (yield = 73 °). Example 3: [1-(dimethyl aluminum) ring Synthesis of pentadienyl-1-(dimethyl aluminum) indenylcyclobutane] [l- (Dimethylaluniinum) cycl〇pentadienyl-l-(Dimet hylaluminum) indenylcyclobutane] Synthesis of 0.94 g (4.0 mmole) 1-Cyclopentyl-1-indenylcyclobutane 1-Cyclopentadienyl-1-indenylcyclobutane] was placed in a 100 m 1 round-bottomed flask, 50 m 1 of toluene was added, and 0.3 2 g (8 · 0 mmole) κ Η, heat to reflux for 12 hours, reduce the temperature to room temperature, slowly add 8.8 ml (1.0M, 8.8 mmole) dimethylaluminum chloride, continue to stir for 16 hours, filter, and pump Dry all solvents. A pale yellow liquid product can be obtained! 2 g (yield = 87%). # 吕 ^ [匕 I 才 不 t 页> '舌 ^ [匕 Example 4 Take 1 〇rn g (〇 · 〇 1 3 4 mm ο 1 e) The aluminum compound prepared in Example 1 was placed in a 25 ml reaction flask, and 3.58 mg (0 134 mm ole) Z r (NM e 2) 4 was added. Then add 1 3 · 6 m 1 Stir for 24 hours, save this solution for use in the polymerization reaction. Example 5 Take 8.33 mg (0.00 134 mmole) of the aluminum compound prepared in Example 2 into a 25 ml reaction flask and add 3.58 mg (0.034 mmole)

第13頁 490319 ___案號 89115222_γ/年I月> ί曰_修正 _ 五、發明說明(11) Z r ( N M e2) 4,然後加入1 1 . 9 m 1之甲苯,於室溫下攪拌2 4小 時’將此溶液保存留待聚合反應時使用。 . 實施例6 取5 m g ( 〇 . 〇 1 4 5 m m ο 1 e )由實施例3所製得之I呂化合物 置於25 ml反應瓶中,加入3.87 mg(0.0145 mmole) Z r ( N M e2) 4,然後加入1 4 . 4 m 1之甲苯,於室溫下攪拌2 4小 時,將此溶液保存留待聚合反應時使用。 聚合物之合成 實施例A :乙烯/原冰片烯共聚物之合成 將曱笨利用N a加熱迴流以除去水份,其含水量必須經 過線上水份分析儀測定,低於1 0 ppm方可使用。聚合單體 原冰片稀(η 〇 r b 〇 r n e n e )溶液的配製方法是,將5 0 0 g 原冰 片烯加入88g 甲苯配製成85 wt % 之溶液。 先將反應器内的溫度設定到1 0 5 °C加熱並抽真空 1 hr,然後再充填高純度氮氣,經過反覆抽灌氮氣3〜4次 後,再將反應器的溫度設定至聚合反應所需之溫度9 0 °C讓 其維持穩定。待溫度穩定後,以插管的方式用氮氣壓將 1 〇 0 g ( 8 5 w t % ) 之原冰片烯溶液壓至反應槽内,開攪拌 機調整轉速為2 5 0 rpm,然後再將4 ml (1.49 M)之ΜΑ0及3 m 1之T I B A以針筒注入反應器内。 利用乙烯將反應器内的氮氣置換掉然後排放,此動作 連續做兩次’敢後將乙稀建壓至6 K g / c m2,使乙稀在溶液 中的濃度達到飽和。在手套箱取1 m 1由實施例4所製得之觸 媒溶液,加3 m 1 Μ A 0 活化5分鐘,用針筒取出注入聚合反 應器起始聚合反應,攪拌機轉速調整到5 0 0 r p m ,反應時Page 13 490319 ___Case No. 89115222_γ / January > ί Yue_Amendment_ V. Description of the invention (11) Z r (NM e2) 4 and then add 1 1. 9 m 1 of toluene, at room temperature Stir for 24 hours' to save this solution for use in the polymerization. Example 6 Take 5 mg (0.015 mm ο 1 e) of the compound Iru prepared in Example 3 in a 25 ml reaction flask, add 3.87 mg (0.0145 mmole) Z r (NM e2 ) 4, then 14.4 m 1 of toluene was added and stirred at room temperature for 24 hours, and this solution was stored for use in the polymerization reaction. Polymer Synthesis Example A: Synthesis of Ethylene / Protobornene Copolymer. The naphtha was heated under reflux with Na to remove water. Its water content must be measured by an online moisture analyzer, and it can be used below 10 ppm. . Polymerization monomer The original borneol dilute (η 〇 r b 〇 rn ene) solution was prepared by adding 500 g of raw norbornene to 88 g of toluene to prepare an 85 wt% solution. First set the temperature in the reactor to 105 ° C for heating and vacuum for 1 hr, then fill with high-purity nitrogen, and then repeatedly pump nitrogen for 3 to 4 times, and then set the temperature of the reactor to the polymerization reactor. The required temperature is 90 ° C to keep it stable. After the temperature has stabilized, press 1000 g (85 wt%) of the original norbornene solution into the reaction tank by intubation with nitrogen pressure. Turn on the mixer to adjust the rotation speed to 250 rpm, and then 4 ml (1.49 M) of MAO and 3 m of TIBA were injected into the reactor with a syringe. Ethylene was used to replace the nitrogen in the reactor and then discharged. This operation was performed twice in a row, and the pressure of ethylene was reduced to 6 Kg / cm2, so that the concentration of ethylene in the solution was saturated. Take 1 m 1 of the catalyst solution prepared in Example 4 in the glove box, add 3 m 1 Μ A 0 to activate for 5 minutes, take it out with a syringe and inject it into the polymerization reactor to start the polymerization reaction, and adjust the rotation speed of the mixer to 50 0 rpm, reaction time

490319 修正 案號 89115222 五、發明說明(12) 間3 0分鐘。 反應3 0分鐘後,先關閉乙烯進料閥並關閉溫度控制 器,徐徐打開聚合反應器之洩壓閥排除未反應之乙烯壓 力,使壓力降至常壓,將反應器打開,然後將反應液倒入 含稀鹽酸之丙酮溶液,使產物沈澱,並利用丙酮溶液洗2 〜3 次,用抽氣幫浦抽氣過濾,將產品送至真空烘箱烘 乾,溫度設定在8 0 t,加熱烘乾1 2小時。秤重得共聚物6 . 6 g,玻璃轉化溫度2 0 5 °C,結果如表1所示。490319 Amendment No. 89115222 V. Explanation of the invention (12) 30 minutes. After 30 minutes of reaction, first close the ethylene feed valve and close the temperature controller. Slowly open the pressure relief valve of the polymerization reactor to remove the unreacted ethylene pressure, reduce the pressure to normal pressure, open the reactor, and then open the reaction solution. Pour into acetone solution containing dilute hydrochloric acid to precipitate the product, wash with acetone solution 2 to 3 times, filter with suction pump, send the product to a vacuum oven to dry, set the temperature to 80 t, heat and dry Dry for 12 hours. The copolymer weighed 6.6 g and the glass transition temperature was 20 ° C. The results are shown in Table 1.

實施例B至E 結 步驟同實施例A,但改變乙烯壓力和/或反應溫度 果如表1所示。 表Examples B to E were completed in the same manner as in Example A, except that the ethylene pressure and / or reaction temperature were changed as shown in Table 1. table

j 實施例 乙烯壓力 (Kg/cm2) 反應溫度 (°C) 產量 (g) 活性 (g/gZr.hr) Tg (°C) A 6 90 6.6 1.36χ105 205 B 10 90 10.6 2.17χ105 177 C 15 90 18.3 3.73χ105 159 D 20 90 19.0 3.89χ105 130 E 15 100 13.0 2.66X105 155 第15頁 490319 —--- 案號 89115222_9 _ 五、發明說明(13) · 觸媒溶液係由實施例4所製得j Example Ethylene pressure (Kg / cm2) Reaction temperature (° C) Yield (g) Activity (g / gZr.hr) Tg (° C) A 6 90 6.6 1.36χ105 205 B 10 90 10.6 2.17χ105 177 C 15 90 18.3 3.73χ105 159 D 20 90 19.0 3.89χ105 130 E 15 100 13.0 2.66X105 155 Page 15 490319 ----- Case No. 89115222_9 _ V. Description of the invention (13) The catalyst solution was prepared by Example 4

F 將曱苯利用鈉加熱迴流以除去水份,其含水量必須經 過線上水份分析儀測定,低於1 〇 p p m方可使用。聚合單體 原冰片烯(η 〇 r b 〇 r n e n e )溶液的配製方法是,將5 〇 〇 g原冰 片烯加入8 8 g 乾曱苯配製成8 5 w t % 之溶液。 先將反應器内的溫度設定到1 0 5 °C加熱並抽真空 1 hr,然後再充填高純度氮氣,經過反覆抽灌氮氣3〜4次 後’再將反應器的溫度設定至聚合反應所需之溫度8 〇讓 其維持穩定。待溫度穩定後,以插管的方式用氮氣壓將 1 0 0 g ( 8 5 w t % )之原冰片烯溶液壓至反應槽内,開授拌 機調整轉速為2 5 0 rpm,然後再將丨(1·49 M)2MA〇以針 筒注入反應器内。 、*利用乙烯將反應器内的氮氣置換掉然後排放,此動作 連續做兩次,最後將乙烯建壓至15 Kg/cm2,使乙烯在溶 ,中的濃度達到飽和。在手套箱取〇· 25ml由實施例6所製 仟之觸媒溶液,加1 m丨Μ A 0活化5分鐘,用針筒取出注入 ♦合反應為起始聚合反應,攪拌機轉速調整到5 〇 〇 rpin , 反應時間3 0分鐘。 口口 反應3 0分鐘後’先關閉乙烯進料閥並關閉溫度控制 器’徐徐打開聚合反應器之洩壓閥排除未反應之乙烯壓 力,使壓力降至常壓,將反應器打開,然後將反應液倒入 含稀鹽酸之丙酮溶液,使產物沈澱,旅利用丙酮溶液洗2 〜3次,用抽氣幫浦抽氣過濾,將產品送至真空烘箱烘F The toluene is heated under reflux with sodium to remove water, and its water content must be measured by an on-line moisture analyzer before it can be used below 10 p p m. Polymerization monomer The original norbornene (η 〇 r b ○ rn ene) solution was prepared by adding 5,000 g of raw norbornene to 8 g of dried xanthanene to prepare a 85 wt% solution. First set the temperature in the reactor to 105 ° C and heat and evacuate for 1 hr, then fill with high-purity nitrogen, and then repeatedly pump nitrogen for 3 to 4 times, and then set the temperature of the reactor to the polymerization reactor. The required temperature is 80 to keep it stable. After the temperature has stabilized, press 100 g (85 wt%) of the original norbornene solution into the reaction tank with nitrogen pressure by intubation. Turn on the mixer to adjust the rotation speed to 250 rpm, and then (1 · 49 M) 2MA0 was injected into the reactor with a syringe. * Replace the nitrogen in the reactor with ethylene and discharge it. This action is performed twice in a row, and finally the ethylene is compressed to 15 Kg / cm2, so that the concentration of ethylene in the solution is saturated. In the glove box, 0.25 ml of the catalyst solution prepared in Example 6 was added, and activated by adding 1 μM A 0 for 5 minutes. The injection reaction was taken out with a syringe. The polymerization reaction was initiated, and the speed of the mixer was adjusted to 5 °. 〇rpin, the reaction time is 30 minutes. After 30 minutes of mouth reaction, 'close the ethylene feed valve and close the temperature controller' slowly open the pressure relief valve of the polymerization reactor to remove the unreacted ethylene pressure, reduce the pressure to normal pressure, open the reactor, and then The reaction solution is poured into an acetone solution containing dilute hydrochloric acid to precipitate the product. The acetone solution is used to wash the solution 2 to 3 times, and the product is filtered with a suction pump, and the product is sent to a vacuum oven for drying.

第16頁 490319 _案號 89115222_q丨年:y月飞1曰_^_ 五、發明說明(14) * 乾,溫度設定在8 0 °C,加熱烘乾1 2小時。秤重得共聚物 1 0 . 9 g,玻璃轉化溫度1 6 3 °C,結果如表2所示。 實施例G至Η 以實施例F相同之方法製備數種環烯烴共聚物,並使 用相同之觸媒,但改變反應之溫度,聚合反應結果如表2 所示。 表2 實施例 乙烯壓力 (Kg/cm2) 反應溫度 CC) 產量 (g) 活性 (g/gZr.hr) Tg (°C) F 15 80 10.9 2.07χ105 163 G 15 100 15.3 5.9〇χ105 176 Η 15 120 20.4 8.23χ105 185Page 16 490319 _Case No. 89115222_q 丨 Year: y Yuefei 1 _ ^ _ V. Description of the invention (14) * Dry, set the temperature at 80 ° C, heat and dry for 12 hours. The copolymer weighed 10.9 g and the glass transition temperature was 16 3 ° C. The results are shown in Table 2. Examples G to Η Several cyclic olefin copolymers were prepared in the same manner as in Example F, using the same catalyst, but changing the reaction temperature. The results of the polymerization are shown in Table 2. Table 2 Examples of ethylene pressure (Kg / cm2) reaction temperature CC) yield (g) activity (g / gZr.hr) Tg (° C) F 15 80 10.9 2.07χ105 163 G 15 100 15.3 5.9〇χ105 176 Η 15 120 20.4 8.23χ105 185

觸媒溶液係由實施例6所製得The catalyst solution was prepared in Example 6.

由以上結果可知,本發明之觸媒組合物可用於製備乙 烯/環烯烴共聚物,有高環烯烴轉化率和高玻璃轉移溫 度。 雖然本發明·已以較佳實施例揭露如上,然其並非用以From the above results, it can be seen that the catalyst composition of the present invention can be used for preparing an ethylene / cycloolefin copolymer, and has a high cycloolefin conversion rate and a high glass transition temperature. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to

第17頁 490319 修正 案號 89115222 五、發明說明(15) 限定本發明,任何熟習此項技藝者,在不脫離本發明之精 神和範圍内,當可作更動與潤飾,因此本發明之保護範圍 當視後附之申請專利範圍所界定者為準。Page 17 490319 Amendment No. 89115222 V. Description of the invention (15) The invention is limited. Anyone skilled in the art can make changes and decorations without departing from the spirit and scope of the invention. Therefore, the scope of protection of the invention It shall be subject to the definition in the appended patent application scope.

第18頁 490319 _案號 89115222_°ί ί年i月飞I日_修正 圖式簡單說明Page 18 490319 _Case No. 89115222_ ° ί ί Year, month, month, and day I_ Amendment

第19頁Page 19

Claims (1)

490319 六 禾 89115222 修正 1 · 一種用於製備烯烴聚合物之二茂金屬觸媒組合物 包括 a )如以下化學式(I )所示之有機金屬化合物:490319 Liuhe 89115222 Amendment 1 · A metallocene catalyst composition for preparing an olefin polymer includes a) an organometallic compound represented by the following chemical formula (I): 其中 R1可為相同或不同,為擇自由氫、鹵素、具有1至20 個碳原子之烧基·、稀基、芳香基、烧芳基、或芳烧基、和 Ml4。所組成之族群中,或者兩相鄰而連接於不同碳原子之 R1可連接在一起而與其所連接之碳形成一具有4至2 0個碳 原子之環狀系統; R2可為相同或不同,且其定義同R1 ; 至少一個R1為MiR4n ; 至少一個R2為MiR4n ; Μ1為第IIA族或第IIIA族之金屬元素; 和具有1至 或芳烧基所 R4可為相同或不同,為擇自由氫、鹵素 20個碳原子之烷基、烯基、芳香基、烷芳基 組成之族群中;Wherein R1 may be the same or different, and are selected from hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a dilute group, an aromatic group, an aromatic group, or an aromatic group, and Ml4. In the group formed, or two adjacent R1 connected to different carbon atoms may be connected together to form a ring system with 4 to 20 carbon atoms with the carbon to which they are connected; R2 may be the same or different, And its definition is the same as R1; at least one R1 is MiR4n; at least one R2 is MiR4n; M1 is a metal element of group IIA or IIIA; and R4 with 1 to or aryl group can be the same or different, optional In the group consisting of alkyl, alkenyl, aromatic and alkaryl groups of 20 carbon atoms of hydrogen and halogen; 第20頁 490319 _案號89115222_q ί年A月叫日_ 六、申請專利範圍 η為1或2 ;以及 X分: 則連接於每偃 1環戊二 烯部分之一個R1和一 個R2的位 置 1 藉此 取代R1 : 和R 2 , 且X 為捐 [自下歹U 之族群中 R11 I R1] I R11 I R11 P,11 I I 丨3 —M3- I , U -MJ- I 丨3 -f- 7 L 1 n— , R12 丨Γ P, ^ R12 r12 r12 R11 R11 I I R11 I R11 1 1 1 —C—C一 | I , — —C— I 丨3 —〇—丫― R12 R12 R12 R12 —BR11 A1R11 , _Ge — ~Sn— ,—0 — —SO 7 ——S〇2 , =NRn ^ __:1 c〇 ,: PR11 ,- P(〇)RU 其 中 Ru和1?12可為 相 同 或不 同, 為擇自 由氫、鹵素 、c卜“ 丨烧 基 C 1 - i 0 ‘ II烧基 、C, )-10 芳香 基、 1 C6_10 氟 芳香基、(V1{) 烷氧 基、 :2_ i 〇細基 C7_40 烷 基 、c8_ •40方 烯基、( 烧芳基所 組成 之族 群 中 ,或 者 R11和R12可為 .相 同 或不 同, 為具有 1至1 5個碳原 子之 具 有 取 代基 或不具 取 代基之 烷二 •基(alk anediyl gro up) ,其 中 R11 和R12 ^和碳原 子 或M3相 連接 形成一 環狀系統,而 ,烷二 -基 上 之 取代 基為擇 白 由C 1-20烧基 、C!_2。細 「基、C6_2Q芳香 基、 C7-20 芳 院 基、 c7_20烷芳基所組成之 族群中 ,以及 M3為 擇自由 石夕 、鍺、 和鍚 所組成 之族群中;Page 20 490319 _ Case No. 89115222_q The name of the month of the year A_ Six. The scope of patent application η is 1 or 2; and X points: then it is connected to the position 1 of each R1 and the R2 of each cyclopentadiene moiety This replaces R1: and R2, and X is a donation [R11 I R1 in the group of U from U] I R11 I R11 P, 11 II 丨 3 —M3- I , U -MJ- I 丨 3 -f- 7 L 1 n—, R12 丨 Γ P, ^ R12 r12 r12 R11 R11 II R11 I R11 1 1 1 —C—C 一 | I, — —C— I 丨 3 —〇—γ — R12 R12 R12 R12 —BR11 A1R11, _Ge — ~ Sn—, —0 — —SO 7 ——S〇2, = NRn ^ __: 1 c〇 ,: PR11,-P (〇) RU where Ru and 1-12 can be the same or different, For the choice of free hydrogen, halogen, c, "C1-i 0 'II alkyl, C,) -10 aromatic group, 1 C6_10 fluoroaromatic group, (V1 {) alkoxy group,: 2_ i 〇 thin In the group consisting of C7_40 alkyl, c8_ • 40 alkenyl, or (aryl), or R11 and R12 may be the same or different, having 1 Alk anediyl gro up with or without substituents of 15 carbon atoms, in which R11 and R12 are connected to a carbon atom or M3 to form a cyclic system, and The substituents are C1-20 alkyl, C! _2. Fine "C6_2Q aromatic group, C7-20 aromatic group, c7_20 alkylaryl group, and M3 is selected free stone evening In the group of germanium, germanium, and thorium; 第21頁Page 21 490319 _案號 89115222_今/ 年 I 月、/ Q__ 六、申請專利範圍 (b ) 如化學式(II)所示之一金屬化合物: M2R54 (II) Μ2為第I VB族金屬; R5可為相同或不同,且為擇自由氫、鹵素、CrCu 脂 肪族基、C6-C1Q芳香族基、OH、OR6、NR72所組成之族群中, R6和R7獨立地為^-C2()脂肪族基或C6-C1Q芳香族基,將(a)與 (b )先預活化處理形成二茂金屬化合物之後;以及 (c ) 一活化助觸媒,擇自由(1 ) 銘氧院,(2 ) A 1 R83和酸 鹽之混合物,(3 ) A 1 R83和鋁氧烷之混合物所組成之族群 中,其中R8為。^脂肪族基或C6_1Q芳香族基。490319 _ Case No. 89115222_ This month / January // Q__ VI. Patent application scope (b) One of the metal compounds shown by chemical formula (II): M2R54 (II) M2 is a Group VB metal; R5 can be the same Or different, and in the group consisting of selective hydrogen, halogen, CrCu aliphatic group, C6-C1Q aromatic group, OH, OR6, NR72, R6 and R7 are independently ^ -C2 () aliphatic group or C6 -C1Q aromatic group, after (a) and (b) pre-activation treatment to form a metallocene compound; and (c) an activating catalyst, select (1) Ming oxygen institute, (2) A 1 R83 Among the group consisting of a mixture with a salt, (3) a mixture of A 1 R83 and alumoxane, R8 is. ^ Aliphatic or C6_1Q aromatic. 2 .如申請專利範圍第1項所述之觸媒組合物,其中M1 為第I I I A族金屬。 3 .如申請專利範圍第2項所述之觸媒組合物,其中M1 為ί呂。 4.如申請專利範圍第1項所述之觸媒組合物,其中至 少一個Ri為Μ1!?4。,至少一個R2為Μ1!?4,,MiR4n為擇自由A1 (CH3) 2,A1(C2H5)2,A1(C4H9)2,A1C12,GaCl2,Ga(CH3)2, G a ( C2H5) 2及G a ( C4H9 )2所組成之族群中。2. The catalyst composition as described in item 1 of the scope of patent application, wherein M1 is a Group I I I A metal. 3. The catalyst composition according to item 2 of the scope of patent application, wherein M1 is 为. 4. The catalyst composition according to item 1 of the scope of patent application, wherein at least one Ri is M1!? 4. , At least one R2 is M1 !? 4, MiR4n is optional A1 (CH3) 2, A1 (C2H5) 2, A1 (C4H9) 2, A1C12, GaCl2, Ga (CH3) 2, G a (C2H5) 2 and G a (C4H9) 2. 5 .如申請專利範圍第1項所述之觸媒組合物,其中至 少一個R1為M1!?4,,至少一個R2為M1!^,其餘之R1和R2為擇自 由氫、曱基、乙基、丙基、丁基、異丁基、戊基、異戊 基、己基、2-乙基己基、庚基、辛基、乙稀基、稀丙基、 異丙稀基、苯基.、和曱苯基所組成之族群中。 6 .如申請專利範圍第1項所述之觸媒組合物,其中至5. The catalyst composition according to item 1 of the scope of patent application, wherein at least one R1 is M1 !? 4, at least one R2 is M1! ^, And the remaining R1 and R2 are selected from hydrogen, fluorenyl, and ethyl. Propyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, ethyl, dipropyl, isopropyl, phenyl., And stilbene. 6. The catalyst composition according to item 1 of the patent application range, wherein 第22頁 490319 修正 案號 89115222 六、申請專利範圍 少一個R1為Μ1!^^,其餘之R1中,兩相鄰而連接於不同碳原 子之R1連接在一起而與其所連接之碳原子形成一具有4至 2 0個碳原子之環狀系統。 7.如申請專利範圍第6項所述之觸媒組合物,其中至 少一個R1為Μ1!?^,其餘之R1中,兩相鄰而連接於不同碳原 子R1連接在一起而與其所連接之碳原子形成飽合或不飽合 之多環之環戊二烯基配位基。 8 .如申請專利範圍第7項所述之觸媒組合物,其中該 飽合或不飽合之多環之環戊二怫基配位基為萌基、四氫印 基、荞基、或八氫第基。Page 22 490319 Amendment No. 89115222 Six. One patent application scope is one less R1 is M1! ^^ In the remaining R1, two adjacent R1s connected to different carbon atoms are connected together to form a carbon atom with which they are connected A ring system with 4 to 20 carbon atoms. 7. The catalyst composition as described in item 6 of the scope of patent application, wherein at least one R1 is M1!? ^, And in the remaining R1, two adjacent and connected to different carbon atoms R1 are connected together and connected to it. The carbon atoms form a saturated or unsaturated polycyclic cyclopentadienyl ligand. 8. The catalyst composition according to item 7 in the scope of the patent application, wherein the saturated or unsaturated polycyclic cyclopentafluorenyl ligand is a molybdenyl group, a tetrahydroinyl group, a buckwheat group, or Octahydrodiyl. 9.如申請專利範圍第1項所述之觸媒組合物,其中至 少一個R2為Μ1!?4。,其餘之R2中,兩相鄰而連接於不同礙原 子之R2連接在一起而與其所連接之碳原子形成一具有4至 2 0個碳原子之環狀系統。 1 0 .如申請專利範圍第9項所述之觸媒組合物,其中至 少一個R2為Μ1R4 n,其餘之R2中,兩相鄰而連接於不同$炭原 子之R2連接在一起而與其所連接之碳原子形成飽合或不飽 合之多環之環戊二烯基配位基。9. The catalyst composition according to item 1 of the scope of patent application, wherein at least one R2 is M1!? 4. In the remaining R2, two adjacent R2 connected to different interfering atoms are connected together to form a ring system with 4 to 20 carbon atoms. 10. The catalyst composition as described in item 9 of the scope of patent application, wherein at least one R2 is M1R4n, and in the remaining R2, two adjacent R2 adjacent to different carbon atoms are connected together and connected to them. Carbon atoms form a saturated or unsaturated polycyclic cyclopentadienyl ligand. 1 1 .如申請專利範圍第1 0項所述之觸媒組合物,其中 該飽合或不飽合之多環之環戊二烯基配位基為茚基、四氫 茚基、第基、或八氫苐基。 1 2 .如申請專利範圍第1項所述之觸媒組合物,其中 M2R54 為擇自由 Zr (N(CH3)2)4、ZrCl4、Zr(0CH3)4 > Zr (0C〇H5)4 和Zr ( 0C4H9 )4所組成之族君_中°1 1. The catalyst composition as described in item 10 of the scope of patent application, wherein the saturated or unsaturated polycyclic cyclopentadienyl ligands are indenyl, tetrahydroindenyl, and thylyl , Or octahydrofluorenyl. 1 2. The catalyst composition as described in item 1 of the scope of patent application, wherein M2R54 is Zr (N (CH3) 2) 4, ZrCl4, Zr (0CH3) 4 > Zr (0C〇H5) 4 and Family of Zr (0C4H9) 4 第23頁 490319 _案號89115222_W年元月> ί曰__ 六、申請專利範圍 1 3 . —種製備烯烴聚合物之方法,包括在有效催化劑 量之如申請專利範圍第1項所述之觸媒組合物的存在下及 聚合條件下,聚合(a ) —烯烴,或(b )至少一稀烴與至少一 其他單體,其中該聚合(a)或(b) —烯烴,為環烯烴,其中 該聚合(b )至少一其他單體,該其他單體為非環狀烯烴。Page 23 490319 _Case No. 89115222_W January > ί __ VI. Patent application scope 1 3. A method for preparing an olefin polymer, including the effective catalyst amount as described in item 1 of the patent application scope In the presence of the catalyst composition and polymerization conditions, (a)-olefin, or (b) at least one dilute hydrocarbon and at least one other monomer, wherein the polymerized (a) or (b)-olefin is a cyclic olefin Wherein the polymerization (b) is at least one other monomer, and the other monomer is an acyclic olefin. 1 4.如申請專利範圍第1 3項所述之方法,其中該環烯 烴為擇自由二環庚烯類、三環癸烯類、三環十一碳烯類、 四環十二碳稀類、五環十五碳烯類、五環十五碳二稀類、 五環十六碟烯類、六環十七碳烯類、七環二十竣稀類、七 環二十一碳稀類、八環二十二碳稀類、九環二十五碳稀 類、和九環二十六碳烯類所組成之族群中。 1 5 .如申請專利範圍第1 3項所述之方法,其中該非環 狀烯烴為乙烯,或具有3至1 2個碳數的α -烯烴。 1 6 .如申請專利範圍第1 5項所述之方法,其中該α -烯 烴為擇自由丙烯、1- 丁烯、1-戊烯、1-己烯、和1-辛烯所 組成之族群中。 1 7 .如申請專利範圍第1 3項所述之方法,其中該方法 包括聚合(b ) —環烯烴與一非環狀烯烴,其中該環烯烴為 原冰片稀(η 〇 r b 〇 r n e n e ),且該非環狀稀烴為乙稀。14. The method as described in item 13 of the scope of patent application, wherein the cyclic olefins are selected from the group consisting of bicycloheptenes, tricyclodecenes, tricyclic undecenes, and tetracyclic dodecenes. , Pentacyclic fifteen carbonenes, pentacyclic fifteen carbon carbenes, pentacyclic hexadecenes, hexacyclic seventeen carbonenes, seven ring tween carbons, seven ring twentieth carbons , Eight-ring twenty-two carbons, nine-ring twenty-five carbons, and nine-ring twenty-six carbons. 15. The method according to item 13 of the scope of patent application, wherein the acyclic olefin is ethylene, or an α-olefin having 3 to 12 carbon numbers. 16. The method according to item 15 of the scope of patent application, wherein the α-olefin is a group consisting of selective propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene in. 17. The method as described in item 13 of the scope of the patent application, wherein the method comprises polymerizing (b) a cyclic olefin and an acyclic olefin, wherein the cyclic olefin is raw borneol (η 〇rb 〇rnene), And the acyclic dilute hydrocarbon is ethylene. 第24頁Page 24
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Publication number Priority date Publication date Assignee Title
TWI549972B (en) * 2011-03-25 2016-09-21 艾克頌美孚化學專利股份有限公司 Vinyl terminated higher olefin copolymers and methods to produce thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI549972B (en) * 2011-03-25 2016-09-21 艾克頌美孚化學專利股份有限公司 Vinyl terminated higher olefin copolymers and methods to produce thereof

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