TW379232B - Process for the preparation of elastomeric copolymers of ethylene and products obtained therefrom - Google Patents
Process for the preparation of elastomeric copolymers of ethylene and products obtained therefrom Download PDFInfo
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- TW379232B TW379232B TW83108203A TW83108203A TW379232B TW 379232 B TW379232 B TW 379232B TW 83108203 A TW83108203 A TW 83108203A TW 83108203 A TW83108203 A TW 83108203A TW 379232 B TW379232 B TW 379232B
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五、發明説明(4 A7 B7 88. 8. Ml'正 年"補充 (A) —種具化學式(I)之金屬錯合物化合物: 根據本發明適用於觸媒之過渡金屬化合物是例如具 有化學式(I)之環戊二烯基化合物: (C5R15.m)R2ffl(C5R15-n1)MQ2 ( E ) 其中 Μ是鈦、结、給或釩; 基(彼此相同或各自不同)是相同或不同取代 之環戊二烯基環; R1 (彼此相同或各自不同)是氫原子、含有從1至 20個碳原子之烷基、烯基、芳基、烷芳基或芳烷基 ,且其也可含有矽或緒原子,或Si(CH3)3基,或 一種同一環戊二烯基之兩個或四個取代基R1也可 形成一個或兩個含有從4至6個碳原子環; R2是橋聯兩個環戊二烯基環之橋聯基,且係選自: CR32, C2R34. SiR32, Si2R34, GeR32 , Ge2R34, R32siCR32, NR1 和PR1 ,其中R3 (彼此相同或各自不同)是定義如 同R1或兩個或四個取代基R3可形成一個或兩個含 有從3至6個碳原子之環; Q (彼此相同或各自不同)是鹵素原子、氫原子、 R1, OR1, SR1, NRS 或 pRi2; m可為0或1 ; 選擇性地Μ —種具化學式(Μ )之鋁有機金屬化合物 加Μ預反應: A1R43.zHz (III) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ----------I 裝------訂------1 ^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印裝 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明(1 ) 本發明係關於一種Μ乙烯為基質之共聚物之製法,且 更特定言之,本發明係闞於一種製造乙烯彈性體共聚物 之漿液聚合法。 在Μ乙烯為基質之彈性體共聚物中,直到本發明之曰 期為止衹有乙烯-丙烯(ΕΡΜ)和乙烯-丙烯-二烯(EPDM)彈 性體是Μ商業規模來製造。 ΕΡΜ和EPDM彈性體之工業生產,目前是在戚格勒-納 他(Ζ丨egler-Natta)釩型觸媒的存在下,藉由溶液或漿 液聚合製法來進行。 在溶液聚合法中,共單體是溶解於溶劑(通常為己烷) 中,其中所形成之聚合物是可溶性。在漿液聚合法中,反應介質主 要是由液體烯烴類所構成,且所形成之聚合物是如网一種懸浮於液相之沉激物。 漿液聚合法比溶液聚合法提供許多優點,亦即: -無攪拌黏度之難題; -非常均勻的反應介質; -容易移除反應熱; -提高反應器生產量,由於在介質中聚合物之濃度較高; -聚合作用之產率較高; -製法非常高分子量聚合物之能力; -節省回收聚合物之能源; -投資與生產成本較低。 然而,漿液聚合法之主要的難題是產生自橡膠材料之 黏著性質。事實上,聚合物之固體顆粒是具傾向於彼此 附著在一起或附著到反應器之器壁表面和攪拌元件上。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)V. Description of the invention (4 A7 B7 88. 8. Ml 'positive year " Supplement (A)-a metal complex compound of formula (I): The transition metal compound suitable for the catalyst according to the present invention is Cyclopentadienyl compounds of formula (I): (C5R15.m) R2ffl (C5R15-n1) MQ2 (E) where M is titanium, junction, donor or vanadium; the radicals (the same or different from each other) are the same or different A substituted cyclopentadienyl ring; R1 (same or different from each other) is a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, or an aralkyl group, and it is also It may contain silicon or Si atoms, or Si (CH3) 3 groups, or two or four substituents of the same cyclopentadienyl group R1 may also form one or two rings containing from 4 to 6 carbon atoms; R2 Is a bridging group that bridges two cyclopentadienyl rings, and is selected from: CR32, C2R34. SiR32, Si2R34, GeR32, Ge2R34, R32siCR32, NR1 and PR1, where R3 (same or different from each other) is defined As R1 or two or four substituents R3 may form one or two rings containing from 3 to 6 carbon atoms; Q (same as each other or each (Different) is halogen atom, hydrogen atom, R1, OR1, SR1, NRS or pRi2; m can be 0 or 1; optionally M-a kind of aluminum organometallic compound with chemical formula (M) plus M pre-reaction: A1R43.zHz (III) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ---------- I Loading ------ Order ----- 1 ^ (please first Read the notes on the back and fill out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, and printed by the Consumer Standards Department of the Central Standards Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Description of the invention (1) The present invention relates to a kind of M ethylene The method for producing a copolymer, and more specifically, the present invention is a slurry polymerization method for producing an ethylene elastomer copolymer. In the M ethylene-based elastomer copolymer, only ethylene is used until the date of the present invention. -Propylene (EPM) and ethylene-propylene-diene (EPDM) elastomers are manufactured on a commercial scale by M. Industrial production of EPM and EPDM elastomers is currently in Zegler-Natta vanadium In the presence of a catalyst, it is carried out by a solution or slurry polymerization method. In the method, the comonomer is dissolved in a solvent (usually hexane), and the polymer formed therein is soluble. In the slurry polymerization method, the reaction medium is mainly composed of liquid olefins, and the polymer formed is It is a kind of precipitate suspended in the liquid phase, such as a mesh. The slurry polymerization method provides many advantages over the solution polymerization method, namely:-no difficulty in stirring viscosity;-very uniform reaction medium;-easy to remove reaction heat;-increase Reactor production, due to the higher polymer concentration in the medium;-Higher yields from polymerization;-The ability to produce very high molecular weight polymers;-Saving energy for polymer recycling;-Lower investment and production costs . However, the main problem with the slurry polymerization method is that it results from the adhesive properties of rubber materials. In fact, the solid particles of the polymer tend to adhere to each other or to the wall surface of the reactor and the stirring element. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)
-L 訂 五、發明説明(6 A7 B7-L Order 5. Description of the invention (6 A7 B7
經濟部中央標準局貝工消费合作社印策 其中:Me =甲基,Et =乙基,Bu = 丁基,Cp =環戊二烯基, Ind = li5 基,H4 Ind = 4,5,6,7-四氫 IP 基,Benz =笨甲基,Μ是鈦、誥、铪或釩,較佳為锆。 若m = 1,特別適用之環戊二烯基化合物是其中之諸 QRk是:環戊二烯基、茚基、2 -甲基-茚基、4,7 -二 甲基-茚基、2,4,7 -三甲基-茚基、4,5,6,7 -四氣節基、 2 -甲基-4,5,6,7-四氫茚基、4,7-二甲基-4,5 ,6,7-四氫 茚基、2,4,7-三甲基-4,5,6,7-四氫茚基或莞基,R2是 一種(CH3)2Si、C2H4 或 C(CH3)2 之二價基,且取 代基Q是氯原子或Ci -C7烴基,較佳為甲基。具有化學式(Π )(其中m = l)之環戊二烯基化合物之非 限制性實例是: Me2S i (Me4Cp) 2MMe2 Me2S i (I nd) 2MMe2 C2H4(Ind)2MMe2 C2H4(H4Ind).2MMe2 Ph2Si(Ind)^Cl2 C2Me4(Ind)2MCl2 C2H4(3-MeInd)2MCl2 C2H4( 2,4,7-MejInd) 2MC12 C2H4(2-MeH4Ind)2MCl2The policy of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: Me = methyl, Et = ethyl, Bu = butyl, Cp = cyclopentadienyl, Ind = li5, H4 Ind = 4,5,6, 7-tetrahydro IP group, Benz = benzylmethyl, M is titanium, hafnium, hafnium or vanadium, preferably zirconium. If m = 1, particularly suitable cyclopentadienyl compounds are the QRk of which are: cyclopentadienyl, indenyl, 2-methyl-indenyl, 4,7-dimethyl-indenyl, 2 , 4,7-trimethyl-indenyl, 4,5,6,7-tetrakisyl, 2-methyl-4,5,6,7-tetrahydroindenyl, 4,7-dimethyl- 4,5,6,7-tetrahydroindenyl, 2,4,7-trimethyl-4,5,6,7-tetrahydroindenyl or guanyl, R2 is a (CH3) 2Si, C2H4 or C (CH3) 2 is a divalent group, and the substituent Q is a chlorine atom or a Ci-C7 hydrocarbon group, preferably a methyl group. A non-limiting example of a cyclopentadienyl compound having the formula (Π) (where m = 1) is: Me2S i (Me4Cp) 2MMe2 Me2S i (Ind) 2MMe2 C2H4 (Ind) 2MMe2 C2H4 (H4Ind) .2MMe2 Ph2Si (Ind) ^ Cl2 C2Me4 (Ind) 2MCl2 C2H4 (3-MeInd) 2MCl2 C2H4 (2,4,7-MejInd) 2MC12 C2H4 (2-MeH4Ind) 2MCl2
Me2Si(Me4Cp)2MCl2 Me2Si(Ind)2MCl2 C2H4(Ind)2MCl2 C2H4(H4Ind)2MCl2 Ph(Me)Si(Ind)2MCl2 C2H4(Me4Cp)2MCl2 C2H4(2-MeInd)2MCl2 C2H4 < 5,6-Me2Ind) 2MC12 C2H4(3,4,7-Me3Ind) 2MC12Me2Si (Me4Cp) 2MCl2 Me2Si (Ind) 2MCl2 C2H4 (Ind) 2MCl2 C2H4 (H4Ind) 2MCl2 Ph (Me) Si (Ind) 2MCl2 C2H4 (Me4Cp) 2MCl2 C2H4 (2-MeInd) 2MCl2 C2H4Ind; 2MC12 C2H4 (3,4,7-Me3Ind) 2MC12
Me2C (Me4Cp) (MeCp) MC12 Me2Si (Me4Cp) 2MC1 (OEt) C2H4(Ind)214(NMe2)2 C2H4 (H4Ind) 2M (NMe2) OMe Me2C(Flu) (Cp)MCl2 Me2SiCH2(Ind)2MCl2 i C2H4( 4,7-Me2Ind)2MCl2 C2H4<4,7-Me2H4Ind>2MCl2 C2H4 (2,4,7 -Me3H41 nd) 2MC12 Me2S i (2 -Me Ind) jMC 12 Me2Si(3-MeInd)2MCl2 Me2Si (4,7 -He2Ind) 2MC12 本紙張尺度逋用中國國家標率(CNS ) A4规格(210X297公釐) I n I n .1 1 n l· I I I I I I 訂— I I I |级 (請先閲讀背面之注意事項再填寫本育) A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明( 2 ) 1 此 會 使 乙 烯 在 反 ttfcr 應 介 質 中 之 擴 散 大 大 地 惡 化,且更嚴重 1 1 I 的 是 會 導 致 密 集 的 反 trtf» 應 器 垢 積 1 因 此 使 得 聚合物之製法 1 1 1 非 常 困 難 0 /·—S 請 1 1 欲 避 免 此 等 難 題 t 可 添 加 溶 劑 (例如甲苯或環己烷)到 閱 讀 背 |. 反 懕 介 質 中 9 其 作 用 如 同 抗 垢 積 劑 和 如 同 觸媒系統之媒 之 1 劑 兩 者 0 使 用 . 種 低 沸 點 稀 釋 劑 (例如丙烷)也已被提議 注 意 1 事 1 趣 〇 而 » 此 結 果 導 致 上 述 漿 液 聚 合 法 之 優點顯著地減 項 再 1 填 上 少 〇 寫 本 I 已 被 提 議 之 另 一 解 決 方 法 是 添 加 抗 靜 電 劑入聚合反應 頁 1 I 器 中 〇 m i->'\ 而 此 解 決 方 法 並 不 是 完 全 令 人 滿 意的,且甚至 1 I 其 畲 具 有 引 介 非 所 欲 得 之 化 合 物 到 最 終 產 物之缺點。 1 1 iff 年 來 » 已 揭 述 在 金 靨 錯 合 物 /銘:氧烷觸媒的存在下 1 訂 製 造 彈 性 體 乙 烯 型 共 聚 物 之 方 法 〇 1 歐 洲 專 利 請案第347 , 128 揭 述 一 種 Μ漿液聚合法 1 丨 9 利 用 —- 種 支 if 在 矽 凝 膠 撐 體 之 衣口 錯 合 物 (girconcene) 1 /鋁氧垸觸媒K製造乙烯/ a -烯烴彈性體之方法。實施 1 例 是 闢 於 在 液 體 丙 烯 中 之 乙烯/丙烯共聚物之製法。其 I 中 之 敘 述 為 * 除 非 觸 媒 在 被 使 用 於 漿 液 聚 合製法之前, 1 1 先 與 乙 烯 或 另 一 種 α -烯烴預聚合, 則反應器垢積會無 I 化 地 非 常 大 量 地 發 生 0 1 | 在 歐 洲 專 利 申 請 案 第 5 35 , 230 α必 中 9 已 提議一種能預 1 1 防發生垢積之製氣乙烯 型 共 聚 物 之 漿 液 聚 合法。此製法 1 I 是 在 一 種 聚 矽 氧 添 加 劑 和 一 種 矽 凝 膠 支 撐型結錯合物 1 1 /甲基鋁氧烷兩者之觸媒的存在下進行* -4- 1所有的實施例 .- 1 1 1 1 1 尺 張 紙 本 準 標 家 國 國 中 用 適Me2C (Me4Cp) (MeCp) MC12 Me2Si (Me4Cp) 2MC1 (OEt) C2H4 (Ind) 214 (NMe2) 2 C2H4 (H4Ind) 2M (NMe2) OMe Me2C (Flu) (Cp) MCl2 Me2SiCH2 (Ind) 2MCl2 i C2H 4,7-Me2Ind) 2MCl2 C2H4 < 4,7-Me2H4Ind > 2MCl2 C2H4 (2,4,7 -Me3H41 nd) 2MC12 Me2S i (2 -Me Ind) jMC 12 Me2Si (3-MeInd) 2MCl2 Me2Si (4,7 -He2Ind) 2MC12 This paper uses China National Standard (CNS) A4 size (210X297 mm) I n I n .1 1 nl · IIIIII Order — III | Grade (Please read the notes on the back before filling in this education ) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) 1 This will greatly worsen the diffusion of ethylene in the anti-ttfcr response medium, and more serious 1 1 I will cause intensive reaction trtf »reactor scale 1 makes polymer preparation 1 1 1 very difficult 0 / · —S please 1 1 To avoid these problems t Solvent (such as toluene or cyclohexane) can be added to the reading back |. 9 in the medium acts like anti-fouling Agent and the same agent as the catalyst system of the 0 agent 0. A low boiling point diluent (such as propane) has also been proposed to pay attention to 1 thing 1 interesting 0 and »This result leads to a significant reduction in the advantages of the above slurry polymerization method Refill 1 less. Script I. Another solution that has been proposed is to add an antistatic agent to the polymerization reactor. 1 m i- > '\ This solution is not completely satisfactory, and Even 1 I has the disadvantage of introducing undesired compounds to the final product. 1 1 iff years »The method of manufacturing elastomeric ethylene copolymers has been disclosed in the presence of a gold complex / Ming: oxane catalyst. 0 European Patent Application No. 347, 128 discloses a slurry of M. Polymerization method 1 丨 9 A method for producing ethylene / a-olefin elastomer by using if-girconcene 1 / aluminum oxide catalyst K in a silicone gel support. The first example is a method for preparing an ethylene / propylene copolymer in liquid propylene. The description in I is * Unless the catalyst is prepolymerized with ethylene or another α-olefin before being used in the slurry polymerization process, the reactor fouling will occur in a very large amount without I 1 0 | In European Patent Application Nos. 5 35, 230 α and B9, a slurry polymerization method has been proposed for gas-generating ethylene-type copolymers that can prevent scale formation. This manufacturing method 1 I is carried out in the presence of a catalyst of both a polysiloxane additive and a silicone gel-supported complex 1 1 / methylalumoxane * All the examples of -4- 1 1 1 1 1 1 Rule paper
I 五、發明説明(7 ) A7 B7I. Description of the invention (7) A7 B7
Me2Si(5,6 -Me2Ind) iMei-2 - Merisi (2,4,7-Me3Ind) 2MC12 Me2Si (3,4,7-Me3Ind)2MCl2 Me2S i (2 -MeH41 nd) 2MC12 >le2S 1(4,7 -Me2H41 nd) 2MC12 Me2Si (2,4,7-Me3H4Ind) 2MC12 Me2Si(Flu)2MCl2 C2H4(Flu)2MCl2 其中M e =甲基,C p =環戊二烯基,I n d = 15基,P 1 u =蒹基, Ph =苯基,H4 Ind = 4,5,6,7 -四氫茚基,M是钛、锆、給 或釩,較佳為誥。 適用於本發明觸媒之另一類型過渡金屬化合物是”受 限制幾何结構”型單環戊二烯基之化合物,係揭述於例 如歐洲專利申請案第EP-420 436號和第EP-520 732號, 其中之內容在此併於本文Μ供參考。 根撺本發明適用於觸媒之鋁的有機金屬化合物是:例 如,含有至少一具類型(IV )之基的線形、分支或環狀鋁 氧烧: R4 R4 -Α1*Me2Si (5,6 -Me2Ind) iMei-2-Merisi (2,4,7-Me3Ind) 2MC12 Me2Si (3,4,7-Me3Ind) 2MCl2 Me2S i (2 -MeH41 nd) 2MC12 > le2S 1 (4, 7 -Me2H41 nd) 2MC12 Me2Si (2,4,7-Me3H4Ind) 2MC12 Me2Si (Flu) 2MCl2 C2H4 (Flu) 2MCl2 where Me = methyl, C p = cyclopentadienyl, I nd = 15 groups, P 1 u = fluorenyl, Ph = phenyl, H4 Ind = 4,5,6,7-tetrahydroindenyl, M is titanium, zirconium, or vanadium, preferably rhenium. Another type of transition metal compound suitable for use in the catalyst of the present invention is a "restricted geometry" type monocyclopentadienyl compound disclosed in, for example, European Patent Application Nos. EP-420 436 and EP-520 No. 732, the content of which is here and incorporated herein by reference. According to the present invention, the organometallic compounds suitable for catalyst aluminum are: for example, linear, branched or cyclic aluminum containing at least one type (IV) group. Oxygen firing: R4 R4-Α1 *
(IV 經濟部中央橾準局貝工消费合作社印製 圮/ 其中諸取代基R4 (彼此相同或各自不同)定義為R1或為 一種-0-A1U4 )2,且任意地某些Θ可為鹵素原子或氫原子。 特定言之,若為線形化合物,則能使用具化學式(V ) 之鋁氧烷類: R1 R1- (請先閲讀背面之注意事項再填寫本頁) R1 R1 A1—0 A1. 0 -9 - A1 ‘R1(IV Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives / where the substituents R4 (which are the same or different from each other) are defined as R1 or a -0-A1U4) 2 and optionally some Θ may be halogen Atom or hydrogen atom. In particular, if it is a linear compound, an alumoxane having the chemical formula (V) can be used: R1 R1- (Please read the precautions on the back before filling this page) R1 R1 A1—0 A1. 0 -9- A1 'R1
(V 本紙張尺度適用中國國家橾準(CNS > A4規格(210X297公嫠) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(2) 係關於乙烯/丙烯彈性體。在未使用聚矽氧烷添加劑之 比較例中,已觀察到堵塞和故障。 在國際專利申請案第PCT/EP93/01528號中,揭逑一種 在金鼷錯合物觸媒的存在下,製造乙烯/1-丁烯或乙烯/ 1-丁烯/二烯彈性體共聚物之方法,其中反應介質是實 質地由液體1-丁烯所構成。此製法是並無反應器之垢積 琨象。 目前已意外地發規:能藉由漿液聚合法K製造含有少 量之一種或多種α -烯烴類之乙烯/丙烯或乙烯/丙烯/多 烯彈性體共聚物,其中反應介質是實質地由液體丙烯和 cx-烯烴之混合物所構成,卻並未依賴觸媒之支撐和/或 預聚合處理。 因此,本發明之目的是一種製造乙烯彈性體共聚物之製法 ,係包括一種包含乙烯、丙烯、至少1 5重量之至少一 具化學式(I )之α -烯烴: CH 2 =CHR ( I ) (其中R是含有從2至10個碳原子之烷基)及選擇性的少 量之至少一多烯之混合物,在一種主要是由液體丙烯和 α-烯烴連同溶解之氣體乙烯之反應介質中,且在一種 Μ屬於Kb、IVb、Vb、VIb族過渡金屬與元素周期表之 _ :系元素之金鼷錯合物化合物為基質之非-預聚合型觸 媒的存在下之漿液聚合反應。 適用於本發明製法之觸媒是:例如,包括藉由將下列 成分相接觸所獲得之產物: -5- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)(V This paper size applies to the Chinese National Standard (CNS > A4 size (210X297 cm)) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) It is about ethylene / propylene elastomer. In a comparative example using a polysiloxane additive, clogging and failure have been observed. In International Patent Application No. PCT / EP93 / 01528, a method for producing ethylene / gold in the presence of a gold complex catalyst is disclosed. 1-butene or ethylene / 1-butene / diene elastomer copolymer method, in which the reaction medium is essentially composed of liquid 1-butene. This method is produced without any scale buildup in the reactor. At present It has been unexpectedly issued that an ethylene / propylene or ethylene / propylene / polyene elastomer copolymer containing a small amount of one or more α-olefins can be produced by a slurry polymerization method K, wherein the reaction medium is substantially composed of liquid propylene and It is composed of a mixture of cx-olefins, but does not rely on the support and / or pre-polymerization treatment of the catalyst. Therefore, the object of the present invention is a method for producing an ethylene elastomer copolymer, which includes an ethylene, propylene, at least 1 5 weight A mixture of at least one α-olefin of formula (I): CH 2 = CHR (I) (where R is an alkyl group containing from 2 to 10 carbon atoms) and optionally a small amount of at least one polyene in a mixture of A kind of reaction medium mainly composed of liquid propylene and α-olefins together with dissolved gas ethylene, and in a M which belongs to Kb, IVb, Vb, VIb transition metals and the periodic table of the element _: gold element complex of element Slurry polymerization in the presence of a non-prepolymerized catalyst whose compound is a matrix. Catalysts suitable for use in the method of the present invention are, for example, products obtained by contacting the following ingredients: -5- paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm)
In n^i nn tm In n I ml ίΛ ^ HI ^^^1 ^^^1 ^^^1 nn ^ 、-口 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明(ιό ).In n ^ i nn tm In n I ml ίΛ ^ HI ^^^ 1 ^^^ 1 ^^^ 1 nn ^,-(please read the precautions on the back before filling this page) A7 B7 V. Description of the invention ( ιό).
OO 1» 實施例 1 62.3 -η 63.6 i ; -a P CO 乙烯 莫耳% 〇〇 cn υο μ-» Ch to 一 13.6 丙烯 莫耳无 05 ΓΟ oo b\ -1 10.2 卜丁烯 莫耳% 1 1 3.89 CO t—* -0 5.66 固有黏度 分升/克 3 Cl 0.69 1 0.43 0.31 —3 P Z3 α. 2.4 ro ro o 3: < 3: 3 rs Q_ 40.0 39.5 Ca5 05 <〇 差示量熱法 zs CL· 〇 cn OO -a to CO 1> Π: Λ-V --------V 袭------.玎-----10 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 —20— 本紙張適用中國國家標準(CNS ) ( 210X297公釐) 五、發明説明(4 A7 B7 88. 8. Ml'正 年"補充 (A) —種具化學式(I)之金屬錯合物化合物: 根據本發明適用於觸媒之過渡金屬化合物是例如具 有化學式(I)之環戊二烯基化合物: (C5R15.m)R2ffl(C5R15-n1)MQ2 ( E ) 其中 Μ是鈦、结、給或釩; 基(彼此相同或各自不同)是相同或不同取代 之環戊二烯基環; R1 (彼此相同或各自不同)是氫原子、含有從1至 20個碳原子之烷基、烯基、芳基、烷芳基或芳烷基 ,且其也可含有矽或緒原子,或Si(CH3)3基,或 一種同一環戊二烯基之兩個或四個取代基R1也可 形成一個或兩個含有從4至6個碳原子環; R2是橋聯兩個環戊二烯基環之橋聯基,且係選自: CR32, C2R34. SiR32, Si2R34, GeR32 , Ge2R34, R32siCR32, NR1 和PR1 ,其中R3 (彼此相同或各自不同)是定義如 同R1或兩個或四個取代基R3可形成一個或兩個含 有從3至6個碳原子之環; Q (彼此相同或各自不同)是鹵素原子、氫原子、 R1, OR1, SR1, NRS 或 pRi2; m可為0或1 ; 選擇性地Μ —種具化學式(Μ )之鋁有機金屬化合物 加Μ預反應: A1R43.zHz (III) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ----------I 裝------訂------1 ^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印裝 五、發明説明()OO 1 »Example 1 62.3 -η 63.6 i; -a P CO ethylene mole% 〇〇cn υο μ-» Ch to -13.6 propene mole no 05 ΓΟ oo b \ -1 10.2 bupropene mole% 1 1 3.89 CO t— * -0 5.66 Intrinsic viscosity deciliter / gram 3 Cl 0.69 1 0.43 0.31 —3 P Z3 α. 2.4 ro ro o 3: < 3: 3 rs Q_ 40.0 39.5 Ca5 05 < 〇 differential Thermal method zs CL · 〇cn OO -a to CO 1 > Π: Λ-V -------- V attack ------. 玎 ----- 10 (Please read the note on the back first Please fill in this page for further information.) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs—20— This paper is applicable to Chinese National Standards (CNS) (210X297 mm) 5. Description of the invention (4 A7 B7 88. 8. Ml 'year " Supplement (A)-a metal complex compound of formula (I): The transition metal compound suitable for use as a catalyst according to the present invention is, for example, a cyclopentadienyl compound of formula (I): (C5R15.m ) R2ffl (C5R15-n1) MQ2 (E) where M is titanium, junction, or vanadium; the radicals (which are the same or different from each other) are the same or different substituted cyclopentadienyl rings; R1 (the same as or different from each other) Is a hydrogen atom, an alkyl group, alkenyl group, aryl group, alkaryl group or aralkyl group containing 1 to 20 carbon atoms, and it may also contain a silicon or a silicon atom, or a Si (CH3) 3 group, or Two or four substituents R1 of the same cyclopentadienyl group may also form one or two rings containing from 4 to 6 carbon atoms; R2 is a bridging group that bridges two cyclopentadienyl rings, and Is selected from: CR32, C2R34. SiR32, Si2R34, GeR32, Ge2R34, R32siCR32, NR1 and PR1, where R3 (same or different from each other) is defined as R1 or two or four substituents R3 can form one or two A ring containing 3 to 6 carbon atoms; Q (same or different from each other) is a halogen atom, hydrogen atom, R1, OR1, SR1, NRS or pRi2; m may be 0 or 1; optionally M—species Pre-reaction of aluminum organometallic compound with chemical formula (M) plus M: A1R43.zHz (III) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ---------- I Pack- ----- Order ------ 1 ^ (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
經濟部智慧財產局員工消費合作社印製_ 補充實施例 補充實施 此實施例 在此所使用 述之較佳α 之金羼錯合 於說明書第 乙烯,丙 至18頁實施 此試驗傺 書第17頁般 備,採用二 基)結作為 共觸媒。 聚合反應 詳細之聚合 污垢産生。 藉由去除 聚合物;如 表1 例以明確支持申請專利範阖之請求。 俗關於乙烯/丙烯/1-己烯三聚物之聚合筲例。 之共聚單髏卜己烯傜已列示於第14頁第6行所 -烯烴種類中。再者,於如下實施例中所使用 物則為Me3 Si(H* Ind)2 ZrCl3 ,其亦已檫示 9頁第2行所述之較佳觸媒領域。 烯及卜己烯之共聚合試驗俗根據說明書第17頁 例1-3所示步驟來進行。 在4. 25升之壓熱器中進行,該壓熱器係如說明 處理;觸媒溶液偽以說明書第17頁所述方法製 氮化二甲基矽烷二基一雙(4, 5, 6, 7-四氫茚 觸媒及Al(iBu)3 (TIBAL)作為烷基括化合物之 傑在溫度50C,總壓22.7巴下進行60分鏞;更 條件傜示於下表1 。在反應器中並未觀察到有 未反應單體且而後於真空下乾燥來分離出所得 此得到之三聚物之特擞參權則示於表2。Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ Supplementary Example The supplementary implementation of this example. The gold used in this example is better. As a general preparation, a two-base) junction is used as a co-catalyst. Polymerization Detailed polymerization Fouling is generated. By removing the polymer; see the example in Table 1 to clearly support the request for patent application. Examples of polymerization of ethylene / propylene / 1-hexene terpolymer. The copolymerized mono-stilbeneene has been listed in the olefin species in line 6 on page 14. Furthermore, the materials used in the following examples are Me3Si (H * Ind) 2 ZrCl3, which has also shown the preferred catalyst field described in line 2 on page 9. The copolymerization test of olefin and dihexene is carried out according to the procedures shown in Examples 1-3 on page 17. It was carried out in a 4.25 liter autoclave, which was treated as described; the catalyst solution was prepared by the method described on page 17 of the instruction manual to produce dimethylsilyl disilyl-bis (4, 5, 6 , 7-tetrahydroindene catalyst and Al (iBu) 3 (TIBAL) as alkyl compound compounds were carried out at a temperature of 50C and a total pressure of 22.7 bar for 60 minutes; more conditions are shown in Table 1 below. In the reactor The unreacted monomers were not observed in the sample and then dried under vacuum to isolate the resulting terpolymer. The specific parameters are shown in Table 2.
Zr (mmoHO·3) AI (mmol) AI/H^ (mol) Cz/liq (g) C^q (g) C/Uq (g) 產量 (g) 活性 (kgoo/grr) 1.875 1.875 2 194 557 722 56 327.4 本紙張尺度適用中國國家標準(CNS ) A4规格(21〇Χ2.97公嫠) I----^丨--^--〗裝------訂--------4 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明(5 ) 其中R4 (彼此相同或各自不同)是含有從1至10個 碳原子之烷基、烯基或烷芳基, 且Z可為0或1 ;和 (B) —種鋁氧烷,選擇性地與一種具化學式(® )之鋁的 有機金鼷化合物混合: airVa (I ) 其中R4和z之定義同上,或一種或多種之能提供 一種金龎錯合物烷基陽離子之化合物。 若m = o ,特別適用之環戊二烯基化合物是其中之諸 CiR1^是:環戊二烯基、五甲基-環戊二鋪基、訪基或 4 , 5 , 6 , 7 -四氫茚基,且諸取代基Q係選自氯原子和 烴基,較佳為甲基或羥基。 具通式(E )(其中m = 0 )之環戊二烯基化合物之非限制Zr (mmoHO · 3) AI (mmol) AI / H ^ (mol) Cz / liq (g) C ^ q (g) C / Uq (g) Yield (g) Activity (kgoo / grr) 1.875 1.875 2 194 557 722 56 327.4 This paper size is applicable to China National Standard (CNS) A4 specification (21〇 × 2.97 cm) I ---- ^ 丨-^ -------------------------- Order --- 4 (Please read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Bayer Consumer Cooperative A7 B7 V. Invention Description (5) where R4 (same or different from each other) contains from 1 Alkyl, alkenyl or alkaryl groups of up to 10 carbon atoms, and Z may be 0 or 1; and (B) an aluminoxane, optionally with an organic gold tincture of aluminum having the chemical formula (®) Compound mixing: airVa (I) wherein R4 and z have the same definitions as above, or one or more compounds capable of providing a gold sulfide alkyl cation. If m = o, particularly suitable cyclopentadienyl compounds are CiR1 ^: cyclopentadienyl, pentamethyl-cyclopentadiyl, alkynyl, or 4, 5, 6, 7-tetracycline Hydroindenyl, and the substituents Q are selected from a chlorine atom and a hydrocarbon group, and are preferably a methyl group or a hydroxyl group. Non-limiting cyclopentadienyl compounds of general formula (E) (where m = 0)
性實例是: (Cp)2MCl2 (MeCp)2MCl2 (BuCp)2MCl2 (Me3Cp)2MCl2 (Me4Cp)2MCl2 (Me5Cp>2MCl2 (Me5Cp)2MMe2 (Me5Cp〉2M(OMeh (Me5Cp)2M(OH)Cl (Me5Cp>2M(OH)2 (Me5Cp)2M(Ci6H5)2 (MejCp)2M(CH3)Cl (EtMe4Cp)2MCl2 [(C6H5)Me4Cp]2MCl2 (Et5Cp)2MCl2 (Me5Cp )^(^5) Cl (Ind)2MCl2 (Ind)2MMe2 (H4Ind〉2MCl2 (H4Ind)2MMe2 {[Si(CH3)3]Cp}2MCl {[Si(CH3)3]2Cp}2MCl2 (Me4Cp) (Me5Cp)MCl2 (Me5Cp)MCl2 (He5Cp)MBenk\, (Ind)MBenz3 (H4Ind)MBenz3 (Cp)MBu3 (Me5Cp)MCl (Me5Cp)MH 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) ---------1 ,衣------訂-------1 (請先閲讀背面之注意事項再填寫本頁) 1 r-—: _ ·* .一 B7 五、發明説明() 1 -V " 二':· V::.. ! > ------------ A7 表2 c: (%mol) C3 (%τηοί) C6 (%mol) I.V. _ Μ„/Μη 72.3 20.9 6.8 3.61 0.63 2.1 在13C-NMR光譜中,並未觀察到顯示在兩俩三级磺原子間 存在有-(CH2 )η -(η為偶數)序列之峰值。 如上資料顯示所得到的三聚物可滿足修正後之申請專利 範圍第6項之每一俩基本特性。由此看來此等申請專利範圍 應足以獲得申請人所提出之實驗結果之支持。而根據此一 補充例來看,應足以支持應無需要將原申請專利範圍第5及 6項併入第1項。 ----i.--:--〗裝------訂-----^--- ^ (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 五、發明説明(6 A7 B7The property examples are: (Cp) 2MCl2 (MeCp) 2MCl2 (BuCp) 2MCl2 (Me3Cp) 2MCl2 (Me4Cp) 2MCl2 (Me5Cp > 2MCl2 (Me5Cp) 2MMe2 (Me5Cp> 2M (OMeh (Me5Cp) 2M (OH) Cl; (OH) 2 (Me5Cp) 2M (Ci6H5) 2 (MejCp) 2M (CH3) Cl (EtMe4Cp) 2MCl2 ((C6H5) Me4Cp) 2MCl2 (Et5Cp) 2MCl2 (Me5Cp) ^ (^ 5) Cl (Ind) 2MCl2 (Ind ) 2MMe2 (H4Ind> 2MCl2 (H4Ind) 2MMe2 {[Si (CH3) 3] Cp} 2MCl {[Si (CH3) 3] 2Cp} 2MCl2 (Me4Cp) (Me5Cp) MCl2 (Me5Cp) MCl2 (He5Cp) MBenk \, Ind) MBenz3 (H4Ind) MBenz3 (Cp) MBu3 (Me5Cp) MCl (Me5Cp) MH The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --------- 1, clothing- ----- Order ------- 1 (Please read the notes on the back before filling out this page) 1 r-—: _ · *. Ⅰ B7 V. Description of the invention () 1 -V " Ⅱ ': · V :: ..! ≫ ------------ A7 Table 2 c: (% mol) C3 (% τηοί) C6 (% mol) IV _ Μ „/ Μη 72.3 20.9 6.8 3.61 0.63 2.1 In the 13C-NMR spectrum, no peaks showing the sequence of-(CH2) η-(η is an even number) between two third-order sulfonic atoms were observed. The above data shows the obtained trimer Can satisfy amended claims Please request the basic characteristics of each of the patent scope item 6. From this, it seems that the scope of these patent applications should be sufficient to support the experimental results proposed by the applicant. According to this supplementary example, it should be sufficient to support the need The 5th and 6th of the scope of the original patent application are merged into the 1st item. ---- i .--: ---------------------------------- ^ (Please read first Note on the back, please fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) V. Description of the invention (6 A7 B7
經濟部中央標準局貝工消费合作社印策 其中:Me =甲基,Et =乙基,Bu = 丁基,Cp =環戊二烯基, Ind = li5 基,H4 Ind = 4,5,6,7-四氫 IP 基,Benz =笨甲基,Μ是鈦、誥、铪或釩,較佳為锆。 若m = 1,特別適用之環戊二烯基化合物是其中之諸 QRk是:環戊二烯基、茚基、2 -甲基-茚基、4,7 -二 甲基-茚基、2,4,7 -三甲基-茚基、4,5,6,7 -四氣節基、 2 -甲基-4,5,6,7-四氫茚基、4,7-二甲基-4,5 ,6,7-四氫 茚基、2,4,7-三甲基-4,5,6,7-四氫茚基或莞基,R2是 一種(CH3)2Si、C2H4 或 C(CH3)2 之二價基,且取 代基Q是氯原子或Ci -C7烴基,較佳為甲基。具有化學式(Π )(其中m = l)之環戊二烯基化合物之非 限制性實例是: Me2S i (Me4Cp) 2MMe2 Me2S i (I nd) 2MMe2 C2H4(Ind)2MMe2 C2H4(H4Ind).2MMe2 Ph2Si(Ind)^Cl2 C2Me4(Ind)2MCl2 C2H4(3-MeInd)2MCl2 C2H4( 2,4,7-MejInd) 2MC12 C2H4(2-MeH4Ind)2MCl2The policy of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: Me = methyl, Et = ethyl, Bu = butyl, Cp = cyclopentadienyl, Ind = li5, H4 Ind = 4,5,6, 7-tetrahydro IP group, Benz = benzylmethyl, M is titanium, hafnium, hafnium or vanadium, preferably zirconium. If m = 1, particularly suitable cyclopentadienyl compounds are the QRk of which are: cyclopentadienyl, indenyl, 2-methyl-indenyl, 4,7-dimethyl-indenyl, 2 , 4,7-trimethyl-indenyl, 4,5,6,7-tetrakisyl, 2-methyl-4,5,6,7-tetrahydroindenyl, 4,7-dimethyl- 4,5,6,7-tetrahydroindenyl, 2,4,7-trimethyl-4,5,6,7-tetrahydroindenyl or guanyl, R2 is a (CH3) 2Si, C2H4 or C (CH3) 2 is a divalent group, and the substituent Q is a chlorine atom or a Ci-C7 hydrocarbon group, preferably a methyl group. A non-limiting example of a cyclopentadienyl compound having the formula (Π) (where m = 1) is: Me2S i (Me4Cp) 2MMe2 Me2S i (Ind) 2MMe2 C2H4 (Ind) 2MMe2 C2H4 (H4Ind) .2MMe2 Ph2Si (Ind) ^ Cl2 C2Me4 (Ind) 2MCl2 C2H4 (3-MeInd) 2MCl2 C2H4 (2,4,7-MejInd) 2MC12 C2H4 (2-MeH4Ind) 2MCl2
Me2Si(Me4Cp)2MCl2 Me2Si(Ind)2MCl2 C2H4(Ind)2MCl2 C2H4(H4Ind)2MCl2 Ph(Me)Si(Ind)2MCl2 C2H4(Me4Cp)2MCl2 C2H4(2-MeInd)2MCl2 C2H4 < 5,6-Me2Ind) 2MC12 C2H4(3,4,7-Me3Ind) 2MC12Me2Si (Me4Cp) 2MCl2 Me2Si (Ind) 2MCl2 C2H4 (Ind) 2MCl2 C2H4 (H4Ind) 2MCl2 Ph (Me) Si (Ind) 2MCl2 C2H4 (Me4Cp) 2MCl2 C2H4 (2-MeInd) 2MCl2 C2H4Ind; 2MC12 C2H4 (3,4,7-Me3Ind) 2MC12
Me2C (Me4Cp) (MeCp) MC12 Me2Si (Me4Cp) 2MC1 (OEt) C2H4(Ind)214(NMe2)2 C2H4 (H4Ind) 2M (NMe2) OMe Me2C(Flu) (Cp)MCl2 Me2SiCH2(Ind)2MCl2 i C2H4( 4,7-Me2Ind)2MCl2 C2H4<4,7-Me2H4Ind>2MCl2 C2H4 (2,4,7 -Me3H41 nd) 2MC12 Me2S i (2 -Me Ind) jMC 12 Me2Si(3-MeInd)2MCl2 Me2Si (4,7 -He2Ind) 2MC12 本紙張尺度逋用中國國家標率(CNS ) A4规格(210X297公釐) I n I n .1 1 n l· I I I I I I 訂— I I I |级 (請先閲讀背面之注意事項再填寫本育) 五、發明説明(7 ) A7 B7Me2C (Me4Cp) (MeCp) MC12 Me2Si (Me4Cp) 2MC1 (OEt) C2H4 (Ind) 214 (NMe2) 2 C2H4 (H4Ind) 2M (NMe2) OMe Me2C (Flu) (Cp) MCl2 Me2SiCH2 (Ind) 2MCl2 i C2H 4,7-Me2Ind) 2MCl2 C2H4 < 4,7-Me2H4Ind > 2MCl2 C2H4 (2,4,7 -Me3H41 nd) 2MC12 Me2S i (2 -Me Ind) jMC 12 Me2Si (3-MeInd) 2MCl2 Me2Si (4,7 -He2Ind) 2MC12 This paper uses China National Standard (CNS) A4 size (210X297 mm) I n I n .1 1 nl · IIIIII Order — III | Grade (Please read the notes on the back before filling in this education ) 5. Description of the invention (7) A7 B7
Me2Si(5,6 -Me2Ind) iMei-2 - Merisi (2,4,7-Me3Ind) 2MC12 Me2Si (3,4,7-Me3Ind)2MCl2 Me2S i (2 -MeH41 nd) 2MC12 >le2S 1(4,7 -Me2H41 nd) 2MC12 Me2Si (2,4,7-Me3H4Ind) 2MC12 Me2Si(Flu)2MCl2 C2H4(Flu)2MCl2 其中M e =甲基,C p =環戊二烯基,I n d = 15基,P 1 u =蒹基, Ph =苯基,H4 Ind = 4,5,6,7 -四氫茚基,M是钛、锆、給 或釩,較佳為誥。 適用於本發明觸媒之另一類型過渡金屬化合物是”受 限制幾何结構”型單環戊二烯基之化合物,係揭述於例 如歐洲專利申請案第EP-420 436號和第EP-520 732號, 其中之內容在此併於本文Μ供參考。 根撺本發明適用於觸媒之鋁的有機金屬化合物是:例 如,含有至少一具類型(IV )之基的線形、分支或環狀鋁 氧烧: R4 R4 -Α1*Me2Si (5,6 -Me2Ind) iMei-2-Merisi (2,4,7-Me3Ind) 2MC12 Me2Si (3,4,7-Me3Ind) 2MCl2 Me2S i (2 -MeH41 nd) 2MC12 > le2S 1 (4, 7 -Me2H41 nd) 2MC12 Me2Si (2,4,7-Me3H4Ind) 2MC12 Me2Si (Flu) 2MCl2 C2H4 (Flu) 2MCl2 where Me = methyl, C p = cyclopentadienyl, I nd = 15 groups, P 1 u = fluorenyl, Ph = phenyl, H4 Ind = 4,5,6,7-tetrahydroindenyl, M is titanium, zirconium, or vanadium, preferably rhenium. Another type of transition metal compound suitable for use in the catalyst of the present invention is a "restricted geometry" type monocyclopentadienyl compound disclosed in, for example, European Patent Application Nos. EP-420 436 and EP-520 No. 732, the content of which is here and incorporated herein by reference. According to the present invention, the organometallic compounds suitable for catalyst aluminum are: for example, linear, branched or cyclic aluminum containing at least one type (IV) group. Oxygen firing: R4 R4-Α1 *
(IV 經濟部中央橾準局貝工消费合作社印製 圮/ 其中諸取代基R4 (彼此相同或各自不同)定義為R1或為 一種-0-A1U4 )2,且任意地某些Θ可為鹵素原子或氫原子。 特定言之,若為線形化合物,則能使用具化學式(V ) 之鋁氧烷類: R1 R1- (請先閲讀背面之注意事項再填寫本頁) R1 R1 A1—0 A1. 0 -9 - A1 ‘R1(IV Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives / where the substituents R4 (which are the same or different from each other) are defined as R1 or a -0-A1U4) 2 and optionally some Θ may be halogen Atom or hydrogen atom. In particular, if it is a linear compound, an alumoxane having the chemical formula (V) can be used: R1 R1- (Please read the precautions on the back before filling this page) R1 R1 A1—0 A1. 0 -9- A1 'R1
(V 本紙張尺度適用中國國家橾準(CNS > A4規格(210X297公嫠) 五、發明説明(8 A7 B7 其中I)是0或為一包含介於1與40之間的整數, 或若為環狀化合物,則能使用具有化學式(VI )之鋁氧烷 類: —R1 A1 —Ο(V This paper size applies to the Chinese National Standard (CNS > A4 size (210X297)) 5. Description of the invention (8 A7 B7 where I) is 0 or an integer between 1 and 40, or if For cyclic compounds, alumoxanes having the chemical formula (VI) can be used: —R1 A1 —〇
(VI 其中η是一包含介於2與4 0之間的整數。 較佳的R 1基是甲基、乙基、異丁基。根據本發明適 用之鋁氧烷之實例是:甲基鋁氧烷(ΜΑ0)和四異丁基二 鋁氧烷(Τ I B A 0 )。 適用於本發明觸媒之一種特殊種類的鋁的有機金屬化 合物,係能藉由將鋁烷基類或烷基氫化物與水,分別在 莫耳比率為包含介於1:1與100:1之間的條件下進行反應 所獲得。此類型之化合物是揭述於歐洲專利申請案第 EP-575 875號,其中之内容在此併於本文Μ供參考。 也適用於本發明觸媒之鋁的有機金靨化合物是具有化 學式(W )之化合物: R1 R1 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印製 Α1—Ν — Α1' R1 〜R1 或具有化學式(硼> : R1 0 R1 (VI ) R1〆 AX _丨· S —....... Ai丨丨 、 Ο (W ) 10 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(9 ) 其中R1之定義同上。 介於鋁與金鼷錯合物化合物金屬之間的莫耳比率,通 常是包含介於約1 0 : 1與約1 〇 , 〇 〇 〇 : 1之間,且較佳為介於 約1 0 0 : 1與約5 , 0 0 0 : 1之間。 能提供一種金鼷錯合物烷基陽雛子之化合物之非限制 性實例是:具化學式Y + Z —之化合物,其中Y +是一種 布忍斯特(Bronsted’s)酸,能提供一質子且與具化學式 (Ϊ)之化合物之取代基0不可逆地反應,且Γ是一種相 容性陰離子,其並不配位,能使得會非常不毽定地從一 種烯烴条基質轉移之源自兩種化合物之反應的活性催化 性物種穩定化。較佳的陰離子z-係包含一個或更多之硼 原子。更佳的陰離子Z —是一種具化學式BAr«之陰離子 ,其中諸取代基A r (彼此相同或各自不同)是芳基(例如 苯基、五氟苯基、雙(三氟甲基)苯基。特佳的是肆-五 氟苯基-硼酸鹽。此外,具化學式B A r 3之化合物是能適當 地被使用。此類型之化合物是揭述於例如所發表之國際 專利申請案第W0 92/00333號,其中之內容在此併於本 文Μ供參考ϋ 使用於本發明製法之觸媒也能使用在惰性撐體上。此 係能藉由將金屬錯合物化合物U),或其與成分(Β)反 應之產物,或成分(Β )與隨後的金鼷錯合物化合物(A ), 沉積在惰性If體(例如矽石、氧化鋁、苯乙烯-二乙烯基 苯共聚物或聚乙烯)上來獲得。 能使用於本發明製法之多孔性有機撐體之特定種類揭 -11 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ----'ll·--------一,4------訂----.——-k (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明(10 ) 述於歐洲專利申請案第94110168.5號中,其中之内容在 此併於本文Μ供參考。 觸媒之諸成分是能在聚合作用之前將彼此相互接觸。 接觸時間通常是包含介於5與2 0分鐘之間。 根據一特定的具體實例,本發明製法是在一種液體丙 烯和1-丁烯之混合物中,在一種包括下列成分之反應產 物之觸媒的存在下進行: (Α)二氯化乙烯-雙(4 ,5,6 ,7 -四氫茚基)锆,和 (Β) —種選自:四異丁基-二鋁氧烷(ΤΙΒΑ0)和三異丁基 鋁(TIBAL)與水之反應產物之化合物。 在此個例中,呈液相之1 - 丁烯之數量通常是包含介於 1 5重量%與9 0重量%之間,較佳為介於2 0重量%與5 0重 量:¾之間。溶解於反應混合物中之乙烯之數量通常是包含 介於8重量%與4 5重量%之間,較佳為介於0重量%與 5重量$之間。二烯之選擇量通常包含介於0重量%與 5重量!K之間。而其差額是由液體丙烯補足1 0 0重量%。 本發明之聚合製法是能不連壤地或連鑛地進行。 聚合溫度通常是包含介於0 與2 0 0 °C之間,特別是在 介於2 0 °C與1 0 0 υ之間,且更特別是在介於3 0 f與8 0 °C 之間。 聚合產率是視觸媒之金屬錯合物成分之純度而定。因 此,藉由本發明製法所獲得之金屬錯合物化合物是能Μ 原狀使用或加以純化處理。 特定言之,藉由本發明製法是能製造乙烯彈性體共聚 -12- 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨0X297公釐) ^^1 ^^^1 ^^^1 ^^^1 In n I 及-—1 I ^^^1 ^^^1 ^^^1 一T>J (請先閲讀背面之注意事項再填寫本頁) B7 五、發明説明(11 ) 物包含:從35莫耳%至85莫耳:¾ ,較佳為從60莫耳%至 80莫耳%之乙烯單元,從10莫耳%至65莫耳SS;,較佳為 從1 5莫耳%至5 0莫耳$之衍生,自丙烯和自至少一具化學 式(I )之α -烯烴: CH 2 =CHR (I ) (其中R之定義同上),和從〇莫耳%至5莫耳% ,較佳 為從〇莫耳%至3莫耳之衍生自多烯單元,且具有下 列之特激: -反應性比率r .r 之乘積是低於1 ,且較佳為低於 e α 0.8; -少於2 $且較佳為少於1 %之C Η 2基包含於(C Η 2 ) η序列 中,其中η是一偶數。 -固有黏度是高於0 . 2分升/克。 共翬體單元之分布之分析是已藉由13碳-核磁共振分 析法(13C_NMR)來進行。賦值(assignments)是已根據揭 述於下列文獻來進行: M. Kakugo et al., Macromolecules 15, 1150-1152 (1982); L. Sun, S. Lin, J. Polym. Sci.- Part A-Polym. Chem. 28, 1237, (1990); 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) E.T. Hsieh, J.C. Randall/ Macromolecules 15, 353 (1983); H.N. Cheng, J. Polym. Phys. 21, 573, (1983). 在乙烯/丙烯/ 1 - 丁烯三聚體之個例中,反應性比率 re . ra之乘積(其中re是乙烯之反應性比且ra是共單體 單元之反應性比),係根據下列公式所計算得: _ 1 3 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(12 ) re-r„ = 4(EE) (PP+BB)/(EP+EB)2 其中EE、PP、BB、EP和EB是分別代表在共聚物中之乙烯 /乙烯、丙烯/丙烯、丁烯/ 丁烯、乙烯/丙烯和乙烯/ 丁 烯之序列。 適用於本發明製法之α -烯烴類是:例如,1 - 丁烯、 1 -戊烯、1 -己烯、4 -甲基-1 -戊烯、烯丙基-三甲基-矽 烷,較佳的是]-丁烯。 適用之多烯類是包括: -能提供不飽和單元之多烯類,例如: -線形、非-共軛二烯類(例如反1,4 -己二烯、順1 , 4 -己 二烯、6 -甲基-1 , 5 -庚二烯、3,7 -二甲基-1 , 6 -辛二烯 、:Π -甲基- ι,]〇 -十二碳二烯); -簞環狀二烯烴類(例如順-1,5 -環辛二烯和5 -甲基-1 , 5 -環辛二稀); -雙環狀二烯烴類(例如4 , 5,8 , 9 -四氫茚基及Γ)和/或7 -甲基-4,5,8,9 -四氫茚); -烯基(alkenyl)或亞烷基(alkyiiden)原冰片烯類 (norborenes)(例如亞乙基原冰Η烯、5-亞異丙 基-2 -原冰Η烯、外-5 -異丙烯基-2 -原冰片烯); 2 7 -多環二烯烴類(例如二環戊二烯、三環-[6 . 2 . 1 . ]- 4 , 9 -十一碳二烯及其4 -甲基-衍生物); -能環聚合之非共扼二烯烴類(例如1 , 5 -己二烯、1,6 -二庚烯、2 -甲基-1 , 5 -己二烯); -共軛二烯類(例如丁二烯和異戊二烯)。 -14- 本紙張尺度適用中國國家標準(CNS ) A4规格(210X297公釐) n mu nl·— m nl· J 1^1 1 1^1 ^^^1 ^^^1 一ov (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明 (13 ) 1 1 具 有 衍 生 白 乙 烯 單 元 之 含 量 是 接 近 85 莫 耳 % 之 上 限 之 1 1 I 共 聚 物 是 具 有 熔 化 焓 高 於 2 0 焦 耳 /克c 1 1 從 本 發 明 製 法 是 能 獲 得 共 聚 物 具 有 固 有 黏 度 為 高 於 請 先 1 2 . 0分升/ 克 » 且 較 佳 為 高 於 3 . 0分升/ 克 〇 固 有 黏 度 能 達 閲 讀 1 背 1 到 4 . 0分升/ 克 和 Μ 上 之 值 0 之 1 通 常 上 述 之 共 聚 物 结 果 是 賦 予 狹 幅 (C 1 〇 s e ) 分 子 量 分 注 意 1 I 事 1 布 〇 分 子 量 分 布 之 指 數 是 Μ Μ ν S? / Μη 比率來表示, 對本 項 再 填 I 發 明 之 共 聚 物 其 通 常 是 低 於 3 . 5 更 佳 為 低 於 3 〇 寫 本 衣 聚 合 物 之 分 子 量 是 能 利 用 不 同 金 屬 錯 合 物 化 合 物 之 混 頁 、—· 1 I 合 物, 或進行幾個聚合溫度不同的聚合反應和/或分子量調節劑之濃度來 1 1 I 變 化 〇 1 1 上 述 聚 物 之 結 構 導 致 高 度 的 區 域 規 律 性 〇 事 實 上 > 1 訂 藉 由 13 碳 -核磁共振術關於包含介於兩個第三 三级碳原子 1 之 間 之 (CH 2 ) η 序 列 之 訊 號 (其中η 是- -偶數) 通 常 是 非 I 常 偵 测 性 Ο 1 | 上 述 共 聚 物 通 常 是 能 溶 解 於 普 通 溶 劑 中 (例如己烷' 、 1 庚 综 和 甲 苯 ) '1 I 能 藉 由 本 發 明 製 法 所 獲 得 之 共 聚 物 所 具 有 之 特 徵 為 : 1 1 具 有 價 值 的 性 質 > 例 如 低 灰 分 含 量 和 共 單 體 在 共 聚 物 m 1 中 之 分 布 均 勻 性 〇 | 此 等 共 聚 物 是 能 使 用 對 ΕΡΜ; 和 EPDM 橡 膠 之 熟 知 的 配 方 1 1 和 方 法 加 K 硫 化 » 例 如 在 過 氧 化 物 或 在 硫 的 存 在 下 操 作 1 I 〇 可 獲 得 賦 予 有 價 值 的 彈 性 體 性 質 之 橡 膠 〇 1 1 獲 白 此 等 共 聚 物 之 橡 膠 是 能 藉 由 通 用 於 熱 塑 性 材 料 之 1 1 | -1 5- 1 1 1 本紙張尺度適用中國國家標準(CNS Μ4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(l4 ) 加工方法(模製、擠製、射出成形、等等)而轉變成為模 製品。所獲得之模製品是賦予令人感興趣的彈性性質且 能用於所有的α -烯烴系彈性體之典型的應用領域。 特別是獲自具有高乙烯單元含量之共聚物之產物是能 有利地用作為電線或電纜之塗覆。 下列實例是提供作為例證用且並不限制本發明。 特件分析 在共聚物中之丙烯和α -烯烴含量是藉由13碳-核磁共 振分析(13 C - N M R )所测得。 共聚物之13碳-核磁共振分析是利用Bruker AC200儀 器,在溫度為120七,且在將約300毫克之聚合物溶解於 約2 . 5立方公分之3 : 1三氯苯/ C 2 D 2 C 1 4之混合物中所 獲得的試樣來進行测試。光譜圖是根據下列參數來記錄: -鬆弛遲延=1 2秒, -掃瞄之數目=2,000:2,500。 固有黏度[??]是在溫度為13 5 υ之四氫莆中所測得。 差示掃瞄量熱法(D . S . C .)之测量是在P e r k i η - Ε 1 m e r Co.之DSC-7儀器根據下列方法來進行。將約10毫克獲自 聚合作用之試樣冷卻至-25 υ,然後K掃瞄速率為相當 於1 0 °C /分鐘下加熱至2 0 0 °C。將試樣維持在2 0 0 °C為期 5分鐘,然後Μ掃瞄速率為相當於1 0 °C /分鐘加Μ冷卻 。然後再根據與第一次相同的方式進行第二次掃瞄。所 報導的數值是在第一次掃瞄所獲得的數值。 分子量分布是利用凝膠透層析術(GPC)在WATERS 150 -1 6 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公董) (請先聞讀背面之注意事項再填寫本頁) i ,ιτ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(15 ) 儀器於135t:之鄰-二氯苯中來進行。 觸媒成分夕製備 二氣化Ζ烯--U _ fi . 7 . 8 -四氣茚基)誥 係根據 H.H. Brintzinger 等人揭述於”<1.(^8311〇1116131· C h e m . , 2 8 8 , 6 3 ( 1 9 8 5 )” 方法所製得。 甲甚鋁氬烷(Μ A 0 ) 使用一種於3 0重量%甲苯溶液中之商品级產物(S c h e r丨n g ,分子量1,400)。在抽真空下將揮發性姐份移除後,將 玻化材料研磨直到獲得一種白色粉末,且將其進一步在 抽真空(0 . 1毫米汞柱)和溫度為4 0 °C下加K處理為期4小 時。藉此所獲得之粉末顯示優良之流動特性。 聚合作用 實瓶例1 - 3 將如表1所示用量之水、乙烯、丙烯和1-丁烯,在室 溫下引介入一種配備有:攪拌器、壓力計、 、溫度指示計、觸媒供應条統、供應單體之管線和恆溫 套箱之在80 CM乙烯沖洗而除氣過之4.25公升不锈鋼 製熱壓器中。然後將熱壓器加熱至低於聚合溫度5 C之 溫度。觸媒之溶液是根據下列方法所製得。將三異丁基 鋁(TIBAL)之甲苯溶液(0.2克TIBAL /毫升溶液)添加到一 種二氯化乙烯-雙(4,5,6,7 -四氫茚基)_之甲苯溶液(2 毫升甲苯/毫克金靨錯合物)中。將混合物保持在溫度為 20 °C並攪拌下為期5分鐘,然後將溶液在乙烯/丙烯混 合物(K 一種能維持反應浴中組成物常數之比率)之壓力 -17- 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -----------一-- (請先閱讀背面之注意事項再填寫本頁)(VI where η is an integer between 2 and 40. Preferred R 1 groups are methyl, ethyl, isobutyl. Examples of alumoxanes suitable according to the invention are: methylaluminum Oxane (ΜΑ0) and tetraisobutyldialuminoxane (TIBA 0). A special kind of aluminum organometallic compound suitable for the catalyst of the present invention can be hydrogenated by aluminyl or alkyl And water, respectively, obtained by carrying out a reaction under a Mohr ratio between 1: 1 and 100: 1. This type of compound is disclosed in European Patent Application No. EP-575 875, in which The content is here and incorporated by reference in this article. The organic gold compound that is also suitable for the aluminum of the catalyst of the present invention is a compound having the chemical formula (W): R1 R1 (Please read the precautions on the back before filling this page) Economy Department of Central Bureau of Standards Consumer Cooperation Du printed Α1—Ν — Α1 'R1 ~ R1 or have the chemical formula (boron): R1 0 R1 (VI) R1〆AX _ 丨 · S —....... Ai 丨丨, Ο (W) 10 This paper size applies to China National Standard (CNS) A4 (210X297 mm) Central Standard of the Ministry of Economic Affairs Printed by employee consumer cooperatives A7 B7 V. Description of the invention (9) where R1 has the same definition as above. The mole ratio between aluminum and gold complex compound metal usually contains between about 10: 1 and about 1 〇, 〇〇〇〇: 1, and preferably between about 100: 1 and about 5,00: 1. Can provide a gold compound complex of alkyl cations Restrictive examples are: compounds of the formula Y + Z —, where Y + is a Bronsted's acid, which can provide a proton and react irreversibly with the substituent 0 of the compound of the formula (Ϊ), and Γ Is a compatible anion, which does not coordinate, and can stabilize the active catalytic species derived from the reaction of two compounds that will be very uncertainly transferred from an olefin strip matrix. The preferred anion z-series Contains one or more boron atoms. A more preferred anion Z is an anion of the formula BAr «in which the substituents A r (which are the same or different from each other) are aryl groups (eg, phenyl, pentafluorophenyl, Bis (trifluoromethyl) phenyl Phenyl-borate. In addition, compounds of the formula BA r 3 can be used appropriately. Compounds of this type are disclosed, for example, in published International Patent Application No. WO 92/00333, the contents of which are here For reference herein, the catalyst used in the production method of the present invention can also be used on an inert support. This is a product that can be reacted with the metal complex compound U), or its reaction with the component (B), or The component (B) and the subsequent gold complex compound (A) are deposited on an inert If body such as silica, alumina, styrene-divinylbenzene copolymer or polyethylene. Specific types of porous organic supports that can be used in the production method of the present invention are disclosed.-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ---- 'll · ------- -I, 4 ------ Order ----.----- k (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention ( 10) described in European Patent Application No. 94110168.5, the contents of which are hereby incorporated herein by reference. The components of the catalyst are able to contact each other before polymerization. The contact time is usually comprised between 5 and 20 minutes. According to a specific embodiment, the method of the present invention is carried out in a mixture of liquid propylene and 1-butene in the presence of a catalyst including a reaction product of the following components: (A) ethylene dichloride-bis ( 4,5,6,7-tetrahydroindenyl) zirconium, and (B)-a product selected from the group consisting of: tetraisobutyl-dialumoxane (TIBAA0) and triisobutylaluminum (TIBAL) and water Of compounds. In this case, the amount of 1-butene in the liquid phase is usually comprised between 15% and 90% by weight, preferably between 20% and 50% by weight: ¾ . The amount of ethylene dissolved in the reaction mixture is usually comprised between 8% and 45% by weight, preferably between 0% and 5% by weight. The selected amount of diene usually contains between 0% by weight and 5% by weight! K. The difference is 100% by weight of liquid propylene. The polymerization method of the present invention can be carried out without contiguous land or continuous ore. The polymerization temperature is usually comprised between 0 and 2 0 ° C, especially between 20 ° C and 1 0 0 υ, and more particularly between 3 0 f and 80 ° C. between. The polymerization yield depends on the purity of the metal complex component of the catalyst. Therefore, the metal complex compound obtained by the production method of the present invention can be used as it is or purified. In particular, by the method of the present invention, it is possible to produce ethylene elastomer copolymerization-12- This paper size is applicable to China National Standard (CNS) A4 specifications (2 丨 0X297 mm) ^^ 1 ^^^ 1 ^^^ 1 ^^ ^ 1 In n I and --1 I ^^^ 1 ^^^ 1 ^^^ 1 One T &J; J (Please read the notes on the back before filling this page) B7 V. Description of the invention (11) The contents include: From 35 mol% to 85 mol: ¾, preferably from 60 mol% to 80 mol% of ethylene units, from 10 mol% to 65 mol SS; and preferably from 15 mol% Derived from 50 mol $ from propylene and from at least one α-olefin of formula (I): CH 2 = CHR (I) (wherein R is as defined above), and from 0 mol% to 5 mol %, Preferably from 0 mole% to 3 moles, derived from a polyene unit and having the following special stimuli:-The product of the reactivity ratio r .r is less than 1, and preferably less than e α 0.8;-C 2 2 groups of less than 2 $ and preferably less than 1% are included in the (C Η 2) η sequence, where η is an even number. -Inherent viscosity is higher than 0.2 dl / g. The analysis of the distribution of the consonant units has been performed by 13C-NMR analysis (13C-NMR). Assignments have been performed based on the disclosures in the following literature: M. Kakugo et al., Macromolecules 15, 1150-1152 (1982); L. Sun, S. Lin, J. Polym. Sci.- Part A- Polym. Chem. 28, 1237, (1990); Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the notes on the back before filling out this page) ET Hsieh, JC Randall / Macromolecules 15, 353 (1983); HN Cheng, J. Polym. Phys. 21, 573, (1983). In the case of ethylene / propylene / 1-butene trimer, the product of the reactivity ratio re.ra (where re is the reactivity ratio of ethylene And ra is the reactivity ratio of the co-monomer units), which is calculated according to the following formula: _ 1 3-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Print A7 B7 V. Description of the invention (12) re-r „= 4 (EE) (PP + BB) / (EP + EB) 2 where EE, PP, BB, EP and EB are respectively represented in the copolymer Sequences of ethylene / ethylene, propylene / propylene, butene / butene, ethylene / propylene, and ethylene / butene. Alpha-olefins suitable for use in the process of the present invention are For example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1 -pentene, allyl-trimethyl-silane, preferably] -butene. Polyenes suitable Classes include:-Polyenes capable of providing unsaturated units, for example:-Linear, non-conjugated diene (eg trans 1,4-hexadiene, cis 1, 4-hexadiene, 6-methyl -1, 5-heptadiene, 3,7-dimethyl-1, 6-octadiene: Π-methyl-ι,] 〇-dodecadiene);-fluorene cyclic diene (E.g. cis-1,5-cyclooctadiene and 5-methyl-1,5-cyclooctadiene); -bicyclic dienes (e.g. 4,5,8,9 -tetrahydroindenyl) And Γ) and / or 7-methyl-4,5,8,9-tetrahydroindene);-alkenyl or alkyiiden norborenes (such as ethylene Borneene, 5-isopropylidene-2 -orbornene, exo-5 -isopropenyl-2 -orbornene); 2 7-polycyclic diene (such as dicyclopentadiene, tri Ring- [6. 2. 1.]-4, 9-undecadiene and its 4-methyl-derivatives);-ring-polymerizable non-conjugated diene (eg 1, 5-hexadiene Ene, 1,6-diheptene, 2-methyl-1 , 5 -hexadiene);-conjugated dienes (such as butadiene and isoprene). -14- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) n mu nl · — m nl · J 1 ^ 1 1 1 ^ 1 ^^^ 1 ^^^ 1 ov (Please read first Note on the back, please fill out this page again) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) 1 1 The content of the derived white vinyl unit is close to the upper limit of 85 mol% 1 1 I copolymerization The substance has a melting enthalpy higher than 20 Joules / gram c 1 1 from the preparation method of the present invention is able to obtain a copolymer having an inherent viscosity of higher than 12.0 deciliters / gram »and preferably higher than 3.0. Deciliter / gram. Intrinsic viscosity can be read. 1 Back 1 to 4.0 Deciliter / gram and the value 0 on M. Usually the above copolymer results in giving a narrow (C 1 〇se) molecular weight. Note 1 I Event 1 The index of the molecular weight distribution is expressed by the ratio of Μ ν ν S? / Μη. The copolymer is usually lower than 3.5, and more preferably lower than 30. The molecular weight of the polymer is a mixture of different metal complex compounds,-1 I compounds, or several polymerization temperatures. The concentration of different polymerization reactions and / or molecular weight regulators varies by 1 1 I. The structure of the above polymers results in a high degree of regional regularity. In fact > 1 is defined by 13 carbon-nuclear magnetic resonance The signal of the (CH 2) η sequence between two third tertiary carbon atoms 1 (where η is--even) is usually not very detectable. 0 1 | The above copolymers are usually soluble in ordinary solvents ( For example, hexane ', 1 heptene and toluene)' 1 I The copolymers that can be obtained by the method of the present invention have the following characteristics: 1 1 valuable properties > such as low ash content and comonomers in Uniformity of distribution in polymer m 1 | These copolymers can be vulcanized using the well-known formulations 1 1 and methods of EPDM and EPDM rubber plus K vulcanization »such as operation in the presence of peroxide or sulfur 1 I 〇The rubbers with valuable elastomer properties can be obtained. 〇 1 1 The rubbers obtained from these copolymers can be used in thermoplastic materials. 1 1 | -1 5- 1 1 1 CNS M4 specification (210X297 mm) A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (14) Processing methods (molding, extrusion, injection molding, etc.) are transformed into molded products. The obtained molded article is a typical field of application which imparts interesting elastic properties and can be used for all α-olefin-based elastomers. In particular, products obtained from copolymers having a high content of ethylene units can be advantageously used as coatings for wires or cables. The following examples are provided for illustrative purposes and do not limit the invention. Feature analysis The propylene and α-olefin contents in the copolymer were measured by 13 carbon-nuclear magnetic resonance analysis (13 C-N M R). The 13-carbon-NMR analysis of the copolymer was performed using a Bruker AC200 instrument at a temperature of 120 ° C and about 300 mg of the polymer was dissolved in about 2.5 cubic centimeters of 3: 1 trichlorobenzene / C 2 D 2 The samples obtained from the C 1 4 mixture were tested. The spectra are recorded according to the following parameters:-relaxation delay = 12 seconds,-number of scans = 2,000: 2,500. Intrinsic viscosity [??] is measured in tetrahydrofluorene at a temperature of 13 5 υ. Differential scanning calorimetry (D.S.C.) measurement was performed on a DSC-7 instrument of Pe r k i η-E 1 m r Co. according to the following method. About 10 mg of the sample obtained from the polymerization was cooled to -25 υ, and then heated to 2000 ° C at a K scan rate equivalent to 10 ° C / minute. The sample was maintained at 200 ° C for 5 minutes, and then the M scanning rate was equivalent to 10 ° C / minute plus M cooling. Then perform a second scan in the same way as the first. The reported values are those obtained during the first scan. The molecular weight distribution is based on Gel Permeation Chromatography (GPC) in WATERS 150 -1 6-This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297), (please read the precautions on the back before filling this page) ) i, ιτ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (15) The instrument was carried out in 135t: o-dichlorobenzene. The catalyst component was used to prepare the digassed Znene--U_fi. 7.8-tetragas indenyl) actinide system according to HH Brintzinger et al., Disclosed in < 1. (^ 83110101116131 · C hem., 2 8 8, 6 3 (1 9 8 5) ”method. Methylaluminum argane (M A 0) is a commercial grade product (Schercherng, molecular weight 1,400) in 30% by weight toluene solution. ). After removing the volatile component under vacuum, grind the vitrified material until a white powder is obtained, and further add it under vacuum (0.1 mm Hg) and a temperature of 40 ° C. The K treatment lasts for 4 hours. The powder obtained therefrom exhibits excellent flow characteristics. Polymerization Example 1-3 Water, ethylene, propylene and 1-butene are used in the amounts shown in Table 1 at room temperature. Involved in a 4.25 liter stainless steel autoclave equipped with: agitator, pressure gauge, temperature indicator, catalyst supply system, supply line and constant temperature box in 80 CM ethylene flushing and degassing .Then heat the autoclave to a temperature lower than the polymerization temperature 5 C. The catalyst solution is prepared according to the following method Toluene solution of triisobutylaluminum (TIBAL) (0.2 g TIBAL / ml solution) was added to a toluene solution of ethylene dichloride-bis (4,5,6,7-tetrahydroindenyl) _ (2 ml Toluene / mg gold tincture complex). Keep the mixture at a temperature of 20 ° C with stirring for 5 minutes, and then place the solution in an ethylene / propylene mixture (K a ratio that can maintain the composition constant in the reaction bath). Pressure-17- This paper size applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) ----------- One-(Please read the precautions on the back before filling this page)
、1T A7 B7 五、發明説明(认) (請先閲讀背面之注意事項再填寫本頁) 下注射入熱壓器中。然後將溫度提高至聚合作用所需要 之值。聚合作用之條件是報導於表1 。未觀察到在反應 器中之垢積現象。將所獲得聚合物藉由移除未反應之單 體而分離出,然後在抽真空下乾燥。關於所獲得聚合物 之特性分析之數據是報導於表2 。在13 C-NMR中,未偵 測到顯示包含介於兩個第三级碳原子之間的-(C Η 2 ) n _ 序存在之尖峰,其中η是一偶數。 實(比較用) 其係根據敘述於實施例1之步驟操作,但是在反應混 合物中之液體1-丁烯之含量是低於根據本發明之最低限 度。聚合作用之條件是報導於表1 。所獲得之聚合物圼 現一種填充在反應:器中之單一物質。關於所獲得聚合物特 性分析之數據是報導於表2 。 實施例4 其係根據敘述於實施例1之步驟操作,但是不含水, 且使用甲基鋁氧烷(ΜΑΟ)以代替三異丁基鋁(TIBAL)。 未觀察到在反應器中之垢積琨象。關於所獲得聚合物特 性分析之數據是報導於表2 。 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐)、 1T A7 B7 V. Description of the invention (recognition) (Please read the precautions on the back before filling in this page) and inject it into the autoclave. The temperature is then increased to the value required for the polymerization. The conditions for the polymerization are reported in Table 1. No fouling was observed in the reactor. The obtained polymer was separated by removing unreacted monomers, and then dried under vacuum. Data on the characterization of the polymers obtained are reported in Table 2. In 13 C-NMR, a peak showing the existence of the-(C Η 2) n _ order between two third-order carbon atoms was not detected, where η is an even number. Actual (comparative) It was operated according to the procedure described in Example 1, but the content of liquid 1-butene in the reaction mixture was below the minimum limit according to the present invention. The conditions for the polymerization are reported in Table 1. The polymer obtained is a single substance filled in a reactor: reactor. Data on the properties of the polymers obtained are reported in Table 2. Example 4 It was performed according to the procedure described in Example 1, but without water, and methylalumoxane (MAO) was used instead of triisobutylaluminum (TIBAL). No scale buildup was observed in the reactor. Data on the properties of the polymers obtained are reported in Table 2. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) Α4 (210 × 297 mm)
7 7 A B 五、發明説明(l7 ) 經濟部中央標準局員工消費合作社印製 t酬 A CO ro 1^ 實肺ί 0.937 1.875 1.875 1.875 1.875 m xlO·3 1.875 -1 1 3.75 ' 3.75 1,875 1.875 I .] st漦 ι| 1 hi ΓΟ ΓΟ ΓΟ | 鋁/水 207.3 228.8 ί 207.3 196.0 174,6 m 16.63 17.9 16.63 15.55 13.19 ;MMX ! § § i 8 § c3液相 1_ 64.15 i 70.3 ! Ί 64.15 55.51 37.76 mm% 239.5 151.1 _] 239.5 364.8 694.4 C4液相 19.21 11.81 1 _1 19.21 28.93 49.05 華暈% 1 30.3 1 1 31.3 _i 29.7 27.8 23.5 總壓 巴 g g g s s 溫度 X: g g § C g i遷 6 i N5 1—* ro ¢3¾ 產率 克 502.9 824.5 2725.1 1426.9 736.8 灘 公斤聚W 克 1 告 -------;---1 私------訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) A7 B7 五、發明説明(ιό ).7 7 AB V. Description of the invention (l7) The t-remuneration printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A CO ro 1 ^ Solid lung 0.937 1.875 1.875 1.875 1.875 m xlO · 3 1.875 -1 1 3.75 '3.75 1,875 1.875 I. ] st 漦 ι | 1 hi ΓΟ ΓΟ ΓΟ | aluminum / water 207.3 228.8 ί 207.3 196.0 174,6 m 16.63 17.9 16.63 15.55 13.19; MMX! § i 8 § c3 liquid phase 1_ 64.15 i 70.3! Ί 64.15 55.51 37.76 mm% 239.5 151.1 _] 239.5 364.8 694.4 C4 liquid phase 19.21 11.81 1 _1 19.21 28.93 49.05 Hua hao% 1 30.3 1 1 31.3 _i 29.7 27.8 23.5 total pressure bar gggss temperature X: gg § C gi move 6 i N5 1— * ro ¢ 3¾ Yield g 502.9 824.5 2725.1 1426.9 736.8 Beach kg poly W g 1 Notice ---------; --- 1 Private -------- Order (Please read the precautions on the back before filling this page) This paper The dimensions are applicable to the Chinese National Standard (CNS) A4 specifications (210X 297 mm) A7 B7 V. Description of the invention (ιό).
OO 1» 實施例 1 62.3 -η 63.6 i ; -a P CO 乙烯 莫耳% 〇〇 cn υο μ-» Ch to 一 13.6 丙烯 莫耳无 05 ΓΟ oo b\ -1 10.2 卜丁烯 莫耳% 1 1 3.89 CO t—* -0 5.66 固有黏度 分升/克 3 Cl 0.69 1 0.43 0.31 —3 P Z3 α. 2.4 ro ro o 3: < 3: 3 rs Q_ 40.0 39.5 Ca5 05 <〇 差示量熱法 zs CL· 〇 cn OO -a to CO 1> Π: Λ-V --------V 袭------.玎-----10 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 —20— 本紙張適用中國國家標準(CNS ) ( 210X297公釐) 五、發明説明()OO 1 »Example 1 62.3 -η 63.6 i; -a P CO ethylene mole% 〇〇cn υο μ-» Ch to -13.6 propene mole no 05 ΓΟ oo b \ -1 10.2 bupropene mole% 1 1 3.89 CO t— * -0 5.66 Intrinsic viscosity deciliter / gram 3 Cl 0.69 1 0.43 0.31 —3 P Z3 α. 2.4 ro ro o 3: < 3: 3 rs Q_ 40.0 39.5 Ca5 05 < 〇 differential Thermal method zs CL · 〇cn OO -a to CO 1 > Π: Λ-V -------- V attack ------. 玎 ----- 10 (Please read the note on the back first Please fill in this page again) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives—20— This paper applies Chinese National Standards (CNS) (210X297 mm) 5. Description of the invention ()
經濟部智慧財產局員工消費合作社印製_ 補充實施例 補充實施 此實施例 在此所使用 述之較佳α 之金羼錯合 於說明書第 乙烯,丙 至18頁實施 此試驗傺 書第17頁般 備,採用二 基)結作為 共觸媒。 聚合反應 詳細之聚合 污垢産生。 藉由去除 聚合物;如 表1 例以明確支持申請專利範阖之請求。 俗關於乙烯/丙烯/1-己烯三聚物之聚合筲例。 之共聚單髏卜己烯傜已列示於第14頁第6行所 -烯烴種類中。再者,於如下實施例中所使用 物則為Me3 Si(H* Ind)2 ZrCl3 ,其亦已檫示 9頁第2行所述之較佳觸媒領域。 烯及卜己烯之共聚合試驗俗根據說明書第17頁 例1-3所示步驟來進行。 在4. 25升之壓熱器中進行,該壓熱器係如說明 處理;觸媒溶液偽以說明書第17頁所述方法製 氮化二甲基矽烷二基一雙(4, 5, 6, 7-四氫茚 觸媒及Al(iBu)3 (TIBAL)作為烷基括化合物之 傑在溫度50C,總壓22.7巴下進行60分鏞;更 條件傜示於下表1 。在反應器中並未觀察到有 未反應單體且而後於真空下乾燥來分離出所得 此得到之三聚物之特擞參權則示於表2。Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ Supplementary Example The supplementary implementation of this example. The gold used in this example is better. As a general preparation, a two-base) junction is used as a co-catalyst. Polymerization Detailed polymerization Fouling is generated. By removing the polymer; see the example in Table 1 to clearly support the request for patent application. Examples of polymerization of ethylene / propylene / 1-hexene terpolymer. The copolymerized mono-stilbeneene has been listed in the olefin species in line 6 on page 14. Furthermore, the materials used in the following examples are Me3Si (H * Ind) 2 ZrCl3, which has also shown the preferred catalyst field described in line 2 on page 9. The copolymerization test of olefin and dihexene is carried out according to the procedures shown in Examples 1-3 on page 17. It was carried out in a 4.25 liter autoclave, which was treated as described; the catalyst solution was prepared by the method described on page 17 of the instruction manual to produce dimethylsilyl disilyl-bis (4, 5, 6 , 7-tetrahydroindene catalyst and Al (iBu) 3 (TIBAL) as alkyl compound compounds were carried out at a temperature of 50C and a total pressure of 22.7 bar for 60 minutes; more conditions are shown in Table 1 below. In the reactor The unreacted monomers were not observed in the sample and then dried under vacuum to isolate the resulting terpolymer. The specific parameters are shown in Table 2.
Zr (mmoHO·3) AI (mmol) AI/H^ (mol) Cz/liq (g) C^q (g) C/Uq (g) 產量 (g) 活性 (kgoo/grr) 1.875 1.875 2 194 557 722 56 327.4 本紙張尺度適用中國國家標準(CNS ) A4规格(21〇Χ2.97公嫠) I----^丨--^--〗裝------訂--------4 (請先閲讀背面之注意事項再填寫本頁) 1 r-—: _ ·* .一 B7 五、發明説明() 1 -V " 二':· V::.. ! > ------------ A7 表2 c: (%mol) C3 (%τηοί) C6 (%mol) I.V. _ Μ„/Μη 72.3 20.9 6.8 3.61 0.63 2.1 在13C-NMR光譜中,並未觀察到顯示在兩俩三级磺原子間 存在有-(CH2 )η -(η為偶數)序列之峰值。 如上資料顯示所得到的三聚物可滿足修正後之申請專利 範圍第6項之每一俩基本特性。由此看來此等申請專利範圍 應足以獲得申請人所提出之實驗結果之支持。而根據此一 補充例來看,應足以支持應無需要將原申請專利範圍第5及 6項併入第1項。 ----i.--:--〗裝------訂-----^--- ^ (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)Zr (mmoHO · 3) AI (mmol) AI / H ^ (mol) Cz / liq (g) C ^ q (g) C / Uq (g) Yield (g) Activity (kgoo / grr) 1.875 1.875 2 194 557 722 56 327.4 This paper size is applicable to China National Standard (CNS) A4 specification (21〇 × 2.97 cm) I ---- ^ 丨-^ -------------------------- Order --- 4 (Please read the precautions on the back before filling this page) 1 r-—: _ · *. One B7 V. Invention Description () 1 -V " Two ': · V :: ..! ≫ ------------ A7 Table 2 c: (% mol) C3 (% τηοί) C6 (% mol) IV _ M „/ Μη 72.3 20.9 6.8 3.61 0.63 2.1 in 13C-NMR spectrum No observed peaks showing the sequence of-(CH2) η-(η is even) between the two third-order sulfonic atoms. The above data shows that the obtained trimer can meet the revised patent application scope No. 6 The basic characteristics of each of these two items. From this, it seems that the scope of these patent applications should be sufficient to support the experimental results proposed by the applicant. According to this supplementary example, it should be sufficient to support the need for the original patent scope Items 5 and 6 are merged into item 1. ---- i .--: ---------------------------------------- ^ (Please read the first Note: Please fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-This paper size applies to China National Standard (CNS) A4 (210X297 mm)
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