[go: up one dir, main page]

TW200904883A - Polymeric material and its manufacture and use - Google Patents

Polymeric material and its manufacture and use Download PDF

Info

Publication number
TW200904883A
TW200904883A TW097102024A TW97102024A TW200904883A TW 200904883 A TW200904883 A TW 200904883A TW 097102024 A TW097102024 A TW 097102024A TW 97102024 A TW97102024 A TW 97102024A TW 200904883 A TW200904883 A TW 200904883A
Authority
TW
Taiwan
Prior art keywords
molecular weight
polymer composition
composition
polyolefin
polyethylene
Prior art date
Application number
TW097102024A
Other languages
Chinese (zh)
Inventor
Patrick Brant
Jeffrey Lawrence Brinen
Zerong Lin
Koichi Kono
Kohtaro Kimishima
Hiroyuki Ozaki
Original Assignee
Tonen Sekiyukagaku Kk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tonen Sekiyukagaku Kk filed Critical Tonen Sekiyukagaku Kk
Publication of TW200904883A publication Critical patent/TW200904883A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cell Separators (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed herein is a polymer composition, its manufacture and use, said composition may comprise greater than about 90 mole % propylene monomer, and having a unique combination of properties, including one or more of the following: a heat of fusion of more than about 108 J/g, a melting point of 165 DEG C or higher, a Melt Flow Rate so low that it is essentially not measurable and a molecular weight of greater than about 1.5 x 10<SP>6</SP>. Further disclosed herein are blends or mixtures of the present novel polymer composition and products, such as, for example, microporous film structures and the like comprising same.

Description

200904883 九、發明說明 【發明所屬之技術領域】 本發明有關包含多於90莫耳％丙烯單體，而 °C之熔融流速低於約0.2dg/分鐘之聚合物組成物 物組成物可於製造微孔膜，包括含有聚乙烯之微 【先前技術】 超高分子量（UHMW )聚合物具有各式各樣 用途。例如，UHMW高密度聚乙烯（UHMWPE ) 括防衝擊紡織品、人工關節材料與微孔 2004/026921八1與美國專利第4,734,196號）》作 隔板時，該微孔膜必須具有均衡的斷路時間、熔 滲透性與針穿刺強度。已發現UHMW聚丙烯（ )適用凝膠紡絲高熔融與高強度纖維，作爲製造 添加劑，以及作爲控制較低分子量聚丙烯熔融流 加劑。 UHMW聚丙烯可使用戚格勒-納塔觸媒並以 二甲氧基矽烷作爲電子施體而製造。詳見 06234811A、 JP 06234812A 與 JP 07292021A。此 料第一者揭示特性黏度自4至1 〇 dl/g之產物， 資料第兩者揭示特性黏度自5至1 〇 dl/g且熔 MFR)低於0.1 g/i〇分鐘之產物。此二產物據稱 有良好斷裂強度與模數之紗。上述參考資料第三 有lxlO6之平均分子量。 且於2 3 0 。該聚合 L膜。 重要商業 可用於包 膜 （WO 爲電池組 毀溫度、 UHM WPP 微孔膜之 變性之添 二環戊基 例如 J P 等參考資 此等參考 融流速（ 可作爲具 者教示具 200904883 JP 62022 808A揭示使用戚格勒-納塔觸媒但不使用二 環戊基二甲氧基矽烷電子施體製造分子量自2xl〇6至5x 106之UHMW聚丙烯。同樣地，JP 03007704A揭示使用使 用戚格勒-納塔觸媒但不使用二環戊基二甲氧基矽烷電子 施體製造分子量自lxlO6之UHMW聚丙稀與共聚物。jp 023 05 8 09A亦揭示於戚格勒-納塔催化之聚合作用中不使 用電子施體製造UHMW聚丙烯。 US 4,413,11〇揭示分子量爲2·1χ106之聚丙烯，揭示 其適用於高強度纖維。US 5,070,05 1 UHMW聚乙烯與聚己 烯而非聚丙烯，其係使用戚格勒-納塔觸媒但不使用二環 戊基二甲氧基矽烷電子施體所製得。 EP 0654476A與EP 0790076A揭示使用金屬錯合物觸 媒製得之聚丙烯。此等參考資料前者當中，產物的分子量 爲 786,500，熔點爲159°C，且分子量分布（Mw/Mn )爲 2.4。參考資料第兩者之產物的分子量爲l.lxlO6，分子量 分布爲2.5且熔點爲159 °C。 雖然已使用金屬錯合物觸媒、戚格勒-納塔觸媒兩者 並使用或不使用二環戊基二甲氧基矽烷電子施體製造聚丙 烯，形成之聚丙烯難以運用於製造微孔膜，特別是用於製 造含有聚丙烯與聚乙烯之微孔膜。例如，美國專利第 6,096,213號揭示由可熔融處理聚合物之摻合物所製得之 微孔膜，該摻合物包括聚乙烯與聚丙烯之摻合物。該專利 揭示僅於聚丙烯的熔融流動指數高於〇 · 2 dg/分鐘時’才會 將其視爲具有熔融處理性。 -6- 200904883 因此’需要可用以製造諸如含有聚乙烯與聚丙烯之微 孔膜的UHMWPP ’特別是其中聚丙烯的熔融流動指數爲 0.2 dg/分鐘或更低之情況。 【發明內容】 一具體實例中’本發明有關以UHMWPP重量爲基準 包含多於約90莫耳％之UHMWPP。該UHMWPP通常具有 一或更多種下列性質：特性黏度大於約1 〇 d 1 /g，熔化熱大 於約108 J/g ’熔點爲165 °C或更高，分子量大於約1.5 X 106’分子量分布爲約2_5至約7，於230°c之熔融流速低 於約0.0 1 dg/分鐘，即，實質上無法測得，可萃取物的含 量（藉由UHMWPP與二甲苯接觸而萃得者）以UHMWPP 的重量計爲0.5重量％或更低，具有內消旋五元體（meso pentad)部分爲多於約96莫耳％ mmmm五元體，且立體 瑕疵的量爲每1〇,〇〇〇個碳原子低於約50。在相關具體實 例中，UHMWPP包含包含多於約90莫耳％之聚丙烯單體 ，此係以U Η M WP P重量爲基準，其於2 3 0 °C之熔融流速低 於約0.0 1 dg/分鐘而且具有至少一種下列性質：特性黏度 大於約10 dl/g，熔化熱大於約108 J/g，熔點爲165°c或 更高，分子量大於約1.5xl〇6’分子量分布爲約2.5至約7 ，可萃取物的含量（藉由UHMWPP與二甲苯接觸而萃得 者）以UHMWPP的重量計爲〇·5重量％或更低，具有內消 旋五元體部分爲多於約96莫耳％ mmmm五元體。且立體 瑕疵的量爲每10,000個碳原子低於約50 ° 200904883 另一具體實例中，本發明有關包含前述UHMWPP之 聚合物組成物。在相關具體實例中，該聚合物組成物另外 包含（a )第二聚合物（例如，聚乙烯，諸如高密度及/或 高分子量聚乙烯）及/或（b )稀釋劑或溶劑（例如，液態 石蠟）。其他相關具體實例中，聚合物組成物係包含前述 UHMWPP以及選擇性含有高密度聚乙烯（HDPE )、超高 分子量聚乙烯（UHMWPE )、第二聚丙烯（例如分子量低 於UHMWPP者）以及稀釋劑或溶劑（其可爲稀釋劑之混 合物或溶劑之混合物或此兩者之混合物）其中一或更多者 之聚烯烴組成物。其他相關具體實例中，本發明有關聚合 物組成物與第二聚合物組成物。第二聚合物組成物可包含 聚烯烴，諸如聚乙烯及/或聚丙烯，例如HDPE、UHMWPE 及第二聚丙烯其中一或更多者。 其他具體實例中，本發明有關用於製造前述UHMWPP 與聚合物組成物之方法。另外之具體實例中，本發明有關 使用前述UHMWPP或聚合物組成物製造物件之方法，此 等物件係諸如例如成型物件、薄板或薄膜，例如微孔膜。 已發現此種微孔膜特別適於作爲例如一次鋰離子電池組與 錘離子蓄電池中的電池組隔板。此等電池組可作爲電荷來 源或接收器。 因此，另一具體實例中，本發明有關含有前述 UHMWPP或聚合物組成物之微孔膜或膜。已發現包含前述 UHMWPP或聚合物組成物之作爲電池組隔板的微孔膜通常 具有均衡的斷路性質、熔毀溫度、滲透性與針穿刺強度。 -8- 200904883 本發明之微孔膜可爲單層薄膜或多層薄膜。因此，一 具體實例中’本發明有關用於製造微孔膜或膜之方法，其 包括： 含有第一層材料之第一微孔層、含有第一層材料之第 三微孔層與含有第二層材料之第二微孔層，將第二微孔層 置於第一與第三微孔層之間。該第一或第二層材料中至少 —者係由U Η M W P P或聚合物組成物製得。除了處理期間 發生之分子量降低量（例如，由剪切稀化造成）較少以外 ’由UHMWPP或聚合物組成物製得之層材料通常包含形 成彼之UHMWPP或聚合物組成物。 另一具體實例中，本發明有關用於製造微孔膜或膜之 方法，其包括： (1 )混合前述UHMWPP (或聚合物組成物）與稀釋 劑（或處理溶劑），形成第一聚烯烴溶液， (3 )經由一或多個衝模而擠出至少一部分第一聚烯 徑溶液，形成擠出物， (4 )將擠出物冷卻，以形成經冷卻的擠出物， (5 )從該經冷卻的擠出物去除至少一部分稀釋劑， 以形成經去除溶劑之薄片，以及 (6 )自該薄片去除至少一部分任何揮發性物質，以 形成微孔膜。 在相關具體實例中，本發明有關用於製造多層薄膜之 方法’其包括： (1 )組合前述UHMWPP或聚合物組成物與稀釋劑（ 200904883 或處理溶劑），形成第一聚細烴丨谷液’ (2 )組合第二聚烯烴或聚烯烴組成物（視情況需要 包括UHMWPP)與第二稀釋劑（或處理溶劑），形成第二 聚烯烴溶液， (3)經由一或多個衝模而擠出至少一部分第一聚烯 烴溶液，並共擠出至少一部分第二聚烯烴溶液，以形成多 層擠出物， (4 )將該多層擠出物冷卻’以形成經冷卻之多層擠 出物， (5 )從該經冷卻的擠出物去除至少一部分處理溶劑 ，以形成經去除溶劑之薄片，以及 (6 )自該薄片去除至少一部分任何揮發性物質，以 形成多層微孔膜。 在具體實例中，該方法係連續或半連續操作。 【實施方式】 本發明的基礎係在於發現一種包含前述UHMWPP之 聚合物組成物，該聚合物組成物通常適於製造諸如微孔膜 等物件。該聚合物組成物通常包含多於90莫耳％之聚丙烯 單體’而且具有一或更多種下列期望性質：聚合物組成物 之特性黏度大於約10 dl/g，熔化熱大於約108 J/g，熔點 爲165 °C或更高，分子量大於約1.5x1 06，分子量分布爲約 2.5至約7 ’於23 (TC之溶融流速低於約〇·〇1 dg/分鐘，即 ’實質上無法測得，可萃取物質的含（藉由令聚合物組成 -10- 200904883 物與沸騰二甲苯接觸而萃得者）量以聚合物組成物的重量 計爲0.5重量％或更低’具有內消旋五元體部分係多於約 96莫耳％ mmmm五元體，且每1〇, 〇〇〇個碳原子低於約50 的立體瑕疵。在相關具體實例中，聚合物組成物包含多於 90莫耳％之聚丙烯單體，而且具有一或更多種下列性質： 聚合物組成物之特性黏度大於約1 0 dl/g，熔化熱大於約 108 J/g，熔點爲165°c或更高，分子量大於約1.5xl06， 分子量分布爲約2.5至約7，於230 °C之熔融流速低於約 0.01 dg/分鐘，即，實質上無法測得，可萃取物的含量（ 藉由令聚合物組成物與沸騰二甲苯接觸而萃得者）以聚合 物組成物的重量計爲0.5重量％或更低，具有內消旋五元 體部分爲多於約96莫耳％ mmmm五元體，且每1〇,〇〇〇個 碳原子低於約5 0的立體瑕疵。已發現即使聚丙烯熔融流 速係0.2 dg /分鐘或更低，或甚至爲〇.1 dg /分鐘或更低， 或甚至O.Oldg /分鐘或更低時，此等聚合物組成物亦可用 以製造微孔膜，特別是包含聚乙烯與聚丙烯之微孔膜。 本文使用之元素週期表編號可見例如 Hawley，s Condensed Chemical Dictionary 8 5 2 ( John Wiley &amp; Sons ，第 13 版 1 997 )。 本文使用之「聚合物」一辭係指聚合反應之產物，而 且包括同元聚合物、共聚物、三聚物及其他。 除非另外指定，否則本文所使用之「共聚物」一辭係 指由至少兩種不同單體之聚合作用所形成的聚合物。例女口 ’ 「共聚物」一辭包括乙烯與α -烯烴（諸如僅以丙嫌或 -11 - 200904883 i -己烯爲例）之共聚反應產物。不過，「共聚物」一辭亦 包括例如乙烯、丙烯、1 -己烯與1 -辛烯之混合物的共聚作 用。 本文所使用之重量百分比一辭（重量％)意指特定組 份相對於含有該組份之混合物總重的重量百分比（除非另 外註明）。例如，若混合物或摻合物包含三磅化合物A與 一镑化合物B，則化合物A佔混合物的7 5重量％，化合物 B佔2 5重量％。 I. UHMWPP與聚合物組成物之性質 在具體實例中，該聚合物組成物包含多於約90莫耳％ 之聚丙烯單體，諸如例如多於約95莫耳％之聚丙烯單體， 且高達多於約99.99莫耳。/。之聚丙烯單體。 在一形式當中，本發明有關具有一或更多種下列性質 之聚合物組成物。可了解到的是該等性質可作爲聚合物組 成物與組成物中之UHMWPP的特徵，當該聚合物組成物 包含UHMWPP以外性質時尤其如此。 一具體實例中’聚合物組成物具有特性黏度大於約1 1 dl/g，或者大於約12 dl/g。聚合物組成物之特性黏度（IV )可藉由例如 W. R. Sorenson 與 Τ· W. Campbell 著之 &quot;PREPARATIVE METHODS OF POLYMER CHEMISTRY&quot;第 43-50 頁（弟 2 版 ’ 1968 年由 Interscience Publishers.出 版）敘述槪要的標準製程測得’或根據A S T M D 1 6 0 1 - 7 8 製程測得。 -12- 200904883 於一具體實例中’聚合物組成物的熔化熱大於約1 〇8 J/g，或大於約110 j/g ’或大於約1 12 J/g。聚合物組成物 的熔化熱可藉由習用方法，例如差示掃描量熱法（DSC ) 測得。 一具體實例中，該聚合物組成物具有高熔點（Tm )， 例如大於約166°C，或甚至大於約168t，甚至大於約170 °C。熔點可藉由習用方法，例如差示掃描量熱法（DSC ) 測得。差示掃描量熱法（DSC )資料可如下使用 PerkinElmer Instrument 之 Pyris 1 DSC 模型獲得。將粹得 約5 _ 5 - 6 · 5 m g之樣本密封於鋁樣本盤中。D S C資料的記錄 如下：以150t/分鐘之速率先將樣本加熱至200°C，稱爲 第一次熔融（無記錄資料）。於施加冷卻-加熱循環之前 ，令樣本在2 0 0 °C維持1 0分鐘。然後以1 〇°C /分鐘之速率 將樣本自200°C冷卻至25°C，稱爲結晶作用，然後於25t 維持分鐘，並以1〇 °C/分鐘之速率加熱至200 °C，稱爲 第二次熔融。記錄結晶與第二次熔融兩者的熱事件。熔融 溫度（Tm )係第二次熔融曲線的尖峰溫度，而結晶溫度（ Tc )係結晶尖峰之尖峰溫度。 一具體實例中，與習用以製造微孔膜與膜（特別是亦 包含聚乙烯之微孔膜）的聚丙烯相較，該聚合物組成物具 有較高分子量。例如，該聚合物組成物可具有大於約1.75 X106之分子量，甚或大於約2xl06，甚或大於約2.25xl〇6 ，諸如例如大於約2.5 xlO6。該聚合物組成物之分子量分 布可爲例如在約2 · 5至約7之較窄範圍內。本文所使用之 -13- 200904883 「分子量」意指平均分子量（Mw) 〇Mw可使用下述之凝 膠滲透層析術測量。分子量分布（MWD )意指Mw除以數 量平均分子量（Μη)。（更多資訊請參考Cozewith等人 之美國專利第4,540,7 53號及其中引用參考資料，以及 Verstrate 等人於 21 Macromolecules 3360 ( 1998)之文章 )。「Mz」係高平均分子量値，如 A.R. Cooper於 CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 63 8-3 9 ( J.I. Kroschwitz 編，John Wiley &amp; Sons 1990)中之討論計算出。分子量分布 Mw/Mn( MWD )係重量平均分子量（以下文稱爲GPC之凝膠滲透層析 術測得的Mw )對數量平均分子量（以下述GPC測得之 Μ η )之比率。 分子量（重量平均分子量Mw以及數量平均分子量 Μη )可使用配備差示繞射指數偵測器（DRI )之高溫尺寸 排阻層析儀（GPC PL 220 ， Polymer Laboratories)、測量。 使用三個 PLgel Mixed-B 柱（Polymer Laboratories)。標 稱流速係1.0 era3 /分鐘，通稱注射體積係300μί。各種輸 送線、柱與DRI偵測器係容納在維持1 60 °C之爐中。此技 術係於&quot;Macromolecules’ 第 34 卷，第 19 號，6812-6820 頁（200 1 )&quot;中討論，該文獻係以提及的方式倂入本文中 〇 GPC分析用之溶劑係含有〜1 000 ppm 丁基化羥基甲苯 (BHT)之經過濾Aldrich試藥級1，2,4-三氯苯（TCB)。 於進入S EC之前以線上除氣器對TCB除氣。將乾燥聚合 -14- 200904883 物置入坡璃容器中，添加所需量之上述TCB溶劑，然後 於1 60 °C加熱此混合物，並連續攪拌約2小時，製備聚合 物溶液。UHMWPP溶液濃度係0.25 mg/ml。 使用一系列狹窄MWD聚苯乙烯標準品來校正管柱組 的分離效率，其反映出樣本預期之MW範圍與該管柱組的 排除界限。使用十八個個別聚乙烯標準（自 Mp〜5 80至 10，000,000)產生校正曲線。由 Polymer Laboratories ( Amherst, ΜΑ)獲得此等聚苯乙烯標準。藉由記錄於每個 PS標準之DRI信號中的尖峰之維持體積並令此資料組符 合二階多項式，而產生校正曲線（logMp對維持體積）。 使用\\^乂6]\/161；1'丨05，111(：.1〇011?1'0分析樣本。 下列Mark-Houwink係數係分別用以計算PP爲基底之 Mw與PS爲基底之MW。 kidL/g) α PS 1.75x10-4 0.67 PP 2.288x10-4 0.705 一具體實例中，該聚合物組成物於23 0 °C與2.16 kg 重之下的熔融流速（MFR)爲〇.2dg/分鐘或更低，或者低 於約O.ldg/分鐘，或甚至低於約〇.〇ldg/分鐘。O.Oldg/分 鐘之値已低到基本上無法測得MFR。熔融流速可根據諸如 ASTMD 1238-95條件L之習用方法測量。 一具體實例中’該聚合物組成物顯示且每10,000個 碳原子低於約5 0的丛體瑕庇，或低於約4 0個，或低於約 30個’甚或每10,〇〇〇個碳原子低於約20的立體瑕疵。例 -15- 200904883 如，該聚合物組成物每10,〇〇〇個碳原子可具有少於約10 的立體瑕疵，或少於約5的立體瑕疵。立體瑕疵可藉由諸 如下列1 3e NMR等習用方法測量： 13c NMR資料係在Varian VXR 400 NMR光譜儀上於 125°C下以1〇〇 MHz獲得。使用90°C脈衝，擷取時間3.0 秒，脈衝延遲20秒。此光譜係寬頻解耦且無閘控解耦合 而獲得者。聚丙烯類之甲基共振預期有相似鬆弛時間與核 歐豪色（Overhauser )效應，此通常爲供定量目的所用之 唯一同元聚合物共振。所收集得之瞬態代表數目爲2 5 0 0。 令本樣本溶解於濃度爲1 5重量％之四氯乙烷-d2。根據內 部四甲基矽烷標準加以記錄所有頻譜。在聚丙烯同元聚合 物實例中，根據21.81 ppm之mmmm加以記錄甲基共振， 其接近內部四甲基矽烷標準之21.855 ppm報告文獻値。 已確立五元體分配。 一具體實例中，該聚合物組成物具有的內消旋五元體 部分大於約96莫耳。/ammmm五元體。 一具體實例中，以該聚合物組成物重量計，聚合物組 成物包含之可萃取物含量（令該聚合物組成物與沸騰二甲 苯接觸而萃取）爲0.5重量％或更低，或爲0.2重量％或更 低’甚或爲〇. 1重量％或更低。可萃取物（諸如相當低分 子量及/或非晶相材料，例如非晶相聚丙烯）之數量係根 據下列製程藉由在135 °C二甲苯中溶解度而測定。秤出2 克樣本（片狀或磨碎片狀形式）並置入3 00ml錐形燒瓶。 藉由攪拌棒將200 ml二甲苯倒入該錐形燒瓶，並將該燒 -16- 200904883 瓶固定在加熱油浴上。啓動該加熱油浴並令該燒瓶於1 3 5 °C油浴中放置約1 5分鐘而使該聚合物熔融。當熔融時， 中止加熱，但整個冷卻過程持續攪拌。令已溶解之聚合物 自然冷卻一夜。以特夫綸（Teflon )濾紙加以過濾該沉澱 物，然後於真空下以9 0 °C乾燥之。可溶解之二甲苯數量係 藉由總聚合物樣本（&quot;A ”）之重量百分比扣除室溫下之沉 澱物（”B”）而測得[可溶解含量=((A-B ) /AxlOO )。 II.製造UHMWPP與聚合物組成物 根據使用通常習用以製造烯烴聚合物之製程條件的下 列方法，諸如溶液聚合、漿體聚合或氣相聚合技術可製造 該聚合物組成物（例如UHMWPP )，其中以液相聚合爲較 佳技術。同樣地，使用適當聚嫌烴觸媒系統’包括習用系 統，諸如烯烴聚合物可戚格勒-納塔（ziegler_Natta )觸媒 或金屬錯合物觸媒，可能製得該烯烴聚合物。適用觸媒與 製程條件之實例係揭示於歐洲專利第〇3 5 0 1 70B2號，該案 全文係以提及的方式倂入本文中’但是不使用添加之氫。 戚格勒-納塔型觸媒係習用觸媒’並在例如Concise Encyclopedia of Polymer Science and Engineering, 1 0 8 7-1107 ( Jacqueline I. Kroschwitz 編，1990 )與 F. A. Cotton &amp; G · Wilkinson, Advanced Inorganic Chemistry, 1 2 80- 1 2 82 (第4版，1 9 80 )中有所討論。代表性承載固 態鎂之觸媒系統與彼之製備方法槪要描述於美國專利第 4,990,479 與 5, 159,021 號’以及 WO 00/44795。例如，戚 -17- 200904883 格勒-納塔觸媒通常係由來自週期表第4-7族之過渡金屬化 合物與來自第1 1 -1 3族之金屬的有機金屬化合物所組成。 已詳知之實例包括TiCl3-Et2AlCl、AlR3-TiCl4，其中Et係 乙基且R表示烷基。此等觸媒包括過渡金屬（特別是鈦、 鉻、釩與錆）之鹵化物與非過渡金屬之有機衍生物（特別 是烷基鋁化合物）的混合物。該戚格勒-納塔型觸媒通常 係與電子施體結合。在戚格勒-納塔觸媒系統的形成方法 中可以兩種方式使用電子施體。第一種，內部電子施體可 用於固態觸媒之形成反應中。內部電子施體之實例包括： 胺類、醯胺類、醚類、酯類、芳酯類、酮類、腈類、膦類 、睇類、胂類、磷醯胺類、硫醚類、硫酯類、醛類、醇化 物類及有機酸類之鹽。觸媒系統中之電子施體的第二種用 途係作爲外部電子施體與聚合反應中之立體規則調節劑。 可將同一種化合物用於此二實例，惟其通常爲不同化合物 。包括習用有機矽化合物之有機矽化合物可作爲電子施體 。是爲有機矽（或「矽烷」）化合物之習用電子施體經揭 示於美國專利第 4,218,339 ; 4,395,360 ; 4,328,122 ; 4,473,660; 6,133,385 與 6,127,303 號。在美國專利第 4,535,068號中提供此二類型之電子施體的描述。 一具體實例中，以液相並使用包含TiCl4/MgC卜含苯 二甲酸二正丁酯之內部電子施體、含二環戊基二甲氧基矽 烷（DCPMS )之電子施體與少量或無添加之氫的之戚格 勒-納塔觸媒製造該聚合物組成物。該方法包含步驟：（1 )令戚格勒-納塔觸媒與DCPMS施體及三乙基鋁（TEA1 ) •18- 200904883 預接觸，（2)令觸媒與丙烯預聚合，（3)在一或更多個 反應器中令經預聚合之觸媒進一步聚合，與（4)回收包 含約90莫耳％丙烯單體以上之聚合物組成物，該聚合物組 成物具有包括特性黏度大於約1 0 dl/g，熔化熱大於約1 〇 8 J/g，溶點爲165°C或更筒’分子量大於約1·5χ106’分子 量分布爲約2.5至7，23 0°C之溶融流速低於約0.01 dg/分 鐘（即，基本上無法測得），可萃取物質（藉由令聚合物 組成物與沸騰二甲苯接觸而萃得者）的量以聚合物組成物 的重量計爲0.5重量％或更低，具有內消旋五元體部分爲 多於約96莫耳％ mmmm五元體，且每1〇,〇〇〇個碳原子低 於50的立體瑕疵之性質組合。一具體實例中，該聚合物 組成物包含本發明之UHMWPP。另一具體實例中，該聚合 物組成物基本上係由UHMWPP組成。在另一具體實例中 ，該聚合物組成物係由UHMWPP組成。在一特別適於製 造該聚合物組成物（例如本發明之UHMWPP )以用於製造 微孔膜（諸如含有聚乙烯者）的具體實例中，可使用下列 條件：聚合製程中不使用添加之氫，該聚合觸媒係TOHO THC-1 35且電子施體係二環戊基二甲氧基矽烷；其餘製程 條件係揭示於歐洲專利第03 5 0 1 70B2號。 除了上述較佳DCPMS施體，其他合適之施體可能包 括但不局限於二（第三丁基）二甲氧基矽烷、環戊基二甲 氧基（第三丁氧基）矽烷、（第三丁基）（第三丁氧基） 二甲氧基砂院。 -19- 200904883 III.使用該聚合物組成物生產製造業之物件 一具體實例中，可例如藉由混合或摻合而令該聚合物 組成物與第二聚合物組成物結合，以生產製造業之物件， 諸如微孔膜。例如，可令該聚合物組成物與例如呈聚乙烯 樹脂形式之聚乙烯混合或摻合。 (a )起始材料 當令該聚合物組成物與第二聚合物組成物結合時，第 一與第二聚合物組成物之相對數量並非關鍵。例如，以結 合之第一與第二聚合物組成物重量計，混合物或摻合物中 該聚合物組成物對第二聚合物組成物之百分比可爲例如約 5至約95重量％，或爲約20至約80重量％。第二聚合物 組成物可包含聚烯烴，例如一或更多種高密度（HD )聚 乙烯及/或高分子量聚乙烯，例如超高分子量（UHMW )聚 乙烯或第二聚丙烯。此等混合物或摻合物中，聚合物組成 物對HD聚乙烯對高分子量（例如UHMW )聚乙烯之重量 比可爲任何5至95: 0至95: 0至95，或者可爲20至80 :20至70:0至20。存在第二聚丙烯時，其數量並非關 鍵，且以第一與第二聚合物組成物之結合重量計，可在例 如約1 〇重量％至約3 0重量％範圍。 一具體實例中，第二聚合物組成物包含第一聚乙烯、 第二聚乙烯或第二聚丙烯其中之至少一者。第一聚乙烯可 爲任何具有分子量爲5xl05或更高，例如分子量爲1χ1〇6 至1_5χ107之聚乙烯，諸如UHMWPE。此種聚乙烯可爲乙 -20- 200904883 稀同兀聚合物或含有少量乙烯以外之α-烯烴的乙烯/α-稀 煙共聚物。該乙烯以外之烯烴可能爲丙烯、丁烯、己 烯-1、戊烯-1、4 -甲基戊烯“、辛烯、乙酸乙烯酯、甲基 丙烯酸甲酯、苯乙烯或其混合。 第二聚乙烯可爲具有Mw分子量係約lxl 04至約 5xl05範圍之聚乙烯。該第二聚乙烯可爲例如高密度聚乙 稀、中密度聚乙烯、支鏈低密度聚乙烯與直鏈低密度聚乙 烯。該第二聚乙烯可爲乙烯同元聚合物或含有少量乙烯以 外之α ·烯烴的乙烯/ α -烯烴共聚物。該乙烯以外之α -烯 烴可能爲丙烯、丁烯-1、己烯-1、戊烯_1、4-甲基戊烯-1 、辛烯 '乙酸乙烯酯、甲基丙烯酸甲酯、苯乙烯或其混合 。雖然並非關鍵，但該第二聚乙烯在聚乙烯中每1 0000個 碳原子具有例如二或更多個末端不飽和。末端不飽和可藉 由例如習用紅外線光譜法測量。 該第二聚丙烯可爲具有重量平均分子量係低於約 7.5 X 1 05，例如爲約 1 X 1 04 至約 7 · 5 X 1 0 5，或爲約 4 5 X 1 〇5 至約7·5χ105，或爲約5χ105至約7χ105。雖然並非關鍵’ 但該第二聚丙烯可具有例如約5至約100’諸如約5至約 5 〇之分子量分布，以及約8 0 J/g或更高’例如約8 0至約 120 J/g之熔化熱。此第二聚丙烯可爲例如以下之一或更 多者：（i)丙烯同元聚合物或（U)丙烯與一或更多種 α -烯烴之共聚物，此等α -烯烴係諸如乙烯、丁烯-1、戊 烯-1、己烯-1、4-甲基戊烯-1、辛烯、乙酸乙烯酯、甲基 丙烯酸甲酯與苯乙烯及其他；與二烯烴類’諸如丁二嫌、 -21 - 200904883 1,5-己二烯、1,7-辛二烯、1,9-癸二烯及其他，以該整體共 聚物爲1 〇〇莫耳％計，其量低於1 0莫耳％。該共聚物可爲 無規或嵌段共聚物。選擇性地，該第二聚丙烯具有下列性 質之一或更多者：（i)該聚丙烯係同排；（ii)該聚丙烯 具有至少約90J/g之熔化熱，例如約90至約120J/g;( iii)該聚丙烯具有至少約16(TC之熔融尖峰（第二次熔融 );(iv )該聚丙烯在約230°C之溫度且應變率爲25 sec·1 測量時之Trout on比爲至少約1 5 ;及/或（v )該聚丙烯在 約23 0°C之溫度且應變率爲25 sec — 1測量之伸長黏度至少 約 5 0,000 Pa sec° 一具體實例中，本發明係關於包含約1重量％至約9 5 重量％該聚合物組成物、〇至約95重量％該第一聚乙烯、〇 至約95重量％該第二聚乙烯與約0至約50重量％該第二 聚丙烯之組成物。在相關具體實例中，本發明係關於包含 數量係爲約1 〇重量％至約8 0重量％，或爲約2 0重量％至 約40重量％範圍之本發明UHMWPP ;數量係爲約0至約 20重量％，或約5重量％至約1 5重量。/。範圍之UHMWPE ; 數量係爲約1 〇至約8 0重量％，或約2 0重量％至約7 0重 量％範圍之HDPE ;以及數量係爲約〇重量％至約50重量 %，或約1 0重量％至約3 0重量％範圍之第二聚丙烯的組成 物。 該聚合物組成物（單獨或與第二聚合物或聚合物組成 物結合者）可選擇性進一步包含有效量之安定劑以避免產 生顏色。習用安定劑（即，本技術中已習知者）可適用。 -22- 200904883 此等安定劑包㈣《'酸㈣㈣鹽類、酸有機憐酸金 屬鹽類、酸性磷酸金屬鹽類與其混合。 該聚合物組成物（單獨或與第二聚合物或聚合物組成 物結合者）可選擇性進一步包含有效量之著色顏料。習用 著色顏料可適用’包括碳黑、酞青藍、駄青綠、意醌染料 、緋紅2b Lake、偶氮化合物、酸偶氮顏料、喹吖啶酮、 鉻酞青吡咯、鹵化酞青素、喹啉、雜環染料、芘酮染料、 蒽二酮（anthracenedione)染料、喔（thi〇zanthene)染料 、吡唑D弄染料、聚次甲基顏料及其混合。 該聚合物組成物（單獨或與第二聚合物或聚合物組成 物結合者）可選擇性進一步包含添加劑或化合物，以對該 組成物提供特定希望之特徵。習用之添加劑與化合物均可 適用，且其使用係技藝人士所知者。此等之實例包括uv 女疋劑、抗氧化劑、光安定劑、耐焰劑、抗靜電劑、殺生 物劑、減黏劑、耐衝擊改良劑、增塑劑、塡料、強化劑、 潤滑劑、脫模劑、發泡劑、成核劑及類似者。 (b )從該UHMWPP或該聚合物組成物所製得之微孔膜的 結構 一具體實例中，該微孔膜係單層膜。製造方法的選擇 並非關鍵，並且可使用可從聚烯烴起始材料形成微孔膜之 任何方法，包括習用方法，諸如美國專利第5,0 5 1,1 8 3號 與美國專利第6,096,2 1 3號中所述者，該等專利案全文係 以提及的方式倂入本文中。其他具體實例中，該微孔膜係 -23- 200904883 多層膜’即具有至少兩層之膜。爲求簡明起見，微孔聚烯 烴膜之製造主要係以兩層與三層膜加以說明，惟熟悉本技 術之人士會認可將相同技術應用於製造具有一層之膜或具 有至少四層之膜。 一具體實例中，此三層微孔膜包含第一與第三微孔層 ，其構成該微孔聚烯烴膜的外層，且第二層係位於該第一 與第三層之間（選擇性令其平面與彼等接觸）。一具體實 例中，該第一與第三層係從第一聚烯烴溶液而製得，該第 二（或裡）層係從第二聚烯烴溶液而製得。另一具體實例 中，該第一與第三層係從第二聚烯烴溶液而製得，該第二 層係從該第一聚烯烴溶液而製得。 一具體實例中，該微孔膜或多層微孔膜之層中至少一 者顯示以較寬孔大小分布爲其特徵之混合結構。如此，該 微孔膜可根據WO 2007/1 1 7042所揭示之方法製得’該案 全文係以提及的方式倂入本文中。繪製差示孔孔體積曲線 時，以上述方法而製得之微孔膜具有較寬之孔大小分布。 孔大小分布可藉由例如習用方法，諸如將資料表示爲差示 孔體積曲線之汞孔隙儀法而測得。 使用汞孔隙儀測量膜中之孔大小分布與孔體積時，慣 常測量孔直徑、孔體積與膜之比表面積。此等測量可用以 判定以dVp-表示之差示孔體積，其中VP係孔體積，而r dLog{r) 係孔半徑，假設其爲圓柱形孔。當y軸繪製差示孔體積且 X軸爲孔直徑時，慣常稱爲「孔大小分布」。就顯示混合 結構之膜而言，差示孔體積之至少約2 5 % ’或至少約3 0 % -24- 200904883 ，或至少約40%，或至少約50% ’或至少約60%係與大小 (直徑）約100奈米或更大之孔有關。換言之’就 對孔直徑之曲線而言’位於該曲線下方' 之來自孔直彳至爲約 1〇〇奈米至約1000奈米的面積孔係在孔大小（或假設爲圓 柱形孔時則指其直徑）約10奈米至約1 0 0 0奈米之孔的曲 線下方總面積的至少約25%，或至少約30% ’或至少約 4 0 %，或至少約5 0 %，或至少約6 0 %。在一具體實例中’ 位於孔直徑爲約1 〇 0奈米至約1 0 0 0奈米之曲線下方的面 積係位於孔直徑約1 0奈米至約1 0 0 0奈米之曲線下方總面 積的約2 5 %至約6 0 %，或約3 0 %至約5 5 %，或約3 5 %至約 5 0 %範圍。 一種可用以測定微孔膜結構之汞侵入孔隙儀法係使用 Pore Sizer 93 20 ( M i c r o m e r i t i c s Company, Ltd.)，壓力範 圍係3.6 kPa至207 MPa，且晶胞容積爲15 cm3。爲進行 測量，可使用之汞的接觸角爲141.3，且汞的表面張力爲 4 8 4達因/ c m。以此方法所得之參數包括孔體積、表面積比 、孔大小之尖峰頂端、平均孔大小與孔隙度。揭示本方法 之參考資料包括 Raymond P. Mayer and Robert A. Stowe， J . P hy s . C hem. 70,1 2( 1 966) ; L . C. Drake, In d . E n g . C h e m ·, 4 1,780( 1 949); H. L. Ritter and L. C. Drake, Ind.Eng. Chem. Anal.，17,782(1945) and E. W. Washburn, Pro c .Nat. Acad. Sci.，7,1 1 5( 1 92 1) ° 該膜可作爲電池組隔板。該膜特別適於作爲鋰與鋰離 子電池組（例如鋰離子原電池組與蓄電池組）之隔板。適 -25- 200904883 用於本發明之代表性電池組與電池組隔板係如 WO 200 7/ 117042中所描述者。 (c )使用UHMWPP或該聚合物組成物製造微孔膜之方法 在一具體實例中，本發明係關於用於製造微孔膜之方 法，包含以下步驟：（1 )組合稀釋劑或溶劑（其可指膜 形成溶劑）與包含UHMWPP或該聚合物組成物之第一聚 烯烴組成物，以製備第一聚烯烴溶液，（2 )選擇性地， 當欲得多層膜時，組合第二聚烯烴組成物和第二膜形成溶 劑以製備第二聚烯烴溶液，（3 )經由至少一個衝模而擠 出第一與第二聚烯烴溶液（較佳係同時擠出），以形成擠 出物，（4 )選擇性地將該擠出物冷卻，以形成經冷卻的 擠出物，例如，凝膠狀薄片，（5 )從該經冷卻的擠出物 或是該擠出物去除至少一部分的膜形成溶劑，以形成經去 除溶劑之薄片’以及（6 )藉由例如乾燥而從該薄片去除 任何揮發性物質，以形成微孔膜。若情況需要，可在步驟 (4 )與（5 )之間進行選擇性拉伸步驟（7 )與選擇性熱 溶劑處理步驟（8 )及其他。若情況需要，可於步驟（6 ) 之後進行拉伸多層微孔膜之選擇性步驟（9 )、選擇性熱 處理步驟（1 0 )、使用游離輻射之選擇性交聯步驟（1 1 ) ，以及選擇性親水處理步驟（1 2 )及其他。該等選擇性步 驟的順序並非關鍵。因第一與第二溶液包含聚烧烴之故， 將彼等稱爲「聚烧烴」溶液。進一步包含並非聚燦烴之物 質的第一與第二溶液係在本發明範圍內。 -26- 200904883 (1 )第一聚烯烴溶液之製備 第一聚烯烴組成物包含UHMWPP ，且若情況需要則包含其他聚烯烴（3 )，藉由例如乾式混合或以適當稀釋舞 )熔融摻合而令彼等結合，以製造該聚 地，該第一聚烯烴溶液可包含各種添力口 種抗氧化劑、細微矽酸鹽粉末（孔形成 條件係在不會令該多層微孔聚烯烴膜的 之濃度範圍下使用此等添加劑。一具體 烴組成物包含UHMWPP或該聚合物組 含第一聚乙烯、第二聚乙烯與第二聚丙 者。對該第一聚烯烴組成物的聚烯烴樹 期望之微孔層或複數層微孔層，例如該 層核心層或一或更多層表面層。 第一稀釋劑或溶劑（例如處理溶劑 爲室溫下爲液態之溶劑。雖然不希望受 限制，但一般認爲使用液態溶劑以形成 可能以較高拉伸倍率進行凝膠狀薄片之 例中，第一膜形成溶劑可爲脂族、脂環 少一者，諸如壬烷、癸烷、十氫萘、對 十二烷、液態石鱲及其他；具有之沸點 沸點的礦物油餾出物；以及於室溫之苯 如苯二甲酸二丁酯、苯二甲酸二辛酯及 或該聚合物組成物 常呈上述樹脂形式 (例如膜形成溶劑 烯烴溶液。選擇性 劑，諸如一或更多 材料）等，其先決 期望性質明顯變差 實例中，第一聚烯 成物，並選擇性包 烯其中之一或更多 脂加以選擇以製造 微孔膜之一或更多 或膜形成溶劑）可 到任何理論或模型 第一聚烯烴溶液令 拉伸。在一具體實 或芳族烴其中之至 二甲苯、Η—院、 相當於上述烴類之 二甲酸酯液體，諸 其他。在一希望獲 -27- 200904883 得具有安定液態溶劑含量之多層凝膠狀薄片的具體實例中 ，可使用非揮發性液態溶劑，諸如液態石蠟，其係單獨使 用或與其他溶劑倂用。選擇性地，可使用呈熔融摻合狀態 時可與聚乙烯互混但於室溫爲固態的溶劑，其係單獨使用 或與液態溶劑倂用。此種固態溶劑可包括例如硬脂醇、蠟 醇、石蠟及其他。雖然並非關鍵，但當該溶液不含液態溶 劑時，會更難均勻拉伸該凝膠狀薄片或所得之膜。 該液態溶劑之黏度並非關鍵參數。例如，於25 °C該液 態溶劑之黏度範圍爲約30 cSt至約500 cSt，或爲約30 cSt至約200 cSt。雖然並非關鍵參數，但當25°C之黏度低 於約3 0 c St時，會更難以避免聚烯烴溶液起泡，此現象會 導致摻合時之困難。另一方面，當黏度大於約500 cSt時 ，更難從該多層微孔聚烯烴膜去除該液態溶劑。 一具體實例中，令用於製造第一聚烯烴組成物之此等 樹脂或其他於例如雙螺桿擠出機或混合器中乾式混合或熔 融摻合。例如，可使用諸如雙螺桿擠出機之習用擠出機（ 或混合器或混合器-擠出機）組合該等樹脂或其他，以形 成第一聚烯烴組成物。可於此製程中任何方便時點將該膜 形成溶劑添加至該聚烯烴組成物（或者添加係用於製造該 聚烯烴組成物之樹脂）。例如，於將第一聚烯烴組成物與 第一膜形成溶劑加以熔融摻合之具體實例中，該溶劑可於 :(i )開始熔融摻合之前、（Π )第一聚烯烴組成物熔融 摻合期間，或（i Π )熔融摻合之後之任何時點，藉由例如 令第一膜形成溶劑供應至第二擠出機或擠出機區之經熔融 -28- 200904883 摻合或部分熔融摻合的聚烯烴組成物而添加至該該聚烯烴 組成物，其中該第二擠出機或擠出機區係位於用以熔融摻 合該聚烯烴組成物之擠出機區的下游。 使用熔融摻合時，熔融摻合溫度並非關鍵。例如，第 一聚烯烴溶液之熔融摻合溫度可爲比第一聚乙烯樹脂Tm, 之熔點高約l〇°C至比Τπμ高約120°C。爲求簡明，此範圍 可以TriM + lOt至Tn^ + KOt表示。在第一聚乙烯樹脂具 有約13(TC至約140°C之溶點的具體實例中，熔融摻合溫度 可爲約140°C至約25(TC，或爲約170°C至約240°C。 將諸如雙螺桿擠出機之擠出機用於溶融摻合時，螺桿 參數並非關鍵’。例如，該螺桿可以雙螺桿擠出機中之螺桿 長度L對螺桿直徑D比L/D爲其特徵，L/D比可爲例如約 20至約100，或爲約35至約70。雖然此參數並非關鍵， 但當L/D小於約20時，熔融摻合會變得較困難，且當 L/D大於約1〇〇時，可能需要較快之擠出機速度以避免聚 烯烴溶液在雙螺桿擠出機中之逗留時間過長（其會導致不 良之分子量變差）。雖然並非關鍵參數，但雙螺桿擠出機 之圓筒（或孔）具有例如約40mm至約1 〇〇mm之內徑。 第一聚烯烴溶液中之第一聚烯烴組成物之量並非關鍵 。一具體實例中，以聚烯烴溶液重量計，第一聚烯烴溶液 中之第一聚烯烴組成物的量可爲約1重量％至約75重量％ ’例如爲約2 0重量％至約7 0重量％。雖然第一聚烯烴溶 液中之第一聚烯烴組成物之量並非關鍵，但當該量少於約 1重量％時，更難以足夠有效的速率製造多層微孔聚烯烴 -29- 200904883 膜。此外，當其量少於1重量％時，更難以避免於擠出期 間位於衝模出口之潤脹或瓶頸，此使得更難形成並支撐係 該製造方法期間所形成之膜前驅體的多層凝膠狀薄片。另 一方面，當第一聚烯烴組成物溶液之量多於約75重量％時 ，可能更難以形成多層凝膠狀薄片。 (2 )第二聚烯烴溶液之製備 可藉由用以製備第一聚烯烴溶液之相同方法製備第二 聚烯烴溶液。例如，可藉由令第二聚烯烴組成物與第二稀 釋劑或溶劑熔融摻合而製備該第二聚烯烴溶液。可從與第 一膜形成溶劑相同之溶劑中選擇該第二膜形成溶劑。雖然 第二膜形成溶劑可（且通常係）獨立於第一膜形成溶劑外 而加以選擇，但該第二膜形成溶劑可與該第一膜形成溶劑 相同，而且可使用與第一聚烯烴溶液中使用之第一膜形成 溶劑的相同相對濃度。 第二聚烯烴組成物通常係獨立於第一聚烯烴組成物外 而加以選擇。該第二聚烯烴組成物通常包含第一聚乙烯、 第二聚乙烯、第一聚丙烯與第二聚丙烯其中之一或更多者 〇 於聚烯烴組成物含有第二聚丙烯之具體實例中，用於 製備第二聚烯烴溶液之方法與用於製備第一聚烯烴溶液之 方法不同之處僅在於混合溫度較佳係在第二聚丙烯之熔點 (Tm2 )至Tm2 + 90°C的範圍，且聚烯烴組成物含量較佳爲 卜50質量％，更佳爲20·4〇質量％。當此方法產生多層微 -30- 200904883 孔膜（例如三層膜）時，該膜可包含含有第一層材料之第 一微孔層'含有第一層材料之第三微孔層，與含有第二層 材料之第二微孔層，該第二微孔層係位於第一與第三微孔 層之間。一具體實例中，第一層材料係從第一聚烯烴溶液 而製得’且第二層材料係從第二聚烯烴溶液而製得。另一 具體實例中，第二層材料係從第一聚烯烴溶液而製得，且 第一層材料係從第二聚烯烴溶液而製得。 (3 )擠出 一具體實例中，將第一聚烯烴溶液從第一擠出機導至 第一衝模，並選擇地，將第二聚烯烴溶液從第二擠出機導 至第二衝模。可從第一與選擇性地從第二衝模擠出單層擠 出物，或視需要爲層狀擠出物，其呈薄片形式（即爲平面 方向明顯大於厚度方向之物體）。選擇性地，該第一與第 二聚烯烴溶液係從第一與第二衝模共擠出，從第一聚烯烴 溶液形成之第一擠出物層的平面表面係與從第二聚烯烴溶 液接點之第一擠出物層的平面表面接觸。擠出物之平面表 面可由該擠出物之縱向的第一向量與該擠出物之橫向的第 二向量所界定。 其他具體實例中，使用複數個衝模，令各衝模連接至 用於將第一或第二聚烯烴溶液導入該衝模之擠出機。例如 ，在一具體實例中，令含有第一聚烯烴溶液之第一擠出機 連接至第一衝模與第三衝模，並令含有第二聚烯烴溶液之 第二擠出機連接至第二衝模。如前述具體實例中之情況， -31 - 200904883 所得之層狀擠出物可從第一、第二與第三衝模 )共擠出’而形成包含從第一聚烯烴溶液製造 層（例如頂層與底層）的第一與第二層；與構 表面層之間且平面與該等表面層接觸之中間或 二層，其中該第二層係從第二聚烯烴溶液形成 又一具體實例中，使用同一衝模但令聚嫌 ’即’令含有第二聚烯烴溶液之第二擠出機連 第三衝模’並令含有第一聚烯烴溶液之第一濟 第二衝模。 前述具體實例之任一者當中，衝模擠出可 模擠出設備進行。例如，擠出可藉由例如平模 而進行。在一可用於共擠出多層凝膠狀薄片之 ，可使用歧管擠出’其中令第一與第二聚烯烴 多層擠出衝模中之分離歧管，並令彼等於衝模 層疊。另一此種具體實例中，使用區塊擠出， 第二聚烯烴溶液係先組合成層流（即，事先進 令該層流連接至一衝模。由於多重歧管與區塊 悉處理聚烯烴膜技術之人士熟知（例如，揭 1 22 1 42 A、JP06- 1 065 99A)，因此慣常認爲不 明其操作。 衝模選擇並非關鍵，並且可使用例如習用 片之平模或充氣衝模。衝模間隙並非關鍵。例 層薄片之平模可具有約0.1 mm至約5 mm之衝 模溫度與擠出速度亦非關鍵參數。例如，該衝 (例如同時 之構成表面 成位於兩層 層間層的第 〇 烴溶液相反 接至第一與 出機連接至 使用習用衝 或充氣衝模 具體實例中 溶液導入一 入口處加以 其中第一與 行），然後 製程已爲熟 示於 J P 0 6 -需要詳細說 形成多層薄 如，形成多 模間隙。衝 模可加熱至 -32- 200904883 擠出期間之衝模溫度爲約140°C至約25 0 °C。擠出速度 例如約0.2 m/分鐘至約15 m/分鐘。層狀擠出物之層 可獨立加以選擇。例如，與層狀擠出物之中間層厚度 ，凝膠狀薄片可具有較厚表面層（或「表」層）。 雖然係以製造一層、兩層與三層擠出物之具體實 明該擠出，但擠出步驟並未受限於此。可使用複數個 及/或衝模組合件，以便使用前述具體實例之擠出方 製造具有四或更多層之多層擠出物。此種層狀擠出物 可使用第一聚烯烴溶液及/或第二聚烯烴溶液製造各 層或中間層。 (4 )經冷卻之擠出物的形成 可藉由例如冷卻而令該擠出物形成凝膠狀薄片。 速率與冷卻溫度並非特別關鍵。例如，可以至少約 分鐘之冷卻速率加以冷卻凝膠狀薄片，直到該凝膠狀 之溫度（冷卻溫度）約等於該凝膠狀薄片之膠凝溫度 更低）爲止。一具體實例中，令擠出物冷卻至約2 5 °C 低之溫度，以便形成凝膠狀薄片。雖然不希望受到任 論或模型限制，但一般認爲冷卻該層狀擠出物固定藉 或更多種膜形成溶劑而分離之第一與第二聚烯烴溶液 烯烴微相。已觀察到通常較低之冷卻速率（例如低於 /分鐘）對該多層凝膠狀薄片提供較大準晶胞單位， 較粗較局等級結構。另一方面’較迅速冷卻速率（例 °C /分鐘）形成較緻密晶胞單位。雖然擠出物之冷卻 可爲 厚度 相較 例說 衝模 法而 中， 表面 冷卻 5 0。。/ 薄片 (或 或更 何理 由一 的聚 5 0°C 導致 如80 速率 -33- 200904883 並非關鍵參數，但當彼低於5 0 °C /分鐘時，可能造 中之聚烯烴結晶度提高，此現象使得後續拉伸步驟 處理該多層凝膠狀薄片。冷卻方法的選擇並非關鍵 ，可使用習用薄片冷卻法。一具體實例中，該冷卻 令該層狀擠出物與冷卻媒介（諸如冷卻空氣、冷卻 他）接觸。或者，可經由令該擠出物與藉由冷卻媒 他冷卻之滾筒接觸而加以冷卻。 (5)第一與第二膜形成溶劑之去除 一具體實例中，從該凝膠狀薄片去除第一與第 成溶劑之至少一部分，以便形成經去除溶劑之薄片 用置換（或「清洗」）溶劑去除（洗掉或置換）該 第二膜形成溶劑。雖然不希望受到任何理論或模型 但一般認爲由於從第一聚烯烴溶液與第二聚烯烴溶 ，該第一聚烯烴與第二聚烯烴）而得之凝膠狀薄片 烯烴相係與膜形成溶劑相分離之故，去除膜形成溶 供多孔膜，其係由形成細微立體網狀結構並具有立 規則之相通孔的原纖維構成。只要清洗溶劑可以溶 換第一及/或第二膜形成溶劑之至少一部分，其選 關鍵。適用之清洗溶劑包括例如一或更多種揮發性 諸如飽和烴類，諸如戊烷、己烷、庚烷或其他；氯 ’諸如二氯甲烷、四氯化碳或其他；醚類，諸如二 二噚烷或其他；酮類，諸如甲基乙基酮或其他；線 化物’諸如三氟乙烷、C6F14、C7F16或其他；環狀 成該層 中更難 。例如 法包含 水或其 介或其 二膜形 。可使 第一與 限制， 液（即 中的聚 劑則提 體且不 解或置 擇並非 溶劑， 化烴類 乙醚、 性氟碳 氫氟碳 -34- 200904883 化物，諸如C5H3F7或其他；氫氟醚’諸如c4f9och3、 C4F9OC2H5或其他·，以及全氟醚’諸如 c4f9ocf3、 c4f9oc2f5 或其他。 用於去除膜形成溶劑之方法並非關鍵，可使用可去除 大量溶劑之任何方法’包括習用溶劑去除法。例如，可令 該多層凝膠狀薄片浸於清洗溶劑中及/或以該清洗溶劑沖 淋該薄片而對彼加以清洗。所使用之清洗溶劑數量並非關 鍵，且通常係視所選用以去除膜形成溶劑之方法而定。例 如，以該凝膨狀薄片之質量計，所使用之清洗溶劑量可在 約3 00至約3 0,000質量份數範圍。雖然所去除之膜形成 溶劑的數量並非特別關鍵，但從該凝膠狀薄片去除至少大 部分第一與第二膜形成溶劑時通常會較高品質（更多孔） 膜。一具體實例中，從凝膠狀薄片去除膜形成溶劑（例如 ’藉由清洗）’直到該凝膠狀薄片中剩餘之膜形成溶劑的 數量以凝膠狀薄片重量計變得低於1重量％爲止。 (6 )乾燥該薄片 一具體實例中，將藉由去除至少一部分膜形成溶劑而 獲得之經去除溶劑的薄片加以乾燥，以便去除該清洗溶劑 。可使用能去除清洗溶劑之任何方法，包括習用方法，諸 如熱乾燥、風乾（流動空氣）或其他。乾燥期間該凝膠狀 薄片之溫度（即，乾燥溫度）並非關鍵。例如，乾燥溫度 可等於或低於結晶分散溫度Tcd。Tcdl係第—聚乙烯樹脂 之結晶分散溫度Tech與第二聚乙烯（當使用彼時）之結 -35- 200904883 晶分散溫度Ted的較低者。例如，乾燥溫度可低於結晶分 散溫度Tcd至少5 t。第一與第二聚乙烯樹脂之結晶分散 溫度可藉由測量根據ASTM D 4065之聚乙烯樹脂的動力 黏彈性之溫度特徵而決定。一具體實例中，第一或第二聚 乙烯樹脂中之至少一者具有在約90°C至約l〇〇°C範圍之結 晶分散溫度。 雖然並非關鍵，但可進行乾燥直到殘留之清洗溶劑量 以乾燥基準（即，以乾燥微孔聚烯烴膜之重量）計爲約5 重量％或更低爲止。另一具體實例中，進行乾燥直到以乾 燥基準計之殘留清洗清洗量爲約3重量％或更低爲止。由 於乾燥不充分通常導致微孔膜之孔隙不良降低，故可認出 乾燥不充分。若觀察到此現象，則應使用較高乾燥溫度及 /或較長乾燥時間。藉由例如乾燥或其他者去除該清洗溶 劑，使得該微孔膜形成。 (7 )拉伸 於去除膜形成溶劑的步驟之前（換言之，於步驟5之 前）’可將薄片加以拉伸以便獲得經拉伸之凝膠狀薄片。 一般認爲’第一與第二膜形成溶劑於凝膠狀薄片中之存在 造成較均勻拉伸倍率。一般亦認爲加熱該凝膠狀薄片，尤 其是於開始拉伸，或於拉伸之較早階段時（即已完成5〇% 拉伸之前）加熱該凝膠狀薄片有助於拉伸之均勻度。 拉伸方法或拉伸倍率之選擇均非特別關鍵。例如，可 使用能將凝膠狀薄片拉伸至預定倍率的任何方法（包括任 -36- 200904883 何選擇性加熱）。在具體實例中，該拉伸可藉由拉幅機拉 伸、滾筒拉伸或充氣拉伸（例如，以空氣進行）中之一或 更多者完成。雖然該選擇並非關鍵，但該拉伸可以單軸（ 即，以縱向或橫向），或雙軸（以縱向或橫向二者）進行 。一具體實例中，其係使用雙軸拉伸。在雙軸拉伸（亦稱 爲雙軸定向）情況中，拉伸可爲雙軸同時拉伸、沿著一平 面軸然後再沿著另一軸依序拉伸（例如，先以橫向再以縱 向拉伸），或多階段拉伸（例如，同時雙軸拉伸與依序拉 伸之組合）。一具體實例中，使用同時雙軸拉伸。 拉伸倍率並非關鍵。在使用單軸拉伸之具體實例中， 線性拉伸倍率可爲例如約2倍或更高，或約3至約3 0倍 。在使用雙軸拉伸之具體實例中，任何平面方向之線性拉 伸倍率可爲例如約3倍或更高。另一具體實例中，由拉伸 而形成之面積放大倍率係至少約9倍，或至少約1 6倍， 或至少約2 5倍。雖然並非關鍵參數，但當該拉伸導致面 積放大倍率爲至少約9倍時，多層微孔聚烯烴膜具有相對 較高之針穿刺強度。當試圖令面積放大倍率大於約400倍 時，會更難以操作拉伸設備。 於拉伸期間該凝膠狀薄片的溫度（換言之，拉伸溫度 )並非關鍵。一具體實例中，拉伸期間該凝膠狀薄片之溫 度可爲約（Tm+10°C )或更低，或選擇性地在高於Ted但 低於Tm之範圍，其中Tm係第一聚乙烯與之熔點Τπμ與 第二聚乙烯（若使用彼時）之熔點Tm2其中之較低者。雖 然此參數並非關鍵，但當拉伸溫度高於約熔點Tm+ 1 0 °C時 -37- 200904883 ，第一或第二聚乙烯其中至少一者會呈熔融狀態，其使得 更難於拉伸期間定向該凝膠狀薄片中之聚烯烴的分子鏈。 且當拉伸溫度低於約Ted時，第一或第二聚乙烯其中之至 少一者可能軟化不充分，而造成難以在不造成斷裂或撕裂 之下拉伸該多層凝膠狀薄片，此會造成無法達到期望之拉 伸倍率。一具體實例中，拉伸溫度在約9(TC至約140°C， 或爲約l〇〇°C至約130°C之範圍。 雖然不希望受到任何理論或模型限制，但一般認爲此 種拉伸導致聚乙烯層之間分離，造成聚乙烯相更細微並形 成更大量原纖維。此等原纖維形成立體網狀結構（立體規 則性連接之網狀結構）。因此，使用此拉伸時通常能更容 易產生具有較大孔大小之較高機械強度微孔膜。一般認爲 此等多層微孔膜特別適於作爲電池組隔板。 選擇性地，拉伸可於厚度方向（即，與微孔聚烯烴膜 平面表面大約垂直之方向）存有溫度梯度之下進行。此情 況中，更容易製造具有經改良機械強度之微孔聚烯烴膜。 本方法之細節係描述於日本專利3 347854。 (8 )熱溶劑處理步驟 雖然並不需要，但可在步驟（4)與（5)之間使用熱 溶劑加以處理該多層凝膠狀薄片。於使用熱溶劑處理時’ 一般認爲此處理提供具有較厚葉脈狀結構之原纖維（諸如 藉由拉伸多層凝膠狀薄片而形成者）。一般認爲此種結構 使得較容易製造具有高強度與滲透性之較大孔的多層微孔 -38- 200904883 膜。「葉脈狀」一辭意指該等原纖維具有厚幹線以及呈網 狀自彼延伸之網纖維。此方法細詳係描述於 WO 2000/20493 ° (9 )多層微孔膜之拉伸（「乾式拉伸」） 一具體實例中，步驟（6 )之經乾燥的微孔膜可經拉 伸’至少經單軸拉伸。所選用之拉伸方法並非關鍵，可使 用諸如拉幅機法或其他之習用拉伸方法。雖然並非關鍵， 但可於拉伸期間對該膜加熱。雖然其選擇並非關鍵，但拉 伸可爲單軸或雙軸拉伸。雖然使用雙軸拉伸，但拉伸可在 兩個軸方向進同時行，或者，可對該多層微孔聚烯烴膜依 序拉伸’例如先以縱向然後再以橫向拉伸。一具體實例中 ，係使用同時拉伸。當該薄片係經步驟（7 )所述般拉伸 時，可將步驟（9 )之乾燥微孔膜稱之爲乾式拉伸、再拉 伸或乾式定向。 於拉伸期間該乾燥微孔膜之溫度（「乾式拉伸溫度」200904883 IX. Description of the Invention [Technical Field] The present invention relates to more than 90 mole % of propylene monomer, and the melting flow rate of ° C is less than about 0. The 2dg/min polymer composition can be used to make microporous films, including micro-containing polyethylene. [Prior Art] Ultra-high molecular weight (UHMW) polymers have a variety of uses. For example, when UHMW high density polyethylene (UHMWPE) includes impact resistant textiles, artificial joint materials and micropores 2004/026921 VIII and U.S. Patent No. 4,734,196), the microporous membrane must have a balanced open circuit time, Melt permeability and needle puncture strength. UHMW polypropylene ( ) has been found to be suitable for use in the manufacture of gel-spun high-melting and high-strength fibers as a manufacturing additive, as well as as a control for lower molecular weight polypropylene melt flow additives. UHMW polypropylene can be produced using a Ziegler-Natta catalyst and using dimethoxydecane as an electron donor. See 06234811A, JP 06234812A and JP 07292021A for details. The first material reveals a product with an intrinsic viscosity from 4 to 1 dl dl/g. The data reveals that the intrinsic viscosity is from 5 to 1 dl dl/g and the melting MFR is less than zero. 1 g/i 〇 minutes of product. These two products are said to have good breaking strength and modulus yarn. The third reference above has an average molecular weight of lxlO6. And at 2 3 0 . The polymerized L film. Important commercial applications can be used for coatings (WO is the battery damaging temperature, UHM WPP microporous membrane denaturation plus dicyclopentyl group such as JP, etc. reference melting flow rate (can be used as a teaching aid 200904883 JP 62022 808A revealed use The UHMW polypropylene having a molecular weight of from 2xl〇6 to 5x106 is produced by using a dicyclopentyldimethoxydecane electron donor without using a dicyclopentyldimethoxydecane electron donor. Similarly, JP 03007704A discloses the use of a 戚格勒-纳UHMW polypropylene and copolymers with molecular weights from lxlO6 are produced by the catalyst but without the use of dicyclopentyldimethoxydecane. The jp 023 05 8 09A is also disclosed in the polymerization of Ziegler-Natta catalysis. UHMW polypropylene is produced using an electronic donor. US 4,413,11 discloses polypropylene having a molecular weight of 2.1 χ 106, which is disclosed as being suitable for high strength fibers. US 5,070,05 1 UHMW polyethylene and polyhexene instead of polypropylene, It is prepared by using a Sigma-Natta catalyst but without the use of a dicyclopentyldimethoxydecane electron donor. EP 0 654 476 A and EP 0 790 076 A disclose polypropylene prepared using a metal complex catalyst. Reference material among the former The molecular weight of the product was 786,500, a melting point of 159 ° C, and a molecular weight distribution (Mw / Mn) of 2. 4. The molecular weight of the product of the first two references is l. LxlO6, molecular weight distribution is 2. 5 and the melting point is 159 °C. Although polypropylene has been produced using both metal complex catalysts, 戚Geller-Natta catalysts, and with or without the use of dicyclopentyldimethoxydecane electron donors, the resulting polypropylene is difficult to apply to microfabrication. Aperture membranes, in particular for the manufacture of microporous membranes comprising polypropylene and polyethylene. For example, U.S. Patent No. 6,096,213 discloses a microporous film made from a blend of melt treatable polymers comprising a blend of polyethylene and polypropylene. This patent discloses that polypropylene is considered to have melt handling properties only when its melt flow index is above 〇 2 dg/min. -6- 200904883 Therefore, there is a need to make UHMWPP' such as a microporous film containing polyethylene and polypropylene, especially in which the melt flow index of polypropylene is 0. 2 dg/min or lower. SUMMARY OF THE INVENTION In one embodiment, the invention relates to UHMWPP comprising more than about 90 mole percent based on the weight of UHMWPP. The UHMWPP typically has one or more of the following properties: an intrinsic viscosity greater than about 1 〇 d 1 /g, a heat of fusion greater than about 108 J/g ‘melting point of 165 ° C or higher, and a molecular weight greater than about 1. The molecular weight distribution of 5 X 106' is from about 2 to about 5 to about 7, and the melt flow rate at 230 ° C is less than about 0. 0 1 dg/min, i.e., substantially unmeasurable, the extractables content (extracted by contact of UHMWPP with xylene) is 0 by weight of UHMWPP. 5% by weight or less, having a meso pentad portion of more than about 96 mol% mmmm pentad, and the amount of stereoquinone is 1 〇, and one carbon atom is lower than About 50. In a related embodiment, the UHMWPP comprises a polypropylene monomer comprising more than about 90 mole percent, based on the weight of U Η M WP P , having a melt flow rate of less than about 0 at 230 °C. 0 1 dg/min and having at least one of the following properties: an intrinsic viscosity greater than about 10 dl/g, a heat of fusion greater than about 108 J/g, a melting point of 165 ° C or higher, and a molecular weight greater than about 1. The molecular weight distribution of 5xl 〇 6' is about 2. 5 to about 7, the extractables content (extracted by contact of UHMWPP with xylene) is 〇·5 wt% or less by weight of UHMWPP, and has a meso pentad fraction of more than about 96 mol % mmmm pentad. And the amount of stereoscopic enthalpy is less than about 50 ° per 10,000 carbon atoms. 200904883 In another embodiment, the invention relates to a polymer composition comprising the aforementioned UHMWPP. In a related embodiment, the polymer composition additionally comprises (a) a second polymer (eg, polyethylene, such as high density and/or high molecular weight polyethylene) and/or (b) a diluent or solvent (eg, Liquid paraffin). In other related specific examples, the polymer composition comprises the aforementioned UHMWPP and optionally high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), second polypropylene (eg, those having a molecular weight lower than UHMWPP), and a diluent. Or a solvent (which may be a mixture of diluents or a mixture of solvents or a mixture of the two) of one or more of the polyolefin compositions. In other related embodiments, the invention relates to a polymer composition and a second polymer composition. The second polymer composition may comprise a polyolefin such as polyethylene and/or polypropylene, such as one or more of HDPE, UHMWPE and second polypropylene. In other specific examples, the invention relates to a process for making the aforementioned UHMWPP and polymer compositions. In another embodiment, the invention relates to a method of making articles using the aforementioned UHMWPP or polymer composition, such as, for example, shaped articles, sheets or films, such as microporous films. Such microporous membranes have been found to be particularly suitable as, for example, battery separators in primary lithium ion batteries and hammer ion batteries. These battery packs can be used as charge sources or receivers. Thus, in another embodiment, the invention relates to a microporous membrane or membrane comprising the aforementioned UHMWPP or polymer composition. It has been found that microporous membranes comprising the aforementioned UHMWPP or polymer composition as a battery separator generally have balanced circuit breaking properties, meltdown temperature, permeability and needle penetration strength. -8- 200904883 The microporous membrane of the present invention may be a single layer film or a multilayer film. Thus, in one embodiment, the invention relates to a method for making a microporous film or film, comprising: a first microporous layer comprising a first layer of material, a third microporous layer comprising a first layer of material, and a A second microporous layer of the second layer of material, the second microporous layer being disposed between the first and third microporous layers. At least one of the first or second layer materials is made of U Η M W P P or a polymer composition. In addition to the amount of molecular weight reduction (e.g., caused by shear thinning) that occurs during processing, the layer material made from UHMWPP or polymer composition typically comprises a UHMWPP or polymer composition formed therefrom. In another embodiment, the invention relates to a method for making a microporous film or film comprising: (1) mixing the aforementioned UHMWPP (or polymer composition) with a diluent (or treating solvent) to form a first polyolefin a solution, (3) extruding at least a portion of the first polyolefin path solution through one or more dies to form an extrudate, (4) cooling the extrudate to form a cooled extrudate, (5) The cooled extrudate removes at least a portion of the diluent to form a solvent-removed sheet, and (6) removes at least a portion of any volatile material from the sheet to form a microporous membrane. In a related embodiment, the invention relates to a method for producing a multilayer film comprising: (1) combining the aforementioned UHMWPP or polymer composition with a diluent (200904883 or a treatment solvent) to form a first polyhydrocarbon solution ' (2) combining a second polyolefin or polyolefin composition (including UHMWPP as appropriate) with a second diluent (or treatment solvent) to form a second polyolefin solution, (3) being squeezed through one or more dies At least a portion of the first polyolefin solution is coextruded and at least a portion of the second polyolefin solution is coextruded to form a multilayer extrudate, (4) the multilayer extrudate is cooled to form a cooled multilayer extrudate, 5) removing at least a portion of the processing solvent from the cooled extrudate to form a solvent-removed sheet, and (6) removing at least a portion of any volatile material from the sheet to form a multilayer microporous membrane. In a specific example, the method is a continuous or semi-continuous operation. [Embodiment] The basis of the present invention is to find a polymer composition comprising the aforementioned UHMWPP, which is generally suitable for the manufacture of articles such as microporous films. The polymer composition typically comprises more than 90 mole % of the polypropylene monomer' and has one or more of the following desirable properties: the polymer composition has an intrinsic viscosity greater than about 10 dl/g and a heat of fusion greater than about 108 J. /g, melting point of 165 ° C or higher, molecular weight greater than about 1. 5x1 06, the molecular weight distribution is about 2. 5 to about 7 'at 23 (TC melt flow rate is less than about 〇·〇1 dg/min, ie 'substantially undetectable, extractable material content (by polymer composition-10-200904883) The amount of the xylene contact is 0. The weight of the polymer composition is 0. 5% by weight or less has a meso pentad body moiety of more than about 96 mole% mmmm pentads, and each enthalpy has a carbon number of less than about 50 steric enthalpy. In a related embodiment, the polymer composition comprises more than 90 mole % of the polypropylene monomer and has one or more of the following properties: The polymer composition has an intrinsic viscosity greater than about 10 dl/g, heat of fusion It is greater than about 108 J/g, has a melting point of 165 ° C or higher, and has a molecular weight greater than about 1. 5xl06, the molecular weight distribution is about 2. 5 to about 7, the melt flow rate at 230 ° C is less than about 0. 01 dg/min, i.e., substantially unmeasurable, the extractables content (obtained by contacting the polymer composition with boiling xylene) is 0 by weight of the polymer composition. 5% by weight or less, having a meso-pentameric moiety of more than about 96 mole% mmmm pentads, and having a carbon atom of less than about 50 Å per 〇. It has been found that even the polypropylene melt flow rate is 0. 2 dg / min or lower, or even 〇. 1 dg / min or lower, or even O. These polymer compositions can also be used to make microporous films, particularly microporous films comprising polyethylene and polypropylene, at Oldg/min or lower. The periodic table number used herein can be found, for example, in Hawley, s Condensed Chemical Dictionary 8 5 2 (John Wiley &amp; Sons, 13th edition 1 997). The term "polymer" as used herein refers to the product of polymerization, and includes homopolymers, copolymers, terpolymers, and others. As used herein, unless otherwise specified, the term "copolymer" as used herein refers to a polymer formed by the polymerization of at least two different monomers. The term "copolymer" includes the copolymerization product of ethylene and an α-olefin such as propylene or -11 - 200904883 i -hexene alone. However, the term "copolymer" also includes, for example, the copolymerization of ethylene, propylene, a mixture of 1-hexene and 1-octene. As used herein, the term "% by weight" means the weight percent of a particular component relative to the total weight of the mixture containing the component (unless otherwise noted). For example, if the mixture or blend contains three pounds of Compound A and one pound of Compound B, Compound A comprises 75 wt% of the mixture and Compound B accounts for 25 wt%. I.  Properties of UHMWPP and Polymer Composition In a specific example, the polymer composition comprises more than about 90 mole % of a polypropylene monomer, such as, for example, more than about 95 mole % of a polypropylene monomer, and up to About 99. 99 moles. /. Polypropylene monomer. In one form, the invention relates to polymer compositions having one or more of the following properties. It will be appreciated that these properties can be characteristic of UHMWPP in polymer compositions and compositions, especially when the polymer composition contains properties other than UHMWPP. In one embodiment, the 'polymer composition has an intrinsic viscosity greater than about 11 dl/g, or greater than about 12 dl/g. The intrinsic viscosity (IV) of the polymer composition can be, for example, by W.  R.  Sorenson and Τ·W.  Campbell's &quot;PREPARATIVE METHODS OF POLYMER CHEMISTRY&quot; pp. 43-50 (different version 2 1968) by Interscience Publishers. Published) The standard process described in the description is measured or measured according to the A S T M D 1 6 0 1 - 7 8 process. -12- 200904883 In one embodiment, the heat of fusion of the polymer composition is greater than about 1 〇 8 J/g, or greater than about 110 j/g ' or greater than about 1 12 J/g. The heat of fusion of the polymer composition can be measured by a conventional method such as differential scanning calorimetry (DSC). In one embodiment, the polymer composition has a high melting point (Tm), such as greater than about 166 °C, or even greater than about 168, and even greater than about 170 °C. The melting point can be measured by a conventional method such as differential scanning calorimetry (DSC). Differential Scanning Calorimetry (DSC) data can be obtained using the Pyris 1 DSC model of PerkinElmer Instrument as follows. A sample of approximately 5 _ 5 - 6 · 5 m g was sealed in an aluminum sample pan. The D S C data was recorded as follows: The sample was first heated to 200 ° C at a rate of 150 t / min, called the first melt (no record data). Allow the sample to stand at 200 °C for 10 minutes before applying the cooling-heating cycle. The sample is then cooled from 200 ° C to 25 ° C at a rate of 1 ° C / min, called crystallization, then held at 25 t for a minute and heated to 200 ° C at a rate of 1 ° C / min, called For the second melt. Thermal events of both crystallization and second melting were recorded. The melting temperature (Tm) is the peak temperature of the second melting curve, and the crystallization temperature (Tc) is the peak temperature of the crystal peak. In one embodiment, the polymer composition has a higher molecular weight than polypropylene which is conventionally used to make microporous films and films, particularly microporous films which also comprise polyethylene. For example, the polymer composition can have greater than about 1. 75 X106 molecular weight, or even greater than about 2xl06, or even greater than about 2. 25xl〇6 , such as for example greater than about 2. 5 xlO6. The molecular weight distribution of the polymer composition can be, for example, in a narrow range of from about 2.5 to about 7. As used herein, -13-200904883 "Molecular weight" means that the average molecular weight (Mw) 〇Mw can be measured using gel permeation chromatography as described below. The molecular weight distribution (MWD) means Mw divided by the number average molecular weight (?n). (For more information, see U.S. Patent No. 4,540,7,53, the entire disclosure of which is hereby incorporated by reference in its entirety, and the entire disclosures of "Mz" is a high average molecular weight 値, such as A. R.  Cooper at CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 63 8-3 9 ( J. I.  The discussion in Kroschwitz, John Wiley &amp; Sons 1990) calculates. The molecular weight distribution Mw/Mn(MWD) is a ratio of the weight average molecular weight (Mw measured by gel permeation chromatography of GPC) to the number average molecular weight (measured by GPC below). The molecular weight (weight average molecular weight Mw and number average molecular weight Μη) can be measured using a high temperature size exclusion chromatography (GPC PL 220, Polymer Laboratories) equipped with a differential diffraction index detector (DRI). Three PLgel Mixed-B columns (Polymer Laboratories) were used. The nominal flow rate is 1. 0 era3 / minute, the general injection volume is 300μί. A variety of conveyor lines, columns and DRI detectors are housed in furnaces maintained at 1 60 °C. This technique is discussed in &quot;Macromolecules' Vol. 34, No. 19, 6812-6820 (200 1 )&quot;, which is incorporated herein by reference in its entirety. 1 000 ppm butylated hydroxytoluene (BHT) filtered Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). Degas the TCB with an on-line degasser before entering the S EC. The dry polymerization -14-200904883 was placed in a glass vessel, the required amount of the above TCB solvent was added, and then the mixture was heated at 1, 60 ° C, and continuously stirred for about 2 hours to prepare a polymer solution. UHMWPP solution concentration is 0. 25 mg/ml. A series of narrow MWD polystyrene standards were used to calibrate the separation efficiency of the column set, which reflects the expected MW range of the sample and the exclusion limits of the column set. A calibration curve was generated using eighteen individual polyethylene standards (from Mp ~ 5 80 to 10,000,000). These polystyrene standards were obtained from Polymer Laboratories (Amherst, ΜΑ). A calibration curve (logMp versus maintenance volume) is generated by maintaining the volume of the spikes recorded in the DRI signal of each PS standard and making the data set conform to the second order polynomial. Use \\^乂6]\/161;1'丨05,111(:. 1〇011?1'0 analysis sample. The following Mark-Houwink coefficients are used to calculate the Mw of the PP as the base and the MW of the PS as the base. kidL/g) α PS 1. 75x10-4 0. 67 PP 2. 288x10-4 0. 705 In one embodiment, the polymer composition is at 23 ° C and 2. The melt flow rate (MFR) below 16 kg is 〇. 2dg/min or lower, or less than about O. Ldg / minute, or even less than about 〇. 〇ldg/min. O. The Oldg/Chain is so low that it is virtually impossible to measure MFR. The melt flow rate can be measured according to a conventional method such as ASTM D 1238-95 Condition L. In a specific example, the polymer composition exhibits a cluster of less than about 50 per 10,000 carbon atoms, or less than about 40, or less than about 30 or even every 10, A stereoscopic enthalpy having a carbon atom of less than about 20. Examples -15- 200904883 For example, the polymer composition may have a stereoscopic enthalpy of less than about 10, or a stereoscopic enthalpy of less than about 5, per 10 carbon atoms. The stereoscopic oxime can be measured by a conventional method such as the following 1 3e NMR: 13c NMR data is obtained on a Varian VXR 400 NMR spectrometer at 125 ° C at 1 〇〇 MHz. Using a 90 ° C pulse, the extraction time 3. 0 seconds, pulse delay 20 seconds. This spectrum is obtained by wide frequency decoupling without gate-controlled decoupling. The methyl resonance of polypropylene is expected to have a similar relaxation time and a nuclear Overhauser effect, which is usually the only homopolymer resonance used for quantitative purposes. The number of transient representations collected is 2,500. The sample was dissolved in tetrachloroethane-d2 at a concentration of 15% by weight. All spectra were recorded according to the internal tetramethyl decane standard. In the case of polypropylene homopolymers, according to 21. 81 ppm mmmm was recorded for methyl resonance, which is close to the internal tetramethyl decane standard 21. 855 ppm report literature値. Five-element distribution has been established. In one embodiment, the polymer composition has a meso pentad fraction greater than about 96 moles. /ammmm pentad. In one embodiment, the polymer composition comprises an extractables content (the polymer composition is contacted with boiling dimethylbenzene for extraction) based on the weight of the polymer composition. 5 wt% or less, or 0. 2% by weight or less, or even 〇.  1% by weight or less. The amount of extractables (such as relatively low molecular weight and/or amorphous phase materials, such as amorphous phase polypropylene) is determined by the solubility in 135 °C xylene according to the following procedure. A 2 gram sample (flaky or milled form) was weighed out and placed in a 300 ml Erlenmeyer flask. 200 ml of xylene was poured into the Erlenmeyer flask by means of a stir bar, and the bottle of -16-200904883 was fixed on a heating oil bath. The heated oil bath was started and the flask was allowed to stand in an oil bath at 135 ° C for about 15 minutes to melt the polymer. When molten, the heating is stopped, but the entire cooling process continues to stir. The dissolved polymer was naturally cooled overnight. The precipitate was filtered through a Teflon filter paper and then dried at 90 ° C under vacuum. The amount of soluble xylene was determined by subtracting the room temperature precipitate ("B") from the weight percent of the total polymer sample (&quot;A") [soluble content = ((AB) / AxlOO). II. Manufacture of UHMWPP and polymer composition The polymer composition (e.g., UHMWPP) can be produced according to the following methods, such as solution polymerization, slurry polymerization or gas phase polymerization techniques, which are conventionally used to produce olefin polymers. Phase polymerization is a preferred technique. Likewise, it is possible to produce the olefin polymer using a suitable polyoxo catalyst system&apos; including conventional systems such as olefin polymer ziegler-Natta catalysts or metal complex catalysts. Examples of suitable catalysts and process conditions are disclosed in European Patent No. 3,501,0B, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in the the the the the the The 戚格勒-Natta type catalyst is a conventional catalyst' and is, for example, Concise Encyclopedia of Polymer Science and Engineering, 1 0 8 7-1107 (Jacqueline I.  Kroschwitz, ed., 1990) and F.  A.  Cotton &amp; G · Wilkinson, Advanced Inorganic Chemistry, 1 2 80- 1 2 82 (4th edition, 1 9 80) is discussed. Representative catalyst systems for carrying solid magnesium and methods for their preparation are described in U.S. Patent Nos. 4,990,479 and 5,159,021, and WO 00/44795. For example, 戚 -17- 200904883 Gele-Natta catalysts are usually composed of organometallic compounds derived from transition metal compounds of Groups 4-7 of the Periodic Table and metals from Groups 1 -1 3 . Examples which have been specifically known include TiCl3-Et2AlCl, AlR3-TiCl4, wherein Et is an ethyl group and R represents an alkyl group. These catalysts include mixtures of halides of transition metals (especially titanium, chromium, vanadium and niobium) with organic derivatives of non-transition metals (especially alkylaluminum compounds). The Zigler-Natta type catalyst is usually combined with an electron donor. The electron donor can be used in two ways in the formation of the Ziegler-Natta catalyst system. First, an internal electron donor can be used in the formation reaction of a solid catalyst. Examples of internal electron donors include: amines, guanamines, ethers, esters, aryl esters, ketones, nitriles, phosphines, anthraquinones, anthraquinones, phosphoniumamines, thioethers, sulfur Salts of esters, aldehydes, alcoholates and organic acids. The second use of the electron donor in the catalyst system serves as a stereoregulator in the external electron donor and polymerization reactions. The same compound can be used in these two examples, but it is usually a different compound. An organic ruthenium compound including a conventional organic ruthenium compound can be used as an electron donor. Conventional electron donors which are organic hydrazine (or "decane") compounds are disclosed in U.S. Patent Nos. 4,218,339; 4,395,360; 4,328,122; 4,473,660; 6,133,385 and 6,127,303. A description of these two types of electronic donors is provided in U.S. Patent No. 4,535,068. In a specific example, an internal electron donor comprising TiCl4/MgC di-n-butyl phthalate, an electron donor containing dicyclopentyldimethoxydecane (DCPMS) and a small amount or none are used in a liquid phase. The polymer composition was produced by a ruthenium-Natta catalyst of added hydrogen. The method comprises the steps of: (1) pre-contacting the Plage-Natta catalyst with the DCPMS donor and triethylaluminum (TEA1) • 18-200904883, (2) prepolymerizing the catalyst with propylene, (3) The prepolymerized catalyst is further polymerized in one or more reactors, and (4) a polymer composition comprising about 90 mole % of propylene monomer or more, the polymer composition having an intrinsic viscosity greater than About 10 dl / g, the heat of fusion is greater than about 1 〇 8 J / g, the melting point is 165 ° C or more than the molecular weight of greater than about 1.5 χ 106' molecular weight distribution is about 2. 5 to 7, 23 ° ° ° melt flow rate is less than about 0. 01 dg/min (i.e., substantially undetectable), the amount of extractable material (extracted by contacting the polymer composition with boiling xylene) is 0 by weight of the polymer composition. 5% by weight or less, having a meso pentad body portion of more than about 96 mole % mmmm pentads, and a combination of properties of one 〇, one carbon atom of less than 50. In one embodiment, the polymer composition comprises UHMWPP of the present invention. In another embodiment, the polymer composition consists essentially of UHMWPP. In another embodiment, the polymer composition consists of UHMWPP. In a specific example particularly suitable for the manufacture of the polymer composition (e.g., UHMWPP of the present invention) for use in the manufacture of microporous films, such as those containing polyethylene, the following conditions may be employed: no added hydrogen is used in the polymerization process. The polymerization catalyst is TOHO THC-1 35 and the electron system is dicyclopentyldimethoxydecane; the remaining process conditions are disclosed in European Patent No. 03 5 0 1 70B2. In addition to the preferred DCPMS donors described above, other suitable donors may include, but are not limited to, bis(t-butyl)dimethoxydecane, cyclopentyldimethoxy(t-butoxy)decane, Tributyl) (t-butoxy) dimethoxy sand court. -19- 200904883 III. In the specific example in which the polymer composition is used to produce articles of manufacture, the polymer composition can be combined with the second polymer composition, for example, by mixing or blending, to produce articles of manufacture, such as micropores. membrane. For example, the polymer composition can be mixed or blended with, for example, polyethylene in the form of a polyethylene resin. (a) Starting material When the polymer composition is combined with the second polymer composition, the relative amounts of the first and second polymer compositions are not critical. For example, the percentage of the polymer composition to the second polymer composition in the mixture or blend may be, for example, from about 5 to about 95% by weight, based on the weight of the first and second polymer compositions combined, or From about 20 to about 80% by weight. The second polymer composition may comprise a polyolefin, such as one or more high density (HD) polyethylene and/or high molecular weight polyethylene, such as ultra high molecular weight (UHMW) polyethylene or a second polypropylene. In such mixtures or blends, the weight ratio of polymer composition to HD polyethylene to high molecular weight (e.g., UHMW) polyethylene can be any 5 to 95:0 to 95:0 to 95, or can be 20 to 80. : 20 to 70: 0 to 20. In the presence of the second polypropylene, the amount is not critical and may range, for example, from about 1% by weight to about 30% by weight, based on the combined weight of the first and second polymer compositions. In one embodiment, the second polymer composition comprises at least one of a first polyethylene, a second polyethylene, or a second polypropylene. The first polyethylene may be any polyethylene having a molecular weight of 5x10 or higher, such as a molecular weight of 1χ1〇6 to 1_5χ107, such as UHMWPE. Such polyethylene may be a B-200-200904883 dilute terpene polymer or an ethylene/α-smoke copolymer containing a small amount of an α-olefin other than ethylene. The olefin other than ethylene may be propylene, butene, hexene-1, pentene-1, 4-methylpentene, octene, vinyl acetate, methyl methacrylate, styrene or a mixture thereof. The diethylene may be a polyethylene having a molecular weight of Mw of from about lxl 04 to about 5 x 105. The second polyethylene may be, for example, high density polyethylene, medium density polyethylene, branched low density polyethylene, and linear low density. Polyethylene. The second polyethylene may be an ethylene homopolymer or an ethylene/α-olefin copolymer containing a small amount of α·olefin other than ethylene. The α-olefin other than ethylene may be propylene, butene-1, and Ethene-1, pentene-1, 4-methylpentene-1, octene 'vinyl acetate, methyl methacrylate, styrene or a mixture thereof. Although not critical, the second polyethylene is in polyethylene Each of the 10,000 carbon atoms has, for example, two or more terminal unsaturations. The terminal unsaturation can be measured by, for example, conventional infrared spectroscopy. The second polypropylene can have a weight average molecular weight of less than about 7. 5 X 1 05, for example, from about 1 X 1 04 to about 7 · 5 X 1 0 5, or from about 4 5 X 1 〇 5 to about 7·5 χ 105, or from about 5 χ 105 to about 7 χ 105. Although not critical 'but the second polypropylene may have a molecular weight distribution of, for example, from about 5 to about 100', such as from about 5 to about 5 Torr, and about 80 J/g or higher, such as from about 80 to about 120 J/ The heat of fusion of g. The second polypropylene may be, for example, one or more of the following: (i) a propylene homopolymer or a copolymer of (U) propylene and one or more α-olefins, such as ethylene , butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene, vinyl acetate, methyl methacrylate and styrene and others; and diolefins such as Second suspect, -21 - 200904883 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene and others, based on the total copolymer of 1 〇〇 mol%, the amount is low At 10% Mo. The copolymer can be a random or block copolymer. Optionally, the second polypropylene has one or more of the following properties: (i) the polypropylene is in the same row; (ii) the polypropylene has a heat of fusion of at least about 90 J/g, such as from about 90 to about 120 J/g; (iii) the polypropylene has a melting peak of at least about 16 (the second melt); (iv) the polypropylene at a temperature of about 230 ° C and a strain rate of 25 sec·1 The Trout on ratio is at least about 1 5; and/or (v) the polypropylene has a temperature at a temperature of about 23 ° C and a strain rate of 25 sec -1 measured at an elongation viscosity of at least about 5,000 Pa sec °. In a specific example, The present invention relates to comprising from about 1% to about 5% by weight of the polymer composition, from about 95% by weight of the first polyethylene, from about 5% to about 95% by weight of the second polyethylene and from about 0 to about 50. % by weight of the composition of the second polypropylene. In a related embodiment, the invention is in the range of from about 1% by weight to about 80% by weight, or from about 20% by weight to about 40% by weight. The UHMWPP of the present invention is in an amount of from about 0 to about 20% by weight, or from about 5% by weight to about 15% by weight of UHMWPE; the amount is about 1 〇 Up to about 80% by weight, or from about 20% by weight to about 70% by weight of HDPE; and the amount is from about 3% by weight to about 50% by weight, or from about 10% by weight to about 3% by weight The composition of the second polypropylene. The polymer composition (alone or in combination with the second polymer or polymer composition) may optionally further comprise an effective amount of a stabilizer to avoid coloration. Conventional stabilizers (ie </ RTI> </ RTI> -22- 200904883 These stabilizers (four) "acid (four) (four) salts, acid organic acid metal salts, acidic metal phosphates mixed with it. The polymer composition (Individually or in combination with a second polymer or polymer composition) may optionally further comprise an effective amount of a color pigment. Conventional coloring pigments may be suitable for use including 'carbon black, indigo blue, indigo green, enamel dye, blush 2b Lake, azo compounds, acid azo pigments, quinacridones, chrome oxapyrroles, anthocyanins, quinolines, heterocyclic dyes, anthrone dyes, anthracenedione dyes, thi〇zanthene ) dye, pyrazole D Dyes, polymethine pigments, and mixtures thereof. The polymer composition (either alone or in combination with a second polymer or polymer composition) may optionally further comprise an additive or compound to provide specific hope for the composition. Features, customary additives and compounds are applicable, and their use is known to those skilled in the art. Examples of such include uv female lotion, antioxidant, light stabilizer, flame retardant, antistatic agent, biocide, Viscosity reducing agents, impact modifiers, plasticizers, tanning agents, reinforcing agents, lubricants, mold release agents, foaming agents, nucleating agents and the like. (b) Structure of Microporous Membrane Prepared from the UHMWPP or the Polymer Composition In a specific example, the microporous membrane is a monolayer membrane. The choice of manufacturing method is not critical, and any method that can form a microporous film from a polyolefin starting material can be used, including conventional methods, such as U.S. Patent No. 5,0 1,1,8, and U.S. Patent No. 6,096,2 In the case of No. 1 No. 3, the full text of these patents is incorporated herein by reference. In other embodiments, the microporous membrane system -23-200904883 multilayer membrane&apos; has a membrane having at least two layers. For the sake of simplicity, the manufacture of microporous polyolefin membranes is primarily illustrated by two and three layers of membranes, but those skilled in the art will recognize that the same techniques can be applied to the manufacture of membranes having one layer or membranes having at least four layers. . In one embodiment, the three-layer microporous membrane comprises first and third microporous layers that form an outer layer of the microporous polyolefin membrane, and a second layer is between the first and third layers (selective Let the plane touch them.) In a specific embodiment, the first and third layers are prepared from a first polyolefin solution and the second (or inner) layer is prepared from a second polyolefin solution. In another embodiment, the first and third layers are made from a second polyolefin solution, and the second layer is made from the first polyolefin solution. In one embodiment, at least one of the layers of the microporous membrane or the multilayer microporous membrane exhibits a mixed structure characterized by a wider pore size distribution. Thus, the microporous membrane can be made according to the method disclosed in WO 2007/1 1 7042. The entire text of which is incorporated herein by reference. When the differential pore volume curve is plotted, the microporous membrane prepared by the above method has a wide pore size distribution. The pore size distribution can be measured by, for example, a conventional method, such as a mercury porosimetry method in which data is expressed as a differential pore volume curve. When the pore size distribution and pore volume in the membrane are measured using a mercury porosimeter, the pore diameter, the pore volume, and the specific surface area of the membrane are conventionally measured. These measurements can be used to determine the differential pore volume represented by dVp-, where VP is the pore volume and r dLog{r) is the pore radius, assuming it is a cylindrical pore. When the y-axis plots the differential pore volume and the X-axis is the pore diameter, it is often referred to as the "hole size distribution". For a film exhibiting a mixed structure, at least about 25 % ' or at least about 30% -24 to 200904883, or at least about 40%, or at least about 50% ' or at least about 60% of the differential pore volume The size (diameter) is about 100 nm or more. In other words, 'in the curve of the hole diameter, 'below the curve', the area from the hole straight to about 1 〇〇 nanometer to about 1000 nm is the hole size (or assuming a cylindrical hole) Refers to at least about 25%, or at least about 30% ' or at least about 40%, or at least about 50% of the total area under the curve of the pores having a diameter of from about 10 nm to about 1 000 nm, or At least about 60%. In one embodiment, the area below the curve of the pore diameter of from about 1 〇0 nm to about 10,000 nm is located below the curve of the pore diameter of from about 10 nm to about 10,000 nm. From about 25 % to about 60%, or from about 30% to about 55%, or from about 35 % to about 50% of the area. A mercury intrusion porosimetry system that can be used to determine the structure of microporous membranes using Pore Sizer 93 20 (M i c r o m e r i t i c s Company, Ltd. ), the pressure range is 3. 6 kPa to 207 MPa and a unit cell volume of 15 cm3. For the measurement, the contact angle of mercury that can be used is 141. 3, and the surface tension of mercury is 4 8 4 dyne / c m. The parameters obtained in this way include pore volume, surface area ratio, peak tip size, average pore size and porosity. References for revealing this method include Raymond P.  Mayer and Robert A.  Stowe, J.  P hy s .  C hem.  70,1 2 ( 1 966) ; L .  C.  Drake, In d.  E n g .  C h e m ·, 4 1,780 ( 1 949); H.  L.  Ritter and L.  C.  Drake, Ind. Eng.  Chem.  Anal. , 17, 782 (1945) and E.  W.  Washburn, Pro c . Nat.  Acad.  Sci. , 7, 1 1 5 ( 1 92 1) ° The film can be used as a battery separator. The membrane is particularly suitable as a separator for lithium and lithium ion batteries, such as lithium ion primary batteries and battery packs. Suitable battery packs and battery separators for use in the present invention are as described in WO 200 7/117042. (c) Method for producing a microporous membrane using UHMWPP or the polymer composition In one embodiment, the present invention relates to a method for producing a microporous membrane comprising the steps of: (1) combining a diluent or a solvent (which Means a film forming solvent) and a first polyolefin composition comprising UHMWPP or the polymer composition to prepare a first polyolefin solution, (2) optionally, when a multilayer film is desired, combining the second polyolefin The composition and the second film form a solvent to prepare a second polyolefin solution, and (3) extruding the first and second polyolefin solutions (preferably simultaneously extruded) via at least one die to form an extrudate, 4) selectively cooling the extrudate to form a cooled extrudate, such as a gelatinous sheet, (5) removing at least a portion of the film from the cooled extrudate or the extrudate A solvent is formed to form a solvent-removed sheet ' and (6) any volatile matter is removed from the sheet by, for example, drying to form a microporous film. If necessary, a selective stretching step (7) and a selective thermal solvent treatment step (8) and others may be carried out between steps (4) and (5). If necessary, the optional step (9) of stretching the multilayer microporous membrane, the selective heat treatment step (10), the selective crosslinking step using free radiation (1 1 ), and the selection may be performed after the step (6). Sexual hydrophilic treatment step (1 2 ) and others. The order of these optional steps is not critical. Since the first and second solutions contain polyalkylene hydrocarbons, they are referred to as "polyalkylene" solutions. It is within the scope of the invention to further include first and second solutions which are not poly-carbonaceous materials. -26- 200904883 (1) Preparation of First Polyolefin Solution The first polyolefin composition comprises UHMWPP and, if necessary, other polyolefin (3), which is melt blended by, for example, dry mixing or dilution with appropriate dilution. The first polyolefin solution may comprise various antioxidants and fine bismuth silicate powders (the pore formation conditions are such that the multilayer microporous polyolefin film is not allowed to be bonded together). The additives are used at a concentration range. A particular hydrocarbon composition comprises UHMWPP or the polymer group comprises a first polyethylene, a second polyethylene and a second polypropylene. Polyolefin tree expectations for the first polyolefin composition a microporous layer or a plurality of microporous layers, such as the core layer or one or more surface layers. The first diluent or solvent (for example, the treatment solvent is a solvent which is liquid at room temperature. Although not wishing to be limited, However, it is generally considered that in the case of using a liquid solvent to form a gel-like sheet which may be subjected to a higher draw ratio, the first film forming solvent may be aliphatic or less alicyclic, such as decane, decane or decahydrogen. Naphthalene, ten Alkane, liquid sarcophagus and others; mineral oil distillate having a boiling point boiling point; and benzene such as dibutyl phthalate, dioctyl phthalate at room temperature and or the polymer composition is usually the above resin Form (eg, film forming solvent olefin solution. Selective agent, such as one or more materials), etc., whose predesed desired properties are significantly deteriorated, in the example, the first polyolefin, and the selective inclusion of one or more The grease is selected to make one or more of the microporous membranes or the membrane forming solvent) can be stretched to any theoretical or model first polyolefin solution. In a specific or aromatic hydrocarbon to xylene, Η-院And a dibasic gel-like liquid corresponding to the above-mentioned hydrocarbons, and others. In a specific example of a multilayer gel-like sheet which is desired to have a stable liquid solvent content from -27 to 200904883, a non-volatile liquid solvent such as a non-volatile liquid solvent may be used. Liquid paraffin, which is used alone or in combination with other solvents. Alternatively, a solvent which is intermixed with polyethylene in a melt blended state but is solid at room temperature may be used alone or in combination with The solvent may be used. Such a solid solvent may include, for example, stearyl alcohol, wax alcohol, paraffin wax, and others. Although not critical, when the solution does not contain a liquid solvent, it is more difficult to uniformly stretch the gel-like sheet or obtain The viscosity of the liquid solvent is not a critical parameter. For example, the viscosity of the liquid solvent ranges from about 30 cSt to about 500 cSt, or from about 30 cSt to about 200 cSt at 25 ° C. Although not a critical parameter, When the viscosity at 25 ° C is less than about 30 c St, it is more difficult to avoid foaming of the polyolefin solution, which may cause difficulty in blending. On the other hand, when the viscosity is greater than about 500 cSt, it is more difficult to The multilayer microporous polyolefin membrane removes the liquid solvent. In one embodiment, the resins used to make the first polyolefin composition or other dry blends or melt blends in, for example, a twin screw extruder or mixer. For example, the resins or other may be combined using a conventional extruder (or mixer or mixer-extruder) such as a twin-screw extruder to form the first polyolefin composition. The film forming solvent may be added to the polyolefin composition at any convenient point in the process (or added to the resin used to make the polyolefin composition). For example, in a specific example in which the first polyolefin composition is melt-blended with the first film forming solvent, the solvent may be melt-doped after the (i) first melt-blending, (Π) the first polyolefin composition During the combination, or (i Π ) any time after melt blending, by blending or partially melt-blending, for example, the first film forming solvent is supplied to the second extruder or the extruder zone by melting -28-200904883. The polyolefin composition is added to the polyolefin composition, wherein the second extruder or extruder zone is located downstream of the extruder zone for melt blending the polyolefin composition. The melt blending temperature is not critical when using melt blending. For example, the melt blending temperature of the first polyolefin solution may be higher than the melting point of the first polyethylene resin Tm by about 10 ° C to about 120 ° C higher than Τπμ. For simplicity, this range can be expressed as TriM + lOt to Tn^ + KOt. In a specific example in which the first polyethylene resin has a melting point of about 13 (TC to about 140 ° C, the melt blending temperature may range from about 140 ° C to about 25 (TC, or from about 170 ° C to about 240 °). C. When using an extruder such as a twin-screw extruder for melt blending, the screw parameters are not critical. For example, the screw can be screw length L to screw diameter D ratio L/D in a twin-screw extruder Characteristically, the L/D ratio may be, for example, from about 20 to about 100, or from about 35 to about 70. Although this parameter is not critical, when L/D is less than about 20, melt blending may become more difficult, and When L/D is greater than about 1 Torr, a faster extruder speed may be required to avoid excessive residence time of the polyolefin solution in the twin-screw extruder (which may result in poor molecular weight degradation). Key parameters, but the cylinder (or orifice) of the twin-screw extruder has an inner diameter of, for example, from about 40 mm to about 1 mm. The amount of the first polyolefin composition in the first polyolefin solution is not critical. In an example, the amount of the first polyolefin composition in the first polyolefin solution may be about 1 weight by weight of the polyolefin solution. From about 75% by weight 'for example from about 20% by weight to about 70% by weight. Although the amount of the first polyolefin composition in the first polyolefin solution is not critical, when the amount is less than about 1% by weight At this time, it is more difficult to manufacture a multilayer microporous polyolefin-29-200904883 film at a sufficiently effective rate. Further, when the amount is less than 1% by weight, it is more difficult to avoid swelling or bottleneck at the die exit during extrusion, which makes It is more difficult to form and support a multilayer gel-like sheet which is a film precursor formed during the production method. On the other hand, when the amount of the first polyolefin composition solution is more than about 75% by weight, it may be more difficult to form a multilayer. a gel-like sheet. (2) Preparation of a second polyolefin solution The second polyolefin solution can be prepared by the same method as used to prepare the first polyolefin solution. For example, by making the second polyolefin composition and the first The second polyolefin solution is prepared by melt blending a diluent or a solvent. The second film forming solvent may be selected from the same solvent as the first film forming solvent. Although the second film forming solvent may (and usually is) independent First The film forming solvent is selected in addition to the solvent, but the second film forming solvent may be the same as the first film forming solvent, and the same relative concentration as that of the first film forming solvent used in the first polyolefin solution may be used. The olefin composition is generally selected independently of the first polyolefin composition. The second polyolefin composition typically comprises one of the first polyethylene, the second polyethylene, the first polypropylene, and the second polypropylene or Further, in a specific example in which the polyolefin composition contains the second polypropylene, the method for preparing the second polyolefin solution is different from the method for preparing the first polyolefin solution only in that the mixing temperature is better. In the range of the melting point (Tm2) to Tm2 + 90 °C of the second polypropylene, the content of the polyolefin composition is preferably 50% by mass, more preferably 24.0% by mass. When the method produces a multilayer micro-30-200904883 aperture film (eg, a three layer film), the film may comprise a first microporous layer comprising a first layer of material 'a third microporous layer containing the first layer of material, and containing a second microporous layer of the second layer of material, the second microporous layer being between the first and third microporous layers. In one embodiment, the first layer of material is made from the first polyolefin solution and the second layer of material is made from the second polyolefin solution. In another embodiment, the second layer of material is prepared from the first polyolefin solution and the first layer of material is prepared from the second polyolefin solution. (3) Extrusion In one embodiment, the first polyolefin solution is conducted from the first extruder to the first die, and selectively, the second polyolefin solution is guided from the second extruder to the second die. The single layer extrudate can be extruded from the first and selectively from the second die, or optionally as a layered extrudate, in the form of a sheet (i.e., an object that is substantially larger in the planar direction than the thickness direction). Optionally, the first and second polyolefin solutions are coextruded from the first and second dies, the planar surface of the first extrudate layer formed from the first polyolefin solution and the second polyolefin solution The planar surface of the first extrudate layer of the joint is in contact. The planar surface of the extrudate can be defined by a first vector in the machine direction of the extrudate and a second vector in the transverse direction of the extrudate. In other specific examples, a plurality of dies are used to connect the dies to an extruder for introducing the first or second polyolefin solution into the dies. For example, in one embodiment, the first extruder containing the first polyolefin solution is coupled to the first die and the third die, and the second extruder containing the second polyolefin solution is coupled to the second die . As in the case of the foregoing specific examples, the layered extrudate obtained from -31 to 200904883 may be coextruded from the first, second, and third dies) to form a layer comprising the first polyolefin solution (eg, top layer and First and second layers of the bottom layer; intermediate or two layers between the surface layer and the plane in contact with the surface layers, wherein the second layer is formed from the second polyolefin solution in yet another embodiment, using The same die but the polyether "that is," the second extruder containing the second polyolefin solution is connected to the third die' and the second die containing the first polyolefin solution. In any of the foregoing specific examples, the die extrusion is performed by a die extruding apparatus. For example, extrusion can be carried out, for example, by a flat die. In one can be used to coextrude a plurality of multi-layer gel-like sheets, a manifold can be used to extrude the separation manifolds in the first and second polyolefin multilayer extrusion dies, and to align them with the dies. In another such specific embodiment, the block extrusion is used, and the second polyolefin solution is first combined into a laminar flow (i.e., the laminar flow is connected to a die. Due to the multi-manifold and block processing of the polyolefin film Those skilled in the art are familiar with (for example, 1 22 1 42 A, JP 06-1 065 99 A), and it is customary to think that their operation is not known. Die selection is not critical, and a flat die or an inflatable die such as a conventional piece may be used. The key. The flat die of the layer can have about 0. Die temperatures and extrusion speeds from 1 mm to about 5 mm are also not critical. For example, the punch (for example, simultaneously forming a surface of the second hydrocarbon layer located in the two layers of the layer is connected to the first and the outlet is connected to the inlet of the solution using the conventional punch or the inflatable die body to be introduced into the inlet. Line), then the process has been cooked to JP 0 6 - need to be detailed to form a multi-layer thin, forming a multi-mode gap. The die can be heated to -32- 200904883 during the extrusion process at a die temperature of from about 140 ° C to about 25 ° C. The extrusion speed is, for example, about 0. 2 m/min to approx. 15 m/min. The layers of the layered extrudate can be selected independently. For example, the gelatinous sheet may have a thicker surface layer (or "sheet" layer) than the thickness of the intermediate layer of the layered extrudate. Although the extrusion is carried out in a specific embodiment for producing one, two and three layers of extrudates, the extrusion step is not limited thereto. A plurality of and/or die assemblies can be used to produce a multilayer extrudate having four or more layers using the extrusions of the foregoing specific examples. Such a layered extrudate can be used to make layers or intermediate layers using a first polyolefin solution and/or a second polyolefin solution. (4) Formation of the cooled extrudate The extrudate can be formed into a gel-like sheet by, for example, cooling. Rate and cooling temperature are not particularly critical. For example, the gelatinous sheet can be cooled at a cooling rate of at least about a minute until the gelatinous temperature (cooling temperature) is approximately equal to the gelation temperature of the gelatinous sheet is lower. In one embodiment, the extrudate is allowed to cool to a temperature of about 25 ° C to form a gelatinous sheet. While not wishing to be limited by theory or model, it is generally believed that cooling the layered extrudate fixes the first and second polyolefin solution olefin microphases separated by more or more film forming solvents. It has been observed that a generally lower cooling rate (e.g., less than /min) provides a larger quasi-unit cell to the multi-layer gel-like sheet, a coarser, more hierarchical structure. On the other hand, the faster cooling rate (for example, ° C / min) forms a denser unit cell. Although the cooling of the extrudate may be in the thickness of the die, for example, the surface is cooled by 50. . / flakes (or more or less the reason that the concentration of 50 °C results in a rate of -33-200904883 is not a critical parameter, but when it is below 50 ° C / min, the crystallinity of the polyolefin may be increased, This phenomenon causes the subsequent stretching step to process the multilayer gel-like sheet. The choice of cooling method is not critical and conventional sheet cooling can be used. In one embodiment, the cooling causes the layered extrudate to be cooled with a cooling medium (such as cooling air) , cooling him) contact. Alternatively, it may be cooled by contacting the extrudate with a roller that is cooled by a cooling medium. (5) Removal of the first and second film forming solvents In a specific example, from the condensation The gelatinous sheet removes at least a portion of the first and first solvent to form a solvent-removed sheet to remove (wash or replace) the second film forming solvent with a replacement (or "cleaning" solvent. Although not wishing to be bound by any theory Or a model but generally considered to be a gel-like flake olefin phase and a film forming solvent due to dissolution of the first polyolefin solution from the second polyolefin, the first polyolefin and the second polyolefin) Therefore, separation of the removed film-forming solution for the porous membrane, which lines are formed by the fine fibril network structure and having three-dimensional communicating hole Rules upright configuration. As long as the cleaning solvent can dissolve at least a portion of the first and/or second film forming solvent, it is critical. Suitable cleaning solvents include, for example, one or more volatiles such as saturated hydrocarbons such as pentane, hexane, heptane or others; chlorine such as dichloromethane, carbon tetrachloride or others; ethers such as two or two Decane or others; ketones such as methyl ethyl ketone or others; linear compounds such as trifluoroethane, C6F14, C7F16 or others; it is more difficult to form a ring into the layer. For example, the method comprises water or a medium thereof or a film thereof. The first and the restriction can be made, and the liquid (ie, the medium polymerization agent is extracted and not solved or is not a solvent, and the hydrocarbon ether, the fluorocarbon fluorocarbon-34-200904883 compound, such as C5H3F7 or others; Ethers such as c4f9och3, C4F9OC2H5 or others, and perfluoroethers such as c4f9ocf3, c4f9oc2f5 or others. The method for removing the solvent for forming a film is not critical, and any method which can remove a large amount of solvent can be used, including conventional solvent removal. The multi-layer gel-like sheet may be immersed in a cleaning solvent and/or the sheet is washed with the cleaning solvent to wash the sheet. The amount of the cleaning solvent used is not critical and is usually selected to remove the film formation. Depending on the method of the solvent, for example, the amount of the cleaning solvent used may range from about 300 to about 30,000 parts by mass based on the mass of the condensed sheet. Although the amount of film-forming solvent removed is not particularly critical. However, a higher quality (more pores) film is generally removed from the gelatinous sheet when at least a majority of the first and second film forming solvents are removed. In one embodiment, from the condensation The gel-like sheet removes the film forming solvent (for example, 'by washing') until the amount of the film-forming solvent remaining in the gel-like sheet becomes less than 1% by weight based on the weight of the gel-like sheet. (6) Drying In a specific example of the sheet, the solvent-removed sheet obtained by removing at least a part of the film forming solvent is dried to remove the cleaning solvent. Any method capable of removing the cleaning solvent, including a conventional method such as thermal drying, may be used. Air drying (flowing air) or other. The temperature of the gelatinous sheet during drying (ie, drying temperature) is not critical. For example, the drying temperature may be equal to or lower than the crystal dispersion temperature Tcd. Tcdl is the crystal dispersion of the first polyethylene resin. The temperature Tech and the second polyethylene (when used) are the lower of the crystal dispersion temperature Ted of -35 - 200904883. For example, the drying temperature may be lower than the crystal dispersion temperature Tcd by at least 5 t. The first and second polyethylene The crystal dispersion temperature of the resin can be determined by measuring the temperature characteristics of the dynamic viscoelasticity of the polyethylene resin according to ASTM D 4065. In a specific example At least one of the first or second polyethylene resins has a crystal dispersion temperature in the range of from about 90 ° C to about 10 ° C. Although not critical, drying can be carried out until the amount of residual cleaning solvent is on a dry basis ( That is, it is about 5% by weight or less based on the weight of the dry microporous polyolefin film. In another specific example, drying is performed until the residual cleaning amount on a dry basis is about 3% by weight or less. If the drying is insufficient, the pores of the microporous membrane are generally poorly reduced, so that insufficient drying is recognized. If this phenomenon is observed, a higher drying temperature and/or a longer drying time should be used. For example, by drying or other. The cleaning solvent is removed to form the microporous film. (7) Stretching Before the step of removing the film forming solvent (in other words, before step 5), the sheet may be stretched to obtain a stretched gel-like sheet. It is considered that the presence of the first and second film-forming solvents in the gel-like sheet causes a relatively uniform stretching ratio. It is also generally believed that heating the gelatinous sheet, especially at the beginning of stretching, or at an earlier stage of stretching (i.e., before 5% of stretching has been completed), helps to stretch the gelatinous sheet. Evenness. The choice of stretching method or draw ratio is not particularly critical. For example, any method capable of stretching the gel-like sheet to a predetermined magnification (including any -36-200904883 selective heating) can be used. In a specific example, the stretching can be accomplished by one or more of tenter stretching, drum stretching, or aerated stretching (e.g., in air). While this choice is not critical, the stretching can be performed uniaxially (i.e., in the machine direction or in the cross direction) or in the biaxial direction (either in the machine direction or in the cross direction). In one embodiment, it uses biaxial stretching. In the case of biaxial stretching (also known as biaxial orientation), the stretching can be simultaneous stretching of the two axes, stretching along a plane axis and then along another axis (eg, first in the transverse direction and then in the longitudinal direction). Stretching, or multi-stage stretching (for example, a combination of simultaneous biaxial stretching and sequential stretching). In a specific example, simultaneous biaxial stretching is used. Stretching ratio is not critical. In a specific example using uniaxial stretching, the linear stretching ratio may be, for example, about 2 times or more, or about 3 to about 30 times. In the specific example in which biaxial stretching is used, the linear stretching ratio in any plane direction may be, for example, about 3 times or more. In another embodiment, the area magnification formed by stretching is at least about 9 times, or at least about 16 times, or at least about 25 times. Although not critical, the multilayer microporous polyolefin membrane has a relatively high needle penetration strength when the stretching results in an area magnification of at least about 9 times. When attempting to make the area magnification greater than about 400 times, it is more difficult to operate the stretching apparatus. The temperature of the gelatinous sheet (in other words, the stretching temperature) during stretching is not critical. In a specific example, the temperature of the gelatinous sheet during stretching may be about (Tm + 10 ° C) or lower, or selectively higher than Ted but lower than Tm, wherein the Tm is first concentrated. The lower of the melting point Tm2 of ethylene and its melting point Τπμ and the second polyethylene (if used). Although this parameter is not critical, when the stretching temperature is above about the melting point Tm + 10 °C -37-200904883, at least one of the first or second polyethylene will be in a molten state, which makes it more difficult to orient during stretching. The molecular chain of the polyolefin in the gelatinous sheet. And when the stretching temperature is lower than about Ted, at least one of the first or second polyethylene may be insufficiently softened, thereby making it difficult to stretch the multilayer gel-like sheet without causing breakage or tearing, This will result in a failure to achieve the desired draw ratio. In one embodiment, the stretching temperature is in the range of from about 9 (TC to about 140 ° C, or from about 10 ° C to about 130 ° C. Although not wishing to be bound by any theory or model, it is generally considered Stretching results in separation between the polyethylene layers, resulting in a finer polyethylene phase and a larger amount of fibrils. These fibrils form a three-dimensional network structure (a network of three-dimensionally regular connections). Therefore, using this stretching Higher mechanical strength microporous membranes having larger pore sizes are generally more readily produced. These multilayer microporous membranes are generally considered to be particularly suitable as battery separators. Alternatively, stretching can be in the thickness direction (ie, It is carried out under a temperature gradient in a direction approximately perpendicular to the plane surface of the microporous polyolefin film. In this case, it is easier to manufacture a microporous polyolefin film having improved mechanical strength. The details of the method are described in Japanese patents. 3 347854. (8) Although the hot solvent treatment step is not required, the multilayer gel-like sheet may be treated with a hot solvent between steps (4) and (5). When treated with a hot solvent, it is generally considered This processing For fibrils having a thicker vein-like structure (such as formed by stretching a multi-layered gel-like sheet). This structure is generally considered to make it easier to fabricate multi-layered pores having larger pores with high strength and permeability. -38- 200904883 Membrane. The term "leaf vein" means that the fibrils have thick trunks and web fibers extending from the web. This method is described in detail in WO 2000/20493 ° (9) multilayer micropores. Film Stretching ("Dry Stretching") In one embodiment, the dried microporous film of step (6) can be stretched 'at least uniaxially stretched. The selected stretching method is not critical and can be used Such as the tenter method or other conventional stretching methods. Although not critical, the film can be heated during stretching. Although the choice is not critical, the stretching can be uniaxial or biaxial stretching. The shaft is stretched, but the stretching can be carried out simultaneously in the two axial directions, or the multilayer microporous polyolefin film can be sequentially stretched, for example, first in the longitudinal direction and then in the transverse direction. In a specific example, Use simultaneous stretching. When the sheet is subjected to steps 7) When the stretching is performed, the dried microporous film of the step (9) may be referred to as dry stretching, re-stretching or dry orientation. The temperature of the dried microporous film during stretching ("dry stretching" temperature"

)並非關鍵。一具體實例中，該乾式拉伸溫度約等於熔點 Tm或更低，例如在約結晶分散溫度Ted至約熔點Tm之 範圍。當乾式拉伸溫度高於Tm時，可能更難以製造具有 較高抗壓縮或且具有較均勻透氣特徵之微孔膜，特別是橫 向拉伸該乾燥多層微孔聚烯烴膜時，其橫向更難獲得此等 特徵。當拉伸溫度低於Ted時，可能更難充分軟化第一與 第二聚烯烴，此會導致拉伸時之撕裂，並且缺乏均勻拉伸 。一具體實例中，乾式拉伸溫度範圍爲約90°C至約135°C -39- 200904883 ，或爲約95°C至約130°C。 使用乾式拉伸時，拉伸倍率並非關鍵。例如，該多層 微孔膜之至少一平面方向（例如橫向）的拉伸倍率範圍爲 約1 .1倍至約1 .8倍。如此，在單軸拉伸情況下，縱向（ 例如「機械方向」）或橫向的拉伸倍率範圍可爲約1 . 1倍 至約1. 8倍，視該膜係縱向或橫向拉伸而定。單軸拉伸亦 可沿著介於縱向與橫向之間的平面軸完成。 一具體實例中，使用雙軸拉伸（即，沿著兩平面軸拉 伸），其沿著兩個拉伸軸例如縱向與橫向二者之拉伸倍率 爲約1.1倍至約1.8倍。縱向之拉伸倍率不必與橫向之拉 伸倍率相同。換言之，雙軸拉伸中，可獨立選擇拉伸倍率 。一具體實例中，兩個拉伸方向之乾式拉伸倍率相同。若 需要，可令該膜拉伸至大於1 · 8倍之倍率，特別是於後續 處理（例如熱處理）期間，該膜的拉伸方向鬆弛（或收縮 )而達到乾式定向步驟開始時該膜大小的約1 . 1至約1 . 8 倍。 (1 〇 )熱處理 一具體實例中’可於步驟（6 )之後熱處理該經乾燥 之微孔膜。一般認爲熱處理令該經乾燥之多層微孔膜中的 聚烯烴結晶安定，而形成均勻層狀。一具體實例中，該熱 處理包含熱固及/或退火。使用熱固時，可使用習用方法 諸如拉幅機法及/或滾筒法進行。雖然並非關鍵，但該經 乾燥之微孔膜於熱固期間的溫度（即，「熱單溫度」）可 -40- 200904883 在Ted至約Tm之範圍。一具體實例中，熱固溫度爲約該 多層微孔聚烯烴膜之乾式拉伸溫度的±5 °C ’或約該多層微 孔聚烯烴膜之乾燥拉伸溫度的±3 °C。 退火與熱固的不同之處在於其係未對多層微孔聚烯烴 膜施加負荷之熱處理。退火方法的選擇並非關鍵’並且可 例如藉由使用具有帶式輸送器之加熱室或氣浮式加熱室進 行。或者，該退火可於熱固且拉幅機夾鬆開之後進行。退 火期間該微孔聚烯烴膜之溫度（即，退火溫度）並非關鍵 。一具體實例中，退火溫度可爲約熔點Tm或更低，或在 約60°C至（Tm-10°C )之範圍。一般認爲退火使得更容易 製造具有較高滲透性與強度之微孔膜。 (1 1 )交聯 一具體實例中，可於步驟（6 )之後令該多層微孔聚 烯烴膜交聯（例如，藉由游離輻射射線，諸如α射線、冷 射線、7射線、電子束或其他）。例如，使用照射電子束 進行交聯時，電子束射之量可爲約0.1 Mrad至約100 Mrad，使用之加速電壓爲約100 kV至約300 kV之範圍。 一般認爲交聯溫度使得更容易製造具有較高熔毀溫度之微 孔膜。 (1 2 )親水化處理 一具體實例中，可對該微孔膜進行親水處理（即，令 該微孔聚烯烴膜更具親水性之處理）。親水處理可爲例如 -41 - 200904883 單體接枝處理、表面處理、電暈放電處理或其他。一具體 實例中，於交聯處理之後使用單體接枝處理。 使用表面處理時，可使用非離子界面活性劑、陽離子 界面活性劑、陰離子界面活性劑與兩性界面活性劑之任何 一者，例如單獨或組合使用。一具體實例中，使用非離子 界面活性劑。界面活性劑之選擇並非關鍵。例如，可令該 多層微孔聚烯烴膜浸於界面活性劑與水或低碳醇（諸如甲 醇、乙醇、異丙醇或其他）之溶液中，或例如藉由刮刀塗 佈法塗覆該溶液。 實施例 藉由參考下列實施例將更充分了解本案所述及所請之 聚合物，但並非限制本案所請之範圍。 連續聚合實施例 實施例1 樣本係於迴路漿體試驗廠設施中連續聚合而製得。單 位設計包括原位預聚合設施、兩個串聯之六英吋迴路反應 器，以及粒料處理組。經由注射泵將觸媒固體TOHO THC-135進料至預接觸容器，於該處令彼與二環戊基二甲 氧基矽烷（DCPMS )及三乙基鋁（TEA1 )結合。這三種觸 媒組份之莫耳進料比係示於表1。隨後於6 5 °F進行預聚合 ，將經預聚合之觸媒進料至主反應器。用以製造所有樣本 之反應條件係示於表1。該等樣本之特徵結果係示於表2 -42- 200904883 表1:用於製備UHMW-ΡΡ樣本之聚合條件 前置反應器 後方反應器 觸媒進料 製造 樣本 T P H2進料 T P H2進料 Si/Ti Al/Ti 速率 效率 (F) (PSIG) (莫耳 PPM) (F) (PSIG) (莫耳 PPM) (莫耳比） (莫耳比） (lb/hr) (lb/lb 觸媒） 2-1 158.0 526.7 253.0 158.1 525.4 330.1 25.6 101.0 54.8 41,897 4-1 158.0 526.2 142.4 158.1 525.0 313.7 25.2 102.4 50.5 41,530 4-25 158.0 525.8 102.3 157.9 524.7 221.5 27.0 106.4 50.6 41,390 4-26 158.0 526.4 136.2 158.0 525.1 441.1 26.4 109.8 54.7 44,843 4-28 158.0 525.3 158.1 157.9 523.9 412.5 26.1 111.2 56.5 46,277 5-11 158.0 526.1 100.7 158.1 524.8 156.9 25.6 110.0 58.5 47,399 5-12 158.1 523.6 123.9 158.0 522.2 194.2 23.9 107.1 63.0 48,545 5-13 158.0 521.3 107.1 158.0 520.0 179.6 23.6 104.6 55.7 42,870 8-1 158.0 526.5 7.19 158.0 525.1 7.71 26.0 94.7 45.9 17,971 8-2 158.1 526.5 7.68 158.1 525.2 6.94 28.0 95.0 55.8 21,259 8-3 157.9 526.5 6.64 157.9 525.1 7.43 27.S 99.0 65.1 24,771 8-4 158.0 526.6 7.58 158.0 525.2 6.12 28.4 98.4 69.8 28,587 8-5 158.0 526.4 8.27 158.0 525.1 7.31 29.6 98.2 61.7 27,529 8-6 158.7 526.5 7.50 158.7 525.1 6.58 29.7 98.8 53.1 23,676 9-1 165.0 526.4 7.80 164.9 525.1 6.02 29.3 96.7 57.7 22,095 9-2 165.0 526.5 6.88 165.0 525.2 9.19 29.2 97.6 61.1 25,239 9-3 165.0 526.4 6.50 165.0 525.1 5.79 29.4 95.9 61.3 25,282 9-4 165.0 526.5 6.94 165.2 525.1 7.85 31.6 75.6 51.9 21,399 10-1 165.0 526.5 8.41 165.0 525.2 7.84 60.1 124.2 36.1 20,080 10-2 165.0 526.5 8.30 165.0 525.2 7.39 60.3 113.5 42.3 23,551 10-3 165.0 526.5 7.92 165.0 525.2 6.61 54.5 106.2 56.0 30,563 10-4 165.0 526.4 7.79 165.0 525.2 7_01 54.1 104.9 53.6 28,676 10-6 165.0 526.4 7.13 165.0 525.1 6.93 57.1 112.1 52.1 30,935 10-7 165.0 526.4 6.08 165.0 525.1 9.05 56.3 108.4 43.4 26,109 10-8 165.0 526.5 9.10 165.0 525.2 9.90 47.6 95.1 53.1 28,142 10-9 165.0 526.5 7.54 165.0 525.2 7.47 48.1 96.8 51.5 27,344 10-10 161.5 526.4 7.07 161.5 525.1 6.56 46.6 97.4 54.0 28,753 11-1 158.0 526.4 6.62 158.0 525.0 5.64 29.8 98.5 50.5 25,584 11-2 158.0 526.3 6.62 158.0 525.0 6.80 29.1 97.4 55.4 22,613 11-3 158.0 526.3 6.13 158.0 524.9 7.09 28.8 97.6 64.2 23,488 11-4 158.0 526.3 7.02 158.0 524.9 6.48 30.1 98.6 73.7 25,318 11-5 158.0 526.3 5.90 158.0 525.0 8.31 30.0 98.6 71.5 24,569 11-6 158.0 526.4 6.40 158.0 525.0 6.59 31.1 97.0 74.0 25,509 11-7 158.0 526.3 7.37 158.0 525.0 6.82 32.4 99.0 65.7 22,593 11-8 158.0 526.3 6.16 158.0 524.9 7.27 32.3 98.2 69.7 24,037 -43- 200904883 表2:特徵結果 GPC資料 DSC資料(於1601進行） 樣本 Mn Mw Mz Mw/Mn Mz/Mw To Tm Δί^2η£]熔融 2-1 110.4 166.5 4-1 110.9 166.4 4-25 284,622 1,116,115 2,784,586 3.921 2.495 108.9 167.3 4-26 253,314 1,058,606 2,605,484 4.179 2.461 109.3 167.2 4-28 236,906 1,013,416 2,559,084 4.278 2.525 107.2 167.3 5-11 271,271 1,286,818 3,145,858 4.744 2.445 108 167.4 5-12 278,450 1,260,087 3,044,149 4.525 2.416 103.3 170.5 5-13 282,281 1,221,237 2,954,388 4.326 2.419 108.5 167 8-1 538,453 2,507,248 4,912,427 4.656 1.959 8-2 679,104 2,706,388 5,181,996 3.985 1.915 8-3 493,536 2,371,032 4,811,511 4.804 2.029 113.9 168.5 106.3 8-4 676,084 2,609,119 5,014,015 3.859 1.922 114.0 168.5 106.7 8-5 578,458 2,469,363 4,912,367 4.269 1.989 8-6 548,847 2,295,717 4,596,040 4.183 2.002 9-1 549,515 2,314,742 4,547,995 4.212 1.965 9-2 544,751 2,396,423 4,730,467 4.399 1.974 113.6 169.0 103.8 9-3 560,778 2,524,893 4,947,423 4.502 1.959 113.7 168.6 104.8 9-4 547,492 2,370,769 4,779,957 4.330 2.016 10-1 660,526 2,605,372 4,916,287 3.944 1.887 10-2 499,009 2,337,835 4,748,418 4.685 2.031 10-3 422,567 2,324,090 4,558,326 5.500 1.961 10-6 555,903 2,503,972 4,866,556 4.504 1.944 10-7 573,800 2,606,311 5,137,486 4.542 1.971 10-8 703,540 2,710,085 5,125,726 3.852 1.891 10-9 630,851 2,393,363 4,597,628 3.794 1.921 10-10 567,308 2,545,611 4,986,914 4.487 1.959 11-1 532,880 2,551,912 5,033,611 4.789 1.972 11-2 482,296 2,168,567 4,680,286 4.496 2.158 11-3 498,212 2,274,154 4,902,267 4.565 2.156 11-4 489,874 2,368,001 4,938,035 4.834 2.085 11-5 436,541 2,527,145 5,225,997 5.789 2.068 11-6 511，177 2,171,947 4,661,074 4.249 2.146 11-7 551,146 2,348,289 4,809,928 4.261 2.048 11-8 548,161 2,419,214 4,731,490 4.413 1.956 -44- 200904883 實施例2 藉由乾式摻合100質量份數包含1質量％之UHMW聚 乙烯、49質量％之HD聚乙烯與50質量％之實施例1產物 (樣本8-3)的聚烯烴（PO)組成物與0.5質量份數之二 丁基羥基甲苯作爲抗氧化劑，而製備實施例1之產物（樣 本8-3)與具有2.5M06之分子量的UHMW及具有3.〇xl〇5 之分子量的HD聚乙烯之摻合物。獨立測量顯示出此摻合 物之聚乙烯組成物具有135。(：之熔點以及90°C之結晶分散 溫度。 將3 5質量份數該所得之摻合物裝入強力摻合之雙螺 桿擠出機，該雙螺桿擠出機具有之內徑爲58 mm且L/D爲 42，並經由側進料器將65質量份數之液態石蠟[40cst ( 4 0°C )]供應至該該雙螺桿擠出機。以210°C與200 rpm進 行熔融摻合，以製備聚烯烴溶液。令此聚烯烴溶液形成凝 膠狀薄片。 使用實驗室拉伸機械，以114 °C令該凝膠狀薄片同時 雙軸拉伸，如此縱向（MD )與橫向（TD )二者之拉伸倍 率均爲5倍。令經拉伸之膜固定於2〇Cmx20cm之鋁框架 ，並浸於受控在25°C之二氯甲烷[表面張力：27.3 mN/m (2 5 °C ) ’沸點·· 4 0.0 °C ]，並以1 0 0 r p m振盪清洗3分鐘 。令形成之膜於室溫空氣冷卻，並於固定在鋁框架的同時 以1 25 °C熱固1 〇分鐘，以製造微孔膜。 此實施例之微孔膜的性質係藉由下列方法加以測量。 -45- 200904883 (1 )平均厚度（μιη ) i. 該微孔膜之厚度係藉由接觸式厚度計在30 cm( 平均）之寬度以5 - m m之M D間距而測得’並發現其爲 3 3 μιη 〇 (2 )透氣性（秒/100“/20μιη ): i. 藉由式？2=(?以20) /1\將根據JIS P8117而在 具有T 1之厚度的微孔膜上測得之透氣性P !轉換成厚度爲 2〇 μιη之透氣性P2，並發現其爲23 3秒/100cc/2(^m。 (3 )孔隙度（％ ) i. 此係藉由重量法測量，並發現其爲4 1 %。 (4)針穿刺強度 （ηιΝ/20μιη): i· 最大負荷係當以直徑1mm並具有球面末端表面 (曲率半徑R : 〇.5rnm )之針且速度爲2mm/秒刺該具有T! 之厚度的微孔膜時測得。以式L 2 = ( L 1 X 2 0 ) / T !將所測得 之最大負荷轉換成厚度爲20 μηι之最大負荷L2,並將 彼作爲針穿刺強度。已發現其爲1 893 mN/2〇 μιη。 (5 )停機溫度（°C ) i.使用熱機械分析儀（可得自Seik〇 Instruments Inc. 之 TMA/SS60〇〇) ’ 將 i〇mm ( TD) x3mni ( md)之試樣 以5 C /分鐘之速率從室溫開始加熱，同時在載重2 下 -46- 200904883 以縱向拉該試樣’且將在試樣熔點附近觀察得之樣本長度 的反屈點溫度界疋爲「停機溫度」。已發現其爲133 〇C。 (6 )熔毀溫度（t：): 以具有直徑爲12mm之圓形開口的塊狀夾住5cmx5cm 之微孔膜樣本，並將直徑爲1 〇mm碳化鎢球置於該微孔膜 之圓形開口中。在以5 °C /分鐘之升溫速度加熱的同時，測 量該微孔膜因溶融而破裂之溫度。發現其爲178 °C。 對照實例1 藉由使用甲基環己基二甲氧基矽烷（MC MS)與三乙 基鋁（TEAL )作爲外部電子施體與輔觸媒進行聚合，而 製得具有與實施例2之溶液相同組成與濃度之聚烯烴溶液 ，但丙烯同元聚合物具有8.4 xlO5之分子量，且熔化熱爲 83_9 J/g 。 此對照實例之微孔膜的性質如下。 已發現平均厚度、透氣性、孔隙度、針穿刺強度、停 機溫度與熔毀溫度分別爲30μιη、483 0秒/100cc/20Mm、) is not the key. In a specific example, the dry stretching temperature is approximately equal to the melting point Tm or lower, for example, in a range from about a crystal dispersion temperature Ted to about a melting point Tm. When the dry stretching temperature is higher than Tm, it may be more difficult to manufacture a microporous film having a higher compression resistance or a more uniform gas permeable characteristic, especially when the dried multilayer microporous polyolefin film is transversely stretched, the lateral direction thereof is more difficult Obtain these features. When the stretching temperature is lower than Ted, it may be more difficult to sufficiently soften the first and second polyolefins, which may cause tearing upon stretching, and lack uniform stretching. In one embodiment, the dry stretching temperature ranges from about 90 ° C to about 135 ° C - 39 to 200904883, or from about 95 ° C to about 130 ° C. When using dry stretching, the draw ratio is not critical. For example, the stretching ratio of at least one of the planar directions (e.g., the transverse direction) of the multilayer microporous film ranges from about 1.1 times to about 1.8 times.倍倍左右。 In the case of uniaxial stretching, the longitudinal direction (for example, "mechanical direction") or the transverse stretching ratio may range from about 1.1 times to about 1.8 times, depending on the longitudinal or transverse stretching of the film. . Uniaxial stretching can also be accomplished along a planar axis between the longitudinal and transverse directions. In one embodiment, biaxial stretching (i.e., stretching along two planar axes) is used, which has a draw ratio of about 1.1 times to about 1.8 times along both stretch axes, e.g., both longitudinal and transverse directions. The longitudinal stretching ratio does not have to be the same as the lateral stretching ratio. In other words, in the biaxial stretching, the stretching ratio can be independently selected. In one embodiment, the dry stretching ratios of the two stretching directions are the same. If desired, the film can be stretched to a magnification greater than 1.8 times, particularly during subsequent processing (eg, heat treatment), the film is relaxed (or shrunk) in the direction of stretching to the extent that the film is at the beginning of the dry orientation step. From about 1.1 to about 1.8 times. (1 〇 ) Heat treatment In a specific example, the dried microporous film may be heat treated after the step (6). It is believed that the heat treatment causes the polyolefin in the dried multilayer microporous film to crystallize to form a uniform layer. In one embodiment, the thermal treatment comprises thermosetting and/or annealing. When thermosetting is used, it can be carried out using a conventional method such as a tenter method and/or a roller method. Although not critical, the temperature of the dried microporous film during thermosetting (i.e., "hot single temperature") may range from -40 to 200904883 from Ted to about Tm. In one embodiment, the thermosetting temperature is about ± 5 ° C' of the dry stretching temperature of the multilayer microporous polyolefin film or about ± 3 ° C of the dry stretching temperature of the multilayer microporous polyolefin film. Annealing differs from thermosetting in that it is not subjected to a heat treatment for applying a load to the multilayer microporous polyolefin film. The choice of annealing method is not critical&apos; and can be performed, for example, by using a heating chamber or a gas floating heating chamber having a belt conveyor. Alternatively, the annealing can be performed after the thermoset and the tenter clip are released. The temperature of the microporous polyolefin film (i.e., annealing temperature) during annealing is not critical. In one embodiment, the annealing temperature may be about a melting point Tm or lower, or in the range of about 60 ° C to (Tm - 10 ° C). Annealing is generally considered to make it easier to produce microporous membranes with higher permeability and strength. (1 1 ) Crosslinking In a specific example, the multilayer microporous polyolefin film may be crosslinked after step (6) (for example, by free radiation rays such as alpha rays, cold rays, 7 rays, electron beams or other). For example, when cross-linking is performed using an illuminating electron beam, the amount of electron beam irradiation may be from about 0.1 Mrad to about 100 Mrad, and the accelerating voltage used is in the range of about 100 kV to about 300 kV. It is believed that the crosslinking temperature makes it easier to produce a microporous film having a higher melting temperature. (1 2 ) Hydrophilization treatment In a specific example, the microporous membrane can be subjected to a hydrophilic treatment (i.e., treatment of the microporous polyolefin membrane to be more hydrophilic). The hydrophilic treatment may be, for example, -41 - 200904883 monomer graft treatment, surface treatment, corona discharge treatment or the like. In a specific example, a monomer grafting treatment is used after the crosslinking treatment. When a surface treatment is used, any one of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant may be used, for example, alone or in combination. In one embodiment, a nonionic surfactant is used. The choice of surfactant is not critical. For example, the multilayer microporous polyolefin membrane can be immersed in a solution of a surfactant with water or a lower alcohol such as methanol, ethanol, isopropanol or the like, or the solution can be applied, for example, by knife coating. . EXAMPLES The polymers described and claimed herein will be more fully understood by reference to the following examples, but without limiting the scope of the invention. CONTINUOUS POLYMERIZATION EXAMPLES Example 1 Samples were prepared by continuous polymerization in a loop slurry test facility. The unit design includes an in-situ prepolymerization facility, two tandem six inch loop reactors, and a pellet processing unit. Catalyst solid TOHO THC-135 was fed via a syringe pump to a precontacted vessel where it was combined with dicyclopentyldimethoxydecane (DCPMS) and triethylaluminum (TEA1). The molar feed ratios of the three catalyst components are shown in Table 1. The prepolymerization is then carried out at 65 °F, and the prepolymerized catalyst is fed to the main reactor. The reaction conditions used to make all the samples are shown in Table 1. The characteristic results of these samples are shown in Table 2-42-200904883 Table 1: Polymerization conditions for preparing UHMW-ΡΡ samples. Pre-reactor reactor Reactor feed preparation sample TP H2 feed TP H2 feed Si /Ti Al/Ti Rate Efficiency (F) (PSIG) (Mole PPM) (F) (PSIG) (MoM PPM) (Morbi) (Mohrby) (lb/hr) (lb/lb Catalyst ) 2-1 158.0 526.7 253.0 158.1 525.4 330.1 25.6 101.0 54.8 41,897 4-1 158.0 526.2 142.4 158.1 525.0 313.7 25.2 102.4 50.5 41,530 4-25 158.0 525.8 102.3 157.9 524.7 221.5 27.0 106.4 50.6 41,390 4-26 158.0 526.4 136.2 158.0 525.1 441.1 26.4 109.8 54.7 44,843 4-28 158.0 525.3 158.1 157.9 523.9 412.5 26.1 111.2 56.5 46,277 5-11 158.0 526.1 100.7 158.1 524.8 156.9 25.6 110.0 58.5 47,399 5-12 158.1 523.6 123.9 158.0 522.2 194.2 23.9 107.1 63.0 48,545 5-13 158.0 521.3 107.1 158.0 520.0 179.6 23.6 104.6 55.7 42,870 8-1 158.0 526.5 7.19 158.0 525.1 7.71 26.0 94.7 45.9 17,971 8-2 158.1 526.5 7.68 158.1 525.2 6.94 28.0 95.0 55.8 21,259 8 -3 157.9 526.5 6.64 157.9 525.1 7.43 27.S 99.0 65.1 24,771 8-4 158.0 526.6 7.58 158.0 525.2 6.12 28.4 98.4 69.8 28,587 8-5 158.0 526.4 8.27 158.0 525.1 7.31 29.6 98.2 61.7 27,529 8-6 158.7 526.5 7.50 158.7 525.1 6.58 29.7 98.8 53.1 23,676 9-1 165.0 526.4 7.80 164.9 525.1 6.02 29.3 96.7 57.7 22,095 9-2 165.0 526.5 6.88 165.0 525.2 9.19 29.2 97.6 61.1 25,239 9-3 165.0 526.4 6.50 165.0 525.1 5.79 29.4 95.9 61.3 25,282 9-4 165.0 526.5 6.94 165.2 525.1 7.85 31.6 75.6 51.9 21,399 10-1 165.0 526.5 8.41 165.0 525.2 7.84 60.1 124.2 36.1 20,080 10-2 165.0 526.5 8.30 165.0 525.2 7.39 60.3 113.5 42.3 23,551 10-3 165.0 526.5 7.92 165.0 525.2 6.61 54.5 106.2 56.0 30,563 10-4 165.0 526.4 7.79 165.0 525.2 7_01 54.1 104.9 53.6 28,676 10-6 165.0 526.4 7.13 165.0 525.1 6.93 57.1 112.1 52.1 30,935 10-7 165.0 526.4 6.08 165.0 525.1 9.05 56.3 108.4 43.4 26,109 10-8 165.0 526.5 9.10 165.0 525.2 9.90 47.6 95.1 53.1 28,142 10-9 165.0 526.5 7.54 165.0 525.2 7.47 48.1 96.8 51.5 27,344 10-10 161.5 526.4 7.07 161.5 525.1 6.56 46.6 97.4 54.0 28,753 11-1 158.0 526.4 6.62 158.0 525.0 5.64 29.8 98.5 50.5 25,584 11-2 158.0 526.3 6.62 158.0 525.0 6.80 29.1 97.4 55.4 22,613 11-3 158.0 526.3 6.13 158.0 524.9 7.09 28.8 97.6 64.2 23,488 11-4 158.0 526.3 7.02 158.0 524.9 6.48 30.1 98.6 73.7 25,318 11-5 158.0 526.3 5.90 158.0 525.0 8.31 30.0 98.6 71.5 24,569 11-6 158.0 526.4 6.40 158.0 525.0 6.59 31.1 97.0 74.0 25,509 11-7 158.0 526.3 7.37 158.0 525.0 6.82 32.4 99.0 65.7 22,593 11-8 158.0 526.3 6.16 158.0 524.9 7.27 32.3 98.2 69.7 24,037 -43- 200904883 Table 2: Characteristic results GPC data DSC data (taken at 1601) Sample Mn Mw Mz Mw/Mn Mz/Mw To Tm Δί ^2η£] Melting 2-1 110.4 166.5 4-1 110.9 166.4 4-25 284,622 1,116,115 2,784,586 3.921 2.495 108.9 167.3 4-26 253,314 1,058,606 2,605,484 4.179 2.461 109.3 167.2 4-28 236,906 1,013,416 2,559,084 4.278 2.525 107.2 167.3 5-11 271,271 1,286,818 3,145,858 4.744 2.445 108 167.4 5-12 278,450 1,260,087 3,044,149 4.525 2.416 103.3 170.5 5-13 282,281 1,221,237 2,954,388 4.326 2.419 108.5 167 8-1 538,453 2,507,248 4,912,427 4.656 1.959 8-2 679,104 2,706,388 5,181,996 3.985 1.915 8-3 493,536 2,371,032 4,811,511 4.804 2.029 113.9 168.5 106.3 8-4 676,084 2,609,119 5,014,015 3.859 1.922 114.0 168.5 106.7 8-5 578,458 2,469,363 4,912,367 4.269 1.989 8-6 548,847 2,295,717 4,596,040 4.183 2.002 9-1 549,515 2,314,742 4,547,995 4.212 1.965 9-2 544,751 2,396,423 4,730,467 4.399 1.974 113.6 169.0 103.8 9-3 560,778 2,524,893 4,947,423 4.502 1.959 113.7 168.6 104.8 9-4 547,492 2,370,769 4,779,957 4.330 2.016 10-1 660,526 2,605,372 4,916,287 3.944 1.887 10-2 499,009 2,337,835 4,748,418 4.685 2.031 10-3 422,567 2,324,090 4,558,326 5.500 1.961 10-6 555,903 2,503,972 4,866,556 4.504 1.944 10-7 573,800 2,606,311 5,137,486 4.542 1.971 10-8 703,540 2,710,085 5,125, 726 3.852 1.891 10-9 630,851 2,393,363 4,597,628 3.794 1.921 10-10 567,308 2,545,611 4,986,914 4.487 1.959 11-1 532,880 2,551,912 5,033,611 4.789 1.972 11-2 482,296 2,168,567 4,680,286 4.496 2.158 11-3 498,212 2,274,154 4,902,267 4.565 2.156 11-4 489,874 2,368,001 4,938,035 4.834 2.085 11-5 436,541 2,527,145 5,225,997 5.789 2.068 11-6 511,177 2,171,947 4,661,074 4.249 2.146 11-7 551,146 2,348,289 4,809,928 4.261 2.048 11-8 548,161 2,419,214 4,731,490 4.413 1.956 -44- 200904883 Example 2 by dry blending 100 parts by mass A polyolefin (PO) composition containing 1% by mass of UHMW polyethylene, 49% by mass of HD polyethylene, and 50% by mass of the product of Example 1 (Sample 8-3) and 0.5 parts by mass of dibutylhydroxyl group Toluene was used as an antioxidant, and a blend of the product of Example 1 (Sample 8-3) with UHMW having a molecular weight of 2.5 M06 and HD polyethylene having a molecular weight of 3.〇xl〇5 was prepared. Independent measurements showed that the polyethylene composition of this blend had 135. (: melting point and crystal dispersion temperature of 90 ° C. 35 parts by mass of the obtained blend was charged into a strongly blended twin-screw extruder having an inner diameter of 58 mm And L/D was 42, and 65 parts by mass of liquid paraffin [40 cst (40 ° C)] was supplied to the twin-screw extruder via a side feeder. Melt doping at 210 ° C and 200 rpm. To prepare a polyolefin solution, the polyolefin solution was formed into a gel-like sheet. The gel-like sheet was simultaneously biaxially stretched at 114 ° C using a laboratory stretching machine, such that the machine direction (MD) and the transverse direction ( TD) Both have a draw ratio of 5 times. The stretched film is fixed to an aluminum frame of 2〇Cmx20cm and immersed in methylene chloride controlled at 25°C [surface tension: 27.3 mN/m ( 2 5 °C) 'Boiling point · 4 0.0 °C ', and rinsed at 100 rpm for 3 minutes. Allow the formed film to cool at room temperature and heat at 1.25 °C while fixing to the aluminum frame. The microporous film was fabricated for 1 minute. The properties of the microporous film of this example were measured by the following methods: -45- 200904883 (1) Average thickness (μιη) i. The thickness of the microporous film is measured by a contact thickness meter at a width of 30 cm (average) with an MD spacing of 5 - mm and found to be 3 3 μηη 〇 (2) gas permeability (seconds) /100"/20μιη): i. The gas permeability P! measured on the microporous film having a thickness of T1 according to JIS P8117 is converted into a thickness by the formula 2 = (? with 20) / 1\ The gas permeability P2 of 2〇μηη was found to be 23 3 sec / 100 cc / 2 (^m. (3 ) Porosity (%) i. This was measured by the gravimetric method and found to be 41%. 4) Needle puncture strength (ηιΝ/20μιη): i· The maximum load is a needle having a diameter of 1 mm and having a spherical end surface (curvature radius R: 〇.5rnm) and a speed of 2 mm/sec. The microporous film was measured. The maximum load measured was converted into a maximum load L2 with a thickness of 20 μηι by the formula L 2 = ( L 1 X 2 0 ) / T !, and the same as the needle puncture strength. It is 1 893 mN/2〇μιη. (5) Shutdown temperature (°C) i. Use a thermomechanical analyzer (available from Seik〇 Instruments Inc. TMA/SS60〇〇) ' will i〇mm (TD) Sample of x3mni (md) at 5 C / min Start of heating rate from room temperature while under load 2-46-200904883 recurvation boundary point temperature of the sample piece goods longitudinal pull 'by observation and the melting point of the sample length in the vicinity of the specimen is "shutdown temperature." It has been found to be 133 〇C. (6) Melting temperature (t:): A 5 cm x 5 cm microporous film sample was sandwiched by a block having a circular opening having a diameter of 12 mm, and a tungsten carbide ball having a diameter of 1 mm was placed in the circle of the microporous film. In the shape of the opening. The temperature at which the microporous membrane was broken by melting was measured while heating at a temperature elevation rate of 5 °C /min. It was found to be 178 °C. Comparative Example 1 was prepared by the same procedure as in Example 2 by using methylcyclohexyldimethoxydecane (MC MS) and triethylaluminum (TEAL) as an external electron donor and a secondary catalyst. The composition and concentration of the polyolefin solution, but the propylene homopolymer has a molecular weight of 8.4 x 10, and the heat of fusion is 83_9 J/g. The properties of the microporous membrane of this comparative example are as follows. It has been found that the average thickness, gas permeability, porosity, needle puncture strength, shutdown temperature and meltdown temperature are 30 μm, 483 0 / 100 cc / 20 Mm, respectively.

2 5 % ' 443 7 ιηΝ/2 0μιη、1 3 3 〇C 與 1 74°C 實施例3 -47- 200904883 表1.實驗室UHMW iPP聚合與特徵資料 樣本Π) 觸媒/施體3 活性,g/g/hr Mw，kb Mw/Mn Tm；C △H，J/g 24186-181 C-133/DCPMS 9584 2440 5.88 165.79 112.03 24186-182 C-133/DCPMS 5015 2400 5.55 164.62 108.34 24186-183 C-135/DCPMS 13550 2410 5.15 166.80 112.05 24186-184 C-133/DCPMS 6372 2413 5.28 164.63 111.78 24186-185° C-135/DCPMS 8538 2477 5.00 165.65 108.48 24186-188 C-135/DCPMS 14351 2406 4.64 167.17 111.55 24186-189 C-135/DCPMS 7756 2657 4.54 166.67 111.00 24186-190d C-135/DCPMS 16010 2273 4.53 167.00 108.81 24186-191 C-135/DCPMS 14680 2450 4.41 166.50 109.74 24186-192 C-135/DCPMS 9574 2145 4.11 166.76 108.66 24186-193 C-135/DCPMS 7840 2304 3.45 166.08 111.27 24186-194 C-135/DCPMS 10099 166.10 109.92 24186-195 C-135/DCPMS 6553 166.09 109.59 aDCPMS =二環戊基二甲氧基矽烷 bGPC 係於1 60°C進行 。特性黏度=12.28 dl/g d特性黏度=13.61 dl/g 實施例3證實可使用戚格勒-納塔觸媒與二環戊基二 甲氧基矽烷外部施體製備UHMW高結晶度PP。 丙烯聚合 THC-C-133 與 THC-C-135 係由 Toho Catalyst Company所製造之戚格勒-納塔觸媒。藉由令丙烯通過經 還原的R3-1 1銅觸媒、經脫氫之R3-1 1銅觸媒、經脫氫之 3A分子篩與經脫氫之Selexsorb COS氧化鋁柱而將彼加以 -48- 200904883 純化。在氮流中於l〇〇-120°C清潔一 2L之Zipperclave反 應器1小時，然後將反應器溫度降至室溫。典型地，添加 2-4mL於己烷中之1.0M三乙基鋁溶液、2-12mL於己烷中 之0.1M二環戊基二甲氧基矽烷溶液，以及i 000mL丙烯 。開始攪拌。藉由添加250mL丙烯而將約10-30mg之固 態觸媒於5重量％礦物油中的漿體注入該反應器，並令該 反應器在5分鐘內加熱至60或70 °C。於注入觸媒60分鐘 之後，藉由停止加熱並通風排除揮發性物質而終止聚合。 差不掃描量熱法（DSC) 尖峰熔融溫度（Tm )、尖峰結晶溫度（Tc )與熔化 熱（△ Η )係使用 A S TM D 3 4 1 8 - 0 3作爲參考而測得。差 示掃描量熱（DSC)資料係使用 PerkinElmer儀Pyris 1 DSC型而獲得。將秤重約5.5-6.5mg之樣本密封在鋁樣本 盤中。以150°C/分鐘之速率先將樣本加熱至200°C而記錄 該DSC資料，稱爲第一次熔融（無記錄資料）。於施加 冷卻-加熱循環之前，令該樣本於2 0 0 °C維持1 〇分鐘。以 l〇°C/分鐘之速率將該樣本自200°C冷卻至25°C，稱爲結 晶，然後於25t維持1〇分鐘，並以l〇°C/分鐘之速率加 熱至20 0 °C，稱爲第二次熔融。將結晶與第二次熔融中之 熱變化項目加以記錄。熔融溫度（Tm )係第二次熔融曲線 之尖峰溫度，且結晶溫度（Tc )係結晶尖峰之尖峰溫度。 -49-2 5 % ' 443 7 ιηΝ/2 0μιη, 1 3 3 〇C and 1 74 ° C Example 3 -47- 200904883 Table 1. Laboratory UHMW iPP polymerization and characteristic data samples Π) Catalyst/body 3 activity, g/g/hr Mw,kb Mw/Mn Tm;C △H,J/g 24186-181 C-133/DCPMS 9584 2440 5.88 165.79 112.03 24186-182 C-133/DCPMS 5015 2400 5.55 164.62 108.34 24186-183 C -135/DCPMS 13550 2410 5.15 166.80 112.05 24186-184 C-133/DCPMS 6372 2413 5.28 164.63 111.78 24186-185° C-135/DCPMS 8538 2477 5.00 165.65 108.48 24186-188 C-135/DCPMS 14351 2406 4.64 167.17 111.55 24186 -189 C-135/DCPMS 7756 2657 4.54 166.67 111.00 24186-190d C-135/DCPMS 16010 2273 4.53 167.00 108.81 24186-191 C-135/DCPMS 14680 2450 4.41 166.50 109.74 24186-192 C-135/DCPMS 9574 2145 4.11 166.76 108.66 24186-193 C-135/DCPMS 7840 2304 3.45 166.08 111.27 24186-194 C-135/DCPMS 10099 166.10 109.92 24186-195 C-135/DCPMS 6553 166.09 109.59 aDCPMS = Dicyclopentyldimethoxydecane bGPC 1 at 60 ° C. Intrinsic viscosity = 12.28 dl/g d intrinsic viscosity = 13.61 dl/g Example 3 demonstrates that UHMW high crystallinity PP can be prepared using an external donor of a Sigma-Natta catalyst and a dicyclopentyl dimethyl decane. Propylene Polymerization THC-C-133 and THC-C-135 are 戚Gle-Natta catalysts manufactured by Toho Catalyst Company. By propylene passing the reduced R3-1 1 copper catalyst, dehydrogenated R3-1 1 copper catalyst, dehydrogenated 3A molecular sieve and dehydrogenated Selexsorb COS alumina column - 200904883 Purification. A 2 L Zipperclave reactor was cleaned at 1 Torr to 120 ° C for 1 hour in a nitrogen stream, and then the reactor temperature was lowered to room temperature. Typically, 2-4 mL of a 1.0 M solution of triethylaluminum in hexane, 2-12 mL of a 0.1 M solution of dicyclopentyldimethoxydecane in hexane, and i 000 mL of propylene are added. Start stirring. A slurry of about 10-30 mg of solid catalyst in 5 wt% mineral oil was injected into the reactor by adding 250 mL of propylene, and the reactor was heated to 60 or 70 °C in 5 minutes. After 60 minutes of injection of the catalyst, the polymerization was terminated by stopping the heating and venting to remove volatiles. Differential Scanning Calorimetry (DSC) The peak melting temperature (Tm), peak crystallization temperature (Tc), and heat of fusion (Δ Η ) were measured using A S TM D 3 4 1 8 - 0 3 as a reference. Differential Scanning Calorimetry (DSC) data was obtained using the PerkinElmer instrument Pyris 1 DSC type. A sample weighing approximately 5.5-6.5 mg was sealed in an aluminum sample pan. The DSC data was recorded by first heating the sample to 200 ° C at a rate of 150 ° C / minute, called the first melt (no recorded data). The sample was maintained at 200 °C for 1 〇 minutes before applying the cooling-heating cycle. Cooling the sample from 200 ° C to 25 ° C at a rate of 10 ° C / min, called crystallization, then maintaining at 25 t for 1 〇 minutes, and heating to 20 ° C at a rate of 10 ° C / min It is called the second melt. The crystallization and thermal change items in the second melt were recorded. The melting temperature (Tm) is the peak temperature of the second melting curve, and the crystallization temperature (Tc) is the peak temperature of the crystal peak. -49-

Claims (1)

200904883 十、申請專利範圍 1. 一種聚合物組成物，其包含多於90莫耳％之丙烯 單體，該組成物之特性黏度大於10 dl/g，熔化熱大於108 J/g，熔點爲165°C或更高，分子量大於1.5xl〇6，分子量 分布爲2.5至7，230°C之熔融流速低於0.01 dg/分鐘，可 萃取物含量以聚合物組成物的重量計爲0.5重量％或更低 ，且每10,000個碳原子低於50的立體瑕疵。 2 ·如申請專利範圍第1項之聚合物組成物，其具有 mmmm五元體（pentad )部分係爲多於 96莫耳％mmmm 五元體。 3-如申請專利範圍第1或2項之聚合物組成物，其 包含多於99.99莫耳％之丙烯單體。 4.如申請專利範圍第1或2項之聚合物組成物，其 分子量大於1.75xl06。 5 ·如申請專利範圍第1或2項之聚合物組成物，其 特性黏度大於1 1 dl/g，熔化熱大於1 10 J/g，熔點爲166 °C或更高，分子量大於1.5xl06，分子量分布爲2.5至7, 23 0 °C之熔融流速低於0.01 dg/分鐘，且每1 0,000個碳原 子低於40的立體瑕疵。 6. 如申請專利範圍第1或2項之聚合物組成物，其 包含多於95莫耳％之丙烯單體。 7. 如申請專利範圍第5項之聚合物組成物，其包含 多於99.99莫耳％之丙烯單體。 8-如申請專利範圍第5項之聚合物組成物，其分子 -50- 200904883 量大於2.0 χ 1 0 6。 9 如申請專利範圍第1或2項之聚合物組成物，其 進一步含有第二聚烯烴。 10.—種組成物，其包含聚乙烯與一種含有多於90 莫耳％丙烯單體之丙烯聚合物組成物，該丙烯聚合物組成 物具有特性黏度大於10 dl/g，熔化熱大於108 J/g，熔點 爲165°C或更高，分子量大於1.5X106，分子量分布爲2.5 至7，230 °C之熔融流速低於0.2 dg/分鐘，且每10,000個 碳原子低於50的立體瑕疵。 11 ·如申請專利範圍第1 〇項之組成物，其中聚乙烯 包含分子量爲5x1 05或更高之第一聚乙烯、分子量爲lx 1〇4或更高且低於5x1 05之第二聚乙烯，或包含第一與第 二聚乙烯兩者。 12. 如申請專利範圍第1 0或1 1項之組成物，其中第 一聚乙烯包含超高分子量聚乙烯，而第二聚乙烯包含高密 度聚乙烯、中密度聚乙烯、支鏈低密度聚乙烯以及直鏈低 密度聚乙烯之其中至少一者。 13. 如申請專利範圍第1 2項之組成物，其中超高分 子量聚乙烯係乙烯同元聚合物或含少量乙烯以外之α 烯 烴的乙烯/ α -烯烴共聚物。 1 4 ·如申請專利範圍第1 〇或1 1項之組成物，其中丙 烯聚合物組成物具有特性黏度大於1 1 dl/g ,熔化熱大於 110 J/g，熔點爲166°C或更高，分子量大於ι.5χι〇6，分 子量分布爲2.5至7’ 230 °c之熔融流速低於〇.〇1 dg/分鐘 -51 - 200904883 ’可萃取物含量以丙烯聚合物組成物的重量計爲0.5重量 %或更低，且每1 0,000個碳原子低於40的立體瑕疵。 1 5 . —種微孔膜，其包含申請專利範圍第1 〇或1 1項 之組成物。 16.—種電池組，其包含陽極、陰極、電解質與申請 專利範圍第1 5項之微孔膜，其中該微孔膜至少位於該陽 極與陰極之間。 1 7 · —種製造微孔膜之方法，其包含以下步驟： (1 ) 組合稀釋劑或溶劑與第一聚烯烴組成物，以 製備第一聚烯烴溶液，該第一聚烯烴組成物包含多於90 莫耳％之丙烯單體，而且具有下列一或更多者 (a) 特性黏度大於1 〇 dl/g， (b) 熔化熱大於1〇8 J/g，熔點爲165°C或更高， (c) 分子量大於1·5χ106， (d) 分子量分布爲2.5至7， (e) 23 0°C之熔融流速低於〇.〇1 dg/分鐘， (f) 可萃取物含量以聚烯烴組成物的重量計爲0.5重量 %或更低， (g) 內消旋五元體（meso pentad)部分爲多於96莫耳 %mmmm五元體，且 (h) 每1 〇,〇〇〇個碳原子低於50的立體瑕疵； (2 ) 選擇性地，當欲得多層膜時，組合第二聚烯 烴組成物和第二膜形成溶劑以製備第二聚烯烴溶液， (3 ) 經由至少一個衝模而擠出第一聚烯烴溶液， -52- 200904883 以形成擠出物， (4 ) 選擇性地將該擠出物冷卻，以形成經冷卻白勺 擠出物， (5) 從該經冷卻的擠出物或擠出物去除至少一# 分的膜形成溶劑，以形成經去除溶劑之薄片，以及 (6) 藉由例如乾燥而從該薄片去除任何揮發性物 質，以形成微孔膜。 1 8.如申請專利範圍第1 7項之方法，進一步包含（7 )於步驟（6 )之後拉伸該微孔膜，（8 )於步驟（4 )與 (5 )之間使微孔膜接觸熱溶劑，而且於步驟（6 )之後進 行一或更多次之（9 )拉伸微孔膜，以及（1 0 )使用游離 輻射使微孔膜交聯之步驟。 19.如申請專利範圍第17項之方法，其進一步包含 (2 )組合第二聚烯烴組成物與第二膜形成溶劑以製備第 二聚稀烴溶液’並經由至少一個衝模而擠出第二聚烯烴溶 液’以形成多層擠出物。 2 〇 ·如申請專利範圍第1 7或丨9項之方法，其進一步包 含（4 )於步驟（5 )之前使擠出物冷卻，以形成經冷卻的 擠出物。 -53- 200904883 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無 八 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200904883 X. Patent application scope 1. A polymer composition comprising more than 90 mol% of propylene monomer, the composition having an intrinsic viscosity of more than 10 dl/g, a heat of fusion of more than 108 J/g, and a melting point of 165 °C or higher, molecular weight greater than 1.5xl〇6, molecular weight distribution of 2.5 to 7, 230 ° C melt flow rate of less than 0.01 dg / min, extractables content of 0.5% by weight of the polymer composition or Lower, and less than 50 stereoscopic enthalpy per 10,000 carbon atoms. 2. The polymer composition of claim 1, which has a mmmm pentad portion of more than 96 mol% mmmm pentad. 3- A polymer composition according to claim 1 or 2, which contains more than 99.99 mol% of propylene monomer. 4. The polymer composition of claim 1 or 2, which has a molecular weight of more than 1.75 x 106. 5 · The polymer composition of claim 1 or 2 has an intrinsic viscosity greater than 11 dl/g, a heat of fusion greater than 1 10 J/g, a melting point of 166 ° C or higher, and a molecular weight greater than 1.5 x 106. The molecular weight distribution is 2.5 to 7, and the melt flow rate is less than 0.01 dg/min, and the stereoscopic enthalpy is less than 40 per 10,000 carbon atoms. 6. The polymer composition of claim 1 or 2, which comprises more than 95 mole % of propylene monomer. 7. The polymer composition of claim 5, which comprises more than 99.99 mole % of propylene monomer. 8- The polymer composition of claim 5, the molecular weight of -50-200904883 is greater than 2.0 χ 1 0 6 . 9 The polymer composition of claim 1 or 2, which further comprises a second polyolefin. 10. A composition comprising polyethylene and a propylene polymer composition comprising more than 90 mole % propylene monomer having an intrinsic viscosity greater than 10 dl/g and a heat of fusion greater than 108 J /g, a melting point of 165 ° C or higher, a molecular weight of more than 1.5 X 106, a molecular weight distribution of 2.5 to 7,230 ° C, a melt flow rate of less than 0.2 dg / min, and a stereoscopic enthalpy of less than 50 per 10,000 carbon atoms. 11. The composition of claim 1, wherein the polyethylene comprises a first polyethylene having a molecular weight of 5 x 105 or higher, a second polyethylene having a molecular weight of 1 x 1 4 or higher and less than 5 x 105. Or contain both the first and second polyethylene. 12. The composition of claim 10 or 11 wherein the first polyethylene comprises ultra high molecular weight polyethylene and the second polyethylene comprises high density polyethylene, medium density polyethylene, branched low density poly At least one of ethylene and linear low density polyethylene. 13. The composition of claim 12, wherein the ultrahigh molecular weight polyethylene is an ethylene homopolymer or an ethylene/α-olefin copolymer containing a small amount of an alpha olefin other than ethylene. 1 4 · The composition of claim 1 or 1 in which the propylene polymer composition has an intrinsic viscosity greater than 11 dl/g, a heat of fusion greater than 110 J/g, a melting point of 166 ° C or higher The molecular weight is greater than ι.5χι〇6, and the molecular weight distribution is 2.5 to 7' 230 °c. The melt flow rate is less than 〇.〇1 dg/min -51 - 200904883 'The extractables content is based on the weight of the propylene polymer composition. 0.5% by weight or less, and a stereoscopic enthalpy of less than 40 per 10,000 carbon atoms. A microporous film comprising the composition of claim 1 or item 1 of the patent application. 16. A battery pack comprising an anode, a cathode, an electrolyte and a microporous membrane of the fifteenth aspect of the patent application, wherein the microporous membrane is located at least between the anode and the cathode. A method for producing a microporous film comprising the steps of: (1) combining a diluent or a solvent with a first polyolefin composition to prepare a first polyolefin solution, the first polyolefin composition comprising a plurality of At 90 mol% of propylene monomer, and having one or more of the following (a) an intrinsic viscosity greater than 1 〇 dl/g, (b) a heat of fusion greater than 1 〇 8 J/g, a melting point of 165 ° C or more High, (c) molecular weight greater than 1.5 χ 106, (d) molecular weight distribution 2.5 to 7, (e) 23 0 ° C melt flow rate is less than 〇 〇 1 dg / min, (f) extractables content to The weight of the olefin composition is 0.5% by weight or less, (g) the meso pentad portion is more than 96 mol% mmmm pentad, and (h) every 1 〇, 〇〇 a stereoscopic enthalpy having a carbon atom of less than 50; (2) selectively, when a multi-layer film is desired, combining the second polyolefin composition and the second film to form a solvent to prepare a second polyolefin solution, (3) via Extrusion of the first polyolefin solution by at least one die, -52-200904883 to form an extrudate, (4) selectively cooling the extrudate to form Cooling the extrudate, (5) removing at least one of the film forming solvent from the cooled extrudate or extrudate to form a solvent-removed flake, and (6) by, for example, drying The flakes remove any volatile material to form a microporous membrane. 1 8. The method of claim 17, further comprising (7) stretching the microporous membrane after step (6), and (8) forming a microporous membrane between steps (4) and (5) The hot solvent is contacted, and one or more (9) stretched microporous membranes are carried out after step (6), and (10) a step of crosslinking the microporous membrane using free radiation. 19. The method of claim 17, further comprising (2) combining the second polyolefin composition with the second film forming solvent to prepare the second polysulfide solution 'and extruding the second via at least one die Polyolefin solution 'to form a multilayer extrudate. 2 〇 The method of claim 17 or claim 9, further comprising (4) cooling the extrudate prior to step (5) to form a cooled extrudate. -53- 200904883 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: If there is no eight cases, if there is a chemical formula, please reveal the characteristics that can best show the invention. Chemical formula: none
TW097102024A 2007-01-19 2008-01-18 Polymeric material and its manufacture and use TW200904883A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88124707P 2007-01-19 2007-01-19

Publications (1)

Publication Number Publication Date
TW200904883A true TW200904883A (en) 2009-02-01

Family

ID=37963782

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097102024A TW200904883A (en) 2007-01-19 2008-01-18 Polymeric material and its manufacture and use

Country Status (7)

Country Link
EP (1) EP2104711A1 (en)
JP (1) JP2010516842A (en)
KR (1) KR101126916B1 (en)
CN (1) CN101641406B (en)
CA (1) CA2675424C (en)
TW (1) TW200904883A (en)
WO (1) WO2008140835A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101630473B1 (en) * 2009-01-07 2016-06-14 가부시키가이샤 프라임 폴리머 Polypropylene resin composition for microporous film formation
US9449761B2 (en) * 2009-03-17 2016-09-20 Prime Polymer Co., Ltd. Polypropylene for film capacitor, polypropylene sheet for film capacitor, method for producing the same, and uses of the same
JP5722305B2 (en) 2009-03-30 2015-05-20 東レバッテリーセパレータフィルム株式会社 Microporous membrane, battery separator film, battery and method for producing microporous membrane
CN102414015A (en) 2009-04-23 2012-04-11 东丽东燃机能膜合同会社 Thermoplastic film, method of making the film and use of the film as battery separator
US20120052362A1 (en) 2009-04-23 2012-03-01 Toray Tonen Specialty Separator Godo Kaisha Thermoplastic film, methods for making such film, and the use of such film as battery separator film
US8951677B2 (en) 2009-06-19 2015-02-10 Toray Battery Separator Film Co., Ltd. Microporous membranes, methods for making such membranes, and the use of such membranes as battery separator film
US8338020B2 (en) 2009-06-19 2012-12-25 Toray Battery Separator Film Co., Ltd. Multi-layer microporous film
CN102725054A (en) 2009-12-18 2012-10-10 东丽电池隔膜合同会社 Microporous membranes, methods for making same and their use as battery separator films
WO2011086823A1 (en) 2010-01-13 2011-07-21 Toray Tonen Specialty Separator Godo Kaisha Microporous membranes and methods for producing and using such membranes
US20110223485A1 (en) 2010-03-15 2011-09-15 Toray Tonen Specialty Separator Godo Kaisha Microporous membranes, methods for making these membranes, and the use of these membranes as battery separator films
CN103038277B (en) 2010-08-12 2014-07-23 东丽电池隔膜株式会社 Microporous membrane, method for producing the membrane, and method for using the membrane
CN102148346B (en) * 2011-03-11 2013-04-24 河南义腾新能源科技有限公司 Polyolefin microporous diaphragm and preparation method thereof
CN109810398A (en) * 2017-11-21 2019-05-28 中国石油天然气股份有限公司 A kind of ultra-high molecular weight isotactic polypropylene resin composition and preparation method thereof
CN109876362A (en) * 2019-02-22 2019-06-14 滁州市超顺装备科技有限公司 A kind of processing method of crosslinked foaming gymnastics pad
CN112724509B (en) * 2020-12-18 2022-08-09 金发科技股份有限公司 Polypropylene composite material and preparation method and application thereof
KR102415349B1 (en) * 2021-11-18 2022-07-01 대한유화 주식회사 Method for producing ultra-high molecular weight polypropylene
CN117586579B (en) * 2023-11-29 2025-02-25 金发科技股份有限公司 A high temperature creep resistant polypropylene composition and its preparation method and application

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2691023B2 (en) * 1989-03-20 1997-12-17 株式会社トクヤマ Ultra high molecular weight polypropylene and method for producing the same
US5430119A (en) * 1991-06-11 1995-07-04 Mitsui Petrochemical Industries, Ltd. Stretched molded article of ultra-high-molecular weight polypropylene and process for the preparation of the same
JP3070694B2 (en) * 1991-06-11 2000-07-31 三井化学株式会社 Ultra-high molecular weight stretched polypropylene article and method for producing the same
JPH06234811A (en) * 1993-02-10 1994-08-23 Mitsui Petrochem Ind Ltd Method for producing ultra high molecular weight polyolefin
US6214949B1 (en) * 1993-12-29 2001-04-10 Fina Technology, Inc. Polymerization of polyolefins having low melt flow and high molecular weight
JP4024295B2 (en) * 1994-04-11 2007-12-19 三井化学株式会社 Propylene polymer composition production method and propylene polymer composition
US5948557A (en) * 1996-10-18 1999-09-07 Ppg Industries, Inc. Very thin microporous material
US6346350B1 (en) * 1999-04-20 2002-02-12 Celgard Inc. Structurally stable fusible battery separators and method of making same
JP2001072792A (en) * 1999-09-06 2001-03-21 Tonen Chem Corp Microporous polyolefin film and its production
JP2003519723A (en) * 2000-01-10 2003-06-24 エルジー・ケミカル・カンパニー・リミテッド Highly crystalline polypropylene microporous film, multi-component microporous film, and method for producing the same
WO2006025540A1 (en) * 2004-08-30 2006-03-09 Mitsui Chemicals, Inc. Process for producing propylene polymer

Also Published As

Publication number Publication date
KR20090116745A (en) 2009-11-11
WO2008140835A8 (en) 2009-08-20
CN101641406B (en) 2012-12-26
WO2008140835A1 (en) 2008-11-20
CN101641406A (en) 2010-02-03
EP2104711A1 (en) 2009-09-30
KR101126916B1 (en) 2012-03-21
JP2010516842A (en) 2010-05-20
CA2675424C (en) 2012-04-03
CA2675424A1 (en) 2008-11-20

Similar Documents

Publication Publication Date Title
TW200904883A (en) Polymeric material and its manufacture and use
US8008417B2 (en) Polymeric material and its manufacture and use
JP5680072B2 (en) Microporous membranes, methods for making these membranes, and use of these membranes as battery separator films
CN102196900B (en) Multi-layer microporous membranes and methods for making and using such membranes
CN101291794B (en) Process for producing multilayered microporous polyolefin film
CN102355940B (en) Microporous membranes and methods for making and using such membranes
CN103328552B (en) Microporous membrane, method for producing same, and battery separator using same
TWI399280B (en) Process for polyolefine microporous film
JP2002284918A (en) Polyolefin microporous membrane, its production method and use
CN101223216A (en) Microporous high density polyethylene film and method for making same
JP4752000B2 (en) Polyolefin microporous membrane and method for producing the same
EP1873194B1 (en) Method for producing polyolefin microporous film and microporous film
US20120208090A1 (en) Microporous membranes, methods for making such membranes, and the use of such membranes
JP6996383B2 (en) Method for Producing Polyolefin Microporous Membrane
JP2011228056A (en) Microporous membrane and cell separator including the same
JP2013199597A (en) Polyethylene microporous membrane
JP2024136962A (en) Microporous membrane and method for producing the same
TW200921969A (en) Multi-layer, microporous membrane, battery separator and battery