TW201035112A - Improvement of rapid crack properties in high performance pipe - Google Patents
Improvement of rapid crack properties in high performance pipe Download PDFInfo
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- TW201035112A TW201035112A TW98139324A TW98139324A TW201035112A TW 201035112 A TW201035112 A TW 201035112A TW 98139324 A TW98139324 A TW 98139324A TW 98139324 A TW98139324 A TW 98139324A TW 201035112 A TW201035112 A TW 201035112A
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201035112 六、發明說明: 相關申請案之交互參照 此申請案主張2008年11月24日提出申請之美國專 利臨時申請案第61/1 17,491號之權利。 【發明所屬之技術領域】 本發明一般係關於以乙烯爲基礎之聚合物形成的管。 〇 【先前技術】 如專利文獻所反映者,多模態聚烯烴曾被用以製造各 式各樣的產品,如,膜、片和管。自這些多模態聚烯烴形 成的產品具有強度和其他效能性質的同時,多模態聚烯烴 通常於零度以下的溫度防止龜裂及脆性的能力有限。因此 ,對於自多模態聚烯烴形成具有改良的抗裂性質之管有需 求存在。 〇 【發明內容】 發明總論 本發明之體系包括管件。此管件通常包括二模態聚乙 烯,該二模態聚乙烯所包括之高分子量部分的含量高於低 分子量部分的含量且其中該管件於5巴的臨界溫度低於約 0。。。 體系進一步包括形成管件之方法。此方法通常包括提 供包括約52重量%至約54重量%高分子量部分和約48重 -5- 201035112 量%至約4 6重量%低分子量部分的二丨吴態聚乙稀,及自該 二模態聚乙烯形成管件,其中該管件於5巴的臨界溫度低 於約-5°C。 【實施方式】 簡介和定義 現將提供詳細描述。所附申請專利範圍中之各者定義 個別發明,爲侵權判定之目的,申請專利範圍視爲包括其 f) 中指明的各式各樣要件或限制之對等物。取決於前後文, 下文中“本發明”一詞在一些情況中僅是指某些特定體系。 其他情況中,將認爲“本發明”一詞是指申請專利範圍中之 一或多項,但不須爲全數,所指的標的。下文將詳細描述 本發明之各者,包括特定體系、變體和實例,但本發明不 限於這些體系、變體或實例,當此專利中的資訊與可資利 用的資訊和技術合併時,其含括用以使得嫻於此技藝者製 造及使用本發明。 u 下文出示各式各樣的名詞。若申請專利範圍中使用的 名詞未定義於下,其應爲相關於此技藝之人士所賦予該名 詞的最寬定義,此如印行的文獻和頒佈的專利案於提出申 請時所反映者。此外,除非特別聲明,文中所述的所有化 合物可爲經取代或未經取代者且化合物之表列包括其衍生 物。 除非文中指明,否則所有測試方法係提出申請當時的 方法。 -6 - 201035112 如文中使用者,“室溫”是指幾度的溫度差不會影響硏 究現象,如’製法。一些環境中,室溫可包括約2〇。(3至約 28 °C (68 °F至82 °F)的溫度,而在其他環境中,室溫可包 括’例如,由約50°F至約90°F。但是,室溫測定通常不 包括密切監看方法的溫度並因此而使得引述此用語時沒有 將文中所描述的體系結合至任何預定溫度範圍的意圖。 各式各樣的範圍進一步地示於下文中。應瞭解除非特 0 別聲明,否則試圖使得終點可交替。此外,在此範圍內的 任何點含括於文中所揭示者中。 本發明之體系通常包括自二模態聚乙烯形成的管。 觸媒系統 可用以聚合烯烴單體的觸媒系統包括嫻於此技藝者已 知的任何觸媒系統。例如,該觸媒系統可包括,例如,二 茂金屬觸媒系統、單位置觸媒系統、戚格勒-納他( Ο Ziegler-Natta )觸媒系統或它們的組合。如此技藝已知者 ’該觸媒可經活化用於後續的聚合反應且可以與或未與載 體材料結合。下文含括此觸媒系統的簡短討論,但其不欲 以任何方式將本發明之範圍限於此觸媒。 例如,戚格勒-納他觸媒系統通常由金屬組份(如, 觸媒)與一或多種額外組份(如,觸媒載體、輔觸媒)和 /或例如,一或多種電子授體所形成。 包括金屬組份之戚格勒-納他觸媒的特定實例通常以 下式表示 : 201035112 mrax ; 其中M是過渡金屬,RA是鹵素、烷氧基或羧基而X是過 渡金屬的價數。例如,X可由1至4。 例如,此過渡金屬可選自第IV族至VIB族(如,鈦 、飢或絡)。一體系中’ RA可選自氯、漠、碳酸根、醋 或烷氧基。觸媒組份的例子包括,例如,TiCl4、TiBr4、 Ti(OC2H5)3Cl 、 Ti(OC3H7)2Cl2 、 T i ( O C 6H j 3) 2 C12 、201035112 VI. INSTRUCTIONS: Cross-Reference to Related Applications This application claims the right of U.S. Patent Provisional Application No. 61/1, 17,491, filed on November 24, 2008. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to tubes formed from ethylene-based polymers. 〇 [Prior Art] As reflected in the patent literature, multimodal polyolefins have been used to make a wide variety of products such as films, sheets and tubes. While these multimodal polyolefin products have strength and other performance properties, multimodal polyolefins typically have limited ability to prevent cracking and brittleness at temperatures below zero. Therefore, there is a need for a tube having improved crack resistance properties from a multimodal polyolefin. 〇 SUMMARY OF THE INVENTION The system of the present invention includes a tubular member. The tubular member typically comprises a dimodal polyethylene having a higher molecular weight fraction than the low molecular weight fraction and wherein the tubular member has a critical temperature of less than about 0 at 5 bar. . . The system further includes a method of forming a tubular member. The method generally comprises providing a diterpene polyethylene comprising from about 52% by weight to about 54% by weight of the high molecular weight fraction and from about 48% to about 5,500,351,120% to about 6% by weight of the low molecular weight fraction, and from the second The modal polyethylene forms a tubular member wherein the tubular member has a critical temperature of less than about -5 ° C at 5 bar. [Embodiment] Introduction and Definition A detailed description will now be provided. Each of the scope of the appended claims defines individual inventions, and for the purposes of infringement determination, the scope of the patent application is deemed to include equivalents of the various elements or limitations specified in the f). Depending on the context, the term "invention" in the following refers only to certain specific systems in some cases. In other cases, the term "invention" shall be taken to mean one or more of the scope of the patent application, but not necessarily the full number of the subject matter. The invention is described in detail below, including specific systems, variants and examples, but the invention is not limited to such systems, variants or examples, when the information in this patent is combined with available information and technology, This invention is included to enable the skilled artisan to make and use the invention. u Various types of nouns are shown below. If the noun used in the scope of the patent application is not defined below, it shall be the broadest definition of the term given to persons skilled in the art, as reflected in the published literature and the patents filed at the time of filing. Furthermore, all compounds described herein may be substituted or unsubstituted and the list of compounds includes derivatives thereof unless otherwise stated. Unless otherwise stated in the text, all test methods are presented at the time of the application. -6 - 201035112 For the user of the text, “room temperature” means that a temperature difference of several degrees does not affect the phenomenon of the study, such as the manufacturing method. In some environments, room temperature can include about 2 Torr. (3 to a temperature of about 28 ° C (68 ° F to 82 ° F), while in other environments, room temperature may include 'for example, from about 50 ° F to about 90 ° F. However, room temperature measurement is usually not Included is the temperature of the closely monitored method and thus the intent to incorporate the system described herein into any predetermined temperature range is not quoted. The various ranges are further illustrated below. It should be understood that unless otherwise specified It is stated that otherwise attempts are made to alternate the endpoints. Further, any point within this range is included in the disclosure. The system of the present invention typically includes tubes formed from dimodal polyethylene. Catalyst systems can be used to polymerize olefins. The monomeric catalyst system includes any catalyst system known to those skilled in the art. For example, the catalyst system can include, for example, a metallocene catalyst system, a single position catalyst system, a 戚格勒-纳塔(Ο Ziegler-Natta) Catalyst system or a combination thereof. It is known in the art that the catalyst can be activated for subsequent polymerization and may or may not be combined with a carrier material. The following includes the catalyst system. a short discussion, It is not intended to limit the scope of the invention in any way to the catalyst. For example, a Zigler-Natta catalyst system typically consists of a metal component (eg, a catalyst) with one or more additional components (eg, a catalyst). A carrier, a secondary catalyst, and/or, for example, one or more electron donors. A specific example of a Plage-Nanocatalyst comprising a metal component is generally represented by the following formula: 201035112 mrax ; wherein M is a transition metal, RA is a halogen, alkoxy or carboxyl group and X is a valence of the transition metal. For example, X may be from 1 to 4. For example, the transition metal may be selected from Groups IV to VIB (e.g., titanium, hunger or lanthanum). In one system, 'RA may be selected from chlorine, desert, carbonate, vinegar or alkoxy. Examples of catalyst components include, for example, TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC3H7)2Cl2, T i ( OC 6H j 3) 2 C12,
Ti(OC2H5)2Br2 和 Ti(OC12H25)Cl3。 嫻於此技藝者將瞭解觸媒在用以增進聚反應之前,可 經一些方式“活化”。如下文進一步討論者,藉由使觸媒與 戚格勒-納他活化劑(Z - N活化劑)(有時亦將其稱爲“輔 觸媒”)接觸,可完成活化作用。此Z-N活化劑之體系包 括有機鋁化合物,如,三甲基鋁(TMA )、三乙基鋁( TEA1)和三異丁基鋁(TIBA1 )。 戚格勒-納他觸媒系統可以進一步包括一或多種電子 授體,如,內在電子授體和/或外在電子授體。內在電子 授體可用以降低所得聚合物之雜排(atactic )形式,藉此 降低可溶於聚合物中的二甲苯量。此內在電子授體可包括 例如,胺、醯胺、酯、酮、腈、醚、膦、二醚、丁二酸酯 、酞酸酯或二烷氧基苯。(請參考美國專利案第 5,945,366號和美國專利案第6,399,837號,茲將該等以引 用方式納入本文中。) 外在電子授體可用以進一步控制製造的雜排聚合物的 量。此外在電子授體可包括單官能性或多官能性羧酸、羧 -8 - 201035112 酸酐、羧酸酯、酮、醚、醇、內酯、有機磷化合物和/或 有機矽化合物。一體系中,此外在授體可包括,例如,二 苯基二甲氧基矽烷(DP MS )、環己基甲基二甲氧基矽烷 (CDMS )、二異丙基二甲氧基矽烷和/或二環戊基二甲 氧基矽烷(CDPS )。此外在授體可以與所用的內在授體 相同或不同。 戚格勒-納他觸媒系統的組份(如,觸媒、活化劑和 〇 /或電子授體)可以與或未與載體結合,彼此合倂或彼此 分離。Z-N載體材料可包括,例如,二鹵化鎂(如,二氯 化鎂或二溴化鎂)或矽石。 一特定體系中,戚格勒-納他觸媒係藉由使二烷氧化 鎂化合物與依序漸強的氯化和/或鈦化劑接觸而形成。例 如,此戚格勒-納他觸媒可以包括美國專利案第6,734,134 號和美國專利案第6,1 74,97 1號中所描述者,茲將該等以 引用方式納入本文中。 〇 通常,此戚格勒-納他觸媒可藉通常包括使烷基鎂化 合物與醇接觸以形成二烷氧化鎂化合物的方法形成。例如 ’此反應可於室溫至約9 0 °c的反應溫度進行至多約1 0小 時而發生。醇可以例如,以約0.5至約6當量或約1至約 3當量的量加至烷基鎂化合物中。 該烷基鎂化合物可以下式表示:Ti(OC2H5)2Br2 and Ti(OC12H25)Cl3. Those skilled in the art will appreciate that the catalyst can be "activated" in some manner prior to enhancing the polymerization reaction. As discussed further below, activation can be accomplished by contacting the catalyst with a Ziegler-Nano activator (Z-N activator), sometimes referred to as a "auxiliary catalyst." The system of the Z-N activator comprises an organoaluminum compound such as trimethylaluminum (TMA), triethylaluminum (TEA1) and triisobutylaluminum (TIBA1). The 戚格勒-纳catalyst system can further include one or more electron donors, such as intrinsic electron donors and/or external electron donors. Intrinsic electron donors can be used to reduce the atactic form of the resulting polymer, thereby reducing the amount of xylene soluble in the polymer. Such intrinsic electron donors can include, for example, amines, guanamines, esters, ketones, nitriles, ethers, phosphines, diethers, succinates, phthalates or dialkoxybenzenes. (Refer to U.S. Patent No. 5,945,366 and U.S. Patent No. 6,399,837, the disclosure of each of which is incorporated herein by reference. Further, the electron donor may include a monofunctional or polyfunctional carboxylic acid, a carboxy-8 - 201035112 anhydride, a carboxylate, a ketone, an ether, an alcohol, a lactone, an organophosphorus compound, and/or an organic phosphonium compound. In a system, in addition, the donor may include, for example, diphenyldimethoxydecane (DP MS ), cyclohexylmethyldimethoxydecane (CDMS), diisopropyldimethoxydecane, and/or Or dicyclopentyldimethoxydecane (CDPS). In addition, the donor may be the same or different from the intrinsic donor used. The components of the 戚Geller-Natta catalyst system (e.g., catalyst, activator, and/or electron donor) may or may not be combined with the carrier, or may be separated from each other. The Z-N support material may include, for example, a magnesium dihalide (e.g., magnesium dichloride or magnesium dibromide) or vermiculite. In a particular system, the Ziegler-Natta catalyst is formed by contacting a dioxane magnesium oxide compound with a gradual chlorination and/or titanating agent. For example, such a Plage-Natta catalyst can be included in U.S. Patent No. 6,734,134, and U.S. Patent No. 6,1,74,97, the disclosure of each of which is incorporated herein by reference. 〇 Generally, this 戚-glera-catalyst can be formed by a process which generally involves contacting an alkylmagnesium compound with an alcohol to form a magnesium dialkoxide compound. For example, the reaction can take place at a reaction temperature of from room temperature to about 90 ° C for up to about 10 hours. The alcohol can be added to the alkylmagnesium compound, for example, in an amount of from about 0.5 to about 6 equivalents or from about 1 to about 3 equivalents. The alkyl magnesium compound can be represented by the following formula:
MgR^2 ; 其中R1和R2獨立地選自Cl至C1()烷基。烷基鎂化合物的 非限制例包括,例如,丁基乙基鎂(BEM )、二乙基鎂、 201035112 二丙基鎂和二丁基鎂。 該醇可以下式表示: r3oh ; 其中R3選自c2至c2()烷基。醇的非限制例一般包括’例 如,丁醇、異丁醇和2 -乙基己醇。 然後,此方法可包括使該二烷氧化鎂化合物與第一試MgR^2; wherein R1 and R2 are independently selected from Cl to C1() alkyl. Non-limiting examples of the alkyl magnesium compound include, for example, butyl ethyl magnesium (BEM), diethyl magnesium, 201035112 dipropyl magnesium, and dibutyl magnesium. The alcohol can be represented by the formula: r3oh; wherein R3 is selected from the group consisting of c2 to c2(). Non-limiting examples of alcohols generally include, for example, butanol, isobutanol, and 2-ethylhexanol. Then, the method can include the first magnesium alkoxide compound and the first test
劑接觸而形成反應產物“A”。此反應可以在惰性溶劑存在 下發生。多種烴可以作爲此惰性溶劑,但所選用的任何烴 必須在所有的相關反應溫度下維持液體形式且用以形成負 載觸媒的成份必須至少部分溶解於該烴中。據此,該烴在 此處被視爲溶劑’即使在某些體系中,該成份僅部分溶解 於烴中亦然。 適當的烴溶劑包括經取代和未經取代的脂族烴及經取 代和未經取代的芳族烴。例如,該惰性溶劑可包括己院、The agent contacts to form a reaction product "A". This reaction can take place in the presence of an inert solvent. A wide variety of hydrocarbons can be used as the inert solvent, but any hydrocarbon selected must be maintained in liquid form at all relevant reaction temperatures and the components used to form the load catalyst must be at least partially soluble in the hydrocarbon. Accordingly, the hydrocarbon is considered herein as a solvent', even in certain systems, the component is only partially soluble in the hydrocarbon. Suitable hydrocarbon solvents include substituted and unsubstituted aliphatic hydrocarbons and substituted and unsubstituted aromatic hydrocarbons. For example, the inert solvent may include a home,
庚烷、辛烷、癸院、甲苯、二甲苯、二氯甲烷、三氯甲烷 、1 -氯丁烷或它們的組合。 例如,此反應可進一步在約〇 至約i 〇 〇 π或約2 〇。匸 至約90。(:的溫度發生約0.2小時至約24小時或約丨小時 至約4小時。 第一試劑的非限制例通常以下列式表示 ClA(OxR4)y : 其中a選自鈦' m錫和錯,r4選自ci至Ci〇 院基,如’甲基、乙基、丙基和異丙基,X是0或i而y 是A的價數Μ卜㈣如,第s試劑的非限制例包括氯化三 ' 10- 201035112 異丙氧化鈦 ClTi(〇ipr)3 和 ClSi(Me)3。 然後,此方法可包括使反應產物“A”與第二試 而形成反應產物“B”。該反應可以在惰性溶劑存在 。該惰性溶劑可包括,例如,前文中討論的溶劑中 者。例如,此反應可進一步在約0°C至約100 °C或; 至約90°C的溫度發生約0.2小時至約36小時或約 至約4小時。 〇 該第二試劑可以,例如,約0.5至約5,或約 4或約1 · 5至約2 · 5當量加至反應產物“ A ”中。 該第二試劑可以下列式表示:Heptane, octane, brothel, toluene, xylene, dichloromethane, chloroform, 1-chlorobutane or a combination thereof. For example, the reaction can be further from about 〇 to about i 〇 π π or about 2 〇.匸 to about 90. The temperature of (: is about 0.2 hours to about 24 hours or about 丨 hours to about 4 hours. A non-limiting example of the first reagent is generally represented by the following formula: ClA(OxR4)y: wherein a is selected from titanium 'm tin and wrong, R4 is selected from ci to Ci, such as 'methyl, ethyl, propyl and isopropyl, X is 0 or i and y is the valence of A. (IV) For example, non-limiting examples of the s reagent include Chlorinated three ' 10- 201035112 titanium isopropoxide ClTi(〇ipr)3 and ClSi(Me) 3. Then, the method may include reacting the reaction product "A" with the second test to form a reaction product "B". It may be present in an inert solvent. The inert solvent may include, for example, those in the solvents discussed above. For example, the reaction may further occur at a temperature of from about 0 ° C to about 100 ° C or to about 90 ° C. Hour to about 36 hours or about to about 4 hours. The second reagent may be, for example, from about 0.5 to about 5, or from about 4 or from about 1.5 to about 2.5 equivalents added to the reaction product "A". The second reagent can be represented by the following formula:
TiCl4/Ti(OR5)4 ; 其中R5選自c2至c2G烷基。第二試劑的非限制例 化鈦和烷氧化鈦之摻合物,如,TiCl4/Ti(OBu)4。 此摻合物的TiC 14 : Ti (OR5 )4當量可由約0.5至約6 2至約3。 Ο 然後,此方法可包括使反應產物“B”與第三試 而形成反應產物“C”。該反應可以在惰性溶劑存在 。該惰性溶劑可包括,例如,前文中討論的溶劑中 者。例如’此反應可進一步於室溫發生。 該第三試劑的非限制例包括金屬鹵化物。該金 物可包括嫻於此技藝者已知的任何金屬鹵化物,例 氯化鈦(TiCl4 )。該第三試劑可以,例如,約0.1 ’或約0_25至約4或約0.45至約2.5當量添加。 然後,此方法可進一步包括使反應產物“C”與 劑接觸 下發生 之任何 ^ 2 0°C 1小時 1至約 包括氯 例如, 或由約 劑接觸 下發生 之任何 屬鹵化 如,四 至約5 第四試 -11 - 201035112 劑接觸而形成反應產物“D”。該反應可以在惰性溶 下發生。該惰性溶劑可包括,例如,前文中討論的 之任何者。例如,此反應可進一步在室溫發生。 該第四試劑可以,例如,約0.1至約5,或約 約4或約0.45至約2.0當量加至反應產物“C”中。 該第四試劑的非限制例包括金屬鹵化物。該金 物可包括前文中描述的任何金屬鹵化物。 然後,此方法可包括使反應產物“D”與第五試 以形成觸媒組份。該第五試劑可以,例如,約0.1 或約0.5至約1.2當量加至反應產物“D”。 該第五試劑的非限制例包括有機鋁化合物。該 化合物可包括具有下列式的烷基鋁: air63 ; 其中R6是C!至C 1 〇烷基化合物。烷基鋁化合物的 例包括,例如,三甲基鋁(TMA )、三異丁基鋁I )、三乙基鋁(TEA1 )、正辛基鋁和正己基鋁。 聚合方法 如文中他處所迹示者,觸媒系統用以形成聚烯 物。一旦以前述方式和/或嫻於此技藝者已知的方 觸媒系統,可使用該組成物進行多種方法。取決於 的聚合物之所欲組成和性質,將改變選定的方法中 法使用的設備、方法條件、反應物、添加劑和其他 例如,此方法包括溶液相、氣相、淤漿相、整體相 劑存在 溶劑中 0.25 至 屬鹵化 劑接觸 至約2 有機鋁 非限制 TIB A1 烴組成 式製備 欲形成 之聚合 材料。 、商壓 -12- 201035112 法或它們的組合。(請參考,美國專利案第5,525,67 8號 ;美國專利案第6,420,580號;美國專利案第6,380,328 號;美國專利案第6,359,072號;美國專利案第6,346,586 號;美國專利案第6,340,730號;美國專利案第6,339,134 號;美國專利案第6,300,436號;美國專利案第6,274,684 號;美國專利案第6,271,3 2 3號;美國專利案第6,248,845 號;美國專利案第6,245,868號;美國專利案第6,245,705 〇 號;美國專利案第6,242,545號;美國專利案第6,211,105 號;美國專利案第6,2〇7,606號;美國專利案第6,180,735 號和美國專利案第6,147,173號,茲將該等以引用方式納 入本文中。) 某些體系中,前述方法通常包括使一或多種烯烴單體 聚合而形成聚合物。例如,該烯烴單體可包括C2至C30烯 烴單體’或〇2至C12烯烴單體(如,乙烯、丙烯、丁烯、 戊烯、甲基戊烯、己烯、辛烯和癸烯)。例如,此單體可 C) 包括烯烴系不飽和單體、C4至C8二烯烴、共軛或非共軛 二烯、多烯、乙烯基單體和環狀烯烴。例如,其他單體的 非限制例可包括原冰片烯、原冰片二烯、異丁烯、異戊二 烯、乙烯基苯并環丁烷、苯乙烯、烷基取代的苯乙烯、亞 乙基原冰片烯、二環戊二烯和環戊烯。例如,形成的聚合 物可包括均聚物、共聚物或三聚物。 溶液法的例子述於美國專利案第4,271,060號;美國 專利案第5,001,205號;美國專利案第5,23 6,998號和美 國專利案第5,5 89,5 5 5號,茲將該等以引用方式納入本文 -13- 201035112 中ο 氣相聚合法的一個例子包括連續循 環氣流(或稱爲循環流或流化介質)在 應熱而加熱。藉反應器外部的冷卻系統 自循環氣流移除熱。含有一或多種單體 在反應條件下,在觸媒存在下,連續循 循環氣流通常自流化床排放並循環回到 合物產物可自反應器排放並可以添加新 合的單體。在氣相法中的反應器壓力變 lOOpsig 至約 500psig,或由約 200psig 約250psig至約350psig。氣相反應法 由,例如,約30°C至約120°C,或由約 或由約70°C至約110°C或由約7〇°C至糸 例如,美國專利案第 4,543,399號 4,588,790號;美國專利案第5,028,670 5,317,036號;美國專利案第5,352,749 5,405,922號;美國專利案第5,436,304 5,456,471號;美國專利案第5,462,999 5,616,661號;美國專利案第5,627,242 5,665,8 1 8號;美國專利案第5,677,375 5,668,228號,茲將該等以引用方式納入 淤漿相法通常包括在液態聚合介質 合物之懸浮液,於其中添加觸媒以外, 氫。可以間歇或連續自反應器移出該懸 環系統,其中,循 反應器中藉聚合反 在循環的另一部分 的此循環氣流可以 環通過流化床。此 反應器。同時,聚 的單體以代替已聚 化可以例如,由約 至約400psig或由 中的反應器溫度可 6〇°C 至約 115°C, 句9 5 °C。請參考, ;美國專利案第 號;美國專利案第 號;美國專利案第 號;美國專利案第 號;美國專利案第 號;美國專利案第 號和美國專利案第 本文中。 中形成固態微粒聚 亦添加單體和任意 浮液(其可包括稀 -14- 201035112 釋劑)’反應器中的揮發性組份可自聚合物分離並循環( 任意地在蒸飽之後)至反應器。聚合反應介質中使用之液 化的稀釋劑可包括’例如,c3至c7烷(如,己烷或異丁 烷)。所用介質通常是在聚合反應條件下爲液體者且相當 惰性。整體相法類似於淤漿法,不同之處僅在於整體相法 中的液態介質亦爲反應物(如,單體)。但是,方法可爲 ’例如’整體法、淤漿法或整體淤漿法。 〇 特定體系中’可以在一或多個環流反應器(loop reactor )連續進行淤漿法或整體法。例如,觸媒(淤漿形 式或無水自由流動粉末形式)可以規律地注入反應器環流 中’該環流本身可以充滿循環的淤漿或在稀釋劑中生長的 聚合物粒子。任意地,氫可加至方法中,例如用於所得聚 合物的分子量控制。環流反應器可以維持於,例如,壓力 由約27巴至50巴或由約35巴至約45巴,溫度由約38 °C 至約1 2 1 °C。反應熱可以,例如,藉嫻於此技藝者已知的 Ο 任何方法(如,藉雙重護套管或熱交換器),經由環流壁 移除。 或者’可以使用其他類型的聚合法,例如,串接、並 接的攪拌反應器或二者之組合。自反應器移除之後,聚合 物可以通至聚合物回收系統用以進一步加工,例如,添加 添加劑和/或擠壓。 一或多個體系中’聚合法包括製造多模態聚烯烴。此 處所謂的“多模態”是指聚烯烴具有至少兩個不同的分子量 部分。例如,該聚合物可以具有二模態分子量分佈(即, -15- 201035112 其爲二模態聚合物),如,高分子量部分和低高分子量部 分。 一或多個體系中,該聚合法包括製造二模態聚烯烴。 本發明的一或多個體系可包括使淤漿通過至少兩個反應區 (如’二模態法)。此處所謂的“二模態法”是指聚合法包 括製造具有二模態分子量分佈之聚合物(如,二模態聚合 物)的多個反應區(如,兩個反應區)。例如,包括至少 一可辨視的高分子量部分和至少一可辨視的低分子量部分 之單一組成物被視爲“二模態”聚烯烴。 該高分子量部分的分子量高於該低分子量部分的分子 量。該高分子量部分的分子量例如,由約 50,000至約 10,000,000,或由約 60,000 至約 5,000,000 或由約 65,000 至約1,0 0 0,0 0 0。反之,該低分子量部分的分子量例如, 由約500至約50,000,或由約525至約40,000或由約600 至約 3 5,000。 該二模態聚合物之高分子量部分與低分子量部分的比 ,例如,由約8 0 : 2 0至約2 0 : 8 0,或由約7 0 : 3 0至約 30: 70 或由約 60: 40 至約 40: 60。 該二模態聚烯烴可以在多個串接的反應器中形成。此 反應器可包括前述的任何反應器或反應器之組合。一或多 個體系中,兩個反應器中使用相同的觸媒。在反應器中, 以任何順序製備高分子量部分和低分子量部分,例如,可 以在第一反應器中形成低分子量部分且在第二反應器中形 成高分子量部分,或反之。 -16- 201035112 聚合物產物 經由此處所述之方法形成的聚合物(和其摻合物)可 包括’但不限於,例如,直鏈低密度聚乙烯、彈料、塑料 '高密度聚乙烯、低密度聚乙烯、中密度聚乙烯、二模態 聚乙烯、二模態聚丙烯、聚丙烯和聚丙烯共聚物。 一或多個體系包括以乙烯爲基礎的聚合物。此處所謂 〇 之“以乙烯爲基礎的聚合物”是指聚合物包括,例如,至少 約5 0重量% ’或至少約8 0重量%乙嫌,或至少約8 5重量 %乙稀’或至少約9 0重量%乙嫌,或至少約9 5重量%乙燦 或至少約98重量%乙烯。 一體系中,以乙烯爲基礎的聚合物之密度由約086 克/ cc至約0.97克/ cc’或由約0.90克/ cc至約0.97克 / cc’或由約0.93克/ cc至約0.97克/ cc。 此以乙嫌爲基礎的聚合物之分子量分佈由,例如,約 Ο 1.5至約30或由約5至約25。 此乙燦聚合物的熔流指數(MI2)由,例如,約〇.〇01 分克/分鐘至約1000分克/分鐘,或由約〇.〇1分克/分 鐘至約100分克/分鐘,由約〇.〇2分克/分鐘至約50分 克/分鐘’由約0.03分克/分鐘至約1〇分克/分鐘。 產物應用 聚合物和其摻合物可用於嫻於此技藝者已知的應用中 ’如’成型操作(如,膜、片、管和纖維擠壓和共擠壓及 -17- 201035112 吹塑、射出模塑和旋轉模塑)。膜包括藉擠壓或共擠壓或 層壓而形成的吹塑、定向或澆鑄膜,其可作爲,例如,食 物接觸和非食物接觸應用中的收縮膜、保鮮膜、拉伸膜、 密封膜、定向膜、零食包裝、重型袋、食品包裝袋、烘焙 和冷凍食品包裝、藥品包裝、工業襯墊和薄膜。纖維包括 ’例如’用於梭織或非梭織形式的塡隙膜、單纖絲、熔紡 、溶液紡絲和噴熔纖維操作,其用以製造袋、提袋、繩、 合股線'毯背襯' 毯細紗、濾料、紙尿布織物、醫療用紗 布和地工織物。擠壓物件包括例如,醫療用管、線和電纜 塗層、片、熱成型片、低透氣性蔽幛和池塘襯圈。模塑物 件包括例如,瓶、槽、大的中空物件、硬式食品容器和玩 具的單和多層構造。 一或多個體系中,此聚合物可用以形成管件。例如, 該管件可以包括管、製管材料、模塑接頭、管塗層和它們 的組合。此管件可用於,例如,工業/化學法、採礦操作 、氣體分佈、飲用水分佈、氣體和油製造、光纖導管、下 水道系統和管道整修。 裂紋快速擴大(R C P )係高性能管的一個重要的效能 特性’此因管材必須能夠中止或阻止開始的裂紋之成長。 若RCP性質不足’則裂紋迅速成長且可能會沿著管的大區 段裂開。管材料會因爲暴於冷溫度而變脆,使得RCp進一 步惡化。因此’可藉管材的臨界溫度評估RCP耐力。此處 所謂的“臨界溫度,,是指自柔軟(阻止碎裂的點)變化至脆 (裂紋生長的點)之衝擊反應的溫度。 -18- 201035112 意料之外地,本發明之體系能夠形成對於裂紋快速傳 播(RCP )之耐力改良的管。例如,本發明之體系能夠形 成臨界溫度(藉ISO 13477:1997 (E))低於約〇°C ,或 低於約· 5 °C或低於約· 1 0 °C的管。 例如’一體系中,以乙嫌爲基礎的聚合物之pent( Pennsylvania Notch Tensile Test )由約 5 〇〇 小時至約 12,000小時,或由約1,500小時至約5,0〇〇小時,或由約 〇 3,000小時至約5,000小時或由約3,000小時至約8,000小 時。意料之外地,觀察發現本發明之體系能夠製造具有所 述臨界溫度且未損及PENT效能的管。 實例 已經以一般方式描述本發明,下列實例僅用以說明本 發明的某些體系,及證實其實施和優點。瞭解實例作爲說 明之用且不欲以任何方式限制說明書的範圍或申請專利範 〇 圍。 此處使用的聚合物“A”係二組態高密度管等級,其爲 T 〇 t al P e tr o ch em i cal s U S A In c ·,的市售品 3 344N。 此處使用的聚合物“B”係二組態高密度管等級,其係 使用所述觸媒,經由下文描述的觸媒製法製得且 LMW/HMW 比爲 50.3 ·· 49.7 者。 此處使用的聚合物“C”係二組態高密度管等級,其係 使用下文描述的觸媒製法製得且LMW/HMW比爲47.2: 52.8 者。 -19- 201035112 根據所謂的S4試驗(Small Scale Steady State,由倫 敦的 Imperial College 開發’述於1so 13477:1997 (E)) ,測定樣品的裂紋快速傳播(RCP )耐力。根據RCP-S4 試驗,測試的各個管的軸長度爲860毫米。各個管的外徑 爲110毫米且各個管的壁厚爲毫米。當測定關於本發 明的各個管的R C P性質時,選擇的外徑和壁厚分別是1 1 〇 毫米和10毫米。各個管的外部處於常壓(大氣壓),管 於內部加壓,且管的內壓於壓力0.5MPa正壓下維持穩定 。盤置於各個管內側的軸上以防止在試驗期間內減壓。以 良好規範的形式,朝向管發射投射刀片,以引發迅速運轉 軸破裂。調整試驗設備使得相關的管材開始形成裂紋。測 定各個試驗測定區中的軸裂紋長度並相對於設定的試驗溫 度作圖。若裂紋長度超過44〇毫米’則評估爲裂紋已傳播 。或管於指定溫度通過試驗,則連續降低溫度直到達到管 不再能夠通過試驗的溫度。記錄臨界溫度(Terit )。試驗 結果不於表1。 表1 聚合物B 聚合物C Μη 13414 13028 14079 Mw 242569 258361 302170 Mz 1373384 1528890 2091419 密度(克/cc) 0.9480 0.9490 0.9470 臨界溫度Tcrit (°C) @5巴 12 1 -12 PENT (小時) 112 1780 4020 意料之外地,當樹脂的二模態性遷移至較高比例高分 子量聚合物之分支峰時,臨界溫度明顯改良。 -20- 201035112 前述者係根據本發明之體系,可以在不違背本發明的 基本範圍和藉下列申請專利範圍訂出的範圍的情況下,設 計出本發明的其他和進一步體系。 ΟTiCl4/Ti(OR5)4; wherein R5 is selected from the group consisting of c2 to c2G alkyl. A non-limiting example of the second reagent is a blend of titanium and titanium alkoxide, such as TiCl4/Ti(OBu)4. The blend may have a TiC 14 : Ti (OR5 ) 4 equivalent weight of from about 0.5 to about 62 to about 3. Ο Then, the method may include reacting the reaction product "B" with the third test to form a reaction product "C". The reaction can be present in an inert solvent. The inert solvent may include, for example, those solvents discussed above. For example, this reaction can occur further at room temperature. Non-limiting examples of the third reagent include metal halides. The gold may include any metal halide known to those skilled in the art, such as titanium chloride (TiCl4). The third agent can be added, for example, from about 0.1 ” or from about 0-25 to about 4 or from about 0.45 to about 2.5 equivalents. The method may then further comprise reacting the reaction product "C" with any agent that occurs under contact with the agent for 1 hour 1 to about including chlorine, for example, or any halogenation that occurs under contact with the agent, such as from four to about five. The fourth test-11 - 201035112 agent contacts to form the reaction product "D". This reaction can take place in an inert solution. The inert solvent can include, for example, any of those previously discussed. For example, this reaction can occur further at room temperature. The fourth agent can be added, for example, from about 0.1 to about 5, or from about 4 or from about 0.45 to about 2.0 equivalents to the reaction product "C". Non-limiting examples of the fourth reagent include metal halides. The metal may include any of the metal halides described above. This method can then include reacting the reaction product "D" with a fifth to form a catalyst component. The fifth reagent can be, for example, from about 0.1 or from about 0.5 to about 1.2 equivalents added to the reaction product "D". Non-limiting examples of the fifth reagent include organoaluminum compounds. The compound may include an alkyl aluminum having the formula: air63; wherein R6 is a C! to C1 decyl compound. Examples of the alkyl aluminum compound include, for example, trimethyl aluminum (TMA), triisobutyl aluminum I), triethyl aluminum (TEA1), n-octyl aluminum, and n-hexyl aluminum. Polymerization Process The catalyst system is used to form polyolefins, as traced elsewhere in the text. Once the catalyst system is known in the foregoing manner and/or known to those skilled in the art, the composition can be used in a variety of ways. Depending on the desired composition and nature of the polymer, the equipment, process conditions, reactants, additives, and others used in the method of the selected method will be altered. For example, the process includes a solution phase, a gas phase, a slurry phase, and a bulk phase agent. There is a 0.25 in the solvent to contact the halogenating agent to about 2 organoaluminum non-limiting TIB A1 hydrocarbon composition formula to prepare the polymeric material to be formed. , commercial pressure -12- 201035112 law or a combination of them. (U.S. Patent No. 5,525,67; U.S. Patent No. 6,420,580; U.S. Patent No. 6,380,328; U.S. Patent No. 6,359,072; U.S. Patent No. 6,346,586; U.S. Patent No. 6,340,730; Patent No. 6,339,134; U.S. Patent No. 6,300,436; U.S. Patent No. 6,274,684; U.S. Patent No. 6,271,323, U.S. Patent No. 6,248,845; U.S. Patent No. 6,245,868; U.S. Patent No. 6,245,705 U.S. Patent No. 6,242,545; U.S. Patent No. 6,211,105; U.S. Patent No. 6,2,7,606; U.S. Patent No. 6,180,735 and U.S. Patent No. 6,147,173, Incorporated herein by reference.) In some systems, the foregoing methods generally involve polymerizing one or more olefin monomers to form a polymer. For example, the olefin monomer may include a C2 to C30 olefin monomer' or a 〇2 to C12 olefin monomer (eg, ethylene, propylene, butene, pentene, methylpentene, hexene, octene, and decene) . For example, the monomer may C) include an olefin-based unsaturated monomer, a C4 to C8 diolefin, a conjugated or non-conjugated diene, a polyene, a vinyl monomer, and a cyclic olefin. For example, non-limiting examples of other monomers may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene borneol Alkene, dicyclopentadiene and cyclopentene. For example, the polymer formed can include homopolymers, copolymers or terpolymers. Examples of the solution method are described in U.S. Patent No. 4,271,060; U.S. Patent No. 5,001,205; U.S. Patent No. 5,23,998, and U.S. Patent No. 5,5,89,5,5, An example of a gas phase polymerization process is incorporated herein by reference in its entirety to the disclosure of the present disclosure. The heat is removed from the circulating gas stream by a cooling system external to the reactor. Containing one or more monomers Under continuous reaction conditions, in the presence of a catalyst, a continuous recycle stream is typically discharged from the fluidized bed and recycled to the product. The product can be discharged from the reactor and new monomers can be added. The reactor pressure in the gas phase process is from 100 psig to about 500 psig, or from about 200 psig to about 350 psig to about 350 psig. The gas phase reaction process is, for example, from about 30 ° C to about 120 ° C, or from about or from about 70 ° C to about 110 ° C or from about 7 ° C to, for example, U.S. Patent No. 4,543,399, 4,588,790 U.S. Patent Nos. 5,028,670, 5,317,036; U.S. Patent Nos. 5,352,749, 5,405, 922; U.S. Patent No. 5,436,304, 5, 456, 471; U.S. Patent No. 5,462, 999, 5, 616, 661; U.S. Patent No. 5,627,242, 5, 665, 181; 5,677,375 5,668,228, the disclosure of which is hereby incorporated by reference in its entirety in its entirety in the in the the the the the the The suspension system can be removed from the reactor batchwise or continuously, wherein the recycle gas stream in another portion of the recycle by the polymerization can be passed through the fluidized bed. This reactor. At the same time, the polymerized monomer may be replaced by, for example, from about 400 psig or from a reactor temperature of from 6 ° C to about 115 ° C, at 95 ° C. Please refer to U.S. Patent No.; U.S. Patent No.; U.S. Patent No.; U.S. Patent No.; U.S. Patent No.; U.S. Patent No. 5, and U.S. Patent. The formation of solid particulates also adds monomer and any float (which may include dilute-14-201035112 release agent). The volatile components in the reactor can be separated from the polymer and recycled (optionally after steaming) to reactor. The liquefied diluent used in the polymerization medium may include, for example, a c3 to c7 alkane (e.g., hexane or isobutane). The medium used is usually liquid under the polymerization conditions and is quite inert. The bulk phase method is similar to the slurry process except that the liquid medium in the bulk phase process is also a reactant (e.g., monomer). However, the method can be 'for example' a monolithic process, a slurry process or a monolithic slurry process. 〇 In a particular system, the slurry process or the bulk process can be carried out continuously in one or more loop reactors. For example, the catalyst (in the form of a slurry or anhydrous free flowing powder) can be injected regularly into the reactor loop. The loop itself can be filled with recycled slurry or polymer particles grown in a diluent. Optionally, hydrogen can be added to the process, for example for molecular weight control of the resulting polymer. The loop reactor can be maintained, for example, at a pressure of from about 27 bar to 50 bar or from about 35 bar to about 45 bar, and at a temperature of from about 38 ° C to about 1 21 ° C. The heat of reaction can be removed, for example, by any means known to those skilled in the art (e.g., by a double jacket tube or heat exchanger) via a loop wall. Alternatively, other types of polymerization methods can be used, for example, a series connection, a parallel stirred reactor, or a combination of both. After removal from the reactor, the polymer can be passed to a polymer recovery system for further processing, for example, by the addition of additives and/or extrusion. The polymerization process in one or more systems involves the manufacture of multimodal polyolefins. By "multimodal" herein is meant that the polyolefin has at least two different molecular weight fractions. For example, the polymer may have a dimodal molecular weight distribution (i.e., -15-201035112 which is a dimodal polymer), such as a high molecular weight fraction and a low high molecular weight fraction. In one or more systems, the polymerization process involves the manufacture of a dimodal polyolefin. One or more systems of the present invention can include passing the slurry through at least two reaction zones (e.g., 'two-modality process'). The "dual mode method" as used herein means that the polymerization method comprises a plurality of reaction zones (e.g., two reaction zones) for producing a polymer having a dimodal molecular weight distribution (e.g., a dimodal polymer). For example, a single composition comprising at least one discernible high molecular weight fraction and at least one discernible low molecular weight fraction is considered a "two mode" polyolefin. The molecular weight of the high molecular weight portion is higher than the molecular weight of the low molecular weight portion. The high molecular weight fraction has a molecular weight of, for example, from about 50,000 to about 10,000,000, or from about 60,000 to about 5,000,000 or from about 65,000 to about 1,0,0,0. Conversely, the molecular weight of the low molecular weight moiety is, for example, from about 500 to about 50,000, or from about 525 to about 40,000 or from about 600 to about 35,000. The ratio of the high molecular weight portion to the low molecular weight portion of the dimodal polymer, for example, from about 80:20 to about 2:80, or from about 70:30 to about 30:70 or from about 60: 40 to about 40: 60. The dimodal polyolefin can be formed in a plurality of reactors connected in series. This reactor may comprise any of the reactors or combinations of reactors previously described. In one or more systems, the same catalyst is used in both reactors. In the reactor, the high molecular weight portion and the low molecular weight portion are prepared in any order, for example, a low molecular weight portion may be formed in the first reactor and a high molecular weight portion may be formed in the second reactor, or vice versa. -16- 201035112 Polymers The polymers (and blends thereof) formed by the methods described herein may include, but are not limited to, for example, linear low density polyethylene, elastomer, plastic 'high density polyethylene , low density polyethylene, medium density polyethylene, dimodal polyethylene, dimodal polypropylene, polypropylene and polypropylene copolymer. One or more systems include ethylene-based polymers. By "ethylene-based polymer" herein is meant that the polymer includes, for example, at least about 50% by weight 'or at least about 80% by weight of ethyl, or at least about 85% by weight of ethylene' or At least about 90% by weight of B, or at least about 5% by weight of ethylene or at least about 98% by weight of ethylene. In one system, the density of the ethylene-based polymer ranges from about 086 g/cc to about 0.97 g/cc' or from about 0.90 g/cc to about 0.97 g/cc' or from about 0.93 g/cc to about 0.97. g / cc. The molecular weight distribution of this B-based polymer is, for example, from about 1.5 to about 30 or from about 5 to about 25. The melt flow index (MI2) of the ethylene polymer is, for example, from about 〇.〇01 gram/min to about 1000 dl/min, or from about 〇.〇1 gram/min to about 100 gram/ Minutes, from about 〇.〇2 gram/min to about 50 gram/min' from about 0.03 gram/min to about 1 〇 gram/min. The product application polymers and blends thereof can be used in applications known to those skilled in the art, such as, for example, forming operations (e.g., film, sheet, tube and fiber extrusion and co-extrusion, and -17-201035112 blow molding, Injection molding and rotational molding). The film comprises a blown, oriented or cast film formed by extrusion or co-extrusion or lamination, which can be used, for example, as a shrink film, wrap film, stretch film, sealing film in food contact and non-food contact applications. , oriented film, snack packaging, heavy duty bags, food packaging bags, bakery and frozen food packaging, pharmaceutical packaging, industrial liners and films. Fibers include, for example, crepe films, monofilaments, melt-spinning, solution spinning, and melt-blown fiber operations in woven or non-woven forms for making bags, bags, ropes, ply mats. Backings' blankets, filter media, diaper fabrics, medical gauze and geotextiles. Extruded articles include, for example, medical tubing, wire and cable coatings, sheets, thermoformed sheets, low gas permeable masks, and pond liners. Molded articles include, for example, single and multi-layer constructions of bottles, tanks, large hollow articles, rigid food containers, and toys. In one or more systems, the polymer can be used to form a tubular member. For example, the tubular member can include a tube, a tube material, a molded joint, a tube coating, and combinations thereof. This fitting can be used, for example, in industrial/chemical methods, mining operations, gas distribution, drinking water distribution, gas and oil manufacturing, fiber optic conduits, sewer systems, and pipeline refurbishment. Rapid crack propagation (R C P) is an important performance characteristic of high performance tubes. This is because the tube must be able to stop or prevent the onset of crack growth. If the RCP property is insufficient, the crack grows rapidly and may crack along a large section of the tube. The tube material becomes brittle due to the cold temperature, making the RCp worse. Therefore, the RCP endurance can be evaluated by the critical temperature of the pipe. The term "critical temperature" as used herein refers to the temperature of the impact reaction from softness (the point at which cracking is prevented) to brittleness (the point at which crack growth occurs). -18- 201035112 Unexpectedly, the system of the present invention can be formed Endurance-modified tube with rapid crack propagation (RCP). For example, the system of the present invention is capable of forming a critical temperature (by ISO 13477:1997 (E)) below about 〇 ° C, or below about 5 ° C or below. A tube of about 10 ° C. For example, in a system, the pent (PAFT) of the polymer is from about 5 〇〇 hours to about 12,000 hours, or about 1,500. Hours to about 5,000 hours, or from about 3,000 hours to about 5,000 hours or from about 3,000 hours to about 8,000 hours. Unexpectedly, it has been observed that the system of the present invention is capable of producing the critical temperature and is not damaged. The invention has been described in a general manner, and the following examples are intended to illustrate some of the systems of the invention, and to demonstrate its implementation and advantages. The examples are intended to be illustrative and are not intended to limit the description in any way. The patent "A" is a two-configuration high-density pipe grade, which is a commercial product of T 〇t al P e tr o ch em i cal s USA In c ·. 3 344 N. The polymer "B" used herein is a two-configuration high-density pipe grade which is produced by the catalyst process described below using the catalyst and has a LMW/HMW ratio of 50.3 ··49.7. The polymer "C" used herein is a two-configuration high-density pipe grade which is produced using the catalyst process described below and has a LMW/HMW ratio of 47.2: 52.8. -19- 201035112 According to the so-called S4 test ( Small Scale Steady State, developed by Imperial College in London, described in 1so 13477:1997 (E), for the determination of crack propagation fast (RCP) endurance. According to the RCP-S4 test, the individual tubes tested have a shaft length of 860 mm. The outer diameter of each tube was 110 mm and the wall thickness of each tube was mm. When determining the RCP properties of the respective tubes of the present invention, the selected outer diameter and wall thickness were 1 1 mm and 10 mm, respectively. The outside is at atmospheric pressure (atmospheric pressure) and the tube is pressurized internally. The internal pressure of the tube is maintained at a positive pressure of 0.5 MPa. The disc is placed on the shaft inside the tube to prevent decompression during the test. In a well-formed form, the projection blade is fired towards the tube to initiate rapid rupture of the shaft. Adjusting the test equipment causes the associated tubing to begin to form cracks. The length of the axial crack in each test zone was measured and plotted against the set test temperature. If the crack length exceeds 44 mm', it is evaluated that the crack has propagated. Or pass the test at the specified temperature, then continuously lower the temperature until the temperature at which the tube can no longer pass the test is reached. Record the critical temperature (Terit). The test results are not shown in Table 1. Table 1 Polymer B Polymer C 13 13414 13028 14079 Mw 242569 258361 302170 Mz 1373384 1528890 2091419 Density (g / cc) 0.9480 0.9490 0.9470 Critical Temperature Tcrit (°C) @5巴 12 1 -12 PENT (hours) 112 1780 4020 Unexpectedly, the critical temperature is significantly improved when the dimodality of the resin migrates to the branching peak of the higher proportion of high molecular weight polymer. -20- 201035112 The foregoing is a system according to the present invention, and other and further systems of the present invention can be devised without departing from the basic scope of the invention and the scope of the following claims. Ο
-21 --twenty one -
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US11749108P | 2008-11-24 | 2008-11-24 | |
US12/619,944 US20100129579A1 (en) | 2008-11-24 | 2009-11-17 | Rapid Crack Properties in High Performance Pipe |
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