TW555770B - Method of homo- or co-polymerization of alpha-olefin - Google Patents
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555770 A7 B7 五、發明説明(1 ) 技術範蜂 本發明係關於均-或共-聚合(以後稱爲(共)聚)阿伐·烯 烴之方法,更特別關於在控制聚合物分子量分佈的同時以 高產率製造高立體規則性烯烴(共)聚合物之方法。 發明背景 通常,用經MgCl2撑載的觸媒產生之烯烴聚合物具有窄 分子量分佈。頃作出很多努力增寬分子量分佈,以改良由 此等觸媒產生的產物在處理時之流化性。爲此目的,有一 種方法得到廣泛使用,其中首先在各個不同聚合反應器中 製造不同分子量分佈之聚合物,並在以後混合,但其缺點 爲需要更多時間和努力,且時常發現產物很不均勻。在自 曰本三井石油化學公司(Mitsui Petrochemical of Japan)的最近 一篇報告中有一種方法(韓國專利公告第10-1993-000665 號),其中用兩種特殊電子給體產生具較寬分子量分佈之 烯烴聚合物,用該電子給體以相同聚合條件分別聚合具有 於31.6熔體流速(MFR)之均聚烯烴。然而,在此情況下, 觸媒活性太低,以致於不能工業化,不僅其分子量難以控 制,而且控制聚合物分子量分佈的氫反應性亦很低,對其 操作處理造成很多限制。 同時,已知很多其它先前技藝-技術用固體鈦錯合物組分 作鈦觸媒(共)聚合多於3個碳原子的阿伐-烯烴,該錯合 物組分包含至少以電子給體處理的鎂和鈥及卣,(例如, 曰本專利特許公開案第73-16986號及第73-16987號,德國 專利特許公開案第2,153,520號、第2,230,672號、第 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 555770 A7 B7 五、發明説明(2 ) 2,230,728 號、第 2,230,752 號及第 2,553,104 號)。 此等參考顯示特殊觸媒混合物組分之用途及形成此等觸 媒之方法。正如吾人所熟知,此等含固體鈦錯合物組分之 觸媒根據組分混合物的不同,形成的組合方法不同及組合 條件的不同在不同觸媒間發生變化。因此,幾乎不可能預 料用在所給一組組合條件產生之觸媒是否產生相似結果。 通常產生具有極不完善性能之觸媒。在不使用適合外電子 給體時,即使在適合條件下製造觸媒,此等性能(如聚合 物觸媒活性或立體規則性)通常也證明確實不是足夠。 含至少鎂,鈦和卣之固體鈦錯合物組分也不例外。在氫 存在及使用由鈦和屬於周期表第I至IV族金屬之有機金 屬化合物組成之觸媒(共)聚合含不多於3個碳原子之阿伐 -晞烴時,如果使用由用金屬铭、就或有機銘合物還原四 氯化鈥獲得的三氣化鈥組成之觸媒與已知用於抑制無定形 (共)聚物生成的電子給體,則效果依所用電子給體變化。 可接受由爲,電子給體不只加入,而且更是在電子上和空 間上與鎂及鈦化合物化合,以基本改變固體鈦錯合物觸媒 之微結構。 由使用某種矽酮化合物以比現存方法更高產率產生高立 體規則性聚合物之新方法頃请美國道科寧公司(Dow Corning)(美國專利第5,175,332號和歐洲專利特許公開案第 602,922號)、日本三井石油化學公司(韓國專利公告第10-1992-2488 號及第 10-1993-665 號;美國專利第 4,990,479 號;歐洲專利特許公開案第350,170A號;加拿大專利第 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 555770 A7 B7 五、發明説明(3 ) 1,040,379號)、韓國三星通用化學公司(Samsung General Chemicals of Korea)(韓國專利特許公開案第 10-1998-082629 號)及其它爲我們所熟悉的歐洲公司開發。 發明概要 本發明一個目的爲提供一種以高產率製造高有機立構烯 烴均-或共·聚物之方法及其中所用之觸媒系統,在用於製 造具多於3個碳原子之烯烴均-或共-聚物時,該方法同時 控晞烴均-或共-聚物分子量分佈。 本發明另一目的爲提供一種製造聚丙晞或丙烯共聚物之 方法,該聚合物適用於製造具足夠熱密封性、透明性及防 黏性能之薄膜,亦適用於具優良強度、抗衝擊性及低溫熱 封性之注模產物。 發明詳細説明 該阿伐-烯烴(共)聚合方法包括使用一種觸媒系統,該 觸媒系統包含下列組分: (1) 一種由包括下列步驟之製造方法製備之固體鈦錯合 物觸媒: (a) 將鹵化鎂和周期表第IIIA族之化合物溶於環系 脂、一種或多種醇、嶙化合物及有機碎虎之混合 物溶劑,以製備鍰化合物―溶液; (b) 使該鎂化合物溶液與過渡金屬化合物、矽化合 物、錫化合物或其混合物反應,以沈澱出固體顆 粒;及 (c) 使所沈澱固體顆粒與鈦化合物和電子給體反應。 -6- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 555770 A7 B7 五、發明説明(4 ) (2) —種周期表第IIIA族金屬之有機金屬化合物;及 (3) 包含三種或更多有機矽化合物之外電子給體,其中 在相同·聚合條件下用單一有機矽化合物聚合時獲得 的均聚物MFRs (熔體流速)分別爲5或更小、5〜20 及20或更南。 關於用於本發明(共)聚合阿伐-烯烴方法之觸媒系統, 製造該固體鈦錯合物觸媒之方法爲韓國專利特許公開案第 10-2000-009625號所述之方法,其内容全部以無特殊關聯 方式併於本文。 與習知鈦觸媒比較,本發明均-或共-聚合阿伐-烯烴方 法所用之固體鈦錯合物具有極佳觸媒活度,並能夠產生具 寬分子量分佈之高立體規則性聚合物。 在產生固體鈦錯合物觸媒方法之步驟(a)中,鎂化合物 可包括非還原性液態鎂化合物,例如,卣化鍰,如氣化 鍈、溴化鎂、碘化鎂及氟化鎂;烷氧基函化鎂,如甲氧基 氣化鎂、乙氧基氣化鎂、異丙氧基氣化鎂、丁氧基氣化鎂 及辛氧基氣化鎂;芳氧基鹵化鎂,如苯氧基氣化鎂和甲基 苯氧基氣化化鎂;烷氧基鎂,如乙氧基鎂、異丙氧基鎂、 丁氧基鎂及辛氧基鎂;芳氧基鎂,如苯氧基鎂二甲基苯氧 基鎂;及複酸鎂鹽,如月桂酸鎂—(laurylmagnesium)和硬脂酸 鎂。本發明所用鎂化合物可以錯合化合物形式或與其它金 屬之混合物形式。另外,亦可用兩種或多種鎂化合物之混 合物作爲鎂化合物。較佳鎂化合物爲卣化鎂,如氣化鎂、 烷氧基氯化鎂及芳氧基氯化鎂,更佳爲具CrC14烷氧基之 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 555770 A7 _______B7 五、發明説明(5~) ' ' 燒氧基氯化鍰和芳氧基氣化鎂,更佳爲具C5_c2〇燒氧基芳 氧基氣化錢。 上列鎂化合物一般可由簡單化學通式代表,但有些化合 物依有製造方法不同難以用此方式表達。此時可以相信它 們局此等化合物之混合物。例如,由下列方法獲得的化合 物均被認作爲依賴不同反應劑或不同反應度的不同化合物 之混合物,且此等化合物亦可用於本發明,這些方法爲: 在鹵化矽烷、五氣化磷或亞硫醯氣存在下使鎂金屬與醇或 酚反應之方法’·格利雅試劑熱解方法;藉用結合羥基、 酯、醚基或類似基團之降解方法。 在本發明中主要使用非還原性液態鎂化合物或鎂化合物 溶於烴溶劑之溶液。爲產生此等化合物,可在缺乏或存在 能夠溶解上述鎂化合物之烴溶劑下使上列非還原性鎂化合 物與至少一種或多種電子給體反應,電子給體選自由醇、 有機羧酸、醛、胺或其混合物所組成之群。 爲此使用的烴熔劑包括,例如,脂烴,如戊規、己院、 庚烷、辛烷、癸烷、十二烷和煤油;脂環烴,如環戊烷、 曱基環戊烷、環己烷及甲基環己烷;芳烴,如苯、甲苯、 二甲基、乙苯、異丙基苯及甲基-異丙基苯;及選自如二 氣乙烷、二氣丙烷、二氣乙烯、〜三氣乙烯、四氣化碳和氯 苯之群之_代烴。 _ 在如上製造該固體鈦錯合物觸媒方法之步驟⑷中,函 化鎂化合物和醇之反應較佳在烴溶劑中進行。依南化錢化 合物和醇之類型,反應係於室溫或更高溫度(例如,約3〇 -8 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 555770 A7 B7 五、發明説明(6 ) °C至200 °C,更佳約60 X: mig 150 °C)進行約15分鐘至5 小時(更佳約30分鐘至3小時)。生成液態鎂化合物之電 子給體包括具至少6或較佳6至20個碳原子之化合物, 例如,脂系醇,如2-甲基戊醇、2-乙基丁醇、正庚醇、 正辛醇、20乙基己醇、癸醇、十二烷醇、十四烷醇、十 一碳烯醇、油醇及硬脂醇;脂環系醇,如環己醇和甲基環 己醇;及芳系醇,如苄醇、甲基苄醇、異丙基苄醇、α-甲 基苄醇和α,α-二甲基苄醇。對於具5或更少碳原子的醇, 可使用甲醇、乙醇、丙醇、丁醇、乙二醇和曱基卡必醇 (methycarbitol) 0 在如上製造該固體鈦錯合物觸媒方法之步驟(b)中,如 上產生的液體形式鎂化合物係藉使用四_化矽、烷基鹵化 石夕、四卣化錫、燒基自化錫、氫卣化錫、四_化鈥及類似 物再結晶成球狀固體組分。 在如上製造該固體鈦錯合物觸媒方法之步驟(c)中,欲 與鎂化合物反應的液體鈦化合物較佳爲通式Ti(OR)mX4_m 之四價鈦化合物(其中R爲烴基,X爲鹵原子,m爲 0<m<4之數字)。R代表1-10個碳原子之烷基。可使用各 種鈦化合物,例如,四鹵化鈥,如TiCl4、TiBr4和Til4、 烷氧基三自化鈦,如 Ti(0CHl)Cl3 、 Ti(OC2H5)Cl3 、 Ti(OC4H9)Cl3、Ti(OC2H5)Br3 及 Ti(0(i-C2H5)Br3 ;烷氧基二 鹵化鈦,如 Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(OC4H9)2Cl2 及 Ti(OC2H5)2Br2 ;烷氧基鹵化鈦,如 Ti(OCH3)3Cl 、 Ti(OC2H5)3Cl、Ti(OC4H9)3Cl 及 Ti(OC2H5)3Br ;以及四烷氧 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 555770 A7555770 A7 B7 V. Description of the invention (1) Technical examples The present invention relates to a method of homo- or co-polymerization (hereinafter referred to as (co) polymerization) of avar · olefin, and more particularly to the control of the molecular weight distribution of polymers while Method for producing high stereoregular olefin (co) polymer in high yield. BACKGROUND OF THE INVENTION Generally, olefin polymers produced using MgCl2 supported catalysts have a narrow molecular weight distribution. Many efforts have been made to widen the molecular weight distribution to improve the fluidity of the products produced by these catalysts during processing. For this purpose, there is a method widely used in which polymers of different molecular weight distributions are first produced in different polymerization reactors and then mixed later, but the disadvantages are that more time and effort are required, and the product is often found to be very inefficient. Even. In a recent report from Mitsui Petrochemical of Japan, there is a method (Korean Patent Publication No. 10-1993-000665) in which two special electron donors are used to generate a broad molecular weight distribution For the olefin polymer, the homogeneous polyolefin having a melt flow rate (MFR) of 31.6 was polymerized under the same polymerization conditions using the electron donor. However, in this case, the catalyst activity is too low to be industrialized, not only its molecular weight is difficult to control, but also the hydrogen reactivity of controlling the molecular weight distribution of the polymer is very low, which places many restrictions on its handling. At the same time, many other prior art-techniques are known that use a solid titanium complex component as a titanium catalyst to (co) polymerize avar-olefins having more than 3 carbon atoms, the complex component comprising at least an electron donor Processed magnesium and 卣 and (, for example, Japanese Patent Publications Nos. 73-16986 and 73-16987, German Patent Publications Nos. 2,153,520, 2,230,672, and this paper standard apply to China National Standard (CNS) A4 Specification (210X297 mm) 555770 A7 B7 V. Invention Description (2) No. 2,230,728, No. 2,230,752 and No. 2,553,104). These references show the uses of particular catalyst mixture components and methods for forming these catalysts. As we are all familiar with, these solid titanium complex-containing catalysts have different combination methods and different combination conditions, which vary between different catalysts depending on the component mixture. Therefore, it is almost impossible to predict whether the catalysts used in a given set of combined conditions will produce similar results. Catalysts with extremely imperfect performance are usually produced. When suitable external electron donors are not used, these properties (such as polymer catalyst activity or stereoregularity) often prove to be inadequate, even if the catalyst is manufactured under suitable conditions. Solid titanium complex components containing at least magnesium, titanium and rhenium are no exception. In the presence of hydrogen and the use of a catalyst (co) polymerized with titanium and organometallic compounds belonging to metals of Groups I to IV of the Periodic Table to polymerize avalenic hydrocarbons containing not more than 3 carbon atoms, The tri-gasification catalyst obtained by reduction of tetrachloride with organic or organic compounds and the electron donor known to suppress the formation of amorphous (co) polymers, the effect varies depending on the electron donor used . The acceptable reason is that the electron donor is not only added, but is also combined with magnesium and titanium compounds electronically and in space to basically change the microstructure of the solid titanium complex catalyst. A new method of producing a highly stereoregular polymer from a certain silicone compound at a higher yield than existing methods has been requested from Dow Corning (US Patent No. 5,175,332 and European Patent Publication No. 602,922), Japan's Mitsui Petrochemical Corporation (Korean Patent Publication Nos. 10-1992-2488 and 10-1993-665; U.S. Patent No. 4,990,479; European Patent Patent Publication No. 350,170A; Canadian Patent No. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 555770 A7 B7 V. Invention Description (3) No. 1,040,379), Samsung General Chemicals of Korea 10-1998-082629) and other European companies we are familiar with. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing high organic stereo olefin homo- or copolymers with high yield and a catalyst system used in the method, which is used to produce olefin homo- with more than 3 carbon atoms. In the case of co- or copolymers, this method simultaneously controls the molecular weight distribution of the homo- or co-polymers of fluorene. Another object of the present invention is to provide a method for manufacturing a polypropylene or propylene copolymer. The polymer is suitable for manufacturing a film having sufficient heat-sealing, transparency and anti-sticking properties, and is also suitable for having excellent strength, impact resistance and Low-temperature heat-sealable injection molded product. Detailed description of the invention The avar-olefin (co) polymerization method includes the use of a catalyst system comprising the following components: (1) A solid titanium complex catalyst prepared by a manufacturing method including the following steps: (a) dissolving a magnesium halide and a compound of Group IIIA of the periodic table in a solvent of a mixture of a cyclic lipid, one or more alcohols, a rhenium compound, and an organic crusher to prepare a rhenium compound—a solution; (b) a solution of the magnesium compound Reacting with a transition metal compound, a silicon compound, a tin compound, or a mixture thereof to precipitate solid particles; and (c) reacting the precipitated solid particles with a titanium compound and an electron donor. -6- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 555770 A7 B7 V. Description of the invention (4) (2) — An organometallic compound of Group IIIA metal of the periodic table; and (3) Contains three or more electron donors other than organosilicon compounds, where homopolymer MFRs (melt flow rates) obtained when polymerized with a single organosilicon compound under the same polymerization conditions are 5 or less, 5 to 20, and 20 or more south. Regarding the catalyst system used for the (co) polymerization of the avatar-olefin method of the present invention, the method for manufacturing the solid titanium complex catalyst is the method described in Korean Patent Laid-Open No. 10-2000-009625, and the content thereof All are incorporated herein without special association. Compared with the conventional titanium catalyst, the solid titanium complex used in the homo- or co-polymerized Avar-olefin method of the present invention has excellent catalyst activity and can produce a high stereoregular polymer with a wide molecular weight distribution. . In step (a) of the method for generating a solid titanium complex catalyst, the magnesium compound may include a non-reducing liquid magnesium compound, for example, arsine, such as aerobium, magnesium bromide, magnesium iodide, and magnesium fluoride ; Magnesium alkoxylates, such as magnesium methoxylate, ethoxylate, isopropoxylate, butoxylate and octyloxylate; aryloxyhalides , Such as magnesium phenoxide and methylphenoxy, magnesium alkoxide, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, and octyl magnesium; aryloxy magnesium , Such as phenoxymagnesium dimethylphenoxymagnesium; and magnesium double acid salts, such as magnesium laurate (laurylmagnesium) and magnesium stearate. The magnesium compound used in the present invention may be in the form of a compound compound or a mixture with other metals. Alternatively, a mixture of two or more magnesium compounds may be used as the magnesium compound. The preferred magnesium compound is magnesium hafnium, such as gasified magnesium, alkoxymagnesium chloride and aryloxymagnesium chloride, and more preferably CrC14 alkoxy. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297) (Centi) 555770 A7 _______B7 V. Description of the invention (5 ~) '' Burning oxyfluorene chloride and aryloxy magnesium vaporized, more preferably C5_c2〇 fused oxygen aryloxy gasification. The magnesium compounds listed above are generally represented by a simple chemical formula, but some compounds are difficult to express in this way depending on the manufacturing method. At this point they can be believed to be a mixture of these compounds. For example, compounds obtained by the following methods are all considered as a mixture of different compounds that depend on different reactants or different degrees of reactivity, and these compounds can also be used in the present invention. These methods are: The method of reacting magnesium metal with alcohol or phenol in the presence of thiosulfonium gas. 'The Grignard reagent pyrolysis method; borrows the degradation method that combines hydroxyl, ester, ether or similar groups. In the present invention, a non-reducing liquid magnesium compound or a solution in which a magnesium compound is dissolved in a hydrocarbon solvent is mainly used. To produce these compounds, the non-reducing magnesium compounds listed above can be reacted with at least one or more electron donors in the absence or presence of a hydrocarbon solvent capable of dissolving the magnesium compounds, the electron donors being selected from the group consisting of alcohols, organic carboxylic acids, aldehydes , Amines or mixtures thereof. Hydrocarbon solvents used for this purpose include, for example, aliphatic hydrocarbons such as pentylene, hexamethylene, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, fluorenylcyclopentane, Cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, dimethyl, ethylbenzene, cumene and methyl-isopropylbenzene; and selected from the group consisting of digas ethane, digas propane, dioxane Gas generation of ethylene, ~ three gas ethylene, four gasification carbon and chlorobenzene. _ In step ⑷ of the method for manufacturing the solid titanium complex catalyst as described above, the reaction of the functional magnesium compound and the alcohol is preferably performed in a hydrocarbon solvent. Depending on the type of compound and alcohol, the reaction is at room temperature or higher (for example, about 30-8-this paper size applies to China National Standard (CNS) A4 (210X 297 mm) 555770 A7 B7 five Description of the invention (6) ° C to 200 ° C, more preferably about 60 X: mig 150 ° C) for about 15 minutes to 5 hours (more preferably about 30 minutes to 3 hours). Electron donors that generate liquid magnesium compounds include compounds having at least 6 or preferably 6 to 20 carbon atoms, for example, aliphatic alcohols such as 2-methylpentanol, 2-ethylbutanol, n-heptanol, n- Octanol, 20 ethylhexanol, decanol, dodecanol, tetradecanol, undecenol, oleyl alcohol and stearyl alcohol; alicyclic alcohols, such as cyclohexanol and methylcyclohexanol; And aromatic alcohols, such as benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, α-methyl benzyl alcohol and α, α-dimethyl benzyl alcohol. For alcohols having 5 or less carbon atoms, methanol, ethanol, propanol, butanol, ethylene glycol, and methycarbitol can be used. Steps of the method for manufacturing the solid titanium complex catalyst as above ( In b), the magnesium compound in the liquid form produced as above is recrystallized by using silicon tetrahydroxide, alkyl halide, tin tetrafluoride, tin sulfide, tin hydrogen hydride, tetrakisperylene and the like. Spherical solid component. In step (c) of the method for manufacturing the solid titanium complex catalyst as described above, the liquid titanium compound to be reacted with the magnesium compound is preferably a tetravalent titanium compound of the general formula Ti (OR) mX4_m (where R is a hydrocarbon group, X Is a halogen atom, and m is a number of 0 < m < 4). R represents an alkyl group of 1 to 10 carbon atoms. Various titanium compounds can be used, for example, tetrahalides' such as TiCl4, TiBr4 and Til4, titanium alkoxides such as Ti (0CHl) Cl3, Ti (OC2H5) Cl3, Ti (OC4H9) Cl3, Ti (OC2H5) Br3 and Ti (0 (i-C2H5) Br3; titanium alkoxides such as Ti (OCH3) 2Cl2, Ti (OC2H5) 2Cl2, Ti (OC4H9) 2Cl2 and Ti (OC2H5) 2Br2; titanium alkoxides, Such as Ti (OCH3) 3Cl, Ti (OC2H5) 3Cl, Ti (OC4H9) 3Cl, and Ti (OC2H5) 3Br; and tetraalkoxy This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 555770 A7
基鈥混合物,* Ti(〇CH3)4 ' Ti(OC2H5)4及τ咖你^在 此等化合物中’較佳爲四由化鈦,特別爲四氣化鈦。 在如上製造固體鈦錯合物觸媒之步驟⑷中,内電子给 體之實例-般如下··含氧電子给體,如水 % 、 醛、羧酸、酯、醚和醯胺;與含氮電子給體,如氨、胺、 腈和異腈酸鹽⑷;特別爲具! i 18個碳原子的醇,如 甲醇、乙醇、丙醇、戊醇、己醇、辛醇、+二烷醇、十八 烷醇、苄醇、苯乙醇、枯醇及異丙基苄醇;酮;可含低碳 烷基且具6至15個碳原子的酚,如苯酚、甲苯酚、二甲 基苯酚、乙基苯酚、丙基苯酚、枯基苯酚及莕酚;具2至 15個碳原子的路,如乙醛、丙醛、辛醛、苯甲醛、甲苯 甲趁及奈甲路;具2至18個碳原子的有機酸酯,如甲酸 甲酉EI、乙甲g旨、乙故乙g旨、乙酸乙晞醋、乙酸丙醋、甲 基丙烯酸甲酯、巴豆酸乙酯、環己基羧酸乙酯、苯甲酸苯 酯、苯甲酸芊酯、甲基甲酸甲酯、曱苯甲酸乙酯、甲苯甲 酸戊酯、乙基苯曱酸乙酯、茴香酸曱酯、茴香酸乙酯、乙 氧基苯甲酸乙酯、γ- 丁内酯、δ·戊内酯、α-苯幷吡喃酮、 2-苯幷[c]呋喃酮、乙酸環己酯、丙酸乙酯、丁酸甲酯、戊 酸甲酯、甲苯甲酸曱酯、甲苯甲酸乙酯、苯曱酸丙酯、苯 甲酸丁酯、苯甲酸環己酯、甲苯飞酸戊酯、碳酸伸乙酯及 碳酸伸乙酯;具2至15個碳原子之醯鹵,如乙醯氣、芊 基氣、甲苯甲醯氣(chlorotoluate)和菌香酿氯 (chloroanisate) ; g蠢胺;酸,如曱醚、乙醚、異丙酸、丁 醚、戊醚、四氫吱喃、茴香醚及苯酸;胺,如甲胺、乙 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)Of these compounds, * Ti (〇CH3) 4'Ti (OC2H5) 4 and τCa ^ Among these compounds, ′ is preferably titanium tetraoxide, especially titanium tetragas. Examples of internal electron donors in step ⑷ for the production of solid titanium complex catalysts as described above are generally as follows: oxygen-containing electron donors, such as water%, aldehydes, carboxylic acids, esters, ethers, and amidines; and nitrogen-containing Electron donors, such as ammonia, amines, nitriles, and isocyanates; i Alcohols of 18 carbon atoms, such as methanol, ethanol, propanol, pentanol, hexanol, octanol, + dialkanol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; Ketones; phenols that may contain lower alkyl groups and have 6 to 15 carbon atoms, such as phenol, cresol, dimethylphenol, ethylphenol, propylphenol, cumylphenol, and acetol; 2 to 15 Carbon atom pathways, such as acetaldehyde, propionaldehyde, octanal, benzaldehyde, toluene, and chloroform; organic acid esters with 2 to 18 carbon atoms, such as formate EI, ethyl formaldehyde, ethyl Therefore, ethyl acetate, ethyl acetate, propyl acetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexyl carboxylate, phenyl benzoate, ethyl benzoate, methyl methyl formate, toluene Ethyl formate, amyl toluate, ethyl ethyl benzoate, ethyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, α-benzene Pyranone, 2-phenylhydrazone [c] furanone, cyclohexyl acetate, ethyl propionate, methyl butyrate, methyl valerate, ethyl toluate, ethyl toluate, propyl benzoate Benzene Butyl acid, cyclohexyl benzoate, amyl toluate, ethyl carbonate and ethyl carbonate; halogenated halides with 2 to 15 carbon atoms, such as ethyl arsine gas, arsine base gas, toluene methyl arsine gas (Chlorotoluate) and chloroanisate; g amines; acids, such as ethyl ether, diethyl ether, isopropyl acid, butyl ether, pentyl ether, tetrahydrofuran, anisole, and benzoic acid; amines, such as methylamine 、 B-10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
裝 訂 555770 A7 B7 五 發明説明( 、二乙胺、三丁胺、哌啶、三芊基胺、苯胺、吡啶、松 香烴(pinoline)、四甲基乙二胺;腈,如乙腈、芊腈及甲苯 基氨;及分子中具上述官能團之鋁、矽、錫及類似之化合 物。另一方面’與某些電子給體反應之觸媒在本發明中用 於以乂體規則性改良和更高產率產生阿伐-烯烴聚合物。 在本發明中用於產生觸媒的内電子給體特別爲單乙二醇 (MEG)、二乙二醇(DEG)、三乙二醇(TEG)、聚乙二醇 (PEG)、單丙二醇(MPG)和二丙二醇(DpG)之酯衍生物,如 乙酸酯、丙酸酯、正·及異_ 丁酸酯、苯甲酸酯、甲苯甲酸 酉曰等。作爲以上電子給體之實例,苯甲酸酯包括單苯甲酸 早乙二醇酯、二苯甲酸單乙二醇酯、單苯甲酸二乙二醇 @曰一苯甲酸一乙二醇酯、單苯甲酸二乙二醇酯、單苯甲 酸一乙一醇酯、二苯甲酸三乙二醇酯、單苯甲酸單丙二醇 酯、單苯甲酸二丙二醇酯、二苯甲酸二丙二酸酯、單苯甲 酸三丙二醇酯及類似酯。 一藉使用所產生固體觸媒通過淤漿聚合獲得的聚合物爲具 问堆積密度和良m性的極佳顆粒大小分佈粒狀或球狀 顆粒。 則述固體鈦錯合物觸媒可有.益用於聚合烯烴,如乙烯、 丙晞和卜丁晞或4_甲基+戊缔、?該觸媒尤其用於具3或 多個碳原子之阿-伐晞烴聚合' 其共聚、具小於1〇莫耳% 乙晞的3或多個碳原子阿伐,烴共聚以及3 &多個竣原 子阿伐烴與多不飽和化合物(如共輛或非共耗二晞)之 共聚。Binding 555770 A7 B7 Five invention descriptions (, diethylamine, tributylamine, piperidine, trimethylamine, aniline, pyridine, rosin (pinoline), tetramethylethylenediamine; nitriles, such as acetonitrile, acetonitrile, and Tolyl ammonia; and aluminum, silicon, tin, and similar compounds having the above functional groups in the molecule. On the other hand, a catalyst that reacts with certain electron donors is used in the present invention to improve the regularity and higher yield of the carcass. Aval-olefin polymers are produced at a high rate. The internal electron donors used to generate catalysts in the present invention are especially monoethylene glycol (MEG), diethylene glycol (DEG), triethylene glycol (TEG), poly (ethylene glycol). Ester derivatives of ethylene glycol (PEG), monopropylene glycol (MPG) and dipropylene glycol (DpG), such as acetate, propionate, n- and iso-butyrate, benzoate, toluate Etc. As examples of the above electron donors, benzoates include early ethylene glycol monobenzoate, monoethylene glycol dibenzoate, diethylene glycol monobenzoate, or monoethylene glycol monobenzoate , Diethylene glycol monobenzoate, Monoethylene glycol monobenzoate, Triethylene glycol dibenzoate, Monopropylene dibenzoate Alcohol esters, dipropylene glycol monobenzoate, dimalonic acid dibenzoate, tripropylene glycol monobenzoate, and similar esters. The polymer obtained by slurry polymerization using the solid catalyst produced has a bulk density. Excellent and good particle size distribution of granular and spherical particles. The solid titanium complex catalyst may be used. It is useful for polymerizing olefins, such as ethylene, propidium and butin, or 4-methyl + pentyl, The catalyst is particularly useful for the polymerization of avalvanes having 3 or more carbon atoms, its copolymerization, avalvatones with 3 or more carbon atoms having less than 10 mole% acetam, copolymerization of hydrocarbons, and 3 & Copolymerization of multiple confined atomic avarene with polyunsaturated compounds (such as co-car or non-co-consumer difluorene).
‘裝 訂‘Binding
555770555770
本發月所用有機金屬組分(2)特別包括,三燒基鋁,如 一乙基鋁和二丁基鋁三烯基鋁,如三異戊二晞基鋁;部分 烷氧基化的烷基鋁,例如二烷基烷氧基鋁,如二乙基乙氧 基叙及一丁基丁氧基銘;烷基倍半烷氧化鋁,如乙基倍半 乙氧化銘和丁基倍半乙氧化鋁;烷基二自化鋁,如乙基二 氯化鋁、丙基二氣化鋁及丁基二溴化鋁;部分氫化的鋁, 例如氫化鋁,如二乙基氫化鋁和二丁基氫化鋁;二烷基氫 化銘如一 丁基風化銘;郅分虎氧基化和齒化的燒基銘, 如乙基乙氧基氣化鋁、丁基丁氧基氣化鋁及乙基乙氧基溴 化鋁。 在本發明(共)聚合阿伐-烯烴之方法中,在聚合反應期 間用有機矽化合物作爲外電子給體改良所產生聚合物之立 體規則性。本發明所用有機矽化合物包括乙基三乙氧基矽 燒、正丙基三乙氧基矽烷、第三丁基二乙氧基矽烷、乙烯 基三乙氧基矽烷、二苯基二甲氧基矽烷、苯基甲基二甲氧 基矽烷、雙(對曱苯基)二曱氧基矽烷、對甲苯基甲基二甲 氧基矽烷、二環己基二甲氧基矽烷、環己基甲基二甲氧基 矽烷、2-降莰烷三乙氧基矽烷、2-降莰烷甲基二甲氧基 矽烷、二苯基二乙氧基矽烷等;亦可使用包含環戊基、環 戊晞基、壤戊二晞基之有機金屬死合物或其衍生物。 作爲外電子給體(3),特佳使用二環戊基二甲氧基矽 烷、環己基曱基二甲氧基矽烷及乙烯基三乙氧基矽烷。在 此情況下,二環戊基二甲氧基矽烷對電子給體之莫耳比係 於0.05〜0.7範圍内;環己基甲基二甲氧基矽烷對電子給體 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 扣770 五、發明説明( 之莫耳比係於〇騎9範圍内;乙 广 子給體之莫耳比係於0 05〜0 二乙乳基碎燒對電 二甲氧切燒對電子給體之莫更佳爲,二環戊基 環己基甲基二甲氧切垸對電子给體範圍内, 範圍内,乙烯基三乙氧莫耳比係於〇.2〜0.6 。鄉範園内。 對電子给體之莫耳比係於 合。 永口物時,更適合使用氣相聚 在液相聚合中,可^ 、、 ^ 、 用非活性溶劑作爲反應介質,如己 、凡、庚烷和煤油,但亦可 、、 用烯厶本身作爲反應介質。如果 私仃:目’合’聚合反應系統中固體鈦錯合物觸媒⑴之 W圭很度以鈥原子計爲每升溶劑約〇刪〜$毫莫耳,更佳 約0.001〜〇·5毫莫耳。a : % — 毛旲斗如果進仃氣相聚合,同樣以鈦原子 :十’每:聚合約“·001〜5毫莫耳,較佳約〇〇〇ι毫莫耳〜 約丨·0耄5莫耳,更佳約〇.〇1〜0.5毫莫耳。組分⑺中有機 =屬原子之比例爲固體觸媒⑴中每莫耳鈦原子約 莫耳,較佳約5〜500莫耳。組分⑺之比例(以矽原子計)爲 組分(2)中每莫耳有機金屬原子約〇〇〇1〜1〇莫耳,較佳約 〇·〇1〜2莫耳’更佳約〇.〇5〜1莫.耳Ύ 用本發明觸媒進行聚合反應與使用齊格勒(ziegler)型觸 媒之習知方法方式相同。應注意:該反應實質上在缺乏氧 和水下進行。烯烴聚合反應較佳以約20〜200 °C範圍溫度 (更佳在約50〜180 °C範圍)在約1大氣壓至100大氣壓壓力 • 13· 本紙張尺度適財㈣家標準(CNS) A4規格(21G X 297公爱) 555770 A7 B7 五、發明説明(11 ) 範圍進行(較佳約2〜50大氣壓)。可以分批、半分批或連 續進行反應,亦可用不同反應條件進行二或多個步驟。 本發明以下通過實例和比較性實例進一步説明。然而, 此等實例和比較性實例僅用於説明目的,本發明不受其方 法限制。 實例1 製造固體鈦觸媒組分 聚合阿伐-烯烴所用觸媒根據韓國專利特許公開案第10-2000-0009625號實例1所提出方法產生。關於實例所用聚 合阿伐-烯烴之觸媒產生,韓國專利特許公開案第10-2000-0009625號之説明係全部以無特殊關聯方式併於本文。 載體和觸媒之顆粒大小分佈用雷射顆粒分析儀檢測[邁 爾文儀器公司(Malvern Instrument),Mastersizer X 型]。載體 和觸媒各組分由ICP法分析,表面積使用BET法。觸媒產 率按觸媒最終重量/其中初始放入MgCl2重量確定。以產 生的觸媒顆粒大小爲50微米,其包括3.1重量% Ti 、 18.8 重量 % Mg、250 ppm A1 及 230 ppm Si 。比表面積爲 241米2/克。所產生觸媒之顆粒大小分佈分別爲,di〇=33.6 微米’ d5〇=58.5微米’且d5〇=97.1微米。在此’山〇、(I50 和d90指10%、50%和90%顆粒〜穿別小於33.6微米、58.5 微米和97.1微米。d50定義爲中間顆粒大小。 在根據以下條件經歷預聚和聚合製程後,檢測由該方法 產生的觸媒活度: 預聚合 • 14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 555770 A7 _ B7 五、發明説明(l2 ) 將綱毫升正己燒和6毫莫耳三乙基無放入含4克觸媒 的玻璃瓶,將該觸媒於衆放入保持在15。〇的i升玻璃反 應器。在0.5或更低大氣壓以1〇〇立方厘米/分鐘加入丙缔 同時,用200轉/分鐘攪拌速度預聚合1〇〇分鐘。由此產生 的預聚物預聚度爲3克聚丙晞/克觸媒。 聚合 用40¾克預聚物、7毫升1莫耳/升以正己烷稀釋的三 乙基鋁落液(7耄莫耳,Al/Ti莫耳比Μ,οπ)以及正己烷烯 稀釋的7毫升〇· 1M外電子給體溶液(〇 7毫莫耳,Si/Ti莫 耳比=108 )(作爲外電子給體的環己基甲基二甲氧基矽烷、 一環戊基二甲氧基矽烷及乙烯基三乙氧基矽烷之莫耳比分 別爲0.2、0.4及〇·4)加入2升高壓釜。然後用氮氣將反 應器調節至大氣壓力。在將1000標準毫升氫氣置入反應 器後’加入1200亳升(600克)液態丙烯。在63〇轉/分鐘 攪摔同時,使溫度升至70 X:。保持701溫度1小時進行 聚合。然後停止攪拌,在溫度減至室溫時,用氮氣置換反 應器内部,在此爲聚合完成點。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生之聚合物,其結構.顯示於表1中。 實例2 · ·〜 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含0.3、0.35和0.35相應莫 耳比環己基曱基二甲氧基矽烷、二環戊基二甲氧基矽烷和 乙烯基三乙氧基矽烷作爲外電子給體的7毫升〇1莫耳/升 -15- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 555770 A7 B7 五、發明説明(I3 ) 正己烷稀釋溶液(0.7毫莫耳,Si/Ti莫耳比=1.08 )併入聚合 製程。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生之聚合物,結果顯示於表1中。 實例3 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含0.4、0.3和0.3相應莫耳 比環己基甲基二甲氧基矽烷、二環戊基二曱氧基矽烷及乙 烯基三乙氧基矽烷作爲外電子給體的7毫升0.1莫耳/升正 己烷稀釋溶液(0.7毫莫耳,Si/Ti莫耳比=1.08 )併入聚合製 程0 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表1中。 實例4 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含0.5、0.25和0.25相應莫 耳比環己基甲基二甲氧基矽烷、二環戊基二甲氧基矽烷及 乙烯基三乙氧基矽烷作爲外電子給體的7毫升0.1莫耳/升 正己烷稀釋溶液(0.7毫莫耳,Si/Ti莫耳比=1.08)併入聚合 製程。 •一 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表1中。 實例5 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 -16- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 555770 A7 ___— _B7_ 五、發明説明(l4 ) 1相同的條件下進行,但將包含〇 6、〇·2和〇·2相應莫耳 比環己基甲基二甲氧基矽烷、二環戊基二甲氧基矽烷和乙 晞基三乙氧基矽烷作爲外電子給體的7毫升0.1莫耳/升正 己烷稀釋溶液(〇·7毫莫耳,Si/Ti莫耳比=108 )併入聚合製 程。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表i中。 實例6 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含〇·7、〇 15和〇 15相應莫 耳比環己基甲基二甲氧基矽烷、二環戊基二甲氧基矽烷和 乙晞基三乙氧基矽烷作爲外電子給體的7毫升〇丨莫耳/升 正己烷稀釋溶液(〇·7毫莫耳,Si/Ti莫耳比=108)併入聚合 製程。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等备 析如此產生的聚合物,結果顯示於表1中。 實例7 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含〇·8、〇·1和〇·1相應莫耳 比環己基甲基二甲氧基矽烷、三1 袤戊基二甲氧基矽烷及乙 烯基三乙氧基矽烷作爲外電子給體的7毫升0· 1莫耳/升正 己燒稀釋溶液(0.7毫莫耳,Si/Ti莫耳比=108 )併入聚合製 程0 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 -17- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) m -裝 訂The organometallic component (2) used this month includes, in particular, trisalyl aluminum, such as monoethylaluminum and dibutylaluminum, trienyl aluminum, such as triisoprenyl aluminum; partially alkoxylated alkyl groups Aluminum, such as aluminum dialkyl alkoxy, such as diethyl ethoxy and monobutyl butoxy; aluminum alkyl sesquialkane, such as ethyl sesquiethoxy, and butyl sesquiethyl Aluminium oxide; Alkyl dichloride, such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide; partially hydrogenated aluminum, such as aluminum hydride, such as diethyl aluminum hydride and dibutyl aluminum Aluminum hydride; dialkyl hydride inscriptions such as monobutyl weathering inscription; dioxinated and oxidized calcined inscriptions such as ethyl ethoxy aluminum vaporization, butyl butoxy aluminum vaporization and ethyl Aluminum ethoxylate. In the method for (co) polymerizing avar-olefins of the present invention, the organic regular compound is used as an external electron donor during the polymerization reaction to improve the stereoregularity of the polymer produced. The organic silicon compound used in the present invention includes ethyltriethoxysilane, n-propyltriethoxysilane, third butyldiethoxysilane, vinyltriethoxysilane, diphenyldimethoxy Silane, phenylmethyldimethoxysilane, bis (p-phenyl) dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldisilane Methoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, etc .; cyclopentyl, cyclopentyl Organometallic dead compound or derivative thereof. As the external electron donor (3), dicyclopentyldimethoxysilane, cyclohexylfluorenyldimethoxysilane, and vinyltriethoxysilane are particularly preferably used. In this case, the molar ratio of dicyclopentyldimethoxysilane to the electron donor is in the range of 0.05 to 0.7; cyclohexylmethyldimethoxysilane is an electron donor-12- This paper is applicable to this paper China National Standard (CNS) A4 specification (210 X 297 mm) buckle 770 V. Description of the invention (The Molar ratio is in the range of 0 to 9; the Molar ratio of the donor of Erguangzi is 0 05 ~ 0 2 Ethyl lactate is better for electron donors. Dicyclopentylcyclohexylmethyldimethoxypyridine is for electron donors. Within the range, vinyl triethoxy Mole ratio is between 0.2 and 0.6. In the rural fan garden. Mole ratio for electron donors is in combination. When it is permanent, it is more suitable to use gas phase polymerization in liquid phase polymerization. It can be used in the liquid phase polymerization. Inactive solvents are used as reaction media, such as hexane, vanadium, heptane and kerosene, but olefins themselves can also be used as reaction media. If private: solid titanium complex catalyst in the polymerization system In terms of atomic weight, it is about 0 to $ millimoles per liter of solvent, more preferably about 0.001 to 0.5 millimoles. A:% — gross If the bucket is subjected to gas phase polymerization, the titanium atom: 10 'per: polymerization is about "· 001 ~ 5 millimoles, preferably about 00 millimoles ~ about 丨 · 0 耄 5 moles, more It is preferably about 0.01 to 0.5 millimolar. The proportion of organic = metal atoms in component ⑺ is about Moore per mole of titanium atom in solid catalyst ⑴, preferably about 5 to 500 Moore. The ratio of component ⑺ (Calculated as silicon atom) as component (2), about 0.001 to 10 mol per mole of organometallic atom, preferably about 0.001 to 2 mol ', more preferably about 0.05 to 1 Mo. Ear The polymerization method using the catalyst of the present invention is the same as the conventional method using a Ziegler-type catalyst. It should be noted that the reaction proceeds substantially in the absence of oxygen and underwater. It is better to use a temperature in the range of about 20 to 200 ° C (preferably in the range of about 50 to 180 ° C) at a pressure of about 1 atmosphere to 100 atmospheres. 13 · This paper size is suitable for financial standards (CNS) A4 (21G X 297) (Public love) 555770 A7 B7 V. Description of invention (11) range (preferably about 2 to 50 atmospheres). The reaction can be carried out batchwise, semi-batchwise or continuously, and different reactions can also be used. Two or more steps are performed under conditions. The present invention is further illustrated below by examples and comparative examples. However, these examples and comparative examples are for illustrative purposes only, and the present invention is not limited by its methods. Example 1 Manufacturing a solid titanium catalyst The catalyst used for component polymerization of avar-olefin was produced according to the method proposed in Example 1 of Korean Patent Laid-Open No. 10-2000-0009625. Regarding the catalyst production of polymerized avar-olefin used in the example, Korean Patent Laid-open No. 10 The description of -2000-0009625 is all incorporated in this article in a non-specific way. The particle size distribution of the carrier and catalyst was measured with a laser particle analyzer [Malvern Instrument, Mastersizer X Model]. The components of the carrier and catalyst were analyzed by ICP method, and the surface area was determined by BET method. The catalyst yield is determined by the final weight of the catalyst / the weight of MgCl2 initially placed in it. The resulting catalyst particles are 50 microns in size and include 3.1% by weight Ti, 18.8% by weight Mg, 250 ppm A1, and 230 ppm Si. The specific surface area is 241 m2 / g. The particle size distribution of the produced catalyst was respectively di0 = 33.6 microns 'd50 = 58.5 microns' and d50 = 97.1 microns. Here, shan, I50, and d90 refer to 10%, 50%, and 90% particles ~ Punch is less than 33.6 microns, 58.5 microns, and 97.1 microns. D50 is defined as the intermediate particle size. It undergoes prepolymerization and polymerization processes according to the following conditions After that, the catalyst activity generated by this method was tested: Pre-polymerization • 14- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 555770 A7 _ B7 V. Description of the invention (l2) Ml of n-hexane and 6 millimoles of triethyl were placed in a glass bottle containing 4 g of catalyst, and the catalyst was placed in an i-liter glass reactor maintained at 15.0. At 0.5 or lower atmospheric pressure to 100 cubic centimeters per minute while adding propylene, prepolymerize for 100 minutes with a stirring speed of 200 rpm. The prepolymer degree of the resulting prepolymer is 3 g polypropylene per gram catalyst. 40 ¾ g for polymerization Prepolymer, 7 mL of 1 mol / L triethylaluminum falling solution diluted in n-hexane (7 μmol, Al / Ti molar ratio M, οπ) and 7 mL of 0.1 mL diluted with n-hexane Electron donor solution (07 millimolar, Si / Ti molar ratio = 108) (cyclohexylmethyldimethoxysilane as an external electron donor 1. The molar ratios of monocyclopentyldimethoxysilane and vinyltriethoxysilane are 0.2, 0.4, and 0.4), respectively, and added to a 2 liter autoclave. The reactor is then adjusted to atmospheric pressure with nitrogen. After placing 1000 standard milliliters of hydrogen into the reactor, '1200 liters (600 grams) of liquid propylene was added. While stirring at 63 rpm, the temperature was raised to 70 X :. The temperature was maintained at 701 for 1 hour for polymerization. Then the stirring was stopped. When the temperature is reduced to room temperature, the inside of the reactor is replaced with nitrogen, which is the polymerization completion point. The structure of the polymer thus produced is analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc., and its structure Shown in Table 1. Example 2 · · ~ This example uses the same solid titanium catalyst as in Example 1. The polymerization was performed under the same conditions as in Example 1, but will contain 0.3, 0.35, and 0.35 corresponding mole ratio cyclohexyl 7 ml of fluorenyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane as external electron donors mol / l -15-This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 555770 A7 B7 Note (I3) Diluted n-hexane solution (0.7 millimolar, Si / Ti molar ratio = 1.08) is incorporated into the polymerization process. It is generated by analysis such as activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The polymer is shown in Table 1. Example 3 This example uses the same solid titanium catalyst as in Example 1. The polymerization was performed under the same conditions as in Example 1, but will contain 0.4, 0.3, and 0.3 corresponding mole ratio rings. Hexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane as external electron donors 7 ml 0.1 mol / l n-hexane dilution solution (0.7 millimoles, Si / Ti molar ratio = 1.08) incorporated into the polymerization process 0 The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 4 This example uses the same solid titanium catalyst as Example 1. The polymerization was carried out under the same conditions as in Example 1, but will contain 0.5, 0.25, and 0.25 of the respective molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane. As an external electron donor, 7 ml of a 0.1 mol / l n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 1.08) was incorporated into the polymerization process. • One The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 5 This example uses the same solid titanium catalyst as Example 1. Aggregation was carried out under the same conditions as in Example-16- This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 555770 A7 ___— _B7_ V. Description of the invention (l4) 1 but it will contain 〇6 , 0.2 and 0.2 correspond to 7 ml of 0.1 mol of the molar ratio of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and ethinotriethoxysilane as external electron donors. Ear / liter of n-hexane diluted solution (0.7 millimoles, Si / Ti mole ratio = 108) was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table i. Example 6 This example uses the same solid titanium catalyst as Example 1. The polymerization was carried out under the same conditions as in Example 1, but will contain the corresponding molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and ethynyl groups of 0.7, 0.15, and 0.15. 7 ml of a mol / l n-hexane diluted solution (0.7 mmol, Si / Ti molar ratio = 108) of triethoxysilane as an external electron donor was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 7 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but will include the respective mole ratios of cyclohexylmethyldimethoxysilane, tri-1, pentamyldimethoxysilane and 0.8, 0.1, and 0.1. 7 ml of a 0.1 mol / l di-hexane burned dilute solution of vinyltriethoxysilane as an external electron donor (0.7 millimolar, Si / Ti molar ratio = 108) is incorporated into the polymerization process. , Melt Flow Rate (MFR), NMR, RDS, DSC, etc. -17- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) m-binding
k 555770 A7 _____ B7 五、發明説明(I5 ) 析如此產生的聚合物,結果顯示於表1中。 實例8 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含〇 7、0.15和0.15相應莫 耳比環己基甲基二甲氧基矽烷、二環戊基二甲氧基矽烷及 乙烯基三乙氧基矽烷作爲外電子給體的7毫升〇 1莫耳/升 正己烷稀釋溶液(0.7毫莫耳,Si/Ti莫耳比=108)併入聚合 製程,然後加入500標準毫升氫氣。 由用活度、熔體流速(MFR)、NMR、‘RDS、DSC等分 析如此獲得的聚合物,結果顯示於表1中。 實例9 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將.包含0 7、〇 15和〇 15相應莫 耳比環己基甲基二甲氧基矽烷、二環戊基二甲氧基矽烷和 乙烯基二乙氧基石夕燒作爲外電子給體的7毫升〇1莫耳/升 正己燒稀釋溶液(〇·7毫莫耳,Si/Ti莫耳比=1〇8)併入聚合 製程,然後加入2000標準毫升氫氣。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表i中。 以下提供比較性實例,以比幸交^單元或二元外電子給體 獲得的聚合物與實例中用三元外電子給體獲得的聚合物之 性能。 比較性實例1 本比較性實例使用與實例1相同的固體鈥觸媒。聚合在k 555770 A7 _____ B7 V. Description of the invention (I5) The polymer thus produced was analyzed. The results are shown in Table 1. Example 8 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but it would contain the corresponding molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxy. 7 ml of a 0.1 mol / l n-hexane diluted solution of silane as an external electron donor (0.7 millimolar, Si / Ti molar ratio = 108) was incorporated into the polymerization process, and then 500 standard milliliter of hydrogen was added. The polymer thus obtained was analyzed by activity, melt flow rate (MFR), NMR, 'RDS, DSC, etc., and the results are shown in Table 1. Example 9 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, except that 0, 0, 15 and 0,15 corresponding mole ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and vinyldi 7 ml of a 0.01 ml mol / l dioxane-diluted solution (0.7 mmol, Si / Ti mole ratio = 108) of ethoxylithium as an external electron donor was incorporated into the polymerization process, and then added to 2000 Standard ml of hydrogen. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table i. The following provides comparative examples of the properties of polymers obtained by cross-linking units or binary external electron donors with polymers obtained using ternary external electron donors in the examples. Comparative Example 1 This comparative example uses the same solid'catalyst as in Example 1. Converge on
555770555770
與實例Η目同的條件下進行,但將包含單獨環己基甲基二 甲氧基㈣作爲外電子給體的7毫升〇1莫耳/升正己坑稀 釋溶液(〇.7毫莫耳,Si/Ti莫耳比=1〇8)併入聚合製程。 由用活度、炫體流速⑽R)、NMR、RDs、dsc等分 析如此產生的聚合物,結果顯示於表i中。 比較性實例2 本比較性實例使用與實例!相同的固體鈦觸媒。聚合在 與實例"目同的條件下進行,但將包含單獨二環戊基二甲 氧基矽烷:爲外電子給體的7毫升〇1莫耳,升正己烷稀釋 溶液(0.7耄莫耳,Si/Ti莫耳比=1〇8 )併入聚合製程。 由用活度、熔體流速(MFR)、NMR、RDS、dsc等分 析如此產生的聚合物,結果顯示於表i中。 比較性實例3 本比較性實例使用與實例1相同的固體鈦觸媒。聚合在 與實例1相同的條件下進行,但將包含單獨乙烯基三乙氧 基石夕燒作爲外電子給體的7毫升G1莫耳/升正己燒稀釋溶 液(0.7¾莫耳,Si/Ti莫耳比=108)併入聚合製程。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表1中。 比較性實例4 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含〇5和〇 5相應莫耳比二環 戊基一甲氧基石夕燒和乙晞基三乙氧基石夕炊作爲外電子給體 的7毫升0·1莫耳/升正己烷稀釋溶液(〇 7毫莫耳,Si/Ti -19- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 555770 A7 B7 五、發明説明(Γ7 ) 莫耳比=108 )併入聚合製程,然後加入500標準毫升氫 氣。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表1中。 比較性實例5 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含0.5和0.5相應莫耳比二環 戊基二甲氧基矽烷和乙烯基三乙氧基矽烷作爲外電子給體 的7毫升0.1莫耳/升正己烷稀釋溶液(0.7毫莫耳,Si/Ti 莫耳比=108)併入聚合製程。 由用活度、熔體流速(MFR)、NMR、RDS、DSC等分 析如此產生的聚合物,結果顯示於表1中。 比較性實例6 本實例使用與實例1相同的固體鈦觸媒。聚合在與實例 1相同的條件下進行,但將包含0.5和0.5相應莫耳比二環 戊基二甲氧基矽烷和乙烯基三乙氧基矽烷作爲外電子給體 的7毫升0.1莫耳/升正己烷稀釋溶液(0.7毫莫耳,Si/Ti 莫耳比=108 )併入聚合製程,然後加入2000標準毫升氫 氣0 -20- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 555770 A7 B7 五 、發明説明(2〇 ) *上表中,活度用千克-聚丙晞/克觸媒/小時表示,溶體流 速用克克/10分鐘表示。另外,表中使用以下起首字母: Comp :化合物, E :實例, CE :比較性實例, MR :莫耳比, DCPDMS :二環戊基二甲氧基矽烷, CHMDMS :環己基甲基二甲氧基矽烷, VTES :乙烯基三乙氧基矽烷,及 MWD ··分子量分佈。 *聚合條件:本體聚合,40毫克預聚觸媒(預聚度:3克 聚丙烯/克觸媒),600克液態丙晞,7毫莫耳三乙基鋁, 0.7毫莫耳外電子給體,70.°C,且聚合1小時。 根據本發明提供之方考具有以高氫反應性和熔點流速獲 得寬分子量分佈聚合物之優點,同時在共(聚合)具三個或 更多碳原子阿伐-晞烴期間對於晞烴均-或共-聚物保持高 立體規則性及產率。 -23- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)It was performed under the same conditions as in the example, except that 7 ml of a mol / l n-hexane solution (0.7 mmol, Si) containing cyclohexylmethyldimethoxyfluorene alone as an external electron donor was used. / Ti molar ratio = 108) is incorporated into the polymerization process. The polymer thus produced was analyzed by activity, body flow rate (R), NMR, RDs, dsc and the like, and the results are shown in Table i. Comparative Example 2 This comparative example uses and examples! Same solid titanium catalyst. The polymerization was carried out under the same conditions as in the example, but it will contain a single dicyclopentyldimethoxysilane: 7 ml of 0 mol, a dilute solution of n-hexane (0.7 mol) , Si / Ti molar ratio = 108) is incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, dsc, etc. The results are shown in Table i. Comparative Example 3 This comparative example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, except that 7 ml of a G1 mole / liter di-hexane-diluted solution (0.7¾ mole, Si / Ti mole) containing vinyl triethoxy stone sinter alone as an external electron donor was used. Ear ratio = 108) incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 4 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but using 7 and 5 corresponding molar ratios of dicyclopentyl-methoxybenzoate and ethoxytriethoxylate as the external electron donors. Milliliter of 0.1 mol / L n-hexane diluted solution (07 millimoles, Si / Ti -19- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 555770 A7 B7 V. Description of the invention (Γ7) Molar ratio = 108) was incorporated into the polymerization process, and then 500 standard milliliter of hydrogen was added. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 5 This example uses the same solid titanium catalyst as in Example 1. Polymerization was carried out under the same conditions as in Example 1, but using 7 ml of 0.1 mol / l containing 0.5 and 0.5 corresponding mole ratios of dicyclopentyldimethoxysilane and vinyltriethoxysilane as external electron donors. One liter of n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 108) was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 6 This example uses the same solid titanium catalyst as in Example 1. Polymerization was carried out under the same conditions as in Example 1, but using 7 ml of 0.1 mol / l containing 0.5 and 0.5 corresponding mole ratios of dicyclopentyldimethoxysilane and vinyltriethoxysilane as external electron donors. Liter of n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 108) is incorporated into the polymerization process, and then 2000 standard milliliter hydrogen is added 0 -20- This paper size applies to China National Standard (CNS) A4 specifications (210X297) (Centi) 555770 A7 B7 V. Description of the invention (20) * In the table above, the activity is expressed in kg-polypropionamine / g catalyst / hour, and the solution flow rate is expressed in grams / 10 minutes. In addition, the following initial letters are used in the table: Comp: Compound, E: Example, CE: Comparative Example, MR: Mole ratio, DCPDMS: Dicyclopentyldimethoxysilane, CHMDMS: Cyclohexylmethyldimethyl Oxysilane, VTES: vinyltriethoxysilane, and MWD ·· Molecular weight distribution. * Polymerization conditions: bulk polymerization, 40 mg prepolymerization catalyst (prepolymerization degree: 3 g polypropylene / g catalyst), 600 g liquid propidium, 7 millimoles triethylaluminum, 0.7 millimoles external electron donor Body, 70. ° C, and polymerized for 1 hour. The formula provided according to the present invention has the advantages of obtaining a polymer with a wide molecular weight distribution with high hydrogen reactivity and melting point flow rate, and at the same time during the copolymerization (polymerization) of avalan-hydrocarbons having three or more carbon atoms, Or the co-polymer maintains high stereoregularity and yield. -23- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)
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JP2001197021A JP2002212219A (en) | 2000-12-27 | 2001-06-28 | METHOD FOR HOMOPOLYMERIZATION OR COPOLYMERIZATION OF alpha-OLEFIN |
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