TWI510538B

TWI510538B - Propylene polymers

Info

Publication number: TWI510538B
Application number: TW102143781A
Authority: TW
Inventors: Jeanne M Macdonald; Antonios Doufas; Jerome Sarrazin; William Michael Ferry; Charles J Ruff; Rahul R Kulkarni; Derek W Thurman; Cynthia A Mitchell
Original assignee: Exxonmobil Chem Patents Inc
Priority date: 2012-12-03
Filing date: 2013-11-29
Publication date: 2015-12-01
Also published as: TW201434911A

Description

丙烯聚合物Propylene polymer

相關申請案之交互參照Cross-references to related applications

本申請案主張2013年12月3日申請的U.S.S.N.61/732,451之優先權。This application claims priority from U.S.S.N. 61/732,451, filed on December 3, 2013.

本發明關於可用於擠出應用(諸如模製零件、薄膜、纖維和織物)的具有流變、結晶和立構規整性性質之極佳組合的丙烯聚合物。The present invention relates to propylene polymers having excellent combinations of rheological, crystalline and stereoregular properties that can be used in extrusion applications such as molded parts, films, fibers and fabrics.

聚丙烯傳統上用於生產廣泛的物件(諸如，例如拋棄式衛生用品包括尿布、衛生棉、訓練褲、成人失禁用品、住院服、嬰兒濕巾、濕紙巾、清潔布、等等)之纖維和紡黏非織物。一般聚丙烯非織造織物可模仿梭織物的外觀、質地和強度。與其他材料的組合，彼等提供具有不同性質的產物之範圍，且也單獨使用或作為服裝、家居用品、醫療保健、工程、工業和消費商品的組分。傳統上，存在極佳可紡性(例如，穩定製造而沒有約0.7至2丹尼(尤其是1至1.5丹尼)之細纖維的斷裂)的以丙烯為主之材料(諸如，聚丙烯)遭受不良纖維及/或織物性質(例如，低抗拉強度/韌度)。相反地，呈現可接受的纖維/織物性質(諸如，良好抗拉強度)之聚丙烯組成物具有與紡絲線中纖維斷裂和滴落有關之不良加工性，特別是當製造細纖維(例如，<20微米或相當於<2丹尼)時。因此，一般感興趣於對聚丙烯非織物的縱向(MD)和橫向(TD，也稱為交叉方向，CD)二者賦予優異拉伸強度，同時呈現優異加工性和可紡性，尤其是對於需要改良機械強度的應用諸如拋棄式衛生用品。Polypropylene has traditionally been used to produce a wide range of articles such as, for example, disposable sanitary articles including diapers, sanitary napkins, training pants, adult incontinence products, hospital suits, baby wipes, wet wipes, cleaning cloths, etc. Spunbonded non-woven fabric. Generally, polypropylene nonwoven fabrics mimic the appearance, texture and strength of woven fabrics. In combination with other materials, they provide a range of products having different properties and are also used alone or as components of apparel, household goods, healthcare, engineering, industrial, and consumer goods. Traditionally, there is excellent spinnability (for example, stable manufacturing without about 0.7 to 2 Danny (especially A propylene-based material (such as polypropylene) which is a fracture of fine fibers of 1 to 1.5 denier) suffers from poor fiber and/or fabric properties (e.g., low tensile strength/toughness). Conversely, polypropylene compositions that exhibit acceptable fiber/fabric properties, such as good tensile strength, have poor processability associated with fiber breakage and dripping in the spun yarn, particularly when making fine fibers (eg, <20 microns or equivalent to <2 Danny). Therefore, it is generally of interest to impart excellent tensile strength to both the machine direction (MD) and the cross direction (TD, also referred to as the cross direction, CD) of the polypropylene nonwoven fabric, while exhibiting excellent processability and spinnability, especially for Applications requiring improved mechanical strength such as disposable sanitary articles.

同樣地，一般，於低織物基重(例如，<15克/米² )、高線速度(例如，>600米/分鐘)和高通量率，習知聚丙烯樹脂不提供所要的織物強度性質。因此，需要開發一種以丙烯為主之樹脂，其於低織物基重和高線速度呈現高織物強度。此允許織物轉換器減薄(downgauge)紡黏方法，利用更少聚丙烯樹脂(較低基重織物)而不犧牲織物的機械性能。當用於以高線速度(諸如9000米/分鐘或更大)製備低基重(小於15克/米² )紡黏織物時，一般聚丙烯樹脂當以三束紡黏結構運行時，往往於橫(交叉)向顯示約1N/5公分/gsm或更小(其中gsm為克/米² )之比抗拉強度(抗拉強度(每5公分織物寬度之N)除以織物基重)。Likewise, in general, low fabric basis weight (e.g., <15 g / m ^2), high line speeds (e.g.,> 600 m / min) and high throughput rates, conventional fabric strength properties of a polypropylene resin does not provide desired. Therefore, there is a need to develop a propylene-based resin which exhibits high fabric strength at low fabric basis weight and high line speed. This allows the fabric converter to downgauge the spunbond process, using less polypropylene resin (lower basis weight fabric) without sacrificing the mechanical properties of the fabric. When used to prepare low basis weight (less than 15 g/ ^m2 ) spunbond fabric at high line speeds (such as 9000 m/min or more), polypropylene resins are generally used when operating in a three-spun spunbond structure. The cross (cross) direction shows a specific tensile strength (tensile strength (N per 5 cm fabric width) divided by the basis weight of the fabric) of about 1 N/5 cm/gsm or less (where gsm is gram/ ^m2 ).

其他所關注的參考資料包括：US 7,105,603；US 6,583,076；US 5,723,217；US 5,726,103；US 2010/233927；US 2011/059668；US 2011/081817；US 2012/0116338、US 2010/0233928；US 2008/0182940；US 2008/0172840；US 2009/0022956；WO 2010/087921；WO 2006/044083；WO 2006/118794；WO 2007/024447；WO 2005/111282；WO 2001/94462；JP2007-023398A(JAPAN POLYCHEM CORP、February 1,2007)；及80(8)JOURNAL OF APPLIED POLYMER SCIENCE,1243-1252(2001)。Other references of interest include: US 7,105,603; US 6,583,076; US 5,723,217; US 5,726,103; US 2010/233927; US 2011/059668; US 2011/081817; US 2012/0116338, US 2010/0233928; US 2008/0182940; US 2008/0172840; US 2009/0022956; WO 2010/087921; WO 2006/044083; 2006/118794; WO 2007/024447; WO 2005/111282; WO 2001/94462; JP2007-023398A (JAPAN POLYCHEM CORP, February 1, 2007); and 80 (8) JOURNAL OF APPLIED POLYMER SCIENCE, 1243-1252 (2001) .

本發明關於可用於擠出應用(諸如模製零件、薄膜、纖維和織物)的具有流變、結晶和立構規整性性質之極佳組合的丙烯聚合物組成物。具體而言，本發明關於包含至少50莫耳%丙烯之丙烯聚合物，該聚合物具有：a)10dg/分鐘至21.5dg/分鐘之熔體流動速度(MFR，ASTM 1238，230℃，2.16公斤)；b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)；c)至少131℃之在流動下的結晶之起始溫度T_c,rheol (如以SAOS流變學測定，如下所述之1℃/分鐘，其中該聚合物具有0重量%成核劑存在)；及d)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)。The present invention relates to propylene polymer compositions having excellent combinations of rheological, crystalline, and stereoregular properties that can be used in extrusion applications such as molded parts, films, fibers, and fabrics. In particular, the invention relates to a propylene polymer comprising at least 50 moles of propylene having a: a) melt flow rate of 10 dg/min to 21.5 dg/min (MFR, ASTM 1238, 230 ° C, 2.16 kg) b) the dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 1.5 to 28 (defined by equation (8) below); c) the crystallization under flow at least 131 ° C Starting temperature T _c,rheol (as determined by SAOS rheology, 1 ° C/min as described below, wherein the polymer has 0% by weight of nucleating agent present); and d) at least 97 or higher to ¹³ The average meso run length determined by C NMR.

本文中也揭示許多定義本發明組成物之流變、結晶、和立構規整性特性之其他組合。A number of other combinations defining the rheological, crystalline, and stereoregular properties of the compositions of the present invention are also disclosed herein.

本發明之組成物可為一種反應器級丙烯聚合物或受控流變性(減黏)丙烯聚合物。在減黏丙烯聚合物的情況下，本發明也關於一種製造上述丙烯聚合物之方法，其包含在足以獲得具有MFR之10dg/分鐘或更大(較佳從10至25dg/分鐘，較佳從14至19dg/分鐘)的丙烯聚合物條件下使具有0.1至8dg/分鐘(較佳0.5至6dg/分鐘，較佳0.8至3dg/分鐘)之MFR的丙烯聚合物與減黏劑(諸如過氧化物)接觸，如本文進一步所述。The composition of the present invention may be a reactor grade propylene polymer or a controlled rheological (debonding) propylene polymer. In the case of a reduced-viscosity propylene polymer, the present invention also relates to a process for producing the above propylene polymer which is contained in an amount sufficient to obtain 10 dg/min or more with MFR (preferably from 10 to 25 dg/min, preferably from 14 to 19 dg/min) of a propylene polymer having a MFR of 0.1 to 8 dg/min (preferably 0.5 to 6 dg/min, preferably 0.8 to 3 dg/min) and a viscosity reducing agent (such as peroxidation) under propylene polymer conditions Contact) as further described herein.

本發明也關於可用於製備纖維、織物、非織物、薄膜、模製物件、和其他物件之丙烯聚合物組成物。本發明之組成物有利於導致於低織物基重(例如，小於15gsm)和高織物生產線速度(例如，大於600米/分鐘)之高織物強度(於MD和CD方向二者)以及極佳加工性/可紡性的理想組合之非織物紡黏應用。本發明之組成物也有利於製備呈現高撓曲模數、高降伏抗拉強度和高熱變形溫度的模製零件。The invention also relates to propylene polymer compositions useful in the preparation of fibers, fabrics, nonwovens, films, molded articles, and other articles. The compositions of the present invention are advantageous for high fabric strength (both MD and CD directions) and excellent processing resulting in low fabric basis weight (e.g., less than 15 gsm) and high fabric line speeds (e.g., greater than 600 meters per minute). Non-woven spunbond applications for the ideal combination of properties/spinability. The compositions of the present invention are also advantageous for the preparation of molded parts that exhibit high flexural modulus, high drop tensile strength, and high heat distortion temperature.

詳細說明Detailed description

本發明人已驚訝地發現特徵在於導致可紡性和纖維/織物拉伸性質之優異組合的特定熔體流變、結晶、和立構規整性分子參數之獨特組合的以丙烯為主之組成物。此外，根據旋轉流變儀監測，本發明之組成物理想上具有不同流變(包括熔體彈性)和剪切稀化特性、示差DSC(示差掃描熱量法)性質、和在流動動力學下之結晶。與先前的聚丙烯類相反，本發明之組成物不需要窄分子量分布(M_w /M_n )來達成提高的可紡性和纖維性質。因此，本發明之組成物不需要用茂金屬觸媒製造來獲得窄M_w /M_n ，雖然使用茂金屬觸媒(且窄M_w /M_n )仍然是可行的，只要該組成物符合本文所述之組成屬性的定義範圍。本發明之組成物特別可用於形成紡黏織物、熔噴織物、紡黏和熔噴織物結構之組合以及部分定向紗、完全定向紗、和短纖維。本發明之組成物也有利於製備具有高撓曲模數、高降伏抗拉強度和高熱變形溫度之模製零件。The present inventors have surprisingly discovered propylene-based compositions characterized by a unique combination of specific melt rheology, crystallization, and stereoregular molecular parameters that result in an excellent combination of spinnability and fiber/fabric tensile properties. . Furthermore, according to the rotational rheometer monitoring, the composition of the present invention desirably has different rheology (including melt elasticity) and shear thinning characteristics, differential DSC (differential scanning calorimetry) properties, and under flow kinetics. crystallization. In contrast to previous polypropylene, the composition of the present invention does not require a narrow molecular weight distribution (M _w / M _n) can be achieved to improve the spinnability and fiber properties. Therefore, the composition of the present invention does not need to be fabricated with a metallocene catalyst to obtain a narrow M _w /M _n , although the use of a metallocene catalyst (and a narrow M _w /M _n ) is still feasible as long as the composition conforms to this document. The defined range of the constituent attributes. The compositions of the present invention are particularly useful for forming a combination of spunbond fabrics, meltblown fabrics, spunbond and meltblown fabric structures, as well as partially oriented yarns, fully oriented yarns, and staple fibers. The composition of the present invention is also advantageous in the preparation of molded parts having a high flexural modulus, a high deferred tensile strength, and a high heat distortion temperature.

“烯烴”或者稱為“烯”為一種具有至少一個雙鍵的碳和氫之直鏈、支鏈、或環狀化合物。為了本說明書和其所附申請專利範圍之目的，當聚合物或共聚物稱為包含烯烴(包括但不限於乙烯、丙烯和丁烯)時，存在於該聚合物或共聚物中之烯烴為烯烴之聚合形式。例如，當共聚物據說為具有35重量%至55重量%之“丙烯”含量時，應了解：在聚合反應中共聚物中的單體單元係衍生自丙烯且該等衍生單元係以35重量%至55重量%存在，以共聚物之重量為基準計。“聚合物”具有二或多種相同或不同的單體單元。“均聚物”為具有相同的單體單元之聚合物。“共聚物”為具有二或多種彼此不同的單體單元之聚合物。“三元聚合物”為具有三種彼此不同的單體單元之聚合物。術語“不同”當用以指稱單體單元時，指示：以至少一個原子彼此不同或異構上不同的單體單元。因此，如使用於本文中，共聚物之定義包括三元聚合物等等。“丙烯聚合物”，也稱為“聚丙烯”，為一種包含50莫耳%或更多衍生自丙烯之單元的聚合物。寡聚物通常為一種具有低分子量(該小於25,000克/莫耳，較佳小於2,500克/莫耳之M_n )或低數.目之單體單元(諸如75單體單元或更小)的聚合物。"Alkene" or "alkenyl" is a straight, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the scope of the appended claims, when a polymer or copolymer is referred to as comprising an olefin (including but not limited to ethylene, propylene, and butene), the olefin present in the polymer or copolymer is an olefin The form of polymerization. For example, when the copolymer is said to have a "propylene" content of from 35% to 55% by weight, it is understood that the monomer units in the copolymer are derived from propylene and the derived units are at 35 wt% in the polymerization reaction. It is present at 55% by weight, based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units different from each other. A "terpolymer" is a polymer having three monomer units different from each other. The term "different" when used to refer to a monomer unit, indicates a monomer unit that differs from each other or isomerically different in at least one atom. Thus, as used herein, the definition of a copolymer includes a terpolymer and the like. "Propylene polymer", also known as "polypropylene", is a polymer comprising 50 mole percent or more of units derived from propylene. Oligomers typically having a low molecular weight (less than the 25,000 g / mole, preferably less than 2,500 g / mole of M _n) or a low number. Head of monomer units (monomer units such as 75 or less) polymer.

如使用於本文中，使用如Chemical and Engineering News (63(5),27(1985))所述之週期表族的新符號。As used herein, a new symbol of the family of periodic tables as described in Chemical and Engineering News (63(5), 27 (1985)) is used.

如使用於本文中，“茂金屬觸媒”表示能夠引發烯烴催化作用的具有至少一個環戊二烯基、茚基或茀基與其連接之第4族過渡金屬化合物，通常與活化劑結合。As used herein, "metallocene catalyst" means a Group 4 transition metal compound having at least one cyclopentadienyl, indenyl or fluorenyl group capable of initiating olefin catalysis, typically associated with an activator.

術語“觸媒”和“觸媒化合物”係定義為表示能夠引發催化作用的化合物。在本文之說明中，該觸媒可描述為觸媒前驅物、前觸媒化合物、或過渡金屬化合物，且這些術語可以互換使用。觸媒化合物可以本身使用於引發催化作用或可與活化劑結合使用以引發催化作用。當觸媒化合物與活化劑結合使用以引發催化作用時，該觸媒化合物常稱為前觸媒或觸媒前驅物。“觸媒系統”為一種至少一種觸媒化合物、和隨意活化劑、隨意共活化劑和隨意支撐材料的組合物，其中該系統可將單體聚合成聚合物。為了本發明和其申請專利範圍之目的，當觸媒系統被描述為包含組分之天然穩定形式時，一般技藝人士應熟悉理解：組分的離子形式為與單體反應而產生聚合物的形式。The terms "catalyst" and "catalytic compound" are defined to mean a compound capable of initiating a catalytic action. In the description herein, the catalyst can be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably. The catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator to initiate catalysis. When a catalyst compound is used in combination with an activator to initiate catalysis, the catalyst compound is often referred to as a precatalyst or catalyst precursor. A "catalyst system" is a combination of at least one catalyst compound, and a random activator, a random co-activator, and a free support material, wherein the system can polymerize the monomer into a polymer. For the purposes of the present invention and the scope of its patent application, when the catalyst system is described as comprising a naturally stable form of the components, one of ordinary skill in the art will be familiar with the understanding that the ionic form of the component is in the form of a polymer that reacts with the monomer. .

良好可紡性在本發明中係定義為：當形成用於具有5至25克/米² (較佳7至20克/米² ，較佳8至15克/米² ，較佳9至11克/米² )之基重的織物之0.8至5(較佳0.8至4，較佳 0.8至2.5，較佳1至1.6)丹尼纖維時，於在0.3至0.6ghm(每孔每分鐘克數)範圍之通量率經8小時之運行時間沒有纖維斷裂、滴液或硬塊發生。硬塊是負面影響非織物的均勻性之小塑料聚集體。Good spinnability is defined in the present invention as when formed for having 5 to 25 g/m ² (preferably 7 to 20 g/m ² , preferably 8 to 15 g/m ² , preferably 9 to 11)克/米² ) basis weight of the fabric of 0.8 to 5 (preferably 0.8 to 4, preferably 0.8 to 2.5, preferably 1 to 1.6) denier fiber, at 0.3 to 0.6 ghm per gram per minute The flux rate of the range is not affected by fiber breakage, dripping or lumps over an 8 hour run time. A hard block is a small plastic aggregate that negatively affects the uniformity of the non-woven fabric.

為了本發明和其申請專利範圍之目的，當聚合物描述為具有0重量%成核劑存在時，則表示沒有外來成核劑被加至聚合物。該短語並不表示該聚合物不包含“內成核劑”，即製備時存在於純聚合物中充當成核劑的材料。當聚合物被描述為具有使用0重量%成核劑的某性質時，則表示該測試是用已沒有外部成核劑添加到其中之聚合物進行。例如，短語“具有至少123℃或更高之T_cp (以DSC測量於每分鐘10℃之冷卻速度)使用0重量%成核劑”表示：當在DSC測試之前在其中沒有外部成核劑已被加入到聚合物中的聚合物之樣品測量時，所討論的聚合物具有至少123℃或更高之T_cp 。此短語並不意味著表示：成核劑不可添加到聚合物作正常製備方法的一部分。For the purposes of the present invention and the scope of its patent application, when a polymer is described as having 0% by weight of a nucleating agent, it means that no foreign nucleating agent is added to the polymer. The phrase does not mean that the polymer does not comprise an "internal nucleating agent", ie a material that is present in the neat polymer as a nucleating agent when prepared. When the polymer is described as having a property of using 0% by weight of a nucleating agent, it means that the test is carried out with a polymer to which no external nucleating agent has been added. For example, the phrase "having at least 123 deg.] C or higher of T _cp (measured by DSC at a cooling rate of 10 deg.] C per minute) using 0% by weight of a nucleating agent" means: if before the DSC test in which no external nucleating agent when the measurement has been added to a sample of the polymer in the polymer, the polymer in question has at least 123 ℃ T _cp or more of. This phrase is not meant to mean that a nucleating agent cannot be added to a polymer as part of a normal preparation process.

在本發明之一較佳實施態樣中，該被形成纖維及/或非織物之丙烯聚合物係藉由將丙烯聚合物減黏製備，一般藉由減黏具有0.1至8dg/分鐘(較佳0.6至6dg/分鐘，較佳0.8至3dg/分鐘)之MFR的丙烯聚合物製備。In a preferred embodiment of the present invention, the fiber-forming and/or non-woven propylene polymer is prepared by reducing the viscosity of the propylene polymer, generally by 0.1 to 8 dg/min. A propylene polymer preparation of MFR of 0.6 to 6 dg/min, preferably 0.8 to 3 dg/min.

在本發明之一較佳實施態樣中，該組成物包含減黏(受控流變性)丙烯聚合物或反應器級丙烯聚合物(即，已被處理而減黏之丙烯聚合物)或其組合。在減黏丙烯組成物的情況下，減黏步驟前的初始聚合物將稱為“基本聚合物”。減黏聚合物或反應器級聚合物(即轉化前沒有被減黏)可轉化成有用的物件，包括但不限於纖維、織物、網、模製零件、等等。In a preferred embodiment of the invention, the composition comprises a reduced viscosity (controlled rheology) propylene polymer or a reactor grade propylene polymer (ie, a propylene polymer that has been treated to reduce viscosity) or combination. In the case of a reduced viscosity propylene composition, the initial polymer before the viscosity reduction step will be referred to as "basic poly The reduced viscosity polymer or reactor grade polymer (i.e., not debonded prior to conversion) can be converted into useful articles including, but not limited to, fibers, fabrics, webs, molded parts, and the like.

聚合物組成物Polymer composition

在本發明之一較佳實施態樣中，本發明丙烯聚合物組成物可包含減黏(受控流變性)、反應器級(非減黏)以丙烯為主之聚合物、及/或其組合。本發明丙烯聚合物組成物較佳係形成纖維、網、模製零件、或其他型材。In a preferred embodiment of the present invention, the propylene polymer composition of the present invention may comprise a reduced viscosity (controlled rheology), a reactor grade (non-reduced) polymer based on propylene, and/or combination. The propylene polymer composition of the present invention is preferably formed into fibers, webs, molded parts, or other profiles.

具體而言，本發明關於包含至少50莫耳%丙烯(較佳至少80莫耳%丙烯，較佳至少90莫耳%丙烯，較佳100莫耳%丙烯)之丙烯聚合物，該聚合物具有：a)10至21.5dg/分鐘(較佳12至22dg/分鐘，較佳13至20dg/分鐘，較佳14至19dg/分鐘，較佳14至18dg/分鐘，較佳14至17dg/分鐘)之熔體流動速度(MFR，ASTM 1238，230℃，2.16公斤)；b)從1.5至28(較佳2至15，較佳2.5至6.5)之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)；c)至少131℃(較佳133℃或更高，較佳135℃或更高，較佳136℃或更高，較佳137℃或更高)之在流動下的結晶之起始溫度T_c,rheol (如以SAOS流變學測定，如下所述之1℃/分鐘，其中該聚合物具有0重量%成核劑存在)；及 d)至少97或更高(較佳97至150，較佳100至140，較佳105至130)之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)；及，隨意地，e)從10至70(較佳14至70，較佳35至65，較佳45至55)之在190℃下的於0.1rad/s之角頻率的損耗角正切tanδ(由下述方程式(2)定義)。In particular, the invention relates to a propylene polymer comprising at least 50 mole % propylene (preferably at least 80 mole % propylene, preferably at least 90 mole % propylene, preferably 100 mole % propylene), the polymer having : a) 10 to 21.5 dg/min (preferably 12 to 22 dg/min, preferably 13 to 20 dg/min, preferably 14 to 19 dg/min, preferably 14 to 18 dg/min, preferably 14 to 17 dg/min) Melt flow rate (MFR, ASTM 1238, 230 ° C, 2.16 kg); b) dimensionless stress ratio/loss at 190 ° C from 1.5 to 28 (preferably 2 to 15, preferably 2.5 to 6.5) The tangent index R ₂ (defined by equation (8) below); c) at least 131 ° C (preferably 133 ° C or higher, preferably 135 ° C or higher, preferably 136 ° C or higher, preferably 137) °C or higher) The initial temperature of the crystallization under flow Tc _,rheol (as determined by SAOS rheology, 1 ° C/min as described below, wherein the polymer has 0% by weight of nucleating agent) And d) an average meso run length determined by ¹³ C NMR of at least 97 or higher (preferably 97 to 150, preferably 100 to 140, preferably 105 to 130); Optionally, e) from 10 to 70 (preferably 14 to 70, Jia 35-65, preferably from 45 to 55) of the loss angle at 190 deg.] C in 0.1 rad / s angular frequency of the tangent tanδ ((2 by the following equation) is defined).

在本發明之一較佳實施態樣中，該丙烯聚合物為丙烯均聚物。In a preferred embodiment of the invention, the propylene polymer is a propylene homopolymer.

本文中可使用的較佳本發明丙烯聚合物組成物包括另外具有下列性質中一或多者之丙烯聚合物：1. 30,000至2,000,000克/莫耳(較佳150,000至300,000克/莫耳，更佳190,000至240,000克/莫耳)之M_w ，如以測試方法章節中所述之GPC測量；及/或2. 100℃至200℃(較佳110℃至185℃，較佳115℃至175℃，更佳140℃至170℃，更佳155℃至167℃之)Tm(第二熔體，1℃/分鐘斜坡速度，也稱為“T_mp ”)，如以在測試方法中之下述DSC方法測量；及/或3. 20%至80%(較佳30%至70%，更佳35%至55%)之百分比結晶度(根據結晶之熱)，如以測試方法中之下述DSC方法測量；及/或4. -50℃至120℃(較佳-20℃至100℃，更佳0℃至90℃)之玻璃轉移溫度Tg，如以測試方法中之下述DSC方法測定；及/或5. 15℃至150℃(較佳110℃至150℃，更佳126℃至147℃，較佳129℃至139℃)之結晶溫度Tc(1℃/分鐘斜坡速度，也稱為“T_cp ”)，用具有0重量%成核劑之樣品測定，如以測試方法中之下述DSC方法測量；及/或6. 0.85或更大(較佳0.90或更大，較佳0.95或更大，較佳0.99或更大)之分枝指數(g’_vis )。Preferred propylene polymer compositions of the present invention which may be used herein include propylene polymers which additionally have one or more of the following properties: 1. 30,000 to 2,000,000 g/mole (preferably 150,000 to 300,000 g/mole, more _{Mw of} 190,000 to 240,000 g/mole, as measured by GPC as described in the Test Methods section; and/or 2.100 ° C to 200 ° C (preferably 110 ° C to 185 ° C, preferably 115 ° C to 175) °C, more preferably 140 ° C to 170 ° C, more preferably 155 ° C to 167 ° C) Tm (second melt, 1 ° C / min ramp speed, also known as "T _mp "), as in the test method The DSC method measures; and/or 3.20% to 80% (preferably 30% to 70%, more preferably 35% to 55%) percent crystallinity (according to the heat of crystallization), as in the test method The DSC method measures; and/or the glass transition temperature Tg of -50 ° C to 120 ° C (preferably -20 ° C to 100 ° C, more preferably 0 ° C to 90 ° C), as in the following DSC method in the test method Measured; and/or 5. 15 ° C to 150 ° C (preferably 110 ° C to 150 ° C, more preferably 126 ° C to 147 ° C, preferably 129 ° C to 139 ° C) crystallization temperature Tc (1 ° C / min ramp speed, also Called "T _cp "), with 0% by weight The sample of the nucleating agent is measured, as measured by the following DSC method in the test method; and/or 6. 0.85 or more (preferably 0.90 or more, preferably 0.95 or more, preferably 0.99 or more). Branching index (g' _vis ).

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有1至7(較佳1.2至5，更佳1.5至4)之M_w /M_n ，如以GPC測量。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a M _w /M _{n of} from 1 to 7, preferably from 1.2 to 5, more preferably from 1.5 to 4, as measured by GPC.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有1.5至2.5(更佳1.8至2.2，更佳1.9至2.1)之M_z /M_w ，如以GPC測量。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a M _z /M _{w of} from 1.5 to 2.5 (more preferably from 1.8 to 2.2, more preferably from 1.9 to 2.1) as measured by GPC.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有至少131℃或更高(較佳135℃或更高，較佳136℃或更高，較佳137℃)之在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學測定，1℃/分鐘190℃，其中待測試之聚合物樣品具有0%成核劑，如下所述)。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of at least 131 ° C or higher (preferably 135 ° C or higher, preferably 136 ° C or higher, preferably 137 ° C). The onset temperature of the crystallization under flow Tc _,rheol (determined via SAOS rheology, 1 ° C / min 190 ° C, wherein the polymer sample to be tested has 0% nucleating agent, as described below).

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有1.2至4.5(較佳1.8至3.6，較佳2至3)之在190℃下的無因次應力比指數R₁ (由下述方程式(7)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a dimensionless stress ratio index at 190 ° C of from 1.2 to 4.5, preferably from 1.8 to 3.6, preferably from 2 to 3. R ₁ (defined by the following equation (7)), as determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有1.5至28(較佳2至15，較佳2.5至6.5)之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a dimensionless stress ratio at 190 ° C of from 1.5 to 28 (preferably from 2 to 15, preferably from 2.5 to 6.5). The loss tangent index R ₂ (defined by Equation (8) below) is determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有6至13(較佳6.5至12.5，較佳7至10)之在190℃下的無因次剪切稀化指數R₃ (由下述方程式(9)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have 6 to 13 (preferably 6.5 to 12.5, preferably 7 to 10) dimensionless shear thinning at 190 °C. The index R ₃ (defined by the following equation (9)) is determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有1.5至20(較佳1.7至10.7，較佳2至6)之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a dimensionless loss tangent at 190 ° C of from 1.5 to 20 (preferably from 1.7 to 10.7, preferably from 2 to 6). / Elasticity index R ₄ (defined by equation (10) below) as determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有從14至70(較佳35至65，較佳45至55)之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)(由後文的方程式(2)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a ratio of from 14 to 70 (preferably from 35 to 65, preferably from 45 to 55) at 190 ° C at 0.1 rad/s. The loss tangent (tan δ) of the angular frequency (defined by equation (2) below) is determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有97或更高(較佳100或更高，較佳105或更高)之平均內消旋運行長度(average meso run length)(由下述方程式(16)定義)，如以測試方法章節中之下述¹³ C NMR方法測定。或者，任何本發明的丙烯聚合物組成物可具有97至150(較佳100至140，較佳105至130)之平均內消旋運行長度(由下述方程式(16)定義)。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have an average mesogenic run length of 97 or higher (preferably 100 or higher, preferably 105 or higher) (average) Meso run length) (defined by equation (16) below) as determined by the following ¹³ C NMR method in the Test Methods section. Alternatively, any of the propylene polymer compositions of the present invention may have an average mesogenic running length of 97 to 150 (preferably 100 to 140, preferably 105 to 130) (defined by equation (16) below).

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有120℃或更大(140℃或更大，較佳155℃或更大，較佳160℃或更大)之T_mp (第二熱，以DSC測量於每分鐘1℃之加熱速度)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 120 ° C or greater (140 ° C or greater, preferably 155 ° C or greater, preferably 160 ° C or greater). T _mp (second heat, measured at DSC at a heating rate of 1 ° C per minute) as determined by the following DSC method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有120℃或更高(較佳140℃或更高，較佳155℃或更高，較佳160℃或更高)之T_mp (以DSC測量於每分鐘10℃之加熱速度)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 120 ° C or higher (preferably 140 ° C or higher, preferably 155 ° C or higher, preferably 160 ° C or higher). T _{mp of} high) (measured at 10 ° C per minute by DSC) as determined by the following DSC method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有125℃或更高(較佳126℃或更高，較佳127℃或更高，較佳128℃或更高，較佳129℃，較佳130℃或更高，較佳133℃或更高)之T_cp (以DSC測量於每分鐘1℃之冷卻速度，其中該待測量聚合物具有0重量%成核劑)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 125 ° C or higher (preferably 126 ° C or higher, preferably 127 ° C or higher, preferably 128 ° C or higher. High, preferably 129 ° C, preferably 130 ° C or higher, preferably 133 ° C or higher, T _cp (measured at a cooling rate of 1 ° C per minute as measured by DSC, wherein the polymer to be measured has 0% by weight Nuclear agent), as determined by the following DSC method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有115℃或更高(較佳116℃或更高，較佳117℃或更高，較佳118℃或更高，較佳119℃或更高，較佳120℃或更高，較佳121℃或更高，較佳122℃或更高，較佳123℃或更高)之T_cp (以DSC測量於每分鐘10℃之冷卻速度，其中該待測試聚合物具有0重量%成核劑)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 115 ° C or higher (preferably 116 ° C or higher, preferably 117 ° C or higher, preferably 118 ° C or higher. High, preferably 119 ° C or higher, preferably 120 ° C or higher, preferably 121 ° C or higher, preferably 122 ° C or higher, preferably 123 ° C or higher, T _cp (measured by DSC) A cooling rate of 10 ° C per minute, wherein the polymer to be tested has 0% by weight of a nucleating agent, as determined by the following DSC method in the Test Methods section.

在本文之本發明的任何實施態樣中，該組成物可具有-11℃或更小(較佳-15℃或更小，或較佳小於-17℃)之過冷參數SCP(由下述方程式(12)定義)(以DSC測量於每分鐘1℃之加熱和冷卻速度，其中該待測試聚合物具有0%成核劑)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the composition may have a subcooling parameter SCP of -11 ° C or less (preferably -15 ° C or less, or preferably less than -17 ° C) (by the following Equation (12) defines (heating and cooling rate at 1 ° C per minute as measured by DSC, wherein the polymer to be tested has a 0% nucleating agent) as determined by the DSC method described in the Test Methods section.

在本文之本發明的任何實施態樣中，該組成物可具有-1℃或更小(較佳-3.5℃或更小)之過冷參數SCP(由下述方程式(12)定義)(以DSC測量於每分鐘10℃之加熱和冷卻速度，其中該待測試聚合物具有0%成核劑)，如以測試方法章節中之下述DSC方法測定。In any of the embodiments of the invention herein, the composition may have a subcooling parameter SCP (defined by equation (12) below) of -1 ° C or less (preferably -3.5 ° C or less) The DSC measures the heating and cooling rate at 10 ° C per minute, wherein the polymer to be tested has a 0% nucleating agent, as determined by the following DSC method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有131℃或更高(較佳135℃或更高，較佳136℃或更高，較佳137℃或更高)之在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學測定，1℃/分鐘)，其中該待測試聚合物具有0重量%成核劑)，如以測試方法章節中之下述SAOS流變學方法測定，和1.2至4.5(較佳1.8至3.6，較佳2至3)之在190℃下的無因次應力比指數R₁ (由後文的方程式(7)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 131 ° C or higher (preferably 135 ° C or higher, preferably 136 ° C or higher, preferably 137 ° C or higher. High) the initial temperature of the crystallization under flow T _c,rheol (determined via SAOS rheology, 1 ° C / min), wherein the polymer to be tested has 0% by weight of nucleating agent), as in the test method section The following SAOS rheology method is determined, and the dimensionless stress ratio index R ₁ at 190 ° C of 1.2 to 4.5 (preferably 1.8 to 3.6, preferably 2 to 3) (by the following equation (7) ))), as determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有140℃或更高(較佳155℃或更高，較佳160℃或更高)之T_mp (以DSC測量於每分鐘1℃之加熱)，以測試及材料章節段落中之下述DSC方法測量，和1.2至4.5(較佳1.8至3.6，較佳2至3)之在190℃下的無因次應力比指數R₁ (由下述方程式(7)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a T _{mp of} 140 ° C or higher (preferably 155 ° C or higher, preferably 160 ° C or higher) (by DSC) Measured at 1 ° C per minute), measured by the following DSC method in the Test and Materials section, and 1.2 to 4.5 (preferably 1.8 to 3.6, preferably 2 to 3) at 190 ° C. The stress ratio index R ₁ (defined by equation (7) below) is determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有131℃或更高(較佳135℃或更高，較佳136℃或更高，較佳137℃或更高)之T_c,rheol ，如以測試方法章節中之下述SAOS流變學方法測定，和1.5至20(較佳1.7至10.7，較佳2至6)之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 131 ° C or higher (preferably 135 ° C or higher, preferably 136 ° C or higher, preferably 137 ° C or higher. Tc _{,rheol of} high), as determined by the following SAOS rheology method in the Test Methods section, and dimensionless at 190 ° C of 1.5 to 20 (preferably 1.7 to 10.7, preferably 2 to 6) Loss tangent/elasticity index R ₄ (defined by equation (10) below) as determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有125℃或更高(較佳126℃或更高，較佳127℃或更高，較佳128℃或更高，較佳130℃或更高，較佳133℃或更高)之T_cp (以DSC測量於每分鐘1℃之加熱和冷卻速度，其中該待測試聚合物具有0重量%成核劑)，如以測試一節中之下述DSC方法測定，和1.50至20(較佳1.7至10.7，較佳2至6)之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 125 ° C or higher (preferably 126 ° C or higher, preferably 127 ° C or higher, preferably 128 ° C or higher. High, preferably 130 ° C or higher, preferably 133 ° C or higher, T _cp (heating and cooling rate of 1 ° C per minute as measured by DSC, wherein the polymer to be tested has 0% by weight of nucleating agent) , as determined by the following DSC method in the test section, and the dimensionless loss tangent/elasticity index R ₄ at 190 ° C of 1.50 to 20 (preferably 1.7 to 10.7, preferably 2 to 6) Equation (10) is defined as determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物可具有115℃或更高(較佳116℃或更高，較佳117℃或更大，較佳118℃或更大，較佳119℃或更高，較佳120℃或更高，較佳122℃或更高，較佳123℃或更高)之T_cp (以DSC測量於每分鐘10℃之冷卻速度，其中該待測量聚合物具有0重量%成核劑)，如以測試一節中之下述DSC方法測定，和1.5至20(較佳1.7至10.7，較佳2至6)之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)，如以測試方法章節中之下述SAOS流變學方法測定。In any of the embodiments of the invention herein, the propylene polymer composition of the invention may have a temperature of 115 ° C or higher (preferably 116 ° C or higher, preferably 117 ° C or greater, preferably 118 ° C or higher. Large, preferably 119 ° C or higher, preferably 120 ° C or higher, preferably 122 ° C or higher, preferably 123 ° C or higher, T _cp (measured at 10 ° C per minute by DSC) Wherein the polymer to be measured has 0% by weight of a nucleating agent), as determined by the following DSC method in the test section, and 1.5 to 20 (preferably 1.7 to 10.7, preferably 2 to 6) at 190 ° C The dimensionless loss tangent/elasticity index R ₄ (defined by equation (10) below) is determined by the following SAOS rheology method in the Test Methods section.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物包含具有下列之以丙烯為主之聚合物：(1)在從10dg/分鐘至21.5dg/分鐘之範圍的MFR；(2)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)；(3)至少131℃或更高之具有0%成核劑的在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；及(4)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)。In any of the embodiments of the invention herein, the propylene polymer composition of the invention comprises a propylene-based polymer having: (1) an MFR ranging from 10 dg/min to 21.5 dg/min; (2) dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 1.5 to 28 (defined by equation (8) below); (3) 0% at least 131 ° C or higher The crystallization of the nucleating agent at the onset temperature of the flow T _c,rheol (via SAOS rheology, 1 ° C / min); and (4) at least 97 or higher by ¹³ C NMR, the average meso-determination Average meso run length.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物包含具有下列之以丙烯為主之聚合物：1)在從10dg/分鐘至21.5dg/分鐘之範圍的MFR； 2)從14至70之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)(由下述方程式(2)定義)；3)至少131℃或更高之具有0%成核劑的在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；及4)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)。In any of the embodiments of the invention herein, the propylene polymer composition of the invention comprises a propylene-based polymer having the following: 1) an MFR ranging from 10 dg/min to 21.5 dg/min; a loss tangent (tan δ) at an angular frequency of 0.1 rad/s at 190 ° C from 14 to 70 (defined by equation (2) below); 3) 0% at least 131 ° C or higher. The starting temperature of the nucleating agent under flow, T _c,rheol (via SAOS rheology, 1 ° C/min); and 4) the average mesogenic running length measured by ¹³ C NMR of at least 97 or higher (average meso run length).

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物包含具有下列之以丙烯為主之聚合物：1)範圍在從10dg/分鐘至21.5dg/分鐘之MFR；2)從1.5至20之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)；3)至少125℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘1℃之冷卻速度)；及4)至少97或更高的以¹³ C NMR測定之平均內消旋運行長度。In any of the embodiments of the invention herein, the propylene polymer composition of the invention comprises a propylene-based polymer having the following: 1) an MFR ranging from 10 dg/min to 21.5 dg/min; 2) Dimensionless loss tangent/elasticity index R ₄ (defined by equation (10) below) from 1.5 to 20 at 190 ° C; 3) T _cp with 0% nucleating agent of at least 125 ° C or higher (Measurement rate of cooling at 1 ° C per minute by DSC); and 4) Average mesogenic run length as determined by ¹³ C NMR of at least 97 or higher.

在本文之本發明的任何實施態樣中，本發明的丙烯聚合物組成物包含具有下列之以丙烯為主之聚合物：1)在從10dg/分鐘至21.5dg/分鐘之範圍的MFR；及a)從1.2至4.5之在190℃下的無因次應力比指數R₁ (由下述方程式(7)定義)；或b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)；或 c)從6至13之在190℃下的無因次剪切稀化指數R₃ (由下述方程式(9)定義)；或d)從1.5至20之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)；或e)從14至70之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)(由下述方程式(2)定義)；或f)從3.1至6.1之在190℃下於500s^-1 之剪切速度的應力比(SR)(由下述方程式(6)定義)；及2)a)至少131℃或更高之具有0%成核劑的在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；或b)至少125℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘1℃之冷卻速度)；或c)至少117℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘10℃之冷卻速度)；或d)小於-1℃之具有0%成核劑的過冷參數SCP(以DSC測量於10℃/分鐘之加熱和冷卻速度)；或e)小於-11℃之具有0%成核劑的過冷參數SCP(以DSC測量於1℃/分鐘之加熱和冷卻速度)；及4)a)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度；或b)小於103之每10,000個單體的缺陷總數(立體和區域)。In any of the embodiments of the invention herein, the propylene polymer composition of the invention comprises a propylene-based polymer having: 1) an MFR ranging from 10 dg/min to 21.5 dg/min; a) dimensionless stress ratio index R ₁ at 190 ° C from 1.2 to 4.5 (defined by equation (7) below); or b) dimensionless stress ratio at 190 ° C from 1.5 to 28 / Loss tangent index R ₂ (defined by equation (8) below); or c) dimensionless shear thinning index R ₃ from 6 to 13 at 190 ° C (defined by equation (9) below Or; d) dimensionless loss tangent/elasticity index R ₄ at 190 ° C from 1.5 to 20 (defined by equation (10) below); or e) from 14 to 70 at 190 ° C Loss tangent (tan δ) at an angular frequency of 0.1 rad/s (defined by equation (2) below); or f) stress ratio at a shear rate of 500 s ^-1 at 190 ° C from 3.1 to 6.1 ( SR) (defined by the following equation (6)); and 2) a) at least 131 ° C or higher of the starting temperature of the crystal under flow with a 0% nucleating agent T _c,rheol (via SAOS rheology) Learning, 1 ° C / min); or b) at least 125 ° C or higher with 0% nucleating agent T _cp (measured by DSC at a cooling rate of 1 ℃ per minute); or c) at least 117 deg.] C or higher T _cp 0% of a nucleating agent (as measured by DSC at a cooling rate of 10 deg.] C per minute); or d) subcooling parameter SCP with 0% nucleating agent less than -1 °C (heating and cooling rate measured at 10 °C/min by DSC); or e) 0% nucleating agent with less than -11 °C Cold parameter SCP (heating and cooling rate measured at 1 °C/min by DSC); and 4) a) average mesional running length measured by ¹³ C NMR of at least 97 or higher; or b) less than 103 The total number of defects (stereo and area) of 10,000 monomers.

在本發明之另一較佳實施態樣中，本發明的丙烯聚合物組成物具有：1)在從14dg/分鐘至19dg/分鐘之範圍的MFR；及2)a)從2.0至3.0之在190℃下的無因次應力比指數R₁ (由後文的方程式(7)定義)；或b)從2.5至6.5之在190℃下的無因次應力比/損耗角正切指數R₂ (由後文的方程式(8)定義)；或c)從7.0至10.0之在190℃下的無因次剪切稀化指數R₃ (由下述方程式(9)定義)；或d)從2.0至6.0之在190℃下的無因次損耗角正切/彈性指數R₄ (由下述方程式(10)定義)；或e)從35至65之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)(由下述方程式(2)定義)；或f)從3.3至4.0之在190℃下的於500s^-1 之剪切速度的應力比(SR)(由下述方程式(6)定義)；及3)a)至少134℃或更高之具有0%成核劑的在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；或b)至少133℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘1℃之冷卻速度)；或c)至少123℃或更高之具有0%成核劑的T_cp (以DSC測量於10℃每分鐘之冷卻速度)；或d)小於-3.5℃之具有0%成核劑的過冷參數SCP (以DSC測量於10℃/分鐘之加熱和冷卻速度)；或e)小於-17.0℃之具有0%成核劑的過冷參數SCP(以DSC測量於1℃/分鐘之加熱和冷卻速度)；及4)a)至少100或更高之以¹³ C NMR測定的平均內消旋運行長度；或b)小於100之每10,000個單體的缺陷總數(立體和區域)。In another preferred embodiment of the present invention, the propylene polymer composition of the present invention has: 1) an MFR ranging from 14 dg/min to 19 dg/min; and 2) a) from 2.0 to 3.0 The dimensionless stress ratio index R ₁ at 190 ° C (defined by equation (7) below); or b) the dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 2.5 to 6.5 ( It is defined by the following equation (8); or c) the dimensionless shear thinning index R ₃ (defined by the following equation (9)) at 190 ° C from 7.0 to 10.0; or d) from 2.0 a dimensionless loss tangent/elasticity index R ₄ at 190 ° C (defined by equation (10) below); or e) an angle of 0.1 rad/s at 190 ° C from 35 to 65 The loss tangent of the frequency (tan δ) (defined by equation (2) below); or f) the stress ratio (SR) at a shear rate of 500 s ^-1 at 190 ° C from 3.3 to 4.0 (by Equation (6) defines); and 3) a) at least 134 ° C or higher of the onset temperature of the flowing crystal with a 0% nucleating agent T _c,rheol (via SAOS rheology, 1 ° C / min ); or b) at least 133 deg.] C or higher T _cp 0% of a nucleating agent (as measured by DSC at 1 per minute The cooling rate); or c) at least 123 deg.] C or higher T _cp 0% of a nucleating agent (as measured by DSC at 10 deg.] C per minute cooling rate); or d) of less than -3.5 deg.] C to 0% Subcooling parameter SCP for nucleating agents (heating and cooling rate measured at 10 °C/min by DSC); or e) subcooling parameter SCP with 0% nucleating agent less than -17.0 °C (measured at 1 °C by DSC/ Minute heating and cooling rate); and 4) a) average mesional running length measured by ¹³ C NMR of at least 100 or higher; or b) total number of defects per 10,000 monomers less than 100 (stereo and region) ).

本文中可使用的本發明丙烯聚合物組成物包括：聚丙烯均聚物、聚丙烯共聚物、耐衝擊性共聚物聚丙烯、和其摻合物。均聚物可為同排聚丙烯、對排聚丙烯或其摻合物(包括與雜排聚合物的摻合物)。共聚物可為隨機共聚物、統計共聚物、嵌段共聚物、或其摻合物。製造丙烯聚合物之方法不是關鍵，因為彼等可藉由如US 7,807,769中所述者的漿體、溶液、氣相、超臨界聚合方法、如US 2010/0113718中所述者的超級溶液均相聚合方法或其他適當方法，且藉由使用適合於聚合聚烯烴類的觸媒系統，例如戚格勒-納他型觸媒、茂金屬型觸媒、其他適當觸媒系統，或其組合製造。該等觸媒為此項技藝中所熟知的，且描述於(例如)ZIEGLER CATALYSTS(Gerhard Fink,Rolf Mülhaupt and Hans H.Brintzinger,Eds.,Springer-Verlag 1995)；Resconi等人，Selectivity in Propene Polymerization with Metallocene Catalysts ,100 CHEM.REV.1253-1345(2000)；及I,II METALLOCENE-BASED POLYOLEFINS(Wiley & Sons 2000)。在一較佳實施態樣中，有效丙烯聚合物係藉由US 6,342,566；6,384,142；5,741,563；WO 03/040201；及WO 97/19991中所述之觸媒、活化劑和方法製造。在另一較佳實施態樣中，US 7,807,769和美國專利申請公開號2010/0113718中所述之觸媒可用於製造本文中可使用的丙烯聚合物。The propylene polymer composition of the present invention which can be used herein includes: a polypropylene homopolymer, a polypropylene copolymer, an impact copolymer polypropylene, and a blend thereof. The homopolymer can be the same row of polypropylene, the aligned polypropylene or a blend thereof (including blends with the heteropolymer). The copolymer can be a random copolymer, a statistical copolymer, a block copolymer, or a blend thereof. The method of making propylene polymers is not critical as they can be homogeneous by supersolutions as described in US 7,807,769 for slurry, solution, gas phase, supercritical polymerization processes, as described in US 2010/0113718. The polymerization process or other suitable method is produced by using a catalyst system suitable for polymerizing polyolefins, such as a Ziegler-Nano-type catalyst, a metallocene-type catalyst, other suitable catalyst systems, or a combination thereof. Such catalysts are well known in the art and are described, for example, in ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mülhaupt and Hans H. Brintzinger, Eds., Springer-Verlag 1995); Resconi et al., Selectivity in Propene Polymerization With Metallocene Catalysts , 100 CHEM.REV.1253-1345 (2000); and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000). In a preferred embodiment, the effective propylene polymer is made by the catalysts, activators and methods described in US 6,342,566; 6,384,142; 5,741,563; WO 03/040201; and WO 97/19991. In another preferred embodiment, the catalyst described in US Pat. No. 7,807,769 and U.S. Patent Application Publication No. 2010/0113718 can be used to make propylene polymers useful herein.

在一較佳實施態樣中，本發明的丙烯聚合物組成物可為二或多種丙烯聚合物之單峰反應器級、雙峰反應器級、反應器內摻合物、或擠出機摻合物(例如，36dg/分鐘和2dg/分鐘之MFR的摻合物)。在另一實施態樣中，本發明的丙烯聚合物組成物如以GPC測定可具有聚合物種類之單峰、雙峰或多峰分子量分佈(M_w /M_n )。雙峰或多峰是指：GPC-SEC記錄曲線具有一個以上的峰值或轉折點。轉折點就是曲線之二次微分的符號之改變(例如，由負到正或反之亦然)的點。In a preferred embodiment, the propylene polymer composition of the present invention may be a unimodal reactor stage of two or more propylene polymers, a bimodal reactor stage, an in-reactor blend, or an extruder blend. a compound (for example, a blend of MFR of 36 dg/min and 2 dg/min). In another aspect of the embodiment, the propylene polymer composition of the present invention as measured by GPC of the polymer species may have monomodal, bimodal or multimodal molecular weight distribution (M _w / M _n). Bimodal or multimodal means that the GPC-SEC recording curve has more than one peak or turning point. The turning point is the point at which the sign of the second derivative of the curve changes (for example, from negative to positive or vice versa).

本發明之組成物有利地呈現模製零件的有利物理性質，包括高硬挺度(撓曲模數)、高降伏抗拉強度、高降伏應變和高熱變形溫度，即使沒有使用成核劑。在另一實施態樣中，本發明的丙烯聚合物組成物具有190kpsi或更高(較佳大於200kpsi，較佳大於210kpsi)的以ASTM D790A(具有0%成核劑)測定之1%正割撓曲模數。The compositions of the present invention advantageously present advantageous physical properties of the molded part, including high stiffness (flexural modulus), high drop tensile strength, high relief strain, and high heat distortion temperature, even without the use of a nucleating agent. In another embodiment, the propylene polymer composition of the present invention has a 1% secant of 190 kpsi or higher (preferably greater than 200 kpsi, preferably greater than 210 kpsi) as measured by ASTM D790A (with 0% nucleating agent). Flexural modulus.

在本發明之另一實施態樣中，本發明的丙烯聚合物組成物具有大於4,700psi(較佳大於5,000psi，較佳大於5,100psi)的以ASTM 638(具有0%成核劑)測定之降伏應力。在本發明之另一實施態樣中，該組成物具有大於 7%(較佳大於8% psi，和較佳大於9%)的以測定ASTM 638(具有0%成核劑的)之降伏應變。In another embodiment of the invention, the propylene polymer composition of the invention has an ASTM 638 (with 0% nucleating agent) having greater than 4,700 psi (preferably greater than 5,000 psi, preferably greater than 5,100 psi). Falling stress. In another embodiment of the invention, the composition has a greater than 7% (preferably greater than 8% psi, and preferably greater than 9%) is used to determine the strain at break of ASTM 638 (with 0% nucleating agent).

在本發明之另一實施態樣中，本發明的丙烯聚合物組成物具有4,700psi或更高(較佳大於5,000psi，較佳大於5,100psi)(如以具有0重量%成核劑的ASTM 638測定)之降伏抗拉強度。In another embodiment of the invention, the propylene polymer composition of the invention has 4,700 psi or greater (preferably greater than 5,000 psi, preferably greater than 5,100 psi) (e.g., ASTM with 0% by weight nucleating agent) 638 measured) tensile strength of tensile strength.

在本發明之另一實施態樣中，該組成物具有於66psi的以ASTM D648(具有0%成核劑)測定之95℃或更高(較佳大於98℃，較佳大於100℃，較佳大於105℃)的熱變形溫度。In another embodiment of the invention, the composition has a temperature of 95 ° C or higher (preferably greater than 98 ° C, preferably greater than 100 ° C, as measured by ASTM D648 (with 0% nucleating agent) at 66 psi. The heat distortion temperature is preferably greater than 105 ° C).

聚合物微結構係以如在後文測試方法一節中所述之¹³ C NMR光譜測定，包括同排和對排二單元組(diads)([m]和[r])、三單元組(triads)([mm]和[rr])、和五單元組(pentads)([mmmm]和[rrrr])之濃度。名稱“m”或“r”描述連續丙烯基對的立體化學，“m”係指內消旋和“r”係指外消旋。存在於可使用於本發明之本發明丙烯聚合物組成物之聚合物具有某種程度的立構規整性。較佳地，存在於可使用於本發明之本發明丙烯聚合物組成物之聚合物具有某種程度的同排度。因此，在本發明之一實施態樣中，同排聚丙烯係使用於本發明丙烯聚合物組成物中。類似地，在本發明的丙烯聚合物組成物之另一實施態樣中可使用高同排聚丙烯。如使用於本文中，“同排”係定義為具有至少10%同排五單元組(pentads)根據藉由¹³ C NMR之分析。如使用於本文中，“高同排”係定義為根據藉由¹³ C NMR之分析具有至少60%同排五單元組(pentads)。在本發明之另一實施態樣中，該組成物如以¹³ C NMR測定(描述於測試一節中)可具有大於97(較佳大於100，較佳大於105，較佳97至150，較佳100至140，較佳105至130)之平均內消旋運行長度(average meso run length)MRL(由下述方程式(16)定義)。The polymer microstructure is determined by ¹³ C NMR spectroscopy as described in the Test Methods section below, including the same row and pair of diads ([m] and [r]), triads (triads). ) ([mm] and [rr]), and the concentration of pentads ([mmmm] and [rrrr]). The designation "m" or "r" describes the stereochemistry of a continuous propylene pair, "m" means meso and "r" means racemic. The polymer present in the propylene polymer composition of the present invention which can be used in the present invention has a certain degree of stereoregularity. Preferably, the polymer present in the propylene polymer composition of the present invention which can be used in the present invention has a certain degree of homology. Therefore, in one embodiment of the present invention, the same row of polypropylene is used in the propylene polymer composition of the present invention. Similarly, high side-row polypropylene can be used in another embodiment of the propylene polymer composition of the present invention. As used herein, "same row" is defined as having at least 10% pentads in the same row according to analysis by ¹³ C NMR. As used herein, "high with the row" system defined according to analysis by ¹³ C NMR of at least 60% with the exhaust pentads (pentads). In another embodiment of the invention, the composition may have a value greater than 97 (preferably greater than 100, preferably greater than 105, preferably 97 to 150, as determined by ¹³ C NMR (described in the test section). An average meso run length MRL of 100 to 140, preferably 105 to 130) (defined by equation (16) below).

在本發明之另一實施態樣中，本發明的丙烯聚合物組成物中所使用之該聚合物為對排，較佳高對排。如使用於本文中，“對排”係定義為根據藉由¹³ C NMR之分析具有至少10%對排五單元組(pentads)。如使用於本文中，“高對排”係定義為根據藉由¹³ C NMR之分析具有至少60%對排五單元組。In another embodiment of the present invention, the polymer used in the propylene polymer composition of the present invention is in a row, preferably in a high row. As used herein, "paired" is defined as having at least 10% pentads according to analysis by ¹³ C NMR. As used herein, "high-pair" is defined as having at least 60% pairs of pentads according to analysis by ¹³ C NMR.

在本發明之另一實施態樣中，本發明的丙烯聚合物組成物可包含立體異構聚合物與雜排丙烯聚合物的摻合物。雜排聚丙烯係定義為小於10%同排或對排五單元組(pentads)。較佳雜排聚丙烯通常具有10,000高達1,000,000克/莫耳之M_w 。In another embodiment of the invention, the propylene polymer composition of the invention may comprise a blend of a stereoisomeric polymer and a hetero-displaced propylene polymer. Miscellaneous polypropylene is defined as less than 10% of the same row or pentads. Preferred miscellaneous polypropylenes typically have a _{Mw of} 10,000 up to 1,000,000 grams per mole.

本文中可使用的丙烯聚合物包括彼等由包括具有60%或更大(較佳70%或更大，較佳80%或更大，較佳90%或更大)之組成物分佈寬度指數(CDBI)的丙烯聚合物之茂金屬觸媒系統製備者。CDBI係如WO 93/03093中所述中測量，且忽視任何具有低於25,000克/莫耳的重量平均分子量(M_w )之部分的修正。The propylene polymers which can be used herein include those having a distribution width index consisting of having a composition of 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more. (CDBI) Producer of a metallocene catalyst system for propylene polymers. The CDBI was measured as described in WO 93/03093 and ignored any correction with a weight average molecular weight (M _w ) of less than 25,000 g/mole.

在本發明之另一實施態樣中，本發明的丙烯聚合物組成物可進一步與任何本文所述之聚丙烯(諸如具有22dg/分鐘或更大(較佳20至30dg/分鐘，較佳22至28dg/分鐘，較佳25dg/分鐘之MFR)的均聚丙烯)摻合。本發明的丙烯聚合物組成物以摻合物的重量為基準計可以從1重量%至99重量%(較佳5重量%至50重量%，較佳重量%5至25重量%)存在於該等摻合物中。較佳地，具有22dg/分鐘或更大之MFR的均聚丙烯以摻合物的重量為基準計係以99重量%至1重量%(較佳95重量%至50重量%，較佳95重量%至75重量%)存在於摻合物中和本發明的丙烯聚合物組成物以摻合物的重量為基準計係以從1重量%至99重量%(較佳5重量%至50重量%，較佳5重量%至25重量%)存在於摻合物中。In another embodiment of the present invention, the propylene polymer group of the present invention The product may further be compatible with any of the polypropylenes described herein (such as homopolypropylene having a df of 22 dg/min or greater (preferably 20 to 30 dg/min, preferably 22 to 28 dg/min, preferably 25 dg/min). ) blending. The propylene polymer composition of the present invention may be present in an amount of from 1% by weight to 99% by weight (preferably 5% by weight to 50% by weight, preferably 5% by weight to 25% by weight) based on the weight of the blend. In the blend. Preferably, the homopolypropylene having an MFR of 22 dg/min or greater is from 99% by weight to 1% by weight, based on the weight of the blend, preferably from 95% by weight to 50% by weight, preferably 95% by weight. % to 75% by weight) present in the blend and the propylene polymer composition of the invention is from 1% by weight to 99% by weight (preferably 5% by weight to 50% by weight, based on the weight of the blend) Preferably, 5% to 25% by weight is present in the blend.

使用於減黏之丙烯聚合物Reduced viscosity propylene polymer

在本發明之一較佳實施態樣中，本發明的丙烯聚合物組成物係藉由將具有0.1至8dg/分鐘之MFR的基本丙烯聚合物減黏而製得。本文中可用於製備減黏聚合物的基本丙烯聚合物包括聚丙烯均聚物、聚丙烯共聚物、和其摻合物。均聚物可為同排聚丙烯、對排聚丙烯、或其摻合物(包括與雜排聚丙烯的摻合物)。共聚物可為隨機共聚物、統計共聚物、嵌段共聚物、或其摻合物。製造基本丙烯聚合物之方法不是關鍵，只要其可藉由如US 7,807,769中所述者的漿體、溶液、氣相、超臨界聚合方法、美國專利申請公開第2010/0113718號中所述者的超級溶液均相聚合方法或其他適當方法，且藉由使用適合於聚烯烴類的聚合之觸媒系統(例如戚格勒-納他型觸媒、茂金屬型觸媒、其他適當觸媒系統，或其組合)製造。該等觸媒為此項技藝中所熟知的，且描述於(例如)ZIEGLER CATALYSTS(Gerhard Fink,Rolf Mülhaupt and Hans H.Brintzinger,Eds.,Springer-Verlag 1995)；Resconi等人，Selectivity in Propene Polymerization with Metallocene Catalysts ,100 CHEM.REV.1253-1345(2000)；及I,II METALLOCENE-BASED POLYOLEFINS(Wiley & Sons 2000)。在一較佳實施態樣中，該基本丙烯聚合物係藉由US 6,342,566；6,384,142；5,741,563；WO 03/040201；及WO 97/19991中所述之觸媒、活化劑和方法製造。In a preferred embodiment of the invention, the propylene polymer composition of the invention is prepared by debonding a substantially propylene polymer having an MFR of from 0.1 to 8 dg/min. The basic propylene polymers useful herein to prepare the reduced viscosity polymer include polypropylene homopolymers, polypropylene copolymers, and blends thereof. The homopolymer can be a homogenous polypropylene, an aligned polypropylene, or a blend thereof (including blends with heteropolypropylene). The copolymer can be a random copolymer, a statistical copolymer, a block copolymer, or a blend thereof. The method of making the basic propylene polymer is not critical as long as it can be as described in the slurry, solution, gas phase, supercritical polymerization process, as described in US Pat. No. 7,013,769, the disclosure of which is incorporated herein by reference. Super-solution homogeneous polymerization process or other suitable method, and by using a catalyst system suitable for polymerization of polyolefins (for example, a Zigler-Nano catalyst, a metallocene catalyst, other suitable catalyst systems, Or a combination thereof). Such catalysts are well known in the art and are described, for example, in ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mülhaupt and Hans H. Brintzinger, Eds., Springer-Verlag 1995); Resconi et al., Selectivity in Propene Polymerization With Metallocene Catalysts , 100 CHEM.REV.1253-1345 (2000); and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000). In a preferred embodiment, the basic propylene polymer is produced by the catalysts, activators and methods described in US 6,342,566; 6,384,142; 5,741,563; WO 03/040201; and WO 97/19991.

在一較佳實施態樣中，該基本丙烯聚合物可為二或多種丙烯聚合物之單峰反應器級、雙峰反應器級、反應器內摻合物、或擠出機摻合物(例如，0.8dg/分鐘和2dg/分鐘的MFR之摻合物)。基本聚合物如以GPC測定可具有聚合物種類之單峰、雙峰或多峰分子量分佈(M_w /M_n )。雙峰或多峰是指：GPC-SEC記錄曲線具有一個以上的峰值或轉折點。轉折點就是曲線之二次微分的符號之改變(例如，由負到正或反之亦然)的點。通常，基本聚合物係減黏至較佳在10至25dg/分鐘(更佳14至19dg/分鐘)之範圍的最終MFR。在本發明之另一實施態樣中，該基本聚合物不需要用於增加MFR之過氧化物裂解，只要反應器內基本聚合物具有所要MFR(例如，在10至25 dg/分鐘之範圍和流變特性)。本發明之組成物也可為一種有或沒有過氧化物裂解步驟的二或多種丙烯聚合物的擠出機摻合物，只要在關鍵熔體流變參數、結晶和立構規整性特性的組合是令人滿意的。In a preferred embodiment, the basic propylene polymer can be a unimodal reactor stage, a bimodal reactor stage, an in-reactor blend, or an extruder blend of two or more propylene polymers ( For example, a blend of MFR of 0.8 dg/min and 2 dg/min). As the base polymer measured by GPC of the polymer species may have monomodal, bimodal or multimodal molecular weight distribution (M _w / M _n). Bimodal or multimodal means that the GPC-SEC recording curve has more than one peak or turning point. The turning point is the point at which the sign of the second derivative of the curve changes (for example, from negative to positive or vice versa). Typically, the base polymer is reduced to a final MFR in the range of preferably from 10 to 25 dg/min (more preferably from 14 to 19 dg/min). In another embodiment of the invention, the base polymer is not required to increase peroxide cracking of the MFR as long as the base polymer in the reactor has the desired MFR (eg, in the range of 10 to 25 dg/min and Rheological properties). The composition of the present invention may also be an extruder blend of two or more propylene polymers with or without a peroxide cracking step, as long as the combination of key melt rheological parameters, crystallization and stereoregularity characteristics It is satisfactory.

可用於製造本發明之減黏聚合物的較佳基本丙烯聚合物通常具有：1. 240,000至2,000,000克/莫耳(較佳265,000至800,000，更佳300,0000至600,000)之M_w ，如以在測試方法章節中所描述之GPC方法測量；及/或2. 1至25(較佳1.6至15，更佳2至8，更佳3至6)之M_w /M_n ，如以在測試方法章節中所描述之GPC方法測量；及/或3. 100℃至200℃(較佳120℃至185℃，較佳130℃至175℃，更佳140℃至170℃，甚至更佳155℃至167℃)之Tm(第二熔體，1℃/分鐘斜坡速度，也稱為“T_mp ”)，如以測試方法中之下述DSC方法測量；及/或4. 20%至80%，較佳10%至70%，更佳35%至55%之百分比結晶度(根據結晶之熱)，如以測試方法中之下述DSC方法測量；及/或5. -50℃至120℃(較佳-20℃至100℃，更佳0℃至90℃)之玻璃轉移溫度(Tg)，如以測試方法中之下述DSC方法測定；及/或6. 50℃至170℃(較佳100℃至150℃，更佳110℃至 145℃，較佳115℃至135℃)之具有0%成核劑的結晶溫度(Tc 1℃/分鐘斜坡速度，也稱為“T_cp ”)，如以測試方法中之下述DSC方法測量；及/或7. 0.85或更大(較佳0.90或更大，較佳0.95或更大，較佳0.99或更大)之分枝指數(g’_vis )，如以測試方法章節中所述之GPC方法測量；及/或8. 0.1至8dg/分鐘(較佳0.5至5dg/分鐘，更佳0.8至3dg/分鐘)之MFR(ASTM 1238，230℃，2.16公斤)；及/或9. 至少10%立構規整性(例如，至少對排或至少10%同排)。Preferred base propylene polymers which can be used in the manufacture of the reduced viscosity polymer of the present invention typically have a M _{w of} from 1.240,000 to 2,000,000 grams per mole (preferably from 265,000 to 800,000, more preferably from 300,000 to 600,000). Measured by the GPC method described in the Test Methods section; and/or M _w /M _{n of} 2.1 to 25 (preferably 1.6 to 15, more preferably 2 to 8, more preferably 3 to 6), as in the test GPC method measurement as described in the method section; and / or 3. 100 ° C to 200 ° C (preferably 120 ° C to 185 ° C, preferably 130 ° C to 175 ° C, more preferably 140 ° C to 170 ° C, even better 155 ° C Tm to 167 ° C) (second melt, 1 ° C / min ramp rate, also referred to as "T _mp "), as measured by the following DSC method in the test method; and / or 4. 20% to 80% , preferably from 10% to 70%, more preferably from 35% to 55%, based on the heat of crystallization, as measured by the following DSC method in the test method; and/or from 5.50 ° C to 120 ° C The glass transition temperature (Tg) of (preferably -20 ° C to 100 ° C, more preferably 0 ° C to 90 ° C), as determined by the following DSC method in the test method; and / or 6. 50 ° C to 170 ° C (more Preferably from 100 ° C to 150 ° C, more preferably from 110 ° C to 145 ° C, preferably 115 ° C 135 deg.] C) having a crystallization temperature of 0% of a nucleating agent (Tc 1 ℃ / min ramp rate, also referred to as "T _cp"), as described below in the test methods of measuring the DSC method; and / or 0.85 or 7. a greater (preferably 0.90 or greater, preferably 0.95 or greater, preferably 0.99 or greater) branching index (g' _vis ) as measured by the GPC method described in the Test Methods section; and/or 8. MFR (ASTM 1238, 230 ° C, 2.16 kg) of 0.1 to 8 dg/min (preferably 0.5 to 5 dg/min, more preferably 0.8 to 3 dg/min); and/or 9. at least 10% stereoregularity ( For example, at least for rows or at least 10% in the same row).

本文中可使用的基本丙烯均聚物或丙烯共聚物較佳具有某種程度的同排度。因此，在本發明之一實施態樣中，同排聚丙烯在本文中可用作基本丙烯聚合物。類似地，在另一實施態樣中高同排聚丙烯可用作基本聚合物。在本發明之另一實施態樣中，該基本丙烯聚合物可具有大於50(更佳大於80，更佳大於100，更佳大於105)之平均內消旋運行長度(average meso run length)MRL(由下述方程式(16)定義)，如以¹³ C NMR測定(測試方法章節中所述)。The basic propylene homopolymer or propylene copolymer that can be used herein preferably has some degree of homology. Thus, in one embodiment of the invention, the same row of polypropylene can be used herein as a base propylene polymer. Similarly, in another embodiment, high homopolymer polypropylene can be used as the base polymer. In another embodiment of the invention, the basic propylene polymer may have an average meso run length MRL of greater than 50 (more preferably greater than 80, more preferably greater than 100, still more preferably greater than 105). (defined by equation (16) below) as determined by ¹³ C NMR (described in the Test Methods section).

在本發明之另一實施態樣中，本文中可使用的該基本丙烯聚合為對排，較佳高對排。如使用於本文中，“對排”係定義為根據藉由¹³ C NMR之分析具有至少10%對排五單元組(pentads)。如使用於本文中，“高對排”係定義為根據藉由¹³ C NMR之分析具有至少60%對排五單元組(pentads)。In another embodiment of the invention, the base propylene polymerizable herein can be used in a row, preferably in a high row. As used herein, "paired" is defined as having at least 10% pentads according to analysis by ¹³ C NMR. As used herein, "high-pair" is defined as having at least 60% pentads according to analysis by ¹³ C NMR.

在本發明之另一實施態樣中，本文中可使用的基本丙烯聚合物可包含立體異構聚合物(諸如同排聚丙烯或高同排聚丙烯)與雜排丙烯聚合物之摻合物。雜排聚丙烯係定義為小於10%同排或對排五單元組(pentads)。可使用的雜排聚丙烯通常具有10,000高達1,000,000克/莫耳之M_w 。In another embodiment of the invention, the basic propylene polymer that can be used herein can comprise a blend of a stereoisomeric polymer (such as a homogenous polypropylene or a high homopolymer polypropylene) with a heterodisplaced propylene polymer. . Miscellaneous polypropylene is defined as less than 10% of the same row or pentads. The miscellaneous polypropylene that can be used typically has a _{Mw of} 10,000 up to 1,000,000 grams per mole.

減黏/鏈切斷Viscosity reduction / chain cutting

術語“減黏”和“鏈切斷”可互換使用且定義為使用一或多種自由基引發劑增加聚合物熔體流動速度(MFR)之方法。此描述於US 6,747,114中。“自由基引發劑”係定義為具有一個或多個不成對電子的分子片段。The terms "reduced tack" and "chain cut" are used interchangeably and are defined as a method of increasing the melt flow rate (MFR) of a polymer using one or more free radical initiators. This is described in US 6,747,114. A "radical initiator" is defined as a molecular fragment having one or more unpaired electrons.

當基本聚合物或聚合物的摻合物用自由基引發劑(例如過氧化物)處理(較佳同時聚合物處於熔融狀態下，更佳處於完全熔融狀態下)時，該聚合物根據本發明進行鏈切斷。較佳地，控制該鏈切斷。例如，當使用自由基引發劑時，待處理的聚合物之自由基係藉由過氧化物的熱切斷產生。也可利用其他自由基源諸如重氮化合物、氧、或其他化合物。在任何情況下預期：從引發劑(例如過氧化物)產生的自由基提取聚合物的丙烯殘基上之三級氫。所得的自由基歧化成兩個較低分子量的鏈，一個具有接近末端的烯烴，另一個是飽和聚合物。此方法可繼續產生連續地較低分子量聚合物。因此，在適當條件下，引發鏈切斷而引起聚合物或聚合物摻合物之受控降解。When the base polymer or blend of polymers is treated with a free radical initiator (e.g., a peroxide) (preferably while the polymer is in a molten state, more preferably in a fully molten state), the polymer is in accordance with the present invention Perform chain cutting. Preferably, the chain is controlled to be severed. For example, when a free radical initiator is used, the free radicals of the polymer to be treated are produced by thermal cleavage of the peroxide. Other sources of free radicals such as diazonium compounds, oxygen, or other compounds may also be utilized. It is contemplated in any case that the free radicals generated from the initiator (e.g., peroxide) extract the tertiary hydrogen on the propylene residue of the polymer. The resulting free radical disproportionates into two lower molecular weight chains, one with near end The olefin is at the end and the other is a saturated polymer. This process can continue to produce continuously lower molecular weight polymers. Thus, under appropriate conditions, chain scission is initiated to cause controlled degradation of the polymer or polymer blend.

交聯為一種可在鏈切斷期間發生的競爭過程。在交聯反應中，自由基相結合而形成更高分子量的分枝巨分子。最後，此合成反應可導致聚合物的硫化。在乙烯和丙烯的共聚物中，此交聯和降解的平衡主要取決於共聚物的組成。因為降解反應唯一地與丙烯殘基相關，在共聚物中較低量的丙烯傾向於交聯勝於降解。然而，應該認知到：切斷和交聯反應不互相排除。也就是說，甚至在降解期間，也可發生一些量的分枝。在某些情況下，因為該分枝和切斷反應是隨機的且不導致M_w /M_n 的增加。分枝的量取決於許多變數，主要是反應條件、聚合物的組成和降解的程度。具有較高乙烯含量的隨機共聚物應產生比具有較低乙烯含量者高的分枝水平。因此，在本發明的某些實施態樣中，降解的速度或程度實質上與丙烯和乙烯位置的相對量成比例。例如，如果存在太多的乙烯位置，則過氧化物或其他自由基引發劑的使用可能導致交聯而不是鏈切斷，並且被處理的材料將不降解到較高MFR。因此，本發明的某些特定實施態樣的重要方面關於摻合物中所使用之聚合物的相對量。在基本丙烯聚合物的摻合物中，對於聚合物兩者彼此獨立地發生這些降解過程。Crosslinking is a competitive process that can occur during chain cuts. In the cross-linking reaction, the radicals combine to form a higher molecular weight branched macromolecule. Finally, this synthesis reaction can result in the vulcanization of the polymer. In the copolymer of ethylene and propylene, the balance of this crosslinking and degradation depends mainly on the composition of the copolymer. Since the degradation reaction is uniquely associated with propylene residues, lower amounts of propylene in the copolymer tend to crosslink rather than degrade. However, it should be recognized that the cut-off and cross-linking reactions are not mutually exclusive. That is, some amount of branching can occur even during degradation. In some cases, because of the branching reactions are random and cut without causing increase in M _w / M _n of. The amount of branching depends on a number of variables, primarily the reaction conditions, the composition of the polymer, and the extent of degradation. Random copolymers having a higher ethylene content should produce higher levels of branching than those having a lower ethylene content. Thus, in certain embodiments of the invention, the rate or extent of degradation is substantially proportional to the relative amount of propylene and ethylene sites. For example, if too much ethylene is present, the use of peroxides or other free radical initiators may result in cross-linking rather than chain scission, and the treated material will not degrade to higher MFR. Thus, an important aspect of certain specific embodiments of the invention pertains to the relative amount of polymer used in the blend. In a blend of substantially propylene polymers, these degradation processes occur independently of each other for the polymer.

自由基引發劑(例如，過氧化物)可在聚合物處於固體形式時被添加到聚合物中，例如用引發劑(諸如過氧化物，其可於粉末、液體、或其他形式)塗覆聚合物粒料，在該情況下當引發劑變成活性(其通常在高於聚合物熔點的溫度下發生)時，該聚合物被稱為用引發劑“處理”。然而，較佳地，在聚合物已經形成之後，但在聚合物處於熔融狀態下之時，例如，在後聚合加工期間，諸如當聚合物混合物(其可包括溶劑)被引入到脫揮發分器或擠出機中時，將自由基引發劑添加到聚合物中，其典型地在升高的溫度下進行。A free radical initiator (eg, a peroxide) can be added to the polymer when the polymer is in a solid form, such as with an initiator (such as peroxidation) a polymer, which may be coated in a powder, liquid, or other form, in which case the polymer is said to be active when it becomes active (which typically occurs at temperatures above the melting point of the polymer) To "treat" with an initiator. Preferably, however, after the polymer has been formed, but while the polymer is in a molten state, for example, during a post polymerization process, such as when a polymer mixture (which may include a solvent) is introduced to the devolatilizer In the case of an extruder, a free radical initiator is added to the polymer, which is typically carried out at elevated temperatures.

術語“熔融”係指當任何部分的聚合物被熔融時之聚合物的狀態，且包括完全熔融和部分熔融。較佳地，在聚合物的溫度係在其熔點以上之時，以自由基引發劑處理聚合物。The term "melting" refers to the state of the polymer when any portion of the polymer is melted, and includes complete melting and partial melting. Preferably, the polymer is treated with a free radical initiator while the temperature of the polymer is above its melting point.

在一實施態樣中，該減黏劑為過氧化物和在另一實施態樣中為有機過氧化物，其中至少一甲基或高級烷基或芳基鍵結至過氧化物之一或二個氧原子。在又另一實施態樣中，該減黏劑為位阻過氧化物，其中與各氧原子結合的烷基或芳基為至少一種二級碳，在另一實施態樣中為三級碳。位阻受阻過氧化物(“減黏劑”)之非限制例包括2,5-雙(三級丁過氧)-2,5-二甲基己烷、2,5-二甲基-2,5-雙-(三級丁過氧)-己炔-3,4-甲基-4-三級丁過氧-2-戊酮、3,6,6,9,9-五甲基-3-(乙基乙酸酯)-1,2,4,5-四氧基(textraoxy)環壬烷、α,α’-雙-(三級丁過氧)二異丙基苯和此等與任何其他二級-或三級-受阻過氧化物的混合物。一較佳過氧化物為2,5-雙(三級丁過氧)-2,5-二甲基 -己烷，也已知為商品名：Luperox 101或Trigonox 101。Luperox 101或Trigonox 101可以純液體形式或以在礦油中之母料摻合物(例如Trigonox 101/礦油之50/50重量/重量摻合物)進料至擠出機。用作聚丙烯之減黏劑的另一種常見過氧化物為二-三級-戊基過氧化物，最常見的商品名DTAP。或者，該自由基引發劑可包括重氮化合物，或任何促進自由基之其他化合物或化學品，其於如本文中所指定之足以引起降解之量。In one embodiment, the viscosity reducing agent is a peroxide and in another embodiment is an organic peroxide wherein at least one methyl or higher alkyl or aryl group is bonded to one of the peroxides or Two oxygen atoms. In still another embodiment, the viscosity reducing agent is a hindered peroxide, wherein the alkyl or aryl group bonded to each oxygen atom is at least one secondary carbon, and in another embodiment is a tertiary carbon. . Non-limiting examples of sterically hindered peroxides ("viscosifiers") include 2,5-bis(tri-butyl peroxy)-2,5-dimethylhexane, 2,5-dimethyl-2 , 5-bis-(tri-tert-butyl peroxy)-hexyne-3,4-methyl-4-tri-butylbutoxy-2-pentanone, 3,6,6,9,9-pentamethyl- 3-(ethyl acetate)-1,2,4,5-tetraoxy (textraoxy) cyclodecane, α,α'-bis-(tertiary butylperoxy)diisopropylbenzene and these Mixture with any other secondary- or tertiary-blocked peroxide. A preferred peroxide is 2,5-bis(tri-tert-butylperoxy)-2,5-dimethyl Hexane, also known as the trade name: Luperox 101 or Trigonox 101. Luperox 101 or Trigonox 101 can be fed to the extruder in pure liquid form or as a masterbatch blend in mineral oil (eg, a 50/50 weight/weight blend of Trigonox 101/mineral oil). Another common peroxide used as a viscosity reducing agent for polypropylene is di-tertiary-pentyl peroxide, the most common trade name DTAP. Alternatively, the free radical initiator may comprise a diazonium compound, or any other compound or chemical that promotes free radicals, in an amount sufficient to cause degradation as specified herein.

本文中可使用的較佳丙烯聚合物，包括彼等已用減黏劑處理致使其MFR被增加至少10%(較佳至少50%較佳至少100%，較佳至少300%，較佳至少500%，較佳至少650%)者。倘若聚合物為不同丙烯聚合物的摻合物，則個別摻合物組分之MFR的根據對數重量摻合規則(Robeson,L.M.，“聚合物摻合物”，Carl Hanser Verlag，Munich 2007，第6章，第368頁)之平均MFR係用以測定摻合物之MFR並發現導致研究系統之摻合物MFR的極佳評估。例如，對於二組分系統，ln(摻合物之熔體流動速度)=(組分1之重量分率×ln(組分1之熔體流動速度)+組分2之重量分率×ln(組分2之熔體流動速度)。在另一實施態樣中，該減黏聚合物具有其為大於用以製造減黏聚合物之基本聚合物的從10至25單元(dg/分鐘)(較佳12至22dg/分鐘，較佳14至19dg/分鐘)之MFR。Preferred propylene polymers useful herein, including those which have been treated with a viscosity reducing agent, result in an MFR increase of at least 10% (preferably at least 50%, preferably at least 100%, preferably at least 300%, preferably at least 500). %, preferably at least 650%). If the polymer is a blend of different propylene polymers, the MFR of the individual blend components is based on a logarithmic weight blending rule (Robeson, LM, "Polymer Blends", Carl Hanser Verlag, Munich 2007, The average MFR of Chapter 6, page 368) was used to determine the MFR of the blend and found an excellent assessment of the MFR of the blend that led to the study system. For example, for a two-component system, ln (melt flow rate of the blend) = (weight fraction of component 1 × ln (melt flow rate of component 1) + weight fraction of component 2 × ln (Melt flow rate of component 2). In another embodiment, the viscosity reducing polymer has from 10 to 25 units (dg/min) which is greater than the base polymer used to make the reduced viscosity polymer. MFR (preferably 12 to 22 dg/min, preferably 14 to 19 dg/min).

添加劑additive

各種添加劑可被併入上述實施態樣中，用以製造纖維和織物或用於目的之模製材料。該等添加劑包括(例如)穩定劑、抗氧化劑、填料、著色劑、成核劑和滑動添加劑。一級和二級抗氧化劑包括(例如)受阻酚類、受阻胺類、和磷酸酯類。成核劑包括(例如)苯甲酸鈉、滑石、和其他化學品。且，也可使用其他成核劑諸如戚格勒-納他烯烴產物或其他高結晶性聚合物。也可包括其他添加劑諸如分散劑，例如，Acrowax C。滑動劑包括(例如)油酸醯胺、和芥酸醯胺(erucamide)。亦常用觸媒去活化劑，例如硬脂酸鈣、水滑石及氧化鈣、酸中和劑、及該技藝中已知的其他化學品。Various additives may be incorporated into the above embodiments for the production of fibers and fabrics or molding materials for the purpose. Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents, and slip additives. Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphates. Nucleating agents include, for example, sodium benzoate, talc, and other chemicals. Also, other nucleating agents such as a Ziegler-Natta olefin product or other highly crystalline polymers may be used. Other additives such as dispersants may also be included, for example, Acrowax C. Sliding agents include, for example, decyl oleate, and erucamide. Catalyst deactivators such as calcium stearate, hydrotalcite and calcium oxide, acid neutralizers, and other chemicals known in the art are also commonly used.

其他添加劑可包括(例如)防火劑/阻燃劑、塑化劑、固化劑、固化加速劑、固化阻滯劑、加工助劑、增黏樹脂、等等。前述添加劑也可包括填料及/或強化材料，無論是單獨或併入添加劑添加。實例包括碳碳黑、黏土、滑石、碳酸鈣、雲母、矽石、矽酸鹽及其組合、等等。可用以提高性質之其他添加劑包括抗結塊劑、潤滑劑、和成核劑。本文所述之名單不意欲包括所有可被本發明使用之類型的添加劑在內。成核劑和填料傾向於改良在某些種類的模製零件中特別想要的物件之剛性。Other additives may include, for example, fire retardants/flame retardants, plasticizers, curing agents, curing accelerators, curing retarders, processing aids, tackifying resins, and the like. The aforementioned additives may also include fillers and/or reinforcing materials, either alone or in combination with the addition of additives. Examples include carbon black, clay, talc, calcium carbonate, mica, vermiculite, silicates, combinations thereof, and the like. Other additives that can be used to enhance the properties include anti-caking agents, lubricants, and nucleating agents. The list described herein is not intended to include all additives of the type that can be used by the present invention. Nucleating agents and fillers tend to improve the rigidity of articles that are particularly desirable in certain types of molded parts.

衆所周知，在製造一些熔紡纖維時，界面活性劑及其他活性劑可包括在待熔融加工的聚合物中。僅作為例子，US 3,973,068和4,070,218教示一種混合界面活性劑與聚合物且然後將該混合物熔融加工而形成所要織物的方法。然後處理該織物以促使界面活性劑至纖維的表面上。此經常藉由在串聯熱輥上加熱網來進行並經常稱為“起霜”。作為另一例子，US 4,578,414描述由包含聚烯烴和一或多種界面活性劑的組成物形成之可濕性烯烴聚合物纖維。據稱界面活性劑在纖維表面上起霜，其中界面活性劑中的至少一者保持部分地埋入聚合物基質中。在此方面，可透過添加劑包的組成和濃度更好地控制可濕性的持久性。更進一步地，Nohr等人的US 4,923,914敎示一種適合於藉由熔融擠出加工而形成纖維或薄膜的表面可分開的、可熔融擠出的熱塑性組成物，該纖維或薄膜從該纖維或薄膜的中心到其表面具有微分增加的添加劑濃度。該微分增加的濃度賦予纖維表面所需特性，例如親水性。作為Nohr中的實施態樣，利用各種聚矽氧烷提供具有改良可濕性的聚烯烴纖維非織物網。It is well known that in the manufacture of some melt spun fibers, surfactants and other active agents may be included in the polymer to be melt processed. By way of example only, US 3,973,068 and 4,070,218 teach a mixed surfactant and poly And then the mixture is melt processed to form the desired fabric. The fabric is then treated to promote surfactant to the surface of the fiber. This is often done by heating the web on a tandem heat roll and is often referred to as "blooming". As another example, US 4,578,414 describes wettable olefin polymer fibers formed from a composition comprising a polyolefin and one or more surfactants. The surfactant is said to bloom on the surface of the fiber wherein at least one of the surfactants remains partially embedded in the polymer matrix. In this regard, the persistence of wettability can be better controlled by the composition and concentration of the additive package. No. 4,923,914 to Nohr et al. discloses a surface separable, melt-extrudable thermoplastic composition suitable for forming fibers or films by melt extrusion processing from which the fibers or films are formed. The center has a differentially increased additive concentration to its surface. The increased concentration of the differential imparts desired properties to the surface of the fiber, such as hydrophilicity. As an embodiment in Nohr, a polyolefin fiber nonwoven web having improved wettability is provided using various polyoxyalkylenes.

當然，可根據所需選擇包括在一或多種組分內的特定活性劑或劑等以賦予或改良纖維的特定表面特性並從而改良由其製備之織物的性質。各種活性劑或化學化合物至今已用來賦予或改良各種表面性質，包括但不限於吸收性、可濕性、抗靜電性質、抗微生物性質、抗真菌性質、撥液性(例如，醇或水)、等等。關於特定織物之可濕性或吸收性，許多織物固有地顯示僅對特定液體的良好親和性或吸收特性。例如，聚烯烴非織物網至今已經用來吸收油或以烴為主之液體。在此方面，烯烴非織物擦拭布固有地為親油性和疏水性。因此，聚烯烴非織物可以一些方式處理以賦予對水或水溶液或乳液的良好潤濕特性或吸收性。舉例來說，可以熔融加工以賦予纖維改良可濕性的示例性濕潤劑包括(但不限於)乙氧基化矽酮界面活性劑、乙氧基化烴界面活性劑、乙氧基化氟烴界面活性劑、等等。此外，可用於使熔融加工的熱塑性纖維變得更親水性的示例性化學物質係描述於在US 3,973,068；4,070,218；及US 5,696,191中。Of course, the particular active agent or agent, etc., included in one or more of the components can be selected as desired to impart or modify the particular surface characteristics of the fiber and thereby improve the properties of the fabric prepared therefrom. Various active agents or chemical compounds have heretofore been used to impart or modify various surface properties including, but not limited to, absorbency, wettability, antistatic properties, antimicrobial properties, antifungal properties, liquid repellency (eg, alcohol or water). ,and many more. Regarding the wettability or absorbency of a particular fabric, many fabrics inherently exhibit good affinity or absorption characteristics only for a particular liquid. For example, polyolefin nonwoven webs have hitherto been used to absorb oil or hydrocarbon-based liquids. In this regard, the olefin non-woven wipes are inherently Lipophilic and hydrophobic. Thus, polyolefin nonwovens can be treated in some manner to impart good wetting characteristics or absorbency to water or aqueous solutions or emulsions. For example, exemplary wetting agents that can be melt processed to impart improved wettability to the fibers include, but are not limited to, ethoxylated fluorenone surfactants, ethoxylated hydrocarbon surfactants, ethoxylated fluorocarbons Surfactant, and the like. In addition, exemplary chemistries that can be used to make melt-processed thermoplastic fibers more hydrophilic are described in U.S. Patent Nos. 3,973,068, 4,070,218, and 5,696,191.

在另一方面，經常希望提高織物對特定液體的障壁性質或排斥特性。作為具體例子，在感染控制產品和醫療服裝方面，經常希望提供對水和醇都具有良好障壁或排斥性質的織物。在此方面，熱塑性纖維較佳排斥水或醇的能力可如下賦予：在擠出之前混合具有所需排斥特性的化學組成物與熱塑性聚合物樹脂，且之後將該混合物熔融加工成一或多個片段。該活性劑遷移到聚合物組分的表面，從而改良該聚合物組分的表面性質。此外，據信：暴露在含顯著水平之活性劑的纖維之外表面上的組分之間的距離或間隙足夠小而允許活性劑有效改良整個纖維的功能性質並因此獲得具有所要性質的織物。適合使用於熔融擠出方法並改良撥醇性之化學組成物包括(但不限於)氟化學品。示例性可熔融加工的撥液性劑包括該等以商標名ZONYL氟化學品購自美國杜邦者以及該等以商品名FX-1801購自3M者。適合於將撥醇性賦予至熱塑性纖維之各種活性劑係描述於US 5,145,727；US 4,855,360；US 4,863,983； US 5,798,402；US 5,459,188；及US 5,025,052中。除了撥醇性之外，化學組成物可用以類似地改良對其他低表面張力液體之排斥性或障壁性質。利用本發明，可在纖維的形成期間發現許多上述所討論之有利性質。On the other hand, it is often desirable to increase the barrier properties or repellency properties of the fabric to a particular liquid. As a specific example, in the case of infection control products and medical garments, it is often desirable to provide a fabric having good barrier or repellent properties to both water and alcohol. In this regard, the ability of the thermoplastic fibers to preferably repel water or alcohol can be imparted by mixing a chemical composition having the desired repellency characteristics with a thermoplastic polymer resin prior to extrusion, and then melt processing the mixture into one or more fragments. . The active agent migrates to the surface of the polymer component to improve the surface properties of the polymer component. Furthermore, it is believed that the distance or gap between the components exposed on the outer surface of the fibers containing significant levels of active agent is sufficiently small to allow the active agent to effectively improve the functional properties of the overall fiber and thereby obtain a fabric having the desired properties. Chemical compositions suitable for use in melt extrusion processes and to improve alcohol repellency include, but are not limited to, fluorochemicals. Exemplary melt processable liquid-repellent agents include those available under the trade designation ZONYL Fluorochemicals from DuPont, USA, and those available under the trade designation FX-1801 from 3M. Various active agents suitable for imparting alcohol repellency to thermoplastic fibers are described in US 5,145,727; US 4,855,360; US 4,863,983; US 5, 798, 402; US 5,459, 188; and US 5,025,052. In addition to alcohol repellency, chemical compositions can be used to similarly improve the repellency or barrier properties of other low surface tension liquids. With the present invention, many of the advantageous properties discussed above can be found during the formation of the fibers.

加工油可隨意加至上述實施態樣中。有效加工通常為：(a)基本上由碳和氫組成並可能帶有痕量的雜原子如氧的烴類，或(b)基本由碳、氫和至少一個雜原子組成諸如鄰苯二甲酸二辛酯、醚類和聚醚類的烴類。加工油具有實質上在200℃下不揮發的沸點。這些加工油通常可以淨固體或液體獲得或以這些材料在惰性載體(例如黏土、氧化矽)上的物理吸附混合物而形成自由流動的粉末獲得。The processing oil can be arbitrarily added to the above embodiment. Effective processing is generally: (a) a hydrocarbon consisting essentially of carbon and hydrogen and possibly with traces of heteroatoms such as oxygen, or (b) consisting essentially of carbon, hydrogen and at least one hetero atom such as phthalic acid Hydrocarbons of dioctyl esters, ethers and polyethers. The processing oil has a boiling point that is substantially nonvolatile at 200 °C. These processing oils are typically obtained as a neat solid or liquid or as a free flowing powder from a physically adsorbed mixture of these materials on an inert carrier such as clay, cerium oxide.

加工油通常包括很多種可由線型、無環但分枝、環狀和芳族的含碳結構組成之化學化合物的混合物。另一族的加工油是某些具有分子量(M_n )小於10,000之有機酯類和烷基醚酯類。該等加工油的例子包括但不限於來自美國PA,Marcus Hook之The Sun Manufacturing Company的Sunpar^TM 150和220、來自美國Ergon(郵政信箱1639，Jackson,Mass.39215-1639)的Hyprene^TM V750和Hyprene^TM VI 200，以及來自Princeton,La之Calumet Lubricants Co.的IRM903。也可預期：加工油的組合(其之每個係如上所述)可用於本發明的實務中。Process oils typically comprise a wide variety of chemical compounds which may be comprised of linear, acyclic, branched, cyclic and aromatic carbonaceous structures. Another family of process oils having a certain molecular weight (M _n) is less than the organic esters and alkyl ether esters of 10,000. Examples of such processing include, but are not limited to oils derived from U.S. PA, Marcus Hook's of The Sun Manufacturing Company Sunpar ^TM 150 and 220, Hyprene ^TM V750 from United States Ergon (PO Box 1639, Jackson, Mass.39215-1639) and Hyprene ^TM VI 200, and IRM903 from Calumet Lubricants Co. of Princeton, La. It is also contemplated that a combination of processing oils, each of which is as described above, can be used in the practice of the present invention.

在另一實施態樣中，該加工油可為美國專利申請公開號2004/0106723之第3頁第[0050]段至第9頁第[0110]段中所述的任何油類。In another embodiment, the processing oil can be from page 3 [0050] to page 9 [0110] of US Patent Application Publication No. 2004/0106723. Any of the oils described.

加工油加至聚合物可藉由該技藝已知的習用方法中的任何一種來進行。配混步驟可在分批混合器諸如磨機或密閉混合器諸Banbury混合器中進行。配混操作也可以連續方法諸如雙螺桿擠出機進行。The addition of processing oil to the polymer can be carried out by any of the conventional methods known in the art. The compounding step can be carried out in a batch mixer such as a mill or a closed mixer Banbury mixer. The compounding operation can also be carried out in a continuous process such as a twin screw extruder.

本發明的丙烯聚合物組成物可包括每百份的總聚合物之在從1至50之範圍(較佳在從2至20之範圍)重量份的加工油。The propylene polymer composition of the present invention may comprise a processing oil in an amount ranging from 1 to 50, preferably in the range of from 2 to 20, per hundred parts of the total polymer.

在某些實施態樣中，本發明的丙烯聚合物組成物以及其摻合物之各種組分可包括各種量的塑化劑。在一實施態樣中，該塑化劑包含C₆ 至C₂₀₀ 石蠟類和在另一實施態樣中C₈ 至C₁₀₀ 石蠟類。在另一實施態樣中，該塑化劑基本上由C₆ 至C₂₀₀ 石蠟類組成和在另一實施態樣中基本上由C₈ 至C₁₀₀ 石蠟類組成。為了本發明和本文說明之目的，術語“石蠟”包括所有異構物諸如正石蠟類、支鏈石蠟類、異石蠟類，且可包括環狀脂族種類，及其摻合物，也可以該技藝中已知的方法，或以符合本文所述之所要NFP的要求之方式，從精製原油合成得到。In certain embodiments, the propylene polymer compositions of the present invention, as well as the various components of the blends, can include various amounts of plasticizer. In one aspect of the embodiment, the plasticizer comprises C ₆ to C ₂₀₀ paraffins in another embodiment and aspect of the C ₈ to C ₁₀₀ paraffins. In another embodiment, the plasticizer consists essentially of C ₆ to C ₂₀₀ paraffin and in another embodiment consists essentially of C ₈ to C ₁₀₀ paraffin. For the purposes of the present invention and the description herein, the term "paraffin" includes all isomers such as norparaffins, branched paraffins, isoparaffins, and may include cyclic aliphatic species, and blends thereof, as well as Methods known in the art, or synthetically derived from refined crude oil in a manner consistent with the requirements of the desired NFP described herein.

適當塑化劑也包括“異石蠟類”、“聚α烯烴”(PAOs)和“聚丁烯類”。此三種的化合物可描述為石蠟類，其可包括支鏈、環狀和正常結構、及其摻合物。彼等在一實施態樣中可描述為包含C₆ 至C₂₀₀ 石蠟類及在另一實施態樣中C₈ 至C₁₀₀ 石蠟類。Suitable plasticizers also include "isoparaffins", "polyalphaolefins" (PAOs) and "polybutenes". These three compounds can be described as paraffin, which can include branched, cyclic, and normal structures, and blends thereof. They may be described as comprising C ₆ to C ₂₀₀ paraffin in one embodiment and C ₈ to C ₁₀₀ paraffin in another embodiment.

塑化劑可存在於個別組分及/或本發明之摻合物中，在一實施態樣中從0.1重量%至60重量%，在另一實施態樣中從0.5重量%至40重量%，在又另一實施態樣中從1重量%至20重量%，及在又另一實施態樣中從2重量%至10重量%，其中所要範圍可包含本文所述之任何上限重量%與任何下限重量%。Plasticizers may be present in the individual components and/or blends of the invention, In one embodiment, from 0.1% by weight to 60% by weight, in another embodiment from 0.5% by weight to 40% by weight, in yet another embodiment from 1% by weight to 20% by weight, and In still another embodiment, from 2% by weight to 10% by weight, wherein the desired range can include any of the upper limit weight % and any lower limit weight % described herein.

纖維和織物形成Fiber and fabric formation

從聚烯烴類和彼等的摻合物形成非織物通常需要藉由擠出製造纖維並接著固結或黏結。擠出方法通常伴有纖維的機械或氣動拉伸。本發明的織物可藉由任何該技藝中已知的技術製造。該等方法和設備是眾所周知的。例如，紡黏非織物可藉由德國(Troisdorf)的Reifenhauser GmbH & Co.製造的紡黏非織物生產線製造。此利用如US 4,820,142；US 6,918,750；及EP 1340 843 A1中所述的槽縫拉伸技術。另外的有效方法包括該等美國專利申請案公開號2012/0116338 A1和2010/0233928 A1中所揭示者。The formation of non-woven fabrics from polyolefins and their blends typically requires the manufacture of fibers by extrusion followed by consolidation or bonding. Extrusion methods are often accompanied by mechanical or pneumatic stretching of the fibers. The fabric of the present invention can be made by any of the techniques known in the art. These methods and devices are well known. For example, spunbond nonwovens can be made by a spunbond nonwoven line manufactured by Reifenhauser GmbH & Co. of Troisdorf, Germany. This utilizes the slot stretching technique as described in US 4,820,142; US 6,918,750; and EP 1340 843 A1. Other effective methods include those disclosed in the U.S. Patent Application Publication Nos. 2012/0116338 A1 and 2010/0233928 A1.

傳統細丹尼纖維Traditional fine denier fiber

三種較傳統的纖維類型：連續長絲、蓬鬆絲、和短纖維及製造彼等的相關製造方法被預期為本發明纖維之應用。例如，該聚合物熔體可透過直徑介於0.3毫米至0.8毫米之間的模具(紡嘴)的孔擠出。該聚合物的低熔融黏度是重要的且可透過使用所用聚合物的高熔融溫度(例如，230℃至280℃)及高熔融流速(例如10g/10分鐘至 40g/10分鐘)達成。較大的擠出機通常可配備歧管以將高輸出量的熔融PP分配至一排2至50(或者8至20)個紡嘴。各個紡絲頭通常配備單獨的齒輪泵以透過紡絲頭、被“碎料板”支撐的過濾組件，及該頭部內的紡絲板調節輸出量。該紡絲板中的孔數決定紗中的長絲數且隨不同紗結構而顯著地改變，但是其通常在40至100,000(或者50至250)的範圍。該等孔可群集為圓形、環狀或矩形圖案以幫助驟冷空氣流的良好分佈。Three more conventional fiber types: continuous filaments, fluffy filaments, and staple fibers and related manufacturing methods for their manufacture are contemplated for use in the fibers of the present invention. For example, the polymer melt can be extruded through a hole of a mold (spinning nozzle) having a diameter of between 0.3 mm and 0.8 mm. The low melt viscosity of the polymer is important and can be achieved by using the high melting temperature of the polymer used (for example, 230 ° C to 280 ° C) and high melt flow rates (eg 10 g/10 min to 40g/10 minutes) reached. Larger extruders can typically be equipped with manifolds to distribute high output molten PP to a row of 2 to 50 (or 8 to 20) spinning nozzles. Each spinneret is typically equipped with a separate gear pump to regulate the output through the spinneret, the filter assembly supported by the "flap board", and the spinneret within the head. The number of holes in the spinneret determines the number of filaments in the yarn and varies significantly with different yarn configurations, but it is typically in the range of 40 to 100,000 (or 50 to 250). The holes can be clustered into a circular, circular or rectangular pattern to aid in the good distribution of the quench air flow.

連續長絲Continuous filament

連續長絲紗通常範圍從40丹尼至2,000丹尼(丹尼=克數/9000米)。長絲範圍可從1至20丹尼/長絲(dpf)且範圍正不斷擴大。紡絲速度通常為10至10,000米/分鐘(或者800米/分鐘至1500米/分鐘)。示例性的方法將如下進行。長絲係以3：1或更大之拉伸比(一階段或兩階段拉伸)並捲繞到包裝上。兩階段拉伸允許達成較高的拉伸比。捲繞速度為2,000米/分鐘或更大，或者3,500米/分鐘或更大，是有用的。Continuous filament yarns typically range from 40 Danny to 2,000 Danny (Danny = grams / 9000 meters). Filaments range from 1 to 20 denier per filament (dpf) and the range is expanding. The spinning speed is usually from 10 to 10,000 m/min (or from 800 m/min to 1500 m/min). An exemplary method will be performed as follows. The filaments are drawn at a draw ratio of 3:1 or greater (one-stage or two-stage stretch) and wound onto a package. Two-stage stretching allows for a higher draw ratio. A winding speed of 2,000 m/min or more, or 3,500 m/min or more, is useful.

部分定向紗(POY)Partially oriented yarn (POY)

部分定向紗(POY)為無固態拉伸之直接由纖維紡絲製造的纖維(如上述連續長絲)。該纖維中之分子的定向剛好在該熔融聚合物離開紡嘴之後才以熔融態完成。一旦該纖維固化，很少或沒有纖維的拉伸發生且將該纖維纏在包裝中。該POY紗(與透過固態定向且具有較高抗拉強度和較低伸長率的完全定向紗或FOY相反)傾向具有較高伸長率及較低韌度。Partially oriented yarns (POY) are fibers made directly from fiber spinning without solid state stretching (such as the continuous filaments described above). The orientation of the molecules in the fiber is completed in a molten state just after the molten polymer exits the spinning nozzle. Once the fiber is cured, little or no fiber stretching occurs and the fiber is wrapped around In the package. The POY yarn (as opposed to a fully oriented yarn or FOY oriented through a solid state and having a higher tensile strength and lower elongation) tends to have a higher elongation and a lower toughness.

蓬鬆連續絲Fluffy continuous wire

蓬鬆連續絲(“CF”)製造方法分成兩種基本類型，一步驟和兩步驟。例如，在兩步驟方法中，以小於1,000米/分鐘(3,300呎/分鐘)，通常750m/分鐘，將未拉伸紗紡絲，並置於包裝上。將該紗拉伸(通常以二階段)並在所謂的組織形成機的機器上“蓬鬆”。捲取和拉伸速度被蓬鬆或組織形成裝置限制於2,500米/分鐘(8,200呎/分鐘)或更小。當今最常見的方法為一步驟紡絲/拉伸/組織形成(SDT)法。其類似於一步驟CF法，不同的是膨鬆裝置是在線內。膨鬆或質地改變紗外觀，分離長絲並添加足夠溫和的彎曲和折疊以使紗線看起來更豐厚(更膨鬆)。The fluffy continuous filament ("CF") manufacturing process is divided into two basic types, one step and two steps. For example, in a two-step process, the undrawn yarn is spun at less than 1,000 meters per minute (3,300 Å/min), typically 750 m/min, and placed on a package. The yarn is stretched (usually in two stages) and "fluffed" on a so-called tissue forming machine. The take-up and stretching speed is limited to 2,500 meters per minute (8,200 inches per minute) or less by fluffy or tissue forming devices. The most common method today is a one-step spinning/stretching/tissue formation (SDT) process. It is similar to the one-step CF method except that the bulking device is in-line. Loose or texture changes the appearance of the yarn, separating the filaments and adding a gentle enough bend and fold to make the yarn look richer (more bulky).

短纖維short fibre

有兩種基本短纖維製造方法：傳統和緊密紡絲。傳統方法通常包括兩個步驟：1)製造、施加整理劑(finish)和捲繞，接著2)拉伸，二次整理劑施加，捲曲，並切成短纖維。長絲範圍可例如從0.5dpf至>70dpf(dpf=每長絲丹尼)，其取決於應用。短纖維長度可短至3毫米或長達200毫米(0.25吋到8吋)以適合應用。對於許多應用，纖維是經捲曲。捲曲係藉由用一對壓料輥將絲束過量供入蒸汽加熱的填塞箱來完成。過量供入促使絲束在箱中折疊，在長絲中形成彎曲或捲曲。這些彎曲係藉由注射入箱中的蒸汽進行熱固。There are two basic methods of making short fibers: traditional and compact spinning. Conventional methods typically involve two steps: 1) making, applying finish and winding, followed by 2) stretching, secondary finishing application, crimping, and cutting into staple fibers. The filament range can range, for example, from 0.5 dpf to > 70 dpf (dpf = Danny per filament), depending on the application. Short fiber lengths can be as short as 3 mm or as long as 200 mm (0.25 吋 to 8 吋) to suit the application. For many applications, the fibers are crimped. Curl is supplied in excess by using a pair of nip rolls Steam heated stuffer box to complete. Excessive feeding causes the tow to fold in the box, forming a bend or curl in the filament. These bends are thermoset by injection of steam into the tank.

熔噴織物/纖維Meltblown fabric/fiber

熔噴纖維為藉由下列形成之纖維：透過多個細(通常是圓形)模毛細管將熔融熱塑性材料擠出成熔融線或長絲，其通常進入聚集(通常熱和高速氣體流，例如空氣)以將熔融熱塑性材料之長絲變細而形成纖維。在熔噴方法期間，熔融長絲之直徑係藉由拉伸空氣滅小至所要尺寸。其後，藉由高速氣流載運熔噴纖維並將其沈積在收集表面上以形成實質上隨機分配的熔噴纖維的網。該種方法係揭示在例如US 3,849,241；US 4,526,733；及US 5,160,746中。熔噴纖維可為連續或不連續的且通常平均直徑小於十微米。Meltblown fibers are fibers formed by extruding a molten thermoplastic material into a molten strand or filament through a plurality of fine (usually circular) mold capillaries, which typically enter agglomerates (typically hot and high velocity gas streams, such as air). The fibers are formed by tapering the filaments of the molten thermoplastic material. During the meltblowing process, the diameter of the molten filaments is reduced to the desired size by stretching the air. Thereafter, the meltblown fibers are carried by a high velocity gas stream and deposited on a collecting surface to form a web of substantially randomly distributed meltblown fibers. Such a method is disclosed in, for example, US 3,849,241; US 4,526,733; and US 5,160,746. Meltblown fibers can be continuous or discontinuous and typically have an average diameter of less than ten microns.

在習知熔噴方法中，將熔融聚合物提供給配置在一對形成主空氣噴嘴的空氣板之間的模具。標準熔噴設備包括沿著刀口具有單排毛細管的模具頂端。典型的模具頂端具有大約30個毛細管出口孔/線性吋之模具寬度。模具頂端通常是聚集在刀口於毛細管所處的位置之60°楔形塊。在許多已知的熔噴噴嘴中的空氣板以嵌入式結構安裝，使得模具頂端從主空氣噴嘴向後移。然而，在一些噴嘴中的空氣板以齊平結構安裝，其中空氣板端部與模具頂端在同一水平面；在其他噴嘴中，模具頂端呈突出或“伸出”結構，使得模具頂端沿伸經過空氣板的端部。再者，如US 5,160,746中所揭示者，可以提供多於一個空氣流體流用於噴嘴中。In the conventional melt blowing method, molten polymer is supplied to a mold disposed between a pair of air plates forming a main air nozzle. Standard meltblowing equipment includes a mold tip having a single row of capillaries along the edge. A typical mold tip has a mold width of approximately 30 capillary exit holes/linear turns. The top end of the mold is typically a 60° wedge that gathers at the location where the knife edge is at the location of the capillary. The air plates in many known meltblown nozzles are mounted in an embedded configuration such that the die tip moves rearward from the main air nozzle. However, the air plates in some of the nozzles are mounted in a flush configuration, wherein the end of the air plate is at the same level as the top end of the mold; in other nozzles, the top end of the mold is in a protruding or "extended" configuration. The tip of the mold is extended along the end of the air plate. Furthermore, as disclosed in US 5,160,746, more than one air fluid stream can be provided for use in the nozzle.

在一些已知的熔噴噴嘴之結構中，熱空氣係透過在模具頂端每一側上形成的主空氣噴嘴提供。熱空氣加熱模具並因此防止當熔融聚合物離開並冷卻時模具之凍結。以此方式，防止模具變得被固化中的聚合物堵塞。熱空氣也將熔體拉伸或變細成纖維。使用加熱氣體維持儲器中的聚合物溫度而防止模具凍結的其他方案(諸如US 5,196,207中詳述的方案)也是已知的。在周圍溫度以上的溫度下的副空氣或驟冷空氣已知透過模具頭提供，如US 6,001,303中者。主熱空氣流速通常為從20至24標準立方呎/分鐘/吋模具寬度(SCFM/吋)。In some known meltblown nozzle configurations, hot air is provided through a primary air nozzle formed on each side of the top end of the mold. Hot air heats the mold and thus prevents freezing of the mold as it leaves and cools. In this way, the mold is prevented from becoming clogged with the polymer in the solidification. Hot air also stretches or thins the melt into fibers. Other solutions that use a heated gas to maintain the temperature of the polymer in the reservoir to prevent mold freezing, such as the ones detailed in US 5,196,207, are also known. Secondary or quench air at temperatures above ambient temperature is known to be provided through the die head, as in US 6,001,303. The main hot air flow rate is typically from 20 to 24 standard cubic feet per minute per helium mold width (SCFM/吋).

就在模頭中出口之前的位置處主空氣壓力通常為5至10磅/平方吋表壓(psig)。主空氣溫度通常範圍從232℃至315℃，但是398℃的溫度也不是不正常。主熱空氣流的具體溫度將取決於被拉伸的具體聚合物以及熔噴網中所要的其他特性。The primary air pressure at the location just prior to the exit in the die is typically 5 to 10 pounds per square foot gauge (psig). The main air temperature typically ranges from 232 ° C to 315 ° C, but the temperature of 398 ° C is not abnormal. The specific temperature of the main hot air stream will depend on the particular polymer being stretched and other characteristics desired in the meltblown web.

按每單位時間模具之聚合物材料流動每吋的量表示，聚合物通量通常為0.5至1.25克/孔/分鐘(ghm)。因此，對於具有30個孔/吋的模具，聚合物通量通常為2至5磅/吋/小時(PIH)。The polymer flux is typically from 0.5 to 1.25 grams per hole per minute (ghm), expressed as the amount of polymer material flowing per unit time per unit time. Thus, for molds with 30 holes per helium, the polymer flux is typically 2 to 5 pounds per liter per hour (PIH).

再者，為了從聚合物熔體的五磅/吋/小時之輸入形成熔噴纖維，需要一百磅/吋/小時的熱空氣來拉伸或使熔體變細成離散纖維。為了維持模具頂端的合適熱，必須將此拉伸空氣加熱到約204℃至315℃的溫度。Furthermore, in order to form meltblown fibers from a five lb/ft/hr input of the polymer melt, one hundred pounds per ton per hour of hot air is required to stretch or melt the melt. Thinned into discrete fibers. In order to maintain proper heat at the tip of the mold, this stretched air must be heated to a temperature of about 204 ° C to 315 ° C.

因為必須使用該等高溫，所以通常從纖維除去大量的熱，以便使離開模具口的纖維驟冷或固化。已經使用冷卻氣體(例如空氣)以加速熔噴纖維的冷卻和固化。具體來說，在US 5,075,068和US 5,080,569中，以相對於纖維伸長方向之交叉流垂直(或90°)方向流動的副空氣已用來將熔噴纖維驟冷並產生較小直徑的纖維。此外，US 5,607,701使用冷卻器加壓的驟冷空氣，該驟冷空氣填充室71並導致纖維的更快冷卻和固化。在US 4,112,159中，當希望降低纖維的變細時，使用冷空氣流使纖維變細。Because of the high temperatures that must be used, a significant amount of heat is typically removed from the fibers to quench or solidify the fibers exiting the die ports. A cooling gas, such as air, has been used to accelerate the cooling and solidification of the meltblown fibers. In particular, in US 5,075,068 and US 5,080,569, secondary air flowing in a vertical (or 90°) direction relative to the cross-flow direction of the fiber has been used to quench the meltblown fibers and produce fibers of smaller diameter. Furthermore, US 5,607,701 uses a quench air pressurized with a chiller that fills the chamber 71 and results in faster cooling and solidification of the fibers. In US 4,112,159, when it is desired to reduce the tapering of the fibers, the flow of cold air is used to make the fibers thin.

透過控制空氣和模具頂端溫度、空氣壓力和聚合物進料速度，可調節在熔噴方法期間形成的纖維直徑。例如，典型的熔噴聚丙烯纖維具有3至4微米的直徑。The diameter of the fibers formed during the meltblowing process can be adjusted by controlling the air and die tip temperature, air pressure, and polymer feed rate. For example, typical meltblown polypropylene fibers have a diameter of from 3 to 4 microns.

在冷卻之後，收集纖維以形成非織物網。具體來說，在成型網上收集纖維，該成型網包括位於模具頂端以下的移動網篩或帶子。為了在模具頂端下方提供用於纖維形成、變細和冷卻的足夠空間，在典型熔噴方法中在聚合物模具頂端和網篩的頂部之間需要至少8至12吋的成形距離。After cooling, the fibers are collected to form a nonwoven web. Specifically, the fibers are collected on a forming wire that includes a moving mesh screen or tape located below the top end of the mold. In order to provide sufficient space for fiber formation, tapering and cooling below the top end of the mold, a forming distance of at least 8 to 12 inches is required between the top of the polymer mold and the top of the screen in a typical meltblowing process.

然而，低如4吋的成形距離係描述於Lau的US 4,526,733(下文中稱為Lau專利)中。如Lau專利的實施例3中所述，用比熔融聚合物的溫度冷至少大約37℃的變細空氣流達到較短的成形距離。例如，Lau專利揭示對於在266℃的溫度下之聚丙烯熔體使用在65℃下的變細空氣以允許模具頂端和成形帶之間4吋的成形距離。該Lau專利結合被動空氣間隙36(顯示於Lau專利的圖4中)以將模具頂端絕緣。However, a forming distance as low as 4 描述 is described in US 4,526,733 (hereinafter referred to as the Lau patent) of Lau. As described in Example 3 of the Lau patent, at least about 37 ° C is cooled by the temperature of the molten polymer. The thinned air flow reaches a shorter forming distance. For example, the Lau patent discloses the use of a fine air at 65 ° C for a polypropylene melt at a temperature of 266 ° C to allow a forming distance of 4 之间 between the die tip and the forming belt. The Lau patent incorporates a passive air gap 36 (shown in Figure 4 of the Lau patent) to insulate the mold tip.

在一較佳實施態樣中，用本文中所述之聚合物製備熔噴纖維。在熔噴方法中熔融聚合物從擠出機移動至特殊熔噴模具。在熔融長絲退出模具時，彼等接觸高溫、高速空氣(稱為處理或主空氣)。此空氣迅速抽出，並與驟冷空氣結合，固化長絲。整個纖維形成過程通常需要在離紡嘴7毫米(0.25吋)處發生。該織物係藉由從紡嘴直接噴出長絲在形成線上形成，200毫米至400毫米(8吋至15吋)。可用於本發明中之熔噴微纖維可如Van A.Wente,“Superfine Thermoplastic Fibers”，48 INDUSTRIAL ENGINEERING CHEMISTRY，1342-1346，和Van A.Wente等人於1954年5月25日出版之Naval Research Laboratories報告編號4364，標題“Manufacture of Superfine Organic Fibers”中所述製備。In a preferred embodiment, meltblown fibers are prepared from the polymers described herein. In the meltblowing process, the molten polymer is moved from the extruder to a special meltblowing die. When the molten filaments exit the mold, they are exposed to high temperature, high velocity air (referred to as processing or primary air). This air is quickly extracted and combined with quench air to solidify the filaments. The entire fiber formation process typically takes place 7 mm (0.25 ft) from the spinner. The fabric is formed on the forming line by directly ejecting filaments from the spun nozzle, 200 mm to 400 mm (8 吋 to 15 吋). Meltblown microfibers useful in the present invention are available from Van A. Wente, "Superfine Thermoplastic Fibers", 48 INDUSTRIAL ENGINEERING CHEMISTRY, 1342-1346, and Van A. Wente et al., May 25, 1954, Naval Research. Laboratories Report No. 4364, prepared as described in the title "Manufacture of Superfine Organic Fibers".

紡黏織物Spunbond fabric

本發明之一特殊實施態樣包含在製造紡黏織物中使用本發明之聚合物。習用紡黏方法係說明於US 3,825,379；Uw4,813,864；US 4,405,297；US 4,208,366；及US 4,334,340中。紡黏方法是織物製造技藝中熟知者。通常，連續纖維被擠出、置於循環皮帶上，然後彼此黏合，且常藉由加熱之壓延輥或添加黏合劑以附加在第二層(諸如熔噴層)上。可從由田納西諾克斯維爾大學TANDEC贊助之L.C.Wadsworth和B.C.Goswami的Nonwoven Fabrics：“Spunbonded and Melt Blown Processes”proceedings Eight Annual Nonwovens Workshop(1990年7月30日至8月3日)獲得紡黏之概論。A particular embodiment of the invention encompasses the use of the polymers of the invention in the manufacture of spunbond fabrics. Conventional spunbonding processes are described in U.S. Patent No. 3,825,379, U.S. Patent No. 4, 813, 864, U.S. Patent No. 4,405, 297, U.S. Patent No. 4,208,366, and U.S. Patent No. 4,334,340. Spunbonding methods are well known in the art of fabric making. through Often, the continuous fibers are extruded, placed on an endless belt, and then bonded to one another, and are often attached to a second layer, such as a meltblown layer, by heated calender rolls or by the addition of a binder. Available from LCWadsworth and BCGoswami's Nonwoven Fabrics: "Spunbonded and Melt Blown Processes" proceedings Eight Annual Nonwovens Workshop (July 30-August 3, 1990), sponsored by TANDEC, University of Tennessee Knoxville Introduction.

典型之紡黏方法由下列組成：連續長絲擠出、接著拉伸、使用某種類型的噴射器形成網、及黏合該網。首先，在本發明之一實施態樣中，獲得具有10至25g/10分鐘之MFR的以丙烯為主之聚合物(或已被減黏而具有10至25dg/分鐘之MFR的丙烯聚合物)且較佳轉化成顆粒。然後將粒化10至25dg/分鐘MFR以丙烯為主之樹脂進料至擠出機。在擠出機中，藉由加熱熔融螺桿使顆粒同時被熔融且強制通過此系統。在螺桿末端，紡絲泵計量經過濾器至紡嘴之熔融聚合物，其中熔融聚合物在壓力下以0.3至1.0克/孔/分鐘之速度通過毛細管而擠出。紡嘴含有數千個通常測量直徑0.4至0.6毫米之毛細管。聚合物係在其熔點以上30℃至100℃(通常50℃至100℃)之溫度下加熱以達成足夠低之供擠出的熔融黏度。藉由冷高速空氣噴射使離開紡嘴之纖維驟冷且拉伸成直徑測為10至40微米之細纖維。固化之纖維隨機置放在移動帶上以形成在此技藝中已知為網之隨機網狀結構。在網形成後，該網係使用此技藝中已知為熱黏合壓延機之加熱紡織壓延機黏合以達成其最終強度。壓延機由二個加熱鋼輥組成；一輥是平坦的，而另一個則具有凸點之圖案。將該網輸送到壓延機，其中藉由在100℃至200℃之黏合溫度下在輥間加壓該網以形成織物。A typical spunbond process consists of continuous filament extrusion, subsequent stretching, forming a web using some type of ejector, and bonding the web. First, in one embodiment of the present invention, a propylene-based polymer having an MFR of 10 to 25 g/10 minutes (or a propylene polymer having been viscosified to have an MFR of 10 to 25 dg/min) is obtained. It is preferably converted into granules. The propylene-based resin, which was granulated at 10 to 25 dg/min MFR, was then fed to the extruder. In the extruder, the particles are simultaneously melted and forced through the system by heating the molten screw. At the end of the screw, the spinning pump meters the molten polymer passing through the filter to the spinning nozzle, wherein the molten polymer is extruded through the capillary at a rate of 0.3 to 1.0 g/hole/min under pressure. The nozzle contains thousands of capillaries that typically measure 0.4 to 0.6 mm in diameter. The polymer is heated at a temperature above 30 ° C to 100 ° C (typically 50 ° C to 100 ° C) above its melting point to achieve a sufficiently low melt viscosity for extrusion. The fibers exiting the spinning nozzle were quenched by cold high velocity air jet and drawn into fine fibers having a diameter of 10 to 40 microns. The cured fibers are randomly placed on the moving belt to form a random network of structures known in the art as webs. After the web is formed, the web is bonded using a heated textile calender known in the art as a thermal bond calender. Into its ultimate strength. The calender consists of two heated steel rolls; one roll is flat and the other has a pattern of bumps. The web is conveyed to a calender wherein the web is formed by pressing the web between rolls at a bonding temperature of from 100 ° C to 200 ° C.

雖然黏合在廣溫度範圍內發生，但必須將黏合溫度最佳化以達成具有最大機械強度之織物。過度黏合(亦即在高於最佳溫度之溫度下黏合)導致在黏合點周圍纖維顯著較弱之纖維，此係因纖維之過度熔融。這些變成織物中之弱點。在黏合下(亦即在低於最佳溫度之溫度下黏合)，導致在纖維對纖維之連接處有不足之黏合。最佳之黏合溫度取決於製成纖維之材料的性質。Although bonding occurs over a wide temperature range, the bonding temperature must be optimized to achieve the fabric with maximum mechanical strength. Excessive bonding (i.e., bonding at temperatures above the optimum temperature) results in fibers that are significantly weaker around the bond point due to excessive melting of the fibers. These become weaknesses in the fabric. Adhesion (i.e., bonding at temperatures below the optimum temperature) results in insufficient bonding at the fiber-to-fiber junction. The optimum bonding temperature depends on the nature of the material from which the fiber is made.

退火annealing

本發明之另一部分為上述機械性質可藉由將聚合物纖維退火獲得。退火常常與機械定向合併。較佳為在方法中採用退火步驟。退火也可在由該等纖維製造非織材料之後進行。退火部分減輕伸張纖維中的內應力且恢復該纖維中之摻合物的彈性恢復性質。退火已顯示導致該晶體結構的內部構造之顯著改變及非晶形和半晶體相的相對排序。此導致該彈性的回復。聚合物摻合物之熱退火可藉由使該聚合物摻合物或由該等摻合物製得之物件在介於室溫(下文23℃)與最高160℃或更高之間的溫度，較佳至最高130℃之間的溫度下保持5分鐘至小於7天期間來進行。典型退火期間係於50℃之3天或於100℃之5分鐘。任何特定摻合物組成物之退火時間與溫度可藉由實驗調整。雖然在退火在沒有機械定向下進行，但後者可為製備彈性材料所需對纖維(通過擠出操作)之退火方法的一部分。機械定向可藉由在使聚合物纖維在沒有拉伸力下鬆弛之前，短暫強迫延長一段短時間週期來進行。定向聚合物纖維係藉由將由摻合物製成的聚合物纖維或物件於100%至700%的伸長率保持0.1秒至24小時而獲得。典型定向為在室溫下瞬時200%的伸長率。Another part of the invention is that the above mechanical properties can be obtained by annealing polymer fibers. Annealing is often combined with mechanical orientation. Preferably, an annealing step is employed in the method. Annealing can also be carried out after the nonwoven material is made from the fibers. The annealed portion mitigates internal stress in the stretched fibers and restores the elastic recovery properties of the blend in the fibers. Annealing has been shown to result in significant changes in the internal structure of the crystal structure and relative ordering of the amorphous and semi-crystalline phases. This results in a response to this elasticity. Thermal annealing of the polymer blend can be achieved by subjecting the polymer blend or articles made from the blends to temperatures between room temperature (23 ° C below) and temperatures up to 160 ° C or higher. It is preferably carried out at a temperature between 130 ° C and a temperature of from 5 minutes to less than 7 days. The typical annealing period is 3 days at 50 ° C or 5 minutes at 100 ° C. Any specific The annealing time and temperature of the blend composition can be adjusted experimentally. While the annealing is carried out without mechanical orientation, the latter may be part of an annealing process for the fibers (by extrusion operations) required to prepare the elastomeric material. Mechanical orientation can be carried out by briefly forcing a short period of time before allowing the polymer fibers to relax without stretching. The oriented polymer fibers are obtained by maintaining the polymer fibers or articles made from the blend at an elongation of from 100% to 700% for from 0.1 second to 24 hours. A typical orientation is an instantaneous 200% elongation at room temperature.

為了定向，使聚合物纖維在高溫(但低於聚合物的結晶熔點)下從纖維進料輥繞過以不同表面速度驅動的兩個輥，最後到達捲取輥。最靠近捲取輥的從動輥比最靠近進料輥的從動輥更快，致使纖維在從動輥之間被拉伸。該組件可包括使纖維冷卻之在第二輥和捲取輥中間的輥。第二輥和捲取輥可以相同的圓周速度驅動以使纖維保持在拉伸狀態下。如果不使用補充冷卻，則纖維將在捲取輥上冷卻至周圍溫度。For orientation, the polymer fibers are passed from the fiber feed rolls at two temperatures at a high temperature (but below the crystalline melting point of the polymer) and are driven at different surface speeds, finally reaching the take-up rolls. The driven roller closest to the take-up roll is faster than the driven roll closest to the feed roll, causing the fibers to be stretched between the driven rolls. The assembly can include a roller that cools the fibers intermediate the second roll and the take-up roll. The second roll and the take-up roll can be driven at the same peripheral speed to maintain the fibers in a stretched state. If supplemental cooling is not used, the fibers will cool to the ambient temperature on the take-up rolls.

在其他實施態樣中，本發明的非織物幾乎不需要後製造加工。在另一實施態樣中，本發明之織物在壓延期間在低張力下藉由加熱輥(導輥)以單一步驟進行退火。取決於最終用途應用，顯而易見：什麽技術是適當的及需要什麽樣的方法參數之改變來用以獲得所要織物性質。In other embodiments, the non-woven fabric of the present invention requires little post-manufacturing processing. In another embodiment, the fabric of the present invention is annealed in a single step by a heated roll (guide roll) under low tension during calendering. Depending on the end use application, it is obvious what technology is appropriate and what method parameters are required to achieve the desired fabric properties.

本文所述之組成物轉化成纖維和織物之裝置和方法為該技藝中已知的，參見，例如，EP 1 340 843 A1。Apparatuses and methods for converting the compositions described herein into fibers and fabrics are known in the art, see, for example, EP 1 340 843 A1.

本文所述之丙烯組成物也可使用一種用於連續製造長絲的紡黏網之裝置形成纖維，該裝置具有紡嘴、其中可***用於冷卻長絲的處理空氣之冷卻室、位於紡嘴和冷卻室之間的單體排放裝置、拉伸單元、及用於將長絲沈積成紡黏非織物之沈積裝置，其中該冷卻室分成兩個冷卻室段，其中來自第一上冷卻室段的處理空氣可以體積流量VM拉(諸如使用真空)至單體排放裝置，來自第一上冷卻室段的該處理空氣以體積流量V1逸出到第二下冷卻室段中且該體積流量比為VM/V1 0.1至0.3，較佳0.12至0.25。The propylene composition described herein can also be used for continuous manufacturing. a spunbonding device for forming a fiber, the device having a spinning nozzle, a cooling chamber into which process air for cooling the filaments can be inserted, a monomer discharge device between the spinning nozzle and the cooling chamber, a stretching unit, and a deposition apparatus for depositing filaments into a spunbond nonwoven fabric, wherein the cooling chamber is divided into two cooling chamber sections, wherein the process air from the first upper cooling chamber section can be pulled by a volume flow VM (such as using a vacuum) to the monomer The discharge means, the process air from the first upper cooling chamber section escapes into the second lower cooling chamber section at a volumetric flow rate V1 and the volumetric flow ratio is VM/V1 0.1 to 0.3, preferably 0.12 to 0.25.

尤佳體積流量比為從0.15至0.2 VM/V1。適當測量流速，以m³ /s表示。術語處理空氣特別是指用於長絲冷卻之冷卻空氣。較佳地，該等長絲在拉伸單元中被氣動拉伸。本發明之一非常特佳實施態樣特徵在於長絲係製成單組分長絲。原則上，也可製成二組分長絲或多組分長絲。The preferred volumetric flow ratio is from 0.15 to 0.2 VM/V1. The flow rate is measured as appropriate, expressed in m ³ /s. The term process air refers in particular to the cooling air used for filament cooling. Preferably, the filaments are pneumatically stretched in a stretching unit. A very preferred embodiment of the invention is characterized in that the filaments are made into single component filaments. In principle, two-component filaments or multicomponent filaments can also be produced.

本發明之推薦實施態樣的特徵在於：處理空氣以體積流量V2從第二下冷卻室段逸出且特徵在於：從第一上冷卻室段逸出之體積流量V1對從第二下冷卻室段逸出之體積流量V2的體積流量比(V1/V2)為從0至0.5，較佳0.05至0.5，和特佳0.1至0.45。在本發明的範圍內者為從第二下冷卻室段逸出之長絲和從第二下冷卻室段逸出之處理空氣係引進拉伸單元。A preferred embodiment of the invention is characterized in that the process air escapes from the second lower cooling chamber section at a volume flow rate V2 and is characterized by a volume flow V1 escaping from the first upper cooling chamber section and a second lower cooling chamber The volume flow ratio (V1/V2) of the volume flow rate V2 of the stage escape is from 0 to 0.5, preferably from 0.05 to 0.5, and particularly preferably from 0.1 to 0.45. It is within the scope of the invention to introduce a stretching unit for the filaments that escape from the second lower cooling chamber section and the process air that escapes from the second lower cooling chamber section.

本發明之一較佳實施態樣特徵在於：來自第一上冷卻室段的該處理空氣以速度V1逸出到第二下冷卻室段中，該處理空氣以速度V2從第二下冷卻室段逸出，該速度比V1/V2為0.2至0.5，較佳0.25至0.5，和優選地0.3至 0.5。成功的實施例變型後，速度比V1/V2為從0.35至0.45且特別是例如0.4。在本發明範圍內者為中間通道位於冷卻室和拉伸單元之間。從冷卻室的出口至拉伸單元之隱蔽通道的入口之中間通道係楔形聚集於垂直段。方便地，中間通道楔形聚集於在拉伸通道的入口寬度上之垂直段中的隱蔽通道之入口。因此，在本發明之一較佳實施態樣中，除了在冷卻室中供給處理空氣之外，沒有空氣供應提供於冷卻室的範圍內和在冷卻室和拉伸單元之間的過渡區中。在此方面，本發明適用於封閉系統。較佳地，除了在冷卻室中供給處理空氣之外，在冷卻室之段中，在中間通道的區域中和在拉伸單元的區域中將沒有從外部提供空氣供應。建議至少一個擴散器應排列在拉伸單元和存儲裝置之間。該類擴散器有利地具有朝向漸擴段或漸擴側壁的段之儲存裝置。因此長絲至不均勻網之故障安全(fail-safe)沈積比較容易。較佳地，沈積裝置為無接縫循環輸送帶。長絲沈積在用於紡黏非織物之此輸送帶上且該織物隨後被適當地壓實及/或凝固，較佳地該凝固在壓延機中發生。A preferred embodiment of the present invention is characterized in that the process air from the first upper cooling chamber section escapes into the second lower cooling chamber section at a velocity V1 from the second lower cooling compartment section at a velocity V2. Escaped, the speed ratio V1/V2 is 0.2 to 0.5, preferably 0.25 to 0.5, and preferably 0.3 to 0.5. After a successful embodiment variant, the speed ratio V1/V2 is from 0.35 to 0.45 and in particular for example 0.4. It is within the scope of the invention that the intermediate passage is located between the cooling chamber and the stretching unit. The intermediate passage from the outlet of the cooling chamber to the inlet of the concealed passage of the drawing unit is wedge-shaped in the vertical section. Conveniently, the intermediate channel wedges are gathered at the entrance of the concealed channel in the vertical section of the entrance width of the stretch channel. Thus, in a preferred embodiment of the invention, no air supply is provided in the range of the cooling chamber and in the transition zone between the cooling chamber and the drawing unit, except that the process air is supplied in the cooling chamber. In this regard, the invention is applicable to closed systems. Preferably, in addition to the supply of process air in the cooling chamber, in the section of the cooling chamber, no air supply is provided from the outside in the region of the intermediate channel and in the region of the stretching unit. It is recommended that at least one diffuser be arranged between the stretching unit and the storage device. Such a diffuser advantageously has a storage means facing the section of the diverging section or the diverging side wall. Therefore, fail-safe deposition of filaments to uneven webs is relatively easy. Preferably, the deposition apparatus is a seamless loop conveyor belt. The filaments are deposited on the conveyor belt for spunbonding the nonwoven fabric and the fabric is then suitably compacted and/or solidified, preferably the solidification takes place in a calender.

為了解決上述技術問題，本發明進一步教示一種連續製造熱塑性材料長絲的紡黏非織物之方法，其中該等長絲透過紡嘴紡絲且引導經過單體排放裝置進入冷卻室，其中該等長絲在冷卻室中用處理空氣冷卻，其中該冷卻室係分成二個冷卻室段，其中來自第一上冷卻室段的處理空氣可以體積流量VM拉(諸如使用真空)至單體排放裝置，來自第一上冷卻室段的該處理空氣以體積流量V1逸出到第二下冷卻室段中且該體積流量比為VM/V1 0.1至0.3，較佳0.12至0.25，其中該等長絲離開冷卻室之後被引進拉伸單元和其中長絲然後沉積在用於紡黏非織物之輸送帶上。In order to solve the above technical problems, the present invention further teaches a method of continuously producing a spunbond non-woven fabric of thermoplastic filaments, wherein the filaments are spun through a spun nozzle and guided through a monomer discharge device into a cooling chamber, wherein the length is equal. The filament is cooled in the cooling chamber by process air, wherein the cooling chamber is divided into two cooling chamber sections, wherein the process air from the first upper cooling chamber section can be pulled by a volume flow VM (such as using a vacuum) to the monomer discharge device. The process air from the first upper cooling chamber section escapes into the second lower cooling chamber section at a volumetric flow rate V1 and the volumetric flow ratio is VM/V1 0.1 to 0.3, preferably 0.12 to 0.25, wherein the filaments leave The cooling chamber is then introduced into the drawing unit and the filaments therein and then deposited on a conveyor belt for spunbonding nonwovens.

在本發明範圍內者為長絲被製備成單組分長絲。It is within the scope of the invention that the filaments are prepared as single component filaments.

也在本發明範圍內者為進行長絲之延伸以獲得直徑從0.3至5丹尼(或者從0.3至2丹尼，或者從0.3至0.9丹尼)之長絲。便利地，本發明的長絲之長絲直徑小於3丹尼(或者小於2.5丹尼，或者小於2丹尼，或者小於1丹尼)。長絲直徑係於紡黏非織物沈積長絲進行測量。It is also within the scope of the invention to carry out the extension of the filaments to obtain filaments having a diameter of from 0.3 to 5 denier (or from 0.3 to 2 denier, or from 0.3 to 0.9 denier). Conveniently, the filaments of the present invention have a filament diameter of less than 3 deniers (or less than 2.5 deniers, or less than 2 deniers, or less than 1 denier). The filament diameter is measured on spunbonded non-woven deposited filaments.

在一較佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，任何根據本發明製備之纖維或織物(諸如非織物)具有至少1N/5公分/gsm(較佳至少1.1N/5公分/gsm，較佳至少1.2N/5公分/gsm)之CD比抗拉強度(從按全世界策略聯盟(Worldwide Strategic Partners)測試110.4(5)(WSP 110.4(05)測量之力-伸長率曲線之峰值負載測定)。CD比抗拉強度(N/5公分/gsm)為CD強度(N/5公分)除以織物基重(gsm)(正規化)。In a preferred embodiment, for a basis weight of 8 to 12 gsm, prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), any A fiber or fabric (such as a non-woven fabric) prepared in accordance with the present invention has a CD specific tensile strength of at least 1 N/5 cm/gsm (preferably at least 1.1 N/5 cm/gsm, preferably at least 1.2 N/5 cm/gsm). (Measured from the peak load of the force-elongation curve measured by World Strategic Partners, 110.4(5) (WSP 110.4(05)). The CD specific tensile strength (N/5 cm/gsm) is CD strength (N/5 cm) divided by fabric basis weight (gsm) (normalized).

在一較佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，任何根據本發明製備之纖維或織物(諸如非織物)具有至少2.7N/5公分/gsm(較佳至少2.9N/5公分/gsm，較佳3.0N/5公分/gsm)之MD比抗拉強度(如以WSP 110.4(05)測量)。MD比抗拉強度(N/5公分/gsm)為MD強度(N/5公分)除以織物基重(gsm)(正規化)。In a preferred embodiment, for a basis weight of 8 to 12 gsm, prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), any According to the invention The prepared fiber or fabric (such as non-woven fabric) has an MD specific tensile strength of at least 2.7 N/5 cm/gsm (preferably at least 2.9 N/5 cm/gsm, preferably 3.0 N/5 cm/gsm) (eg, WSP 110.4 (05) measurement). The MD specific tensile strength (N/5 cm/gsm) is the MD strength (N/5 cm) divided by the fabric basis weight (gsm) (normalized).

在一較佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重任何根據本發明製備之纖維或織物(諸如非織物)具有小於2.7(較佳小於2.6，較佳小於2.6)之定義為MD對CD的比抗拉強度之比率的抗拉強度各向異性(如以WSP 110.4(05)測量)。In a preferred embodiment, any basis for fabric basis weights ranging from 8 to 12 gsm is prepared for line speeds of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute). The fiber or fabric (such as a non-woven fabric) prepared by the present invention has a tensile strength anisotropy (e.g., WSP) defined as a ratio of MD to CD specific tensile strength of less than 2.7 (preferably less than 2.6, preferably less than 2.6). 110.4 (05) measurement).

在一較佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，任何根據本發明製備之纖維或織物(諸如非織物)具有小於6.8克(較佳小於6.6克，較佳小於6.5克)之總手感(如以下測試方法中所述測定)。較佳地，本文中所製備之織物具有小於6.8克且更佳小於6.5克之總手感。In a preferred embodiment, for a basis weight of 8 to 12 gsm, prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), any Fibers or fabrics (such as non-woven fabrics) prepared in accordance with the present invention have a total hand feel of less than 6.8 grams (preferably less than 6.6 grams, preferably less than 6.5 grams) (as determined in the test methods below). Preferably, the fabrics prepared herein have a total hand feel of less than 6.8 grams and more preferably less than 6.5 grams.

在一較佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，任何根據本發明製備之纖維或織物(諸如非織物)具有小於35N/5公分/gsm(較佳小於32N/5公分/gsm，較佳小於30N/5公分/gsm)之MD拉伸模數(如以下測試方法中所述測定)。In a preferred embodiment, for a basis weight of 8 to 12 gsm, prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), any A fiber or fabric (such as a non-woven fabric) prepared in accordance with the present invention has an MD tensile modulus of less than 35 N/5 cm/gsm (preferably less than 32 N/5 cm/gsm, preferably less than 30 N/5 cm/gsm) (eg As determined in the test methods below).

在一特佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，包含本文中所製備之組成物的纖維具有良好可紡性(如上述所定義)結合至少1.1N/5公分/gsm之顯著織物拉伸性質(例如，CD比抗拉強度)、至少2.7N/5公分/gsm之MD比抗拉強度，和小於6.8gm力之總手感或小於32N/5公分/gsm之拉伸模數。In a particularly preferred embodiment, a basis weight of 8 to 12 gsm is prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), inclusive. The fibers of the compositions prepared herein have good spinnability (as defined above) in combination with significant fabric tensile properties (e.g., CD specific tensile strength) of at least 1.1 N/5 cm/gsm, at least 2.7 N/5. The MD/gsm of the centimeters/gsm is greater than the tensile strength, and the total hand feel of less than 6.8 gm force or a tensile modulus of less than 32 N/5 cm/gsm.

在一特佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，包含本文中所製備之組成物的纖維具有良好可紡性(如上述所定義)結合小於2.7之織物拉伸各向異性(如以WSP 110.4(05)測定的MD對CD比抗拉強度之比率)。In a particularly preferred embodiment, a basis weight of 8 to 12 gsm is prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), inclusive. The fibers of the compositions prepared herein have good spinnability (as defined above) in combination with fabric tensile anisotropy of less than 2.7 (e.g., ratio of MD to CD to tensile strength as determined by WSP 110.4 (05)) .

在一特佳實施態樣中，對於以至少600米/分鐘(更佳至少700米/分鐘，和更佳至少800米/分鐘)之線速度製備的範圍在8至12gsm之織物基重，包含本文中所製備之組成物的纖維具有良好可紡性(如上述所定義)結合至少1.2N/5公分/gsm之顯著織物抗拉性質(例如，CD比抗拉強度)、至少2.9N/5公分/gsm之MD比抗拉強度和小於6.6gm力之總手感或小於30N之MD拉伸模數。In a particularly preferred embodiment, a basis weight of 8 to 12 gsm is prepared for a line speed of at least 600 meters per minute (more preferably at least 700 meters per minute, and more preferably at least 800 meters per minute), inclusive. The fibers of the compositions prepared herein have good spinnability (as defined above) in combination Significant fabric tensile properties (eg, CD specific tensile strength) of at least 1.2 N/5 cm/gsm, MD specific tensile strength of at least 2.9 N/5 cm/gsm, and total hand feel of less than 6.6 gm force or less than 30 N MD tensile modulus.

在一特佳實施態樣中，本文中所製備之組成物具有極佳可紡性(例如，穩定製造沒有斷裂)，特別是當製造細(例如，小於18微米或相當於小於2丹尼)的纖維時。In a particularly preferred embodiment, the compositions prepared herein have excellent spinnability (eg, stable manufacturing without fracture), particularly when manufactured finely (eg, less than 18 microns or equivalent to less than 2 Danny). When the fiber.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有：1)當以200毫米/分鐘之速度和100毫米隔距長度測量時(WSP 110.4(05))，40或更大(較佳45或更大)之CD伸長率對CD峰值強度的比率；及2)Y N/5公分/gsm或更大的CD強度，其中Y=-0.0005(X)+1.46(較佳1.48，較佳1.5，較佳1.6)，其中X為織物之生產線速度且為至少400米/分鐘，但該CD強度為至少1.0N/5公分/gsm。根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定CD峰值伸長率(也稱為CD伸長率)和CD峰值強度(也稱為CD強度)，除非另有說明。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have: 1) when measured at a speed of 200 mm/min and a gauge length of 100 mm (WSP 110.4) (05)), a ratio of CD elongation to CD peak intensity of 40 or greater (preferably 45 or greater); and 2) CD strength of YN/5 cm/gsm or greater, where Y = -0.0005 ( X) + 1.46 (preferably 1.48, preferably 1.5, preferably 1.6), wherein X is the line speed of the fabric and is at least 400 meters per minute, but the CD strength is at least 1.0 N/5 cm/gsm. CD peak elongation (also known as CD elongation) and CD peak intensity (also known as CD intensity) were determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min unless otherwise stated .

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大的CD強度，其中Y=-0.0009(X)+1.965(較佳2.1，較佳2.3)，其中X為織物之生產線速度且為至少400米/分鐘。CD強度係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have a CD strength of YN/5 cm/gsm or greater, where Y = -0.0009(X)+ 1.965 (preferably 2.1, preferably 2.3), wherein X is the line speed of the fabric and is at least 400 meters per minute. The CD strength was determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大的CD強度，其中Y=-0.0009(X)+1.965(較佳2.1，較佳2.3)，其中X為織物之生產線速度且為至少400米/分鐘。CD強度係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, the use of the materials described herein is used. Fiber or fabric (such as non-woven) having a CD strength of YN/5 cm/gsm or greater, where Y = -0.0009(X) + 1.965 (preferably 2.1, preferably 2.3), where X is the line speed of the fabric And at least 400 meters / minute. The CD strength was determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大的CD強度，其中Y=-0.0008(X)+1.85(較佳1.95)，其中X為織物之生產線速度且為至少400米/分鐘。CD強度係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have a CD strength of YN/5 cm/gsm or greater, where Y=-0.0008(X)+ 1.85 (preferably 1.95), where X is the line speed of the fabric and is at least 400 meters per minute. The CD strength was determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大之MD強度，其中Y=-0.0007(X)+2.145(較佳2.4)，其中X為織物之生產線速度且為至少400米/分鐘。MD強度(也稱為MD峰值強度)係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have an MD strength of YN/5 cm/gsm or greater, where Y = -0.0007(X)+ 2.145 (preferably 2.4), wherein X is the line speed of the fabric and is at least 400 meters per minute. The MD intensity (also known as the MD peak intensity) is determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大之MD強度，其中Y=-0.0006(X)+2.34(較佳2.4，較佳2.5)，其中X為織物之生產線速度且為至少400米/分鐘。MD強度(也稱為MD峰值強度)係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have an MD strength of YN/5 cm/gsm or greater, where Y = -0.0006(X)+ 2.34 (preferably 2.4, preferably 2.5), wherein X is the line speed of the fabric and is at least 400 meters per minute. The MD intensity (also known as the MD peak intensity) is determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)具有Y N/5公分/gsm或更大之MD強度，其中Y=-0.0007(X)+2.715(較佳2.8，較佳2.9)，其中X為織物之生產線速度且為至少400米/分鐘。MD強度(也稱為MD峰值強度)係根據WSP 110.4(05)使用200毫米的隔距長度和100毫米/分鐘的測試速度測定。In another preferred embodiment, fibers or fabrics (such as non-woven fabrics) made using the materials described herein have an MD strength of YN/5 cm/gsm or greater, where Y = -0.0007(X)+ 2.715 (preferably 2.8, preferably 2.9) wherein X is the line speed of the fabric and is at least 400 meters per minute. The MD intensity (also known as the MD peak intensity) is determined according to WSP 110.4 (05) using a gauge length of 200 mm and a test speed of 100 mm/min.

在另一較佳實施態樣中，使用本文中所述之材料製造的纖維或織物(諸如非織物)係以至少500米/分鐘(較佳至少600米/分鐘，至少700米/分鐘，至少800米/分鐘，至少850米/分鐘，至少900米/分鐘)之線速度製備。In another preferred embodiment, the fibers or fabrics (such as non-woven fabrics) made using the materials described herein are at least 500 meters per minute (preferably at least 600 meters per minute, at least 700 meters per minute, at least Prepare at a line speed of 800 m/min, at least 850 m/min, at least 900 m/min.

產業應用性Industrial applicability

本發明之纖維及織物具有橫跨幾個行業的廣泛應用性。例如，本發明之織物可用於製造衛生用品。實例包括尿布及女性衛生用品。本發明的織物也可用於醫療產品。例子包括用於袍服、床單、毛巾、繃帶、儀器包裝，刷子、面罩、頭部束帶和覆蓋巾(drapes)之醫用織物。此外，本發明的織物可使用於製造消費產品。例子包括座椅套、家庭日用織品、桌布以及汽車罩。也可預期：本發明的織物可構成上述物件的一部分或組件。The fibers and fabrics of the present invention have broad applicability across several industries. For example, the fabric of the present invention can be used to make sanitary articles. Examples include diapers and feminine hygiene products. The fabric of the present invention can also be used in medical products. Examples include medical fabrics for gowns, bed sheets, towels, bandages, instrument packaging, brushes, face masks, head straps, and drapes. Furthermore, the fabric of the present invention can be used to make consumer products. Examples include seat covers, household linen, tablecloths, and car covers. It is also contemplated that the fabric of the present invention may form part or assembly of the above items.

使用本發明之組成物製備的纖維及非織物網可被形成為織物、衣服、服飾、醫療服、手術袍、外科用覆蓋巾、尿布、訓練褲、衛生棉、衛生護墊、失禁服、床褥、袋子、包裝材料、包裝、游泳衣、體液不滲透性背層、體液不滲透層、體液可滲透層、體液可滲透外罩、吸收劑、紙巾、非織物複合材料、襯裡、布襯、擦洗墊、面膜、呼吸器、空氣過濾器、真空包裝袋、油和化學溢出吸附劑、隔熱、急救敷料、醫用覆蓋巾、纖維填充、外衣、棉被填充料、家具填料、過濾介質、擦洗墊、擦拭材料、針織品、汽車座椅、軟墊家具、地毯、地毯底布、過濾介質、丟棄式濕巾、尿布覆蓋材料、園藝織物、土工膜、土工織物、麻袋、家用包覆材料、蒸汽障壁、透氣布、信封、抗破壞織物、保護性包裝和杯墊。Fibers and nonwoven webs prepared using the compositions of the present invention can be formed into fabrics, garments, apparel, medical garments, surgical gowns, surgical coverings, Diapers, training pants, sanitary napkins, sanitary pads, incontinence suits, mattresses, bags, packaging materials, packaging, swimwear, body fluid impervious backing, body fluid impermeable layer, body fluid permeable layer, body fluid permeable cover, Absorbent, paper towel, non-woven composite, lining, cloth lining, scrubbing pad, mask, respirator, air filter, vacuum bag, oil and chemical spill sorbent, heat insulation, first aid dressing, medical cover towel, fiber Filling, outerwear, quilt filler, furniture filler, filter media, scrubbing pad, wiping material, knitwear, car seat, upholstered furniture, carpet, carpet backing, filter media, disposable wipes, diaper covering materials, Gardening fabrics, geomembranes, geotextiles, sacks, household coverings, steam barriers, breathable fabrics, envelopes, tamper resistant fabrics, protective packaging and coasters.

在一較佳實施態樣中，本發明該組成物可用於拋棄式尿布和衛生棉底座結構，包括：嬰兒尿布腿部彈性、尿布正面膠帶、尿布站立腿部收口、尿布底座結構、尿布核心穩定、尿布液體轉移層、尿布外覆蓋積層、尿布鬆緊收口積層、衛生棉核心穩定、及衛生棉膠條。尿布可具有各種適當形狀。例如，尿布可具有整體呈矩形、T形，或大致沙漏形。其他包含本文所述之組成物的可併入尿布的適當組件包括腰襟(waist flap)等等，其通常是熟習該項技術者已知的。適合於本發明相關用途的尿布結構之例子(其可包括其他適用於尿布之組件)係描述於US 4,798,603；US 5,176,668；Uw5,176,672；US 5,192,606；及US 5,509,915中。In a preferred embodiment, the composition of the present invention can be used in a disposable diaper and a sanitary napkin base structure, including: baby diaper leg elastic, diaper front tape, diaper standing leg cuff, diaper base structure, diaper core stable , diaper liquid transfer layer, diaper outer cover layer, diaper elastic closure, sanitary napkin core stability, and sanitary cotton strip. The diaper can have a variety of suitable shapes. For example, the diaper can have a generally rectangular, T-shaped, or generally hourglass shape. Other suitable components that can be incorporated into the diaper comprising the compositions described herein include waist flaps and the like, which are generally known to those skilled in the art. Examples of diaper structures suitable for use in connection with the present invention, which may include other components suitable for diapers, are described in U.S. Patent No. 4,798,603; U.S. Patent No. 5,176,668; U.S. Patent No. 5,176,672;

較佳地，採用各種類型的適當附接方式將包含本發明之纖維和非織物的尿布之各種組件組裝在一起，諸如黏著劑黏合、超音波黏合、熱點式黏合、或其組合。在所示實施態樣中，例如，上片和下片可彼此組裝在一起且與具有黏著劑(諸如熱熔壓敏黏劑)線條之液體滯留結構組裝在一起。Preferably, the invention is encompassed by various types of suitable attachment means. The fibers are assembled with various components of the non-woven diaper, such as adhesive bonding, ultrasonic bonding, hot spot bonding, or combinations thereof. In the illustrated embodiment, for example, the top and bottom sheets can be assembled with one another and assembled with a liquid retention structure having an adhesive (such as a hot melt pressure sensitive adhesive) line.

在另一實施態樣中，本發明之纖維和/或非織物係使用於訓練褲。構造該等訓練褲之各種材料和方法係揭示於WO 00/37009；US 4,940,464；US 5,766,389；及US 6,645,190中。In another embodiment, the fibers and/or non-woven fabrics of the present invention are used in training pants. Various materials and methods for constructing such training pants are disclosed in WO 00/37009; US 4,940,464; US 5,766,389; and US 6,645,190.

本發明之組成物在製造呈現高撓曲模數、高降伏抗拉強度和高熱變形溫度之模製零件(有或沒有添加成核劑下)中是有利的。The compositions of the present invention are advantageous in the manufacture of molded parts exhibiting high flexural modulus, high drop tensile strength and high heat distortion temperature (with or without the addition of a nucleating agent).

由於彼等流變、結晶和立構規整性參數的獨特組合，本發明之組成物也令人驚奇地可用於需要高熔體強度和提高之流動誘導的結晶動力之其他應用，包括但不限於吹塑模製物件、發泡體、薄膜(雙軸、吹塑膜、流延膜)等等，其提供改良加工性和機械性質(例如，抗拉強度、斷裂伸長率、抗刺穿性、耐衝擊性等等)的良好平衡之組合。Due to their unique combination of rheological, crystallization and stereoregularity parameters, the compositions of the present invention are also surprisingly useful for other applications requiring high melt strength and improved flow induced crystallization power, including but not limited to Blow molded articles, foams, films (biaxial, blown film, cast film), etc., which provide improved processability and mechanical properties (eg, tensile strength, elongation at break, puncture resistance, A good balance of impact resistance, etc.).

測試方法testing method

熔體流動速度(MFR)，以每10分鐘之聚合物的克數(克/10分鐘或其等值單位dg/分鐘)方式定義，係按照ASTM D1238(2.16公斤，230℃)測量。Melt flow rate (MFR), defined as grams of polymer per 10 minutes (grams/10 minutes or its equivalent unit dg/minute), is measured in accordance with ASTM D1238 (2.16 kg, 230 °C).

小角度振盪剪切(SAOS)掃頻熔體流變學實驗係在190℃下在MCR301控制應變/應力流變計(Anton Paar GmbH)上使用25毫米錐(1°)和板結構進行。樣品測試片(25毫米直徑，1毫米厚度)係經由使用Schwabenthan實驗室壓機(200T)在190℃下壓縮模製粒料樣品而製得。用於樣品製備之典型循環為在沒有壓力下1分鐘接著在壓力(50巴)下1.5分鐘，然後在水冷卻板之間5分鐘期間冷卻。將樣品先在190℃下平衡13分鐘以清除任何先前的熱和結晶歷史。接下來使用6點/十和位在從應變掃描實驗測定之線性黏彈性區域中的10%之應變值進行角頻率掃描從500rad/s至0.0232rad/s。所有實驗均在氮氣氛圍中進行，以減少樣品在流變測試期間的任何降解。The small angle oscillatory shear (SAOS) swept melt rheology experiment was performed at 190 °C on a MCR301 controlled strain/stress rheometer (Anton Paar GmbH) using a 25 mm cone (1 °) and plate structure. Sample test pieces (25 mm diameter, 1 mm thickness) were prepared by compression molding pellet samples at 190 °C using a Schwabenthan laboratory press (200T). A typical cycle for sample preparation is 1 minute without pressure followed by 1.5 minutes at pressure (50 bar) and then cooled for 5 minutes between water cooled plates. The sample was first equilibrated at 190 °C for 13 minutes to remove any previous heat and crystal history. The angular frequency sweep was then performed from 500 rad/s to 0.0232 rad/s using a 6 point/tenth position and a 10% strain value in the linear viscoelastic region determined from the strain sweep experiment. All experiments were performed in a nitrogen atmosphere to reduce any degradation of the sample during the rheological test.

為了本發明和其申請專利範圍之目的，零剪切速度黏度(η_o )係從頻率相關儲存(G’ )和損耗(G” )動態模數和根據線性回歸之離散鬆弛譜方法(如R.B.Bird,C.F.Curtiss,R.C.Armstrong，和O.Hassager在Dynamics of Polymeric Liquids ，第2版，(Wiley，紐約，1987)第1冊中，及A.K.Doufas,L.Rice,W.Thurston在“Shear and Extensional Rheology of Polypropylene Melts： Experimental and Modeling Studies”， J. Rheology 55 ， 95-126(2011)中所討論)定義如下：其中M為取決於實驗角頻率之範圍的離散鬆弛模式之數目，如伯德等人所概述(1987)，λ _j 為離散譜的離散鬆弛時間和G_j 為對應的剪切模數。For the purposes of the present invention and the scope of its patent application, zero shear velocity viscosity (η _o ) is derived from frequency dependent storage ( G' ) and loss ( G" ) dynamic modulus and discrete relaxation spectrum methods based on linear regression (eg, RBBird) , CFCurtiss, RCArmstrong, and O. Hassager in Dynamics of Polymeric Liquids , 2nd edition, (Wiley, New York, 1987) Volume 1, and AK Doufas, L. Rice, W. Thurston in "Shear and Extensional Rheology of Polypropylene Melts : Experimental and Modeling Studies", discussed in J. Rheology 55, 95-126 (2011)) is defined as follows: Where M is the number of discrete relaxation modes depending on the range of experimental angular frequencies, as outlined by Bird et al. (1987), λ _j is the discrete relaxation time of the discrete spectrum and G _j is the corresponding shear modulus.

其中在終端區(即，G’和ω² 成比例及G” 和ω成比例)尚未達到在實驗的頻率範圍內而因此複合黏度| η^* |不能達到平穩值之組成物的情況下，η_o 應經由如在C.W.Macosko,Rheology Principles,Measurements and Applications (Wiley-VCH，紐約，1994)和Ansari等人，“Rheology of Ziegler-Natta and Metallocene High-Density Polyethylenes：Broad Molecular Weight Distribution Effects,”Rheol.Acta50 ，17-27，2011中所討論之熔融蠕變實驗測量。在本發明中所提出之所有實例中，使用用於測定零剪切速度黏度(η_o )之方程式(1)方程式。從儲存(G’ )和損耗(G” )動態模數(C.W.Macosko,Rheology Principles,Measurements and Applications (Wiley-VCH，紐約，1994))，定義損耗角正切(tanδ)為： Where the terminal region (ie, G' and ω ² are proportional and G" and ω are proportional) have not reached the frequency range of the experiment and thus the composite viscosity | η ^* | cannot reach the composition of the stationary value, η as should _o via CWMacosko, Rheology Principles, Measurements and Applications (Wiley-VCH, New York, 1994) and Ansari, et al., "Rheology of Ziegler-Natta and Metallocene High-Density Polyethylenes: Broad Molecular Weight Distribution Effects," Rheol.Acta Melt creep experimental measurements discussed in 50 , 17-27, 2011. In all of the examples presented in the present invention, equation (1) for determining zero shear velocity viscosity (η _o ) is used. ( G' ) and loss ( G" ) dynamic modulus (CWMacosko, Rheology Principles, Measurements and Applications (Wiley-VCH, New York, 1994)), defining the loss tangent (tan δ) as:

損耗角正切(tanδ)，尤其是在低角頻率(例如，0.1rad/s)，是熔體彈性的一種測度量，且有關組成物之分子特性(例如，短和長鏈的分佈、分子纏結的密度、鏈分枝、等等)。在本發明中，在恆定剪切速度下的穩態剪切流之第一正向應力差(N₁ )係根據動態模數(G’和G” )測定如下(H.M.Laun,“Prediction of elastic strains of polymer melts in shear and elongation,”J.Rheol.30 459- 501(1986))：其中G’和G”係指角頻率ω和SAOS和穩態剪切實驗的溫度二者為相同，N。方程式(3)在此稱為“Laun規則”。在本發明中，穩態剪切應力τ_yx 係根據Cox-Merz規則從複合黏度| η^* |的範數計算(W.P.Cox and E.H.Merz,“Correlation of dynamic and steady flow viscosities,”J.Polym.Sci.28 ,619-621(1958))：其中該複合黏度的範數係根據頻率ω由G’和G” 計算如下(C.W.Macosko,Rheology Principles,Measurements and Applications (Wiley-VCH，紐約，1994))： The tan delta (tan δ), especially at low angular frequencies (eg, 0.1 rad/s), is a measure of melt elasticity and related to the molecular properties of the composition (eg, short and long chain distribution, molecular wraps) The density of the knot, chain branching, etc.). In the present invention, the first forward stress difference (N ₁ ) of the steady shear flow at a constant shear rate is determined as follows according to the dynamic modulus (G' and G" ) (HMLaun, "Prediction of elastic strains Of polymer melts in shear and elongation," J. Rheol. 30 459-501 (1986)): Wherein G' and G" mean that both the angular frequency ω and the temperature of the SAOS and steady-state shear experiments are the same, N. Equation (3) is referred to herein as the "Laun rule." In the present invention, steady shear The stress τ _yx is calculated from the norm of the composite viscosity | η ^* | according to the Cox-Merz rule (WPCox and EHMerz, "Correlation of dynamic and steady flow viscosities," J. Polym. Sci. 28 , 619-621 (1958)). : Where the norm of the composite viscosity is calculated from G' and G" according to the frequency ω (CWMacosko, Rheology Principles, Measurements and Applications (Wiley-VCH, New York, 1994)):

應力比(SR)係定義如下： The stress ratio (SR) is defined as follows:

在Shear and Extensional Rheology of Polypropylene Melts：Experimental and Modeling Studies ，Doufas等人，J.Rheol.55,95(2011)中證明Cox-Merz(Cox和Merz(1957))和Laun(Laun(1986))規則二者於各種聚丙烯系統中之適用性。根據上述流變性質，一些流變指數係與該組成物的分子特性相關地定義，如下：無因次應力比指數R ₁ ：其中η_o (方程式(1))為Pa˙s之單位。The Cox-Merz (Cox and Merz (1957)) and Laun (Laun (1986)) rules are demonstrated in Shear and Extensional Rheology of Polypropylene Melts: Experimental and Modeling Studies , Doufas et al, J. Rheol. 55, 95 (2011). The suitability of both in various polypropylene systems. According to the above rheological properties, some rheological indices are defined in relation to the molecular properties of the composition, as follows: dimensionless stress ratio index R ₁ : Where η _o (equation (1)) is the unit of Pa ̇s.

無因次應力比/損耗角正切指數R ₂ ：其中η_o (方程式(1))係以Pa˙s表示。 Dimensionless stress ratio / loss tangent index R ₂ : Where η _o (equation (1)) is expressed by Pa ̇ s.

無因次剪切稀化指數R₃ ：其中該穩態剪切黏度η(500s^-1 )係由方程式(5)和使用Cox-Merz規則(W.P.Cox和E.H.Merz，“Correlation of dynamic and steady flow viscosities,”J.Polym.Sci.28 ,619-621(1958))計算。Dimensionless shear thinning index R ₃ : Where the steady-state shear viscosity η (500s ^-1 ) is based on equation (5) and using the Cox-Merz rule (WPCox and EHMerz, "Correlation of dynamic and steady flow viscosities," J. Polym. Sci. 28 , 619- 621 (1958)) Calculation.

無因次損耗角正切/彈性指數R ₄ ：其中η_o (方程式(1))係以Pa˙s之單位表示。 Dimensional loss tangent / elastic index R ₄ : Where η _o (equation (1)) is expressed in units of Pa ̇s.

如所述，損耗角正切(tanδ)在低角頻率(例如，0.1rad/s)係對該分子結構敏感且有關熔融最長鬆弛時間以及蠕變相關性質(例如，穩態蠕變柔量和可恢復蠕變柔量)(C.W.Macosko,Rheology Principles,Measurements and Applications (Wiley-VCH，紐約，1994))。因此，組成物固有的流變指數(例如，彼等以方程式(7)-(8)、(10)所定義者)原則上可藉最長鬆弛時間和熔融蠕變性質表示。As stated, the loss tangent (tan δ) is sensitive to the molecular structure at low angular frequencies (eg, 0.1 rad/s) and relates to the longest relaxation time of the melt and creep related properties (eg, steady state creep compliance and Restoring creep compliance) (CW Macosko, Rheology Principles, Measurements and Applications (Wiley-VCH, New York, 1994)). Thus, the rheological indices inherent to the composition (eg, as defined by equations (7)-(8), (10)) can in principle be expressed by the longest relaxation time and the melt creep properties.

經由SAOS流變學之結晶：經由SAOS流變學監測結晶，其中在ARES 2001(TA儀器)受控應變流變計上使用25毫米平行板結構以恆定冷卻速度將樣品從熔融狀態(在190℃下)冷卻。用Carver實驗室壓機在190℃下製造樣品測試片(25毫米直徑，2.5毫米厚度)。使樣品在無壓力下靜置約3分鐘以便熔融且接著在壓力下保持3分鐘以壓縮模製樣品。測試片最初大約2.5毫米厚；然而，樣品修掉平行板之後，使用板之間的1.9毫米間隙。在SAOS測試期間考慮工具的熱膨脹，以在整個測試期間保持固定間隙。首先將樣品從室溫加熱至190℃。將樣品在190℃下平衡(熔融狀態)15分鐘，以清除任何先前的熱和結晶歷史。將溫度重複地控制在±0.5℃內。然後以1℃/分鐘之恆定冷卻速度和1rad/s之角頻率使用位在線性黏彈性區域中的1%之應變將樣品從190℃冷卻。為了終止實驗，使用最大扭矩標準。一旦在流變測試期間開始結晶，當達到最大扭矩時，該儀器進入過載狀態，且自動停止測試。所有實驗均在氮氣氛圍中進行，以減少樣品在流變測試期間的任何降解。藉由複合黏度的急劇/突然增加和損耗角正切tanδ的急劇/突然(階梯狀)減少觀察到結晶(即複合黏度對溫度和損耗角正切對溫度的作圖描繪由於發生結晶的流變性質突然改變的頸狀區域)。“經由流變之結晶開始溫度”(T_c,rheol )係定義為觀察到複合黏度之急劇(即，頸狀)增加且同時tanδ的急劇減少的溫度。T_c,rheol 的重複性係在±1℃內。根據溫度的複合模數和動態模數之再現性係在3%內。Crystallization via SAOS rheology: Crystallization was monitored via SAOS rheology, where the sample was taken from the molten state at a constant cooling rate using a 25 mm parallel plate structure on an ARES 2001 (TA Instruments) controlled strain rheometer (at 190 ° C) )cool down. Sample test pieces (25 mm diameter, 2.5 mm thickness) were fabricated at 190 ° C using a Carver laboratory press. The sample was allowed to stand under no pressure for about 3 minutes to melt and then held under pressure for 3 minutes to compression-mold the sample. The test piece was initially approximately 2.5 mm thick; however, after the sample was trimmed off the parallel plate, a 1.9 mm gap between the plates was used. The thermal expansion of the tool was considered during the SAOS test to maintain a fixed gap throughout the test. The sample was first heated from room temperature to 190 °C. The sample was equilibrated (melted state) at 190 ° C for 15 minutes to remove any previous heat and crystal history. The temperature was repeatedly controlled within ±0.5 °C. The sample was then cooled from 190 ° C using a 1% strain in the linear viscoelastic region at a constant cooling rate of 1 ° C/min and an angular frequency of 1 rad/s. In order to terminate the experiment, the maximum torque standard was used. Once crystallization begins during the rheological test, when the maximum torque is reached, the instrument enters an overload condition and the test is automatically stopped. All experiments were performed in a nitrogen atmosphere to reduce any degradation of the sample during the rheological test. Crystallization is observed by a sharp/sudden increase in the composite viscosity and a sharp/sudden (stepped) decrease in tan tang tan δ (ie, the composite viscosity versus temperature and loss tangent versus temperature plotting due to the rheological properties of crystallization) Changing neck area). The "crystallization starting temperature through rheology" (T _c,rheol ) is defined as the temperature at which a sharp (ie, neck-like) increase in composite viscosity is observed while a sharp decrease in tan δ is observed. The repeatability of T _c,rheol is within ±1 °C. The reproducibility of the composite modulus and dynamic modulus according to temperature is within 3%.

示差掃描熱量法(DSC)Differential Scanning Thermal Method (DSC)

經由示差掃描熱量法(DSC)使用DSCQ200(TA儀器)單元在粒料樣品上測量峰值結晶溫度(T_cp )、峰值融熔溫度(T_mp )和熔解熱(△H_f )。使用四種標準品(錫、銦、環己烷和水)計算DSC之溫度。銦之熱流(28.46J/g)係用以校正熱流信號。將3至5mg之聚合物的樣品(通常於顆粒形式)密封在有平蓋的標準鋁鍋並在室溫下裝入儀器。The peak crystallization temperature (T _cp ), the peak melting temperature (T _mp ), and the heat of fusion (ΔH _f ) were measured on the pellet samples by differential scanning calorimetry (DSC) using a DSCQ200 (TA instrument) unit. The temperature of the DSC was calculated using four standards (tin, indium, cyclohexane, and water). The heat flow of indium (28.46 J/g) is used to calibrate the heat flow signal. A sample of 3 to 5 mg of polymer (usually in particulate form) was sealed in a standard aluminum pan with a flat lid and loaded into the instrument at room temperature.

在測定對應於1℃/分鐘冷卻和加熱速度之T_cp 和T_mp 的情況下，使用下列步驟。樣品首先在25℃下平衡和隨後使用20℃/分鐘之加熱速度加熱至200℃(第一加熱)。將樣品於200℃保持5分鐘以清除任何先前的熱和結晶的歷史。隨後用1℃/分鐘之恆定冷卻速度將樣品冷卻至95℃(第一冷卻)。樣品在以1℃/分鐘之恆定加熱速度加熱至200℃(第二加熱)之前，於95℃之等溫保持5分鐘。使用TA通用分析軟體分析結晶之放熱峰值(第一冷卻)並測定對應於1℃/分鐘冷卻速度之峰值結晶溫度(T_cp )。也使用TA通用分析軟體分析融熔之吸熱峰值 (第二加熱)並測定對應於1℃/分鐘冷卻速度之峰值融熔溫度(T_mp )。In the case of measuring T _cp and T _mp corresponding to a cooling and heating rate of 1 ° C / min, the following procedure was used. The sample was first equilibrated at 25 ° C and subsequently heated to 200 ° C (first heating) using a heating rate of 20 ° C / min. The sample was held at 200 ° C for 5 minutes to remove any previous history of heat and crystallization. The sample was then cooled to 95 ° C (first cooling) with a constant cooling rate of 1 ° C / min. The sample was held at 95 ° C for 5 minutes before being heated to 200 ° C (second heating) at a constant heating rate of 1 ° C / min. The exothermic peak of the crystallization (first cooling) was analyzed using the TA general analysis software and the peak crystallization temperature (T _cp ) corresponding to the cooling rate of 1 ° C / min was measured. The TA general analysis software was also used to analyze the endothermic peak of the melting (second heating) and to determine the peak melting temperature (T _mp ) corresponding to the cooling rate of 1 ° C / min.

在測定對應於10℃/分鐘冷卻和加熱速度之T_cp 和T_mp 的情況下，使用下列步驟。樣品首先在25℃下平衡和隨後使用10℃/分鐘之加熱速度加熱至200℃(第一加熱)。將樣品於200℃保持10分鐘以清除任何先前的熱和結晶的歷史。隨後用10℃/分鐘之恆定冷卻速度將樣品冷卻至25℃(第一冷卻)。樣品在以10℃/分鐘之恆定加熱速度加熱至200℃(第二加熱)之前，於25℃之等溫保持10分鐘。使用TA通用分析軟體分析結晶之放熱峰值(第一冷卻)並測定對應於10℃/分鐘冷卻速度之峰值結晶溫度(T_cp )。也使用TA通用分析軟體分析融熔之吸熱峰值(第二加熱)並測定對應於10℃/分鐘加熱速度之峰值融熔溫度(T_mp )。In the case of measuring T _cp and T _mp corresponding to a cooling and heating rate of 10 ° C / min, the following procedure was used. The sample was first equilibrated at 25 ° C and subsequently heated to 200 ° C (first heating) using a heating rate of 10 ° C / min. The sample was held at 200 ° C for 10 minutes to remove any previous history of heat and crystallization. The sample was then cooled to 25 ° C (first cooling) with a constant cooling rate of 10 ° C / min. The sample was held isothermally at 25 ° C for 10 minutes before being heated to 200 ° C (second heating) at a constant heating rate of 10 ° C / min. The exothermic peak of the crystallization (first cooling) was analyzed using the TA general analysis software and the peak crystallization temperature (T _cp ) corresponding to the cooling rate of 10 ° C / min was measured. The TA general analysis software was also used to analyze the endothermic peak of the melting (second heating) and to determine the peak melting temperature (T _mp ) corresponding to the heating rate of 10 ° C / min.

在測定結晶和融熔峰值溫度之任一方法中，分別在第二(冷卻)和第三(加熱)循環期間，始終保持相同冷卻和加熱速度(1℃/分鐘或10℃/分鐘)。例如，在T_mp 列出其相關之加熱速度的情況下，此暗示：前述循環之冷卻速度係於與加熱循環相同的速度。百分比結晶度(X%)係使用下式計算：[DSC曲線下之面積(J/g)/H°(J/g)]*100，其中該DSC曲線下之面積在此係指第一冷卻循環和H°為主單體組分的均聚物之熔解熱。此等H°之值係得自Polymer Handbook (第四版，紐約John Wiley and Sons出版，1999)，除了使用290J/g之值作為100%結晶聚乙烯的平衡熔解熱(H°)，使用140J/g之值作為100%結晶聚丁烯的平衡熔解熱(H°)，和使用207J/g(H°)之值作為100%結晶聚丙烯的熔解熱之外。In either method of determining the crystallization and melting peak temperatures, the same cooling and heating rates (1 ° C/min or 10 ° C/min) are maintained throughout the second (cooling) and third (heating) cycles, respectively. For example, in the case where T _mp lists its associated heating rate, this implies that the cooling rate of the aforementioned cycle is at the same speed as the heating cycle. The percent crystallinity (X%) is calculated using the following formula: [area under the DSC curve (J/g) / H° (J/g)] * 100, where the area under the DSC curve refers here to the first cooling The heat of fusion of the homopolymer of the main monomer component is recycled and H°. The values of these H° are obtained from the Polymer Handbook (fourth edition, published by John Wiley and Sons, New York, 1999), except that the value of 290 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene, using 140J. The value of /g is taken as the equilibrium heat of fusion (H°) of 100% crystalline polybutene, and the value of 207 J/g (H°) is used as the heat of fusion of 100% crystalline polypropylene.

在本發明中，如以DSC測量(於1℃/分鐘或10℃/分鐘溫度斜坡速度)，融熔和結晶峰值溫度(T_mp -T_cp )之間的差為稱為“過冷範圍”且以℃表示。“過冷極限”，SCL，係根據US 7,807,769和美國專利申請公開號2010/0113718定義，如下：SCL =0.907T _mp -99.64 (11)其中T_mp 和SCL係以℃表示。US 7,807,769和美國專利申請公開號2010/0113718用對應於10℃/分鐘之加熱速度的T_mp (第二加熱)定義SCL；然而，在本發明中，方程式(11)也用以定義於1℃/分鐘之加熱速度(第二加熱)的SCL。下列稱為“過冷參數”SCP之參數在此係定義如下：SCP =T _mp -T _cp -SCL (12)其中在方程式(12)的右側的所有參數均以℃表示，且指所指示的1℃/分鐘或10℃/分鐘任一溫度斜坡速度。在方程式(12)中，SCL係由方程式(11)計算。In the present invention, as measured by DSC (at a ramp rate of 1 ° C / min or 10 ° C / min), the difference between the melting and crystallization peak temperatures (T _{mp -} T _cp ) is called "supercooling range" And expressed in °C. "Subcooling limit", SCL, is defined in accordance with US 7,807,769 and U.S. Patent Application Publication No. 2010/0113718, as follows: SCL = 0.907 T _mp -99.64 (11) wherein T _mp and SCL are expressed in ° C. US 7,807,769 and U.S. Patent Application Publication No. 2010/0113718 define SCL with T _mp (second heating) corresponding to a heating rate of 10 ° C / min; however, in the present invention, equation (11) is also used to define 1 ° C /min The heating rate (second heating) of SCL. The following parameters, referred to as "supercooled parameters" SCP, are defined here as follows: SCP = T _mp - T _cp - SCL (12) where all parameters on the right side of equation (12) are expressed in ° C and refer to the indicated Any temperature ramp rate of 1 ° C / min or 10 ° C / min. In equation (12), the SCL is calculated by equation (11).

藉由凝膠滲透層析(GPC)之分子量(M_w 、M_n 、M_z 和M_v )Molecular weight by gel permeation chromatography (GPC) (M _w , M _n , M _z and M _v )

分子量分布係使用凝膠滲透層析(GPC)(也稱為粒徑篩析層析法(SEC))示性。分子量(重量平均分子量 M_w 、數目平均分子量M_n 、Z平均分子量M_z 和黏度平均分子量M_v )係使用配備示差折射率偵檢器(DRI)之高溫凝膠滲透層析測定。關於測量步驟之實驗詳細資料係由T.Sun,P.Brant,R.R.Chance和W.W.Graessley描述於文獻Macromolecules，第34冊，第19號，6812-6820(2001)及於US 7,807,769中。The molecular weight distribution is characterized using gel permeation chromatography (GPC) (also known as size exclusion chromatography (SEC)). The molecular weight (weight average molecular weight M _w , number average molecular weight M _n , Z average molecular weight M _{z ,} and viscosity average molecular weight M _v ) was determined using a high temperature gel permeation chromatography equipped with a differential refractive index detector (DRI). Experimental details regarding the measurement procedure are described by T. Sun, P. Brant, RRChance and WW Graessley in the literature Macromolecules, Vol. 34, No. 19, 6812-6820 (2001) and US 7,807,769.

使用一種具有三重檢測和三個聚合物實驗室PLgel10微米混合B管柱之聚合物實驗室PL-GPC-220高溫SEC系統。三個串聯檢測器為：首先Wyatt DAWN“EOS”MALLS 18角雷射散射檢測器，接著DRI檢測器及最後接著示差黏度計檢測器。使用Wyatt’s ASTRA軟體收集檢測器輸出信號並使用GPC分析程式分析。詳細GPC條件係列於US 7,807,769之表8中。數據分析之理論基礎也可發現於US 7,807,769中。A polymer laboratory PL-GPC-220 high temperature SEC system with triple detection and three polymer laboratory PLgel 10 micron mixed B columns was used. The three series detectors are: first Wyatt DAWN "EOS" MALLS 18-angle laser scatter detector, followed by DRI detector and finally the differential viscometer detector. The detector output signal was collected using Wyatt's ASTRA software and analyzed using a GPC analysis program. The detailed GPC condition series is in Table 8 of US 7,807,769. The theoretical basis for data analysis can also be found in US 7,807,769.

使用0.5公分³ /分鐘的標稱流量速度，以及300毫升的標稱注射體積。各種轉移管線、管柱和示差折光計(DRI檢測器，主要用於測定溶析溶液濃度)係包含在於145℃之烘箱中。Use a nominal flow rate of 0.5 cm ³ /min and a nominal injection volume of 300 ml. Various transfer lines, columns and differential refractometers (DRI detectors, primarily for determining the concentration of the solution) were included in an oven at 145 °C.

標準品和樣品係在抑制TCB(1,2,4-三氯苯)溶劑中製備。四個NBS聚乙烯(PE)標準品用於校準GPC。PE標準品為NIST 1482a；NIST 1483a；NIST1484a(窄PE標準品)；及NIST 1475a(寬PE標準品)。將樣品準確稱重，稀釋至~1.5毫克/毫升濃度並記錄。將這些標準品和樣品放在PL Labs 260加熱器/振動器於160℃經兩小時。此等通過2.0微米鋼質過濾杯過濾，然後進行分析。Standards and samples were prepared in a solvent that inhibits TCB (1,2,4-trichlorobenzene). Four NBS polyethylene (PE) standards were used to calibrate the GPC. The PE standards were NIST 1482a; NIST 1483a; NIST 1484a (narrow PE standard); and NIST 1475a (wide PE standard). The sample was accurately weighed, diluted to a concentration of ~1.5 mg/ml and recorded. Place these standards and samples in a PL Labs 260 heater/vibrator at 160 ° C for two small Time. These were filtered through a 2.0 micron steel filter cup and analyzed.

分枝指數(g’_vis )係使用SEC-DRI-LS-VIS方法(關於g’係描述於US 7,807,769之第37頁)的輸出計算如下。樣品之平均固有黏度，[η]_avg 藉由下式計算：其中在介於積分限制之間的層析片段(chromotographic slice)(i)上求和。The branching index (g' _vis ) is calculated as follows using the output of the SEC-DRI-LS-VIS method (described on page 37 of the US g., 807,769). The average intrinsic viscosity of the sample, [η] _avg is calculated by: Where is summed on a chromotographic slice (i) between the integral limits.

分枝指數g’vi係定義為：其中，為了本發明及其申請專利範圍之目的，對於線型乙烯聚合物，α=0.695和k=0.000579，對於線型丙烯聚合物，α=0.705和k=0.0002288，和對於線型丁烯聚合物α=0.695和k=0.000179。方程式(12)之分母表示線型聚合物之計算理論固有黏度。M_v 為根據以LS分析測定之分子量的黏度-平均分子量。The branching index g'vi is defined as: For the purposes of the present invention and the scope of the patent application, for linear ethylene polymers, α = 0.695 and k = 0.000579, for linear propylene polymers, α = 0.705 and k = 0.0002288, and for linear butene polymers α = 0.695 and k=0.000179. The denominator of equation (12) represents the calculated theoretical intrinsic viscosity of the linear polymer. M _v is the viscosity-average molecular weight based on the molecular weight determined by LS analysis.

以¹³ C NMR測定之立構規整性Stereorometry measured by ¹³ C NMR

碳NMR光譜係用以測量聚丙烯中的內消旋五單元組(pentads)、立體和區域缺陷濃度。碳NMR光譜係用具有至少100MHz的¹³ C頻率之Varian光譜計上之10毫米寬帶探針獲得。在1,1,2,2-四氯乙烷-d2(TCE)中製備樣品。樣品製備(聚合物溶解)係在140℃下進行，其中將0.25克聚合物溶解在適當量的溶劑中以產生3毫升的最終聚合物溶液。為了最佳化化學位移解析，沒有使用乙醯基丙酮酸鉻弛豫劑製備樣品。Carbon NMR spectroscopy was used to measure the concentration of mesopentads, stereo and regional defects in polypropylene. The carbon NMR spectrum was obtained with a 10 mm wide band probe on a Varian spectrometer with a ¹³ C frequency of at least 100 MHz. Samples were prepared in 1,1,2,2-tetrachloroethane-d2 (TCE). Sample preparation (polymer dissolution) was carried out at 140 ° C where 0.25 grams of polymer was dissolved in a suitable amount of solvent to produce 3 milliliters of final polymer solution. To optimize chemical shift resolution, samples were prepared without the use of a chromium thiopyruvate relaxer.

立體缺陷的化學位移指定(表示為立體五單元組)可發現於文獻(L.Resconi,L.Cavallo,A.Fait,and F.Piemontesi,Chem.Rev.2000，100，1253-1345頁)中。立體五元組(例如，mmmm、mmmr、mrm、等等)可適當地加總，以產生立體三單元組分佈(mm、mr和rr)和莫耳百分比二單元組(m和r)。將三種類型的區域缺陷定量：2,1-赤蘚型、2,1-蘇型和3,1-***型。這些結構和峰值指定也給予於Resconi等人之參考文獻。所有區域缺陷(間斷(punctuation))之濃度表示為每10,000單體單元(D_R )的區域缺陷之數目。因此，立體缺陷(間斷)的濃度表示為每10,000單體單元立體缺陷之數目(D_S )。每10,000單體之缺陷總數(D_總計 )係計算為：D _total =D _S +D _R (15)。The chemical shift designation (denoted as a stereo pentad) of a stereoscopic defect can be found in the literature (L. Resconi, L. Cavallo, A. Fait, and F. Piemontesi, Chem. Rev. 2000, 100, pages 1253-1345). . Stereo pentads (eg, mmmm, mmmr, mrm, etc.) may be summed as appropriate to produce a stereo triad distribution (mm, mr, and rr) and a molar percentage diad (m and r). Three types of regional defects were quantified: 2, 1-erythroform, 2,1-threo, and 3,1-inserted. These structures and peak assignments are also given to Resconi et al. The concentration of all regional defects (punctuation) is expressed as the number of regional defects per 10,000 monomer units (D _R ). Therefore, the concentration of the stereoscopic defect (intermittent) is expressed as the number of stereo defects per 10,000 monomer unit (D _S ). The total number of defects per 10,000 monomers (D _total ) is calculated as: D _total = D _S + D _R (15).

平均內消旋運行長度(average meso run length)(MRL)表示根據10,000個丙烯單體的缺陷之間的丙烯單元(平均而言)之總數(立體和區域)且計算如下： The average meso run length (MRL) represents the total number (stereo and region) of propylene units (on average) between defects of 10,000 propylene monomers and is calculated as follows:

在本發明中MRL的定義[方程式(16)]係根據結構鏈間斷或已以非規則方式發生的丙烯***所產生之缺陷(立體和區域缺陷)的數目。其不包括由於共聚單體(例如，聚丙烯隨機共聚物中之乙烯)存在之間斷。該區域缺陷各在碳NMR光譜中產生多個峰，且將這些全部積分和平均(至與光譜中的其他峰解析之程度)，以改良測量精度。在分析中所使用的解析共振之化學位移偏移係列於US 7,807,769中。各缺陷之平均積分係除以主丙烯信號(CH3、CH、CH2)之一的積分，再乘以10,000以確定每10,000個單體之缺陷濃度。The definition of the MRL in the present invention [Equation (16)] is based on the number of defects (stereo and regional defects) generated by the structural chain discontinuity or the propylene insertion which has occurred in an irregular manner. It does not include the presence of discontinuities due to comonomers (eg, ethylene in a random copolymer of polypropylene). Missing area Each of the traps produces multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent of resolution to other peaks in the spectrum) to improve measurement accuracy. The chemical shift shifts for analytical resonances used in the analysis are described in US 7,807,769. The average integral of each defect is divided by the integral of one of the primary propylene signals (CH3, CH, CH2) and multiplied by 10,000 to determine the defect concentration per 10,000 monomers.

整體物理性質測量Overall physical property measurement

撓曲模數(1%正割撓曲模數)係按照ASTM D790A使用Instron機器，使用1.27毫米/分鐘(0.05吋/分鐘)之十字頭速度和50.8毫米(2.0吋)之支撐跨距測量。Flexural modulus (1% secant flexural modulus) was measured using an Instron machine according to ASTM D790A using a crosshead speed of 1.27 mm/min (0.05 吋/min) and a support span of 50.8 mm (2.0 吋).

抗拉性質諸如降伏抗拉強度(在本文中也稱為降伏應力)和降伏伸長率(在本文中也稱為降伏應變)係按照ASTM D638使用Instron機器，使用50.8毫米/分鐘(2.0吋/分鐘)之十字頭速度和50.8毫米(2.0吋)之隔距長度測量。Tensile properties such as reduced tensile strength (also referred to herein as the undulating stress) and reduced elongation (also referred to herein as the undulating strain) are in accordance with ASTM D638 using an Instron machine using 50.8 mm/min (2.0 Torr/min). ) Crosshead speed and 50.8 mm (2.0 吋) gauge length measurement.

熱變形溫度(HDT)係按照ASTM D648使用所指定之0.45MPa(66psi)或1.8MPa(264psi)的負載測量。The heat distortion temperature (HDT) is measured using a load of 0.45 MPa (66 psi) or 1.8 MPa (264 psi) as specified by ASTM D648.

POY纖維測試POY fiber test

以每9000米的紗之克數表示的POY纖維之總丹尼係藉由測定90米紗的重量測量，該紗係使用Alfred Suter Co.丹尼輪纏繞纖維芯。平均每長絲丹尼數(dpf)係定義為紗的測量丹尼/長絲的數目(72)。所測得的dpf之間發現極佳一致性，且其從每孔之質量通量和捲取速度計算如下： The total denier of the POY fibers expressed in grams per 9000 meters of yarn is measured by measuring the weight of a 90 meter yarn using an Alfred Suter Co. The average number of denier per filament (dpf) is defined as the number of denier/filaments measured by the yarn (72). Excellent agreement was found between the measured dpf, and its mass flux and take-up speed from each well were calculated as follows:

用測試紗和纖維的強度和伸長率之以微處理器為主的機器之Textechno Statimat^TM M單元進行POY纖維的拉伸試驗。所使用的儀器特別是為Statimat M,S/N 23523，CRE型，其配備使用Microsoft操作系統的軟體FPAM 0210E。對於所有測試，隔距長度為100毫米及拉伸速度為1270毫米/分鐘。POY fiber tensile test with a microprocessor-based machine of Textechno Statimat ^TM M units strength and elongation of the test yarns and fibers. The instrument used was in particular Stitimat M, S/N 23523, CRE type, equipped with the software FPAM 0210E using the Microsoft operating system. For all tests, the gauge length was 100 mm and the draw speed was 1270 mm/min.

非織物測試Non-woven test

定義為每單位面積織物的質量之織物基重係以稱重3個12”×12”織物片測量且以克/米² (gsm)表示之平均值報告。Is defined as the mass per unit area of fabric at a fabric basis weight of the weighing system 3 12 "× 12" fabric sheet and measured in g / m ² (gsm) represents the average value reported.

纖維厚度表示為“丹尼”或相等地表示為“每長絲丹尼數”(dpf)，且如該技藝中一般已知的，為每9000米的纖維之重量(克數)。根據下列以紡絲方法之定義和質量平衡為基準的方程式，在本發明中纖維直徑和每長絲丹尼數(dpf)係相關的：其中d為以微米單位表示之單纖維的直徑且為纖維密度 (在本發明中關於聚丙烯取為900公斤/米³ )。The fiber thickness is expressed as "Dani" or equivalently expressed as "Danis per filament" (dpf), and as is generally known in the art, is the weight (grams) of fibers per 9000 meters. According to the following equations based on the definition of the spinning method and the mass balance, in the present invention the fiber diameter is related to the number of denier per filament (dpf): Wherein d is the diameter of the single fiber expressed in micrometer units and is the fiber density (in the present invention, the polypropylene is taken to be 900 kg/m ³ ).

分離纖維且使用下列方法測量彼等的直徑(厚度)：用新雙刃剃刀片從較大的樣品小心地切割一部分的紡黏纖維(取自進入熱黏合步驟之前的輸送帶)和分離小部分的纖維樣品用於厚度測量。要特別注意：處理時，避免纖維伸長率或變形。將纖維安裝在浸沒流體中的載玻片和蓋玻片之間並使用由Media Cybernetics ImagePro影像處理軟體驅動之配備旋轉台、正交偏光、20x物鏡和數位相機(Optronics)的偏振光顯微鏡(Olympus BX50)檢測。在下列條件下檢測纖維：90°正交偏光；聚光器光圈完全打開(以將增加纖維的表觀厚度之繞射效應最小化)；纖維轉至最大亮度的角度。獲得和校準15根纖維的數位影像。使用Media Cybernetics ImagePro影像處理軟體測定纖維直徑至最接近微米。隨後經由方程式(18)從所測得的平均纖維直徑d計算得出纖維丹尼(dpf)。The fibers were separated and their diameter (thickness) was measured using the following method: Carefully cutting a portion of the spunbond fibers from a larger sample with a new double-edged razor blade (taken from the conveyor belt before entering the thermal bonding step) and separate a small portion Fiber samples were used for thickness measurements. Pay special attention to avoid fiber elongation or deformation during handling. Fibers were mounted between slides and coverslips in immersion fluids and polarized light microscopes (Olympus) equipped with a rotary table, orthogonal polarized light, 20x objective and digital camera (Optronics) driven by Media Cybernetics ImagePro image processing software BX50) detection. The fibers were tested under the following conditions: 90° orthogonal polarization; the concentrator aperture was fully open (to minimize the diffraction effect of increasing the apparent thickness of the fiber); the fiber was turned to the angle of maximum brightness. Obtain and calibrate digital images of 15 fibers. The fiber diameter was measured to the nearest micron using the Media Cybernetics ImagePro image processing software. Fiber denier (dpf) is then calculated from the measured average fiber diameter d via equation (18).

根據標準方法WSP 110.4(05)用200毫米的隔距長度和100毫米/分鐘的測試速度測量非織物的抗拉性質諸如縱向(MD)和橫向(CD)二者之抗拉(峰值)強度和%(峰值)伸長率，除非另有說明。織物試樣的寬度為5公分。關於拉伸試驗，使用配備數據分析用Instron Bluehill 2(2.5版)軟體之Instron機器(型號5565)。從力-伸長率抗拉曲線，該軟體報告MD和CD向之拉伸模數值(N/5公分/gsm之單位)，其係根據下列演算法算出：1.搜尋從第一個數據點至最大負載值的數據； 2.使用第一個數據點和最大負載點分別作為起點和終點值；3.將起點和終點值之間的數據分成6個具有0%重疊的相等區域；4.將最小平方配適演算法應用於各區域中所有的點以確定各區域的斜率；5.測定具有最高斜率總和的連續區域對；及6.從此對，測定那個區域具有最高斜率並將所報告之模數值指定於該區域。The tensile (peak) strength of both non-woven tensile properties such as machine direction (MD) and transverse direction (CD) is measured according to standard method WSP 110.4 (05) with a gauge length of 200 mm and a test speed of 100 mm/min. % (peak) elongation unless otherwise stated. The width of the fabric sample was 5 cm. For the tensile test, an Instron machine (Model 5565) equipped with Instron Bluehill 2 (version 2.5) software for data analysis was used. From the force-elongation tensile curve, the software reports the MD and CD tensile modulus values (units of N/5 cm/gsm), which are calculated according to the following algorithm: 1. Search from the first data point to Data of maximum load value; 2. Use the first data point and the maximum load point as the starting point and end point value respectively; 3. Divide the data between the starting point and the ending point value into 6 equal areas with 0% overlap; 4. The least squares fit algorithm Apply to all points in each region to determine the slope of each region; 5. Determine the continuous region pair with the highest slope sum; and 6. From then on, determine which region has the highest slope and assign the reported modulus value to the region .

拉伸模數的較低值為較不僵硬且更柔軟的織物之指示。The lower value of the tensile modulus is an indication of a less stiff and softer fabric.

柔軟度或“手感”如其在該技藝中已知的，係使用Thwing-Albert儀器有限公司織物手感測定器(Handle-O-Meter，型號211-10-B/AERGLA)進行測量。“手感”的品質被認為是由於織物材料的表面摩擦之阻力和柔性的組合。織物手感測定器使用LVDT(線性可變示差變壓器線型)測量上述兩個因素以檢測當迫使材料的試樣進入成平行邊緣的狹縫時，葉片所遭遇的阻力。3 1/2數字數位電壓表(DVM)指示直接以克力表示之阻力。給定織物之“總手感”係定義為在兩個織物試樣上取得之8個讀數(每個試樣4個讀數)的平均值。對於各測試試樣(5毫米狹縫寬度)，手感係在二側及二方向(MD和CD)上測量且以克數記錄。“總手感”減少指示織物柔軟性的改良。Softness or "hand feel" as is known in the art, is measured using a Thwing-Albert Instruments Co., Ltd. Fabric Handle Detector (Handle-O-Meter, Model 211-10-B/AERGLA). The "feel" quality is believed to be due to the combination of resistance and flexibility of the surface friction of the fabric material. The fabric feeler uses LVDT (Linear Variable Differential Transformer Line Type) to measure the above two factors to detect the resistance encountered by the blade as it forces the sample of material into the slits that are parallel edges. The 3 1/2 digital voltmeter (DVM) indicates the resistance expressed directly in grams. The "total hand" of a given fabric is defined as the average of 8 readings taken on two fabric samples (4 readings per sample). For each test specimen (5 mm slit width), the hand was measured on both sides and in both directions (MD and CD) and recorded in grams. The "total hand" reduction indicates an improvement in fabric softness.

非織物之Elmendorf撕裂強度(以克/gsm表示)係根據ASTM D1922使用Elmendorf撕裂機(Thwing Albert儀器公司)在MD和CD方向測定。Non-woven Elmendorf tear strength (expressed in grams/gsm) The Elmendorf tearing machine (Thwing Albert Instruments) was used in the MD and CD directions according to ASTM D1922.

CD峰值伸長率(也稱為CD伸長率)和CD峰值強度(也稱為CD強度)係根據WSP 110.4(05)使用100毫米的隔距長度和200毫米/分鐘的測試速度測定。MD峰值伸長率(也稱為MD伸長率)和MD峰值強度(也稱為MD強度)係根據WSP 110.4(05)使用100毫米的隔距長度和200毫米/分鐘的測試速度測定。CD peak elongation (also known as CD elongation) and CD peak intensity (also known as CD intensity) were determined according to WSP 110.4 (05) using a gauge length of 100 mm and a test speed of 200 mm/min. MD peak elongation (also known as MD elongation) and MD peak strength (also known as MD strength) were determined according to WSP 110.4 (05) using a gauge length of 100 mm and a test speed of 200 mm/min.

除非另有說明，上述所有織物測試從織物生產之日起進行至少20天，以確保性質的平衡及導致任何可隨時間改變織物性質之作用。Unless otherwise stated, all of the above fabric tests were conducted for at least 20 days from the date of manufacture of the fabric to ensure a balance of properties and to cause any effect that would change the properties of the fabric over time.

圖1描繪在冷卻SAOS流變實驗下之損耗角正切(tanδ)的演變。Figure 1 depicts the evolution of loss tangent (tan δ) under a cooled SAOS rheology experiment.

圖2描繪實例1、3、10、12、13、14、16和18之複合黏度。Figure 2 depicts the composite viscosity of Examples 1, 3, 10, 12, 13, 14, 16 and 18.

實例Instance

研究許多受控流變性丙烯聚合物，其中具有約0.5至5dg/分鐘且較佳從0.8至3dg/分鐘之MFR的基本PP樹脂係在擠出機中進行過氧化物裂解(受控流變性丙烯聚合物)以獲得在10至25dg/分鐘之範圍的最終MFR。令人驚奇地發現：與具有某範圍的下述關鍵熔體流變、結晶和立構規整性參數的樹脂即使在低基重織物(例如，<15克/米² )呈現極佳可紡性和高纖維/織物強度之意想不到的組合。A number of controlled rheology propylene polymers were studied in which a basic PP resin having an MFR of about 0.5 to 5 dg/min and preferably from 0.8 to 3 dg/min was subjected to peroxide cracking in an extruder (controlled rheological propylene) Polymer) to obtain a final MFR in the range of 10 to 25 dg/min. Surprisingly, it has been found that resins with a range of key melt rheology, crystallization and stereoregularity parameters exhibit excellent spinnability even at low basis weight fabrics (eg, <15 g/ ^m2 ). Unexpected combination of high fiber/fabric strength.

材料material

根據下述過氧化物減黏步驟處理丙烯聚合物PP-1以獲得實例1至8之本發明組成物。PP-1為具有2dg/分鐘之MFR、4.3之M_w /M_n 和164.3℃之T_mp (10℃/分鐘)的於顆粒形式之反應器級戚格勒-納他丙烯均聚物。PP-1包含使典型用於紡熔非織物應用中之添加劑包，例如，如WO2010/087921中所揭示。The propylene polymer PP-1 was treated according to the peroxide debonding step described below to obtain the inventive compositions of Examples 1 to 8. PP-1 is a reactor grade 戚Geller-nata propylene homopolymer in particulate form having an MFR of 2 dg/min, a M _w /M _{n of} 4.3 and a T _{mp of} 164.3 ° C (10 ° C/min). PP-1 comprises an additive package which is typically used in spunbond nonwoven applications, for example as disclosed in WO 2010/087921.

實例9之組成物為二種丙烯聚合物：A和B於60/40之重量比的擠出機(物理)摻合物。具有13dg/分鐘之MFR的聚合物A係根據下述步驟以顆粒形式從丙烯聚合物PP-2之過氧化物減黏處理獲得。PP-2為具有4.5dg/分鐘之MFR、4.7之M_w /M_n 和165℃之T_mp (10℃/分鐘)的反應器級戚格勒-納他丙烯均聚物。具有40dg/分鐘之MFR的聚合物B係根據下述步驟以顆粒形式從丙烯聚合物PP-3之過氧化物減黏處理獲得。PP-3為具有1.7dg/分鐘之MFR的2.75重量%在乙烯中之反應器級戚格勒-納他丙烯-乙烯隨機共聚物。在60/40之重量比的粒化聚合物A和B的擠出機摻合之後，獲得實例9的聚合物，其具有23.5dg/分鐘之MFR和以¹³ C NMR測定之1.3重量%的乙烯含量。The composition of Example 9 was an extruder (physical) blend of two propylene polymers: A and B in a weight ratio of 60/40. Polymer A having an MFR of 13 dg/min was obtained in the form of particles from the peroxide debonding treatment of propylene polymer PP-2 according to the following procedure. PP-2 having 4.5dg / min of MFR, 4.7 of M _w / M _n of 165 ℃ and T _mp (10 ℃ / min) of the reactor grade Ziegler Qi - natamycin propylene homopolymers. Polymer B having an MFR of 40 dg/min was obtained in the form of particles from the peroxide debinding treatment of propylene polymer PP-3 according to the following procedure. PP-3 is a reactor grade 戚Geller-nata propylene-ethylene random copolymer having 2.75% by weight of MFR at 1.7 dg/min in ethylene. After blending with an extruder of granulated polymers A and B in a weight ratio of 60/40, the polymer of Example 9 was obtained having an MFR of 23.5 dg/min and 1.3 wt% of ethylene as determined by ¹³ C NMR. content.

實例20為可以商標名PP3155購自德州休士頓ExxonMobil化學公司之受控流變性均-聚丙烯和丙烯聚合物PP1(皆於顆粒形式)於70/30之重量比在92毫米雙螺桿擠出機上混煉的摻合物。Example 20 is a controlled rheology homo-polypropylene and propylene polymer PP1 (both in granular form) available from ExxonMobil Chemical Company, Houston, Texas under the trade name PP3155 at a weight ratio of 70/30 at 92 mm twin screw extrusion. Mixture blended on board.

本發明實例21為可以商標名PP3155(35dg/分鐘之MFR)購自德州休士頓ExxonMobil化學公司之受控流變性均-聚丙烯和丙烯聚合物PP1(皆於顆粒形式)於70/30之重量比在30毫米雙螺桿擠出機上混煉的摻合物。Inventive Example 21 is a controlled rheology homo-polypropylene and propylene polymer PP1 (both in particulate form) available from ExxonMobil Chemical Company, Houston, Texas, under the trade designation PP3155 (35 dg/min MFR) at 70/30 Blends blended on a 30 mm twin screw extruder.

實例22為受控流變性(減黏)丙烯聚合物，其基本聚合物為可以商標名PP5341E1(0.8dg/分鐘之MFR)購自德州休士頓ExxonMobil化學公司之均-聚丙烯和丙烯聚合物PP1(皆於顆粒形式)於25/75之重量比的摻合物。根據過氧化物減黏步驟在30毫米雙螺桿擠出機上處理該基本聚合物(摻合物)以獲得實例22之本發明組成物。Example 22 is a controlled rheology (reduced viscosity) propylene polymer whose base polymer is available from the ExxonMobil Chemical Company of Texas, Texas, under the trade name PP5341E1 (MFR of 0.8 dg/min). Polypropylene and propylene polymers available from ExxonMobil Chemical Company, Houston, Texas. Blend of PP1 (both in granular form) in a weight ratio of 25/75. The base polymer (blend) was treated on a 30 mm twin screw extruder according to the peroxide debonding step to obtain the inventive composition of Example 22.

實例23為受控流變性(減黏)丙烯聚合物，其聚合物為可以商標名PP5341E1(0.8dg/分鐘之MFR)購自德州休士頓ExxonMobil化學公司之於顆粒形式的反應器級均聚物聚丙烯。根據過氧化物減黏步驟在30毫米雙螺桿擠出機上處理該基本聚合物以獲得實例23之本發明組成物。Example 23 is a controlled rheology (reduced viscosity) propylene polymer having a polymer of the reactor grade homopolymerized in particulate form from ExxonMobil Chemical Company, Houston, Texas under the trade designation PP5341E1 (MFR of 0.8 dg/min). Polypropylene. The base polymer was treated on a 30 mm twin screw extruder according to the peroxide debonding step to obtain the inventive composition of Example 23.

比較例10-12關於具有36至39dg/分鐘之MFR和163℃之T_mp (10℃/分鐘)的戚格勒-納他受控流變性丙烯均聚物，其可以商標名PP 3155E3購自德州休斯頓ExxonMobil化學公司。Comparative Examples 10-12 are Pygler-Nano-controlled rheological propylene homopolymers having an MFR of 36 to 39 dg/min and a T _mp (10 ° C/min) of 163 ° C, which are commercially available under the trade designation PP 3155E3. ExxonMobil Chemical Company, Houston, Texas.

比較例13關於具有24dg/分鐘之MFR和152.5℃之T_mp (10℃/分鐘)的茂金屬反應器級丙烯均聚物，其可以商標名Achieve^TM 3854購自德州休斯頓ExxonMobil化學公司。13 metallocene reactor grade propylene Comparative Example having about 24 dg / minute 152.5 deg.] C and MFR of T _mp (10 ℃ / min) homopolymer under the tradename Achieve ^TM 3854 available from ExxonMobil Chemical Company of Houston, Texas.

比較例14和15表示具有15dg/分鐘之熔體流動指數(230℃，2.16公斤ISO 1133)和153℃之Tm的茂金屬丙烯均聚物，其可以商標名Lumicene^TM MR 2002購自比利時費盧依Total Petrochemicals。Comparative Examples 14 and 15 represent metallocene propylene homopolymers having a melt flow index of 15 dg/min (230 ° C, 2.16 kg ISO 1133) and a Tm of 153 ° C, which are commercially available under the trade name Lumicene ^TM MR 2002 from Felu, Belgium. According to Total Petrochemicals.

比較例16和17表示具有18dg/分鐘之MFR和165℃之T_mp (10℃/分鐘)的戚格勒-納他受控流變性丙烯均聚物，其可以商標名HF420FB購自新澤西港穆雷Borealis Group。Comparative Examples 16 and 17 represent a Pegler-Nano-controlled rheological propylene homopolymer having an MFR of 18 dg/min and a T _mp (10 ° C/min) of 165 ° C, which is commercially available under the trade name HF420FB from Port of New Jersey. Ray Borealis Group.

比較例18為具有13.5dg/分鐘之MFR和163.7℃之T_mp (10℃/分鐘)的戚格勒-納他受控流變性丙烯均聚物，其可以商標名Moplen^TM HP552N購自德州休斯頓Lyondell Basell。Comparative Example 18 having Grenoble Qi 13.5dg / minute and MFR of T 163.7 ℃ _mp (10 ℃ / min) - natamycin controlled rheology propylene homopolymer, which may be commercially available under the trade name Moplen ^TM HP552N from Houston, Texas Lyondell Basell.

比較例19為一種具有17dg/分鐘之MFR和164.7℃之T_mp (10℃/分鐘)的戚格勒-納他受控流變性丙烯均聚物，其可以商標名Moplen^TM PP567P購自德州休斯頓Lyondell Basell。Comparative Example 19 is a Ziegler Qi having 17dg / minute 164.7 deg.] C and MFR of T _mp (10 ℃ / min) - natamycin controlled rheology propylene homopolymer, which may be commercially available under the trade name Moplen ^TM PP567P from Houston, Texas Lyondell Basell.

減黏步驟Viscosity reduction step

在92毫米雙螺桿擠出機(ZSK 92，Werner Pfleiderer)上以3,000磅/小時的生產速度和440rpm的螺桿速度將起始丙烯聚合物進行過氧化物減黏(裂解)。使用200至500ppm Lupersol^TM 101(2,5-雙(三級丁過氧)-2,5-二甲基己烷)之過氧化物的水平以將起始聚合物(本發明實例1-9)裂解至較高MFR(參見表1)。起始丙烯聚合物係描述於上述“材料”項下。該擠出機具有兩個進料器，一個用於聚合物及一個用於過氧化物減黏劑。擠出機區和模具的設定溫度係在190℃至220℃的範圍內，而熔融溫度係在200℃至215℃的範圍內，取決於起始丙烯聚合物和目標最終MFR。所有的擠出機運行使用標準100目網線(150微米標稱孔隙率)。在各實例中，使用水下製粒機製備具有密度(每克的顆粒)在40至50ppg之範圍的顆粒。The starting propylene polymer was subjected to peroxide visbreaking (cracking) on a 92 mm twin screw extruder (ZSK 92, Werner Pfleiderer) at a production speed of 3,000 lbs/hr and a screw speed of 440 rpm. Use 200 to 500ppm Lupersol ^TM 101 (2,5- bis (three butylperoxy) -2,5-dimethylhexane) to the level of peroxides Example (1-9 starting polymer of the present invention ) Cleavage to a higher MFR (see Table 1). The starting propylene polymer is described under the "Materials" above. The extruder has two feeders, one for the polymer and one for the peroxide visbreaker. The set temperature of the extruder zone and the mold is in the range of 190 ° C to 220 ° C, and the melting temperature is in the range of 200 ° C to 215 ° C depending on the starting propylene polymer and the target final MFR. All extruder runs using a standard 100 mesh wire (150 micron nominal porosity). In each of the examples, particles having a density (particles per gram) in the range of 40 to 50 ppg were prepared using an underwater granulator.

本發明和比較組成物的聚合物性質係報告於下表1-7中。The polymer properties of the present invention and comparative compositions are reported in Tables 1-7 below.

圖1描繪根據上述“經由SAOS流變學之結晶”方法在冷卻SAOS流變實驗下該損耗角正切(tanδ)的演變。如圖1和表12中所示，本發明組成物有利地描繪在SAOS流變條件(例如，T_c,rheol >131℃和更佳大於135℃)下之高結晶溫度優於所有先前技術的比較組成物。T_c,rheol 之高值被假定為在導致更穩定的可紡性和導致織物機械性質的顯著平衡之有利結晶微結構的纖維紡絲條件下造成更快流動/應力引起的結晶動力學，如下所述。在圖2中，描繪某些說明性組成物的複合黏度與溫度之對應輪廓。隨溫度之減少，複合黏度以對數線性圖的線性函數增加。然而，低於某一溫度時，由於在SAOS流動下發生結晶，複合黏度急劇增加。Figure 1 depicts the evolution of the tan delta (tan δ) under the cooled SAOS rheology experiment according to the above-described "crystallization via SAOS rheology" method. As shown in Figure 1 and Table 12, the compositions of the present invention advantageously depict high crystallization temperatures in SAOS rheological conditions (e.g., Tc _{, rheo} > 131 ° C and more preferably greater than 135 ° C) over all prior art Compare the composition. The high value of T _c,rheol is assumed to cause faster flow/stress induced crystallization kinetics under fiber spinning conditions that result in more stable spinnability and a favorable crystalline microstructure that results in a significant balance of mechanical properties of the fabric, as follows Said. In Figure 2, the corresponding profiles of the composite viscosity of certain illustrative compositions versus temperature are depicted. As the temperature decreases, the composite viscosity increases as a linear function of the log-linear graph. However, below a certain temperature, the complex viscosity sharply increases due to crystallization under SAOS flow.

然後根據下列步驟將上述聚合物組成物形成纖維和非織物：The above polymer composition is then formed into fibers and non-fabres according to the following steps:

纖維紡絲(部分定向紗)Fiber spinning (partially oriented yarn)

纖維紡絲實驗係在配備Davis標準1½吋擠出機和直徑各為0.60毫米的72孔之紡嘴的Hills試生產線上進行。將聚合物顆粒熔融並以所要通量率擠進計量泵。為了一致性所有樹脂之模具的熔融溫度保持在237℃，除非另有說明。驟冷空氣體系統保持關閉。每孔通量設定為0.53克/分鐘/孔(ghm)。如所示研究兩捲取速度：1500和3500米/分鐘。在這些條件下，對於捲取速度1500米/分鐘和3500米/分鐘，根據方程式(17)每長絲的纖維丹尼數(dpf)分別為3.2和1.4。纖維樣品在設定於所要捲取速度之導輥上拉伸且用捲繞器上將纖維收集在芯上。不進行額外的拉伸步驟。該初紡纖維的抗拉性質顯示於表8中。The fiber spinning experiment was carried out on a Hills pilot line equipped with a Davis standard 11⁄2 inch extruder and a 72-hole diameter nozzle of 0.60 mm each. The polymer particles are melted and squeezed into the metering pump at the desired flux rate. The melting temperature of the mold for consistency of all resins was maintained at 237 ° C unless otherwise stated. The quench air system remains closed. The flux per well was set to 0.53 g/min/hole (ghm). The two take-up speeds were studied as shown: 1500 and 3500 m/min. Under these conditions, for the take-up speeds of 1500 m/min and 3500 m/min, the fiber deniers (dpf) per filament according to equation (17) were 3.2 and 1.4, respectively. The fiber sample was drawn on a guide roll set at the desired take-up speed and the fibers were collected on the core by a winder. No additional stretching steps are performed. The tensile properties of the as-spun fibers are shown in Table 8.

如表8中所見，相對於先前技術之組成物，本發明之組成物整體上產生纖維韌度和斷裂伸長率的極佳平衡。例如，對於1.3dpf之纖維丹尼的二種組成物(~3g/dpf)而言，於相似的纖維韌度，相對於實例15之比較組成物(81%)，實例5的本發明組成物產生顯著較高斷裂伸長率(108%)。對於1.3dpf而言，於高纖維韌度(~2.9g/dpf)，本發明組成物21意外地提供非常高的纖維%伸長率(~171%)。As seen in Table 8, the composition of the present invention produced an excellent balance of fiber toughness and elongation at break as a whole with respect to the composition of the prior art. For example, for the two compositions of 1.3 dpf fiber denier (~3 g/dpf), the composition of the invention of Example 5 was compared to the comparative composition of Example 15 (81%) for similar fiber toughness. A significantly higher elongation at break (108%) was produced. For 1.3 dpf, the composition 21 of the present invention unexpectedly provided a very high % fiber elongation (~171%) at high fiber tenacity (~2.9 g/dpf).

可紡性係經由“斜坡上升至斷裂”實驗評估，根據該實驗紡絲開始於2000米/分鐘，並以固定加速度(480米/分鐘2)增加直到纖維斷裂，而所有其他處理條件保持固定。在觀察到纖維斷裂的速度稱為最大紡絲速度。各斜坡上升至斷裂測試係以0.53ghm和0.32ghm之通量進行。從最大紡絲速度和每孔通量，可估計：根據上述方程式(17)可產生之給定樹脂在斷裂前的每長絲最小丹數。極佳可紡性在此定義為某組成物在0.32至0.52ghm之通量範圍下產生小於2.0和較佳小於1.5之最小dpf的纖維之能力。斜坡上升至斷裂實驗之結果係顯示於表9中。The spinnability was evaluated by a "slope-to-fracture" experiment, according to which the spinning started at 2000 m/min and increased at a fixed acceleration (480 m/min 2) until the fiber broke, while all other processing conditions remained fixed. The rate at which fiber breakage is observed is referred to as the maximum spinning speed. Each ramp was raised to a fracture test with a flux of 0.53 ghm and 0.32 ghm. From the maximum spinning speed and flux per hole, it can be estimated that the minimum number of denier per filament of a given resin can be produced according to equation (17) above. Excellent spinnability is defined herein as the ability of a composition to produce fibers having a minimum dpf of less than 2.0 and preferably less than 1.5 over a flux range of 0.32 to 0.52 ghm. The results of the ramp up to fracture test are shown in Table 9.

如表9中所描述，本發明之組成物存在極佳可紡性，以彼等對於0.32至0.52ghm之通量範圍製造小於1.5dpf之細纖維的能力證明。As described in Table 9, the compositions of the present invention exhibited excellent spinnability, as evidenced by their ability to produce fine fibers of less than 1.5 dpf for a flux range of 0.32 to 0.52 ghm.

紡黏非織物Spunbonded non-woven fabric

紡黏非織物在Reicofil 4(R4)線上製備，其具有3個1.1米寬度之紡黏(SSS)(各具有6300個孔與0.6毫米之孔(模具)直徑的紡嘴。關於Reicofil紡黏方法的詳細說明，請參考EP 1 340 843或US6,918,750。每孔通量為0.53ghm。所有實驗之驟冷空氣溫度為20℃。在這些條件下，製造1至1.4丹尼的纖維，相當於12至15微米(方程式(18))以上的纖維直徑。線速度保持固定於900米/分鐘。所有實例之目標織物基重為為10克/米² (gsm)。Spunbonded non-woven fabrics were prepared on a Reicofil 4 (R4) line with three 1.1 m wide spunbonds (SSS) (single nozzles each having a diameter of 6300 holes and a hole of 0.6 mm (mold).) Reicofil spunbond method For a detailed description, please refer to EP 1 340 843 or US 6,918, 750. The flux per hole is 0.53 ghm. The quench air temperature of all experiments is 20 ° C. Under these conditions, fibers of 1 to 1.4 denier are produced, which is equivalent to Fiber diameters above 12 to 15 microns (Eq. (18)). The line speed was kept fixed at 900 m/min. The target fabric basis weight for all examples was 10 g/ ^m2 (gsm).

藉由通過兩個用於改良織物完整性和改良織物機械性質的加熱輥(壓延機)壓縮所形成的織物而將其熱黏合。織物熱黏合方法之基礎可發現於Michielson等人的評論文章“Review of Thermally Point-bonded Nonwovens：Materials,Processes,and Properties”(J.Applied Polym. Sci.第99冊，第2489-2496頁(2005))或Bhat等人之論文“Thermal Bonding of Polypropylene Nonwovens：Effect of Bonding Variables on the Structure and Properties of the Fabrics,”(J.Applied Polym.Sci.第92冊，第3593-3600頁(2004))。該二輥稱為“壓花“和S輥。在表10中，列出對應於用作輥之加熱介質的設定油溫之二壓延機的設定溫度。壓延機溫度係使用接點式熱電偶在壓花和S輥二者上測量，且一般發現為比設定油溫低10℃至20℃。所有三個紡黏束也有類似的操作條件。代表性操作條件概述於表10中。在典型的試驗中，建立穩定的紡絲條件後，改變壓延機溫度，以產生黏合曲線(即，拉伸強度對壓延機溫度)。在表10的條件下，本發明組成物的可紡性評估為極佳。The formed fabric was heat bonded by compressing the formed fabric by two heating rolls (calenders) for improving fabric integrity and improving the mechanical properties of the fabric. The basis of the fabric thermal bonding method can be found in the review article "Review of Thermally Point-bonded Nonwovens: Materials, Processes, and Properties" by Michielson et al. (J. Applied Polym. Sci. 99, pp. 2489-2496 (2005)) or Bhat et al., "Thermal Bonding of Polypropylene Nonwovens: Effect of Bonding Variables on the Structure and Properties of the Fabrics," (J. Applied Polym. Sci. Book 92, pp. 3593-3600 (2004)). The two rolls are referred to as "embossing" and S rolls. In Table 10, the set temperatures of the two calenders corresponding to the set oil temperature of the heating medium used as the rolls are listed. Calender temperatures were measured on both embossed and S-rollers using contact thermocouples and were generally found to be 10 ° C to 20 ° C lower than the set oil temperature. All three spun bundles have similar operating conditions. Representative operating conditions are summarized in Table 10. In a typical test, after establishing stable spinning conditions, the calender temperature is varied to produce a bond curve (i.e., tensile strength versus calender temperature). Under the conditions of Table 10, the spinnability of the composition of the present invention was evaluated to be excellent.

在表11中，概述對應於產生最大CD抗拉強度之壓延機溫度的織物抗拉性質。在預期惡化織物的機械性質之高線速度(900米/分鐘)、高通量(~0.53ghm)和低基重(10gsm)之嚴格加工條件下，大部分本發明組成物令人驚訝地描述在MD和CD二方向的高比抗拉強度(在MD大於2.7N/5公分/gsm和在CD大於1.1N/5公分/gsm)。本發明之組成物有利地具有較低抗拉強度各向異性(例如，低於2.6)，例如，關於實例15之比較組成物為2.9和關於實例13之比較組成物為3.2。In Table 11, the tensile properties of the fabric corresponding to the calender temperature at which the maximum CD tensile strength is produced are summarized. Most of the compositions of the invention are surprisingly described under stringent processing conditions expected to deteriorate the mechanical properties of the fabric at high line speeds (900 m/min), high throughput (~0.53 ghm) and low basis weight (10 gsm). High specific tensile strength in both MD and CD directions (in MD greater than 2.7 N/5 cm/gsm and in CD greater than 1.1 N/5 cm/gsm). The composition of the present invention advantageously has a lower tensile strength anisotropy (e.g., less than 2.6), for example, 2.9 for the comparative composition of Example 15 and 3.2 for the comparative composition of Example 13.

在表12中，顯示：如以較低拉伸模數(特別是MD模數)和較低總手感二者證明，本發明之組成物導致有利地較柔軟的織物。In Table 12, it is shown that the composition of the present invention leads to advantages, as evidenced by both lower tensile modulus (especially MD modulus) and lower total hand feel. Softer fabric.

本發明和比較例之關於MD和CD織物方向的Elmendorf撕裂強度係顯示於表13中。本發明之組成物產生超過先前技術之組成物的總體上媲美或較高撕裂強度之織物。The Elmendorf tear strengths for the MD and CD fabric directions of the present invention and comparative examples are shown in Table 13. The compositions of the present invention produce fabrics that are generally superior or have higher tear strength than compositions of the prior art.

其他織物性質Other fabric properties

使用舌形試片的織物之撕裂性質係以DIN EN ISO 13937-4測定。非織物梯形抗撕裂性係以DIN EN ISO 9073-4測定。使用抓式拉伸測試的非織物材料之斷裂強度和伸長率的測定係根據DIN EN ISO 9073-18獲得。織物之破裂強度(測定破裂強度和破裂膨脹之氣壓方法)係根據DIN EN ISO 13938-2測定。織物之耐摩性係以Martindale方法(DIN EN ISO 12947-2)測量。非織物彎曲長度係以DIN EN ISO 9073-7測定。非織物之懸垂性(包括懸垂係數)係以DIN EN ISO 9073-9測定。The tear properties of the fabric using the tongue test piece were determined in accordance with DIN EN ISO 13937-4. Non-woven trapezoidal tear resistance is determined in accordance with DIN EN ISO 9073-4. The determination of the breaking strength and elongation of the non-woven material using the grip tensile test is obtained according to DIN EN ISO 9073-18. Burst strength of fabric (air pressure method for determining burst strength and rupture expansion) Measured according to DIN EN ISO 13938-2. The abrasion resistance of the fabric is measured by the Martindale method (DIN EN ISO 12947-2). Non-woven bending lengths are determined in accordance with DIN EN ISO 9073-7. Non-woven drape (including drape coefficient) is determined in accordance with DIN EN ISO 9073-9.

根據以上詳述之紡黏非織物的一般步驟，包括以900米/分鐘之線速度和10克/米² 之標稱織物基重使用3個紡黏束(SSS)將三種聚合物組成物：使用與實例1相同步驟製造之具有16.5dg/分鐘的MFR之聚合物(稱為EX1-A)、Lumicene^TM MR2002、和PP3155形成非織物。特定加工條件係列於下表A中。The three polymer compositions were prepared using three spunbond bundles (SSS) at a line speed of 900 m/min and a nominal fabric basis weight of 10 g/ ^m2 , according to the general procedure of the spunbond nonwoven fabric detailed above: used in the manufacture of the polymer having MFR of 16.5dg / min (referred to as EX1-a) in the same procedures as in example 1, Lumicene ^TM MR2002, PP3155 and nonwoven form. The specific processing conditions are listed in Table A below.

報告於下表B中之抓式拉伸數據係根據DIN EN 9073-18中之步驟獲得。報告於下表C中之切口撕裂數據係根據DIN EN ISO 9073-4測定。報告於表C中之破裂強度係根據ISO 13938-2 1999獲得。The gripping stretch data reported in Table B below was obtained according to the procedure in DIN EN 9073-18. The slit tear data reported in Table C below was determined according to DIN EN ISO 9073-4. The burst strength reported in Table C was obtained according to ISO 13938-2 1999.

將使用與實例1相同步驟製造之具有16.5dg/分鐘的MFR之聚合物(稱為EX1-A)、Achieve^TM 3854和Lumicene^TM MR 2002形成織物且然後試驗各種物理性質。數據係報告於表D和E中。Achieve^TM 3854為可購自德州休斯頓ExxonMobil化學公司之具有24dg/分鐘的MFR之茂金屬丙烯均聚物。Lumicene^TM MR 2002為可購自比利時費盧依Total Petrochemicals的具有15dg/分鐘之熔體流動指數(230℃，2.16公斤ISO 1133)和153℃之Tm的茂金屬丙烯均聚物。藉由如上所述之紡黏非織物方法和條件於10gsm之標稱織物基重形成織物，惟所製備之織物於一紡黏束所使用的300米/分鐘之線速度。The manufacture of a polymer having a MFR of 16.5dg / min (referred to as EX1-A) using the same procedures as in Example 1, Achieve ^TM 3854 and Lumicene ^TM MR 2002 form the fabric, and various physical properties were then tested. The data is reported in Tables D and E. Achieve ^TM 3854 commercially available from ExxonMobil Chemical Company of Houston, Texas, having 24dg / min MFR metallocene of a propylene homopolymer. Lumicene ^TM MR 2002 is commercially available from (230 ℃, 2.16 kilograms ISO 1133) and a metallocene propylene having 15dg / min of melt flow index of 153 ℃ Tm of Feluy, Belgium Total Petrochemicals homopolymer. The fabric was formed by the spunbond nonwoven process as described above and the nominal fabric basis weight of 10 gsm, except that the fabric was prepared at a line speed of 300 m/min used in a spunbond.

已經描述了以編號段落描述於本文中之本發明的各種特徵為：Various of the inventions described herein by numbered paragraphs have been described Features are:

P1.一種丙烯聚合物組成物，其包含至少50莫耳%丙烯，該聚合物組成物具有：a)10dg/分鐘至21.5dg/分鐘之熔體流動速度(MFR，ASTM 1238，230℃，2.16公斤)；b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ ；c)至少131℃之在流動下的結晶之起始溫度T_c,rheol (如以SAOS流變學測定，1℃/分鐘，其中該聚合物具有0重量%成核劑存在)；及d)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)。P1. A propylene polymer composition comprising at least 50 mole % propylene having a: a) melt flow rate of 10 dg/min to 21.5 dg/min (MFR, ASTM 1238, 230 ° C, 2.16 (b), b) dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 1.5 to 28; c) starting temperature of crystal at flow of at least 131 ° C T _c,rheol (eg SAOS rheology measurement, 1 ° C / min, wherein the polymer has 0 wt % nucleating agent present; and d) at least 97 or higher average mesional run length determined by ¹³ C NMR (average meso run) Length).

P2.如申請專利範圍第1項之丙烯聚合物組成物，其中該組成物包含二或多種丙烯聚合物之組合。P2. A propylene polymer composition according to claim 1 wherein the composition comprises a combination of two or more propylene polymers.

P3.如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有1.2至4.5之在190℃下的無因次應力比指數R₁ 及/或從14至70之在190℃下的於0.1rad/s之角頻率的損耗角正切tanδ。P3. The propylene polymer composition of claim 1 or 2, wherein the propylene polymer composition has a dimensionless stress ratio index R _{1 of} from 1.2 to 4.5 at 190 ° C and/or from 14 to 70 The loss tangent tan δ at an angular frequency of 0.1 rad/s at 190 °C.

P4.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有6至13之在190℃下的無因次剪切稀化指數R₃ 。P4. As aforementioned patent application of a range Propylene polymer composition, wherein the propylene polymer composition has a shear thinning index dimensionless R ₃ at 190 deg.] C of 6 to 13.

P5.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有1.5至20之在190℃下的無因次損耗角正切/彈性指數R₄ 。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a dimensionless loss tangent/elasticity index R ₄ of from 1.5 to 20 at 190 °C.

P6.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有120℃或更高之T_mp (第二熔體，1℃/分鐘)。P6. A propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a T _mp (second melt, 1 ° C/min) of 120 ° C or higher.

P7.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有20%至80%之百分比結晶度。P7. A propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a percent crystallinity of from 20% to 80%.

P8.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有-50℃至120℃之玻璃轉移溫度Tg。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a glass transition temperature Tg of from -50 °C to 120 °C.

P9.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有15℃至150℃之結晶溫度Tc(1℃/分鐘)。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a crystallization temperature Tc (1 ° C/min) of from 15 ° C to 150 ° C.

P10.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有0.85或更大之分枝指數(g’_vis )。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a branching index (g' _vis ) of 0.85 or more.

P11.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物包含具有1至7之M_w /M_n 及/或1.5至2.5之M_z /M_w 的丙烯聚合物。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition comprises propylene having a M _w /M _{n of} from 1 to 7 and/or a M _z /M _{w of} from 1.5 to 2.5 polymer.

P12.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有135℃或更高之T_c,rheol 。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a T _{c,rheol of} 135 ° C or higher.

P13.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有120℃或更高之T_mp (每分鐘10℃)和125℃或更高之T_cp (每分鐘1℃)。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a T _{mp of} 120 ° C or higher (10 ° C per minute) and a T _{cp of} 125 ° C or higher ( 1 ° C per minute).

P14.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有-10℃或更小之過冷參數SCP(每分鐘1℃)和-1℃或更小之SCP(每分鐘10℃)。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a subcooling parameter SCP (1 ° C per minute) of -10 ° C or less and -1 ° C or less. SCP (10 ° C per minute).

P15.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有140℃或更高之T_mp (每分鐘1℃)和1.2至4.5之在190℃下的無因次應力比指數R₁ 。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a T _{mp of} 140 ° C or higher (1 ° C per minute) and 1.2 to 4.5 at 190 ° C. The dimensionless stress ratio index R ₁ .

P16.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有125℃或更高之T_cp (每分鐘1℃)或115℃或更高之T_cp (每分鐘10℃)和1.50至20之在190℃下的無因次損耗角正切/彈性指數R₄ 。The propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer composition has a T _{cp of} 125 ° C or higher (1 ° C per minute) or T _{cp of} 115 ° C or higher ( The dimensionless loss tangent/elasticity index R ₄ at 190 ° C of 10.5 ° C) and 1.50 to 20.

P17.一種丙烯聚合物組成物，其包含一種具有下列之丙烯聚合物：1)在從10dg/分鐘至21.5dg/分鐘之範圍的MFR；及2)a)從1.2至4.5之在190℃下的無因次應力比指數R₁ ；或b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ ；或 c)從6至13之在190℃下的無因次剪切稀化指數R₃ ；或d)從1.5至20之在190℃下的無因次損耗角正切/彈性指數R₄ ；或e)從14至70之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)；或f)從3.1至6.1之在190℃下的於500s^-1 之剪切速度的應力比(SR)；及3)a)至少131℃或更高之具有0%成核劑的在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；或b)至少125℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘1℃之冷卻速度)；或c)至少117℃或更高之具有0%成核劑的T_cp (以DSC測量於每分鐘10℃之冷卻速度)；或d)小於-2℃之具有0%成核劑的過冷參數SCP(以DSC測量於10℃/分鐘之加熱和冷卻速度)；或e)小於-13℃之具有0%成核劑的過冷參數SCP(以DSC測量於1℃/分鐘之加熱和冷卻速度)；及4)a)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)；或b)每10,000個單體小於103之缺陷的總數(立體和區域)。P17. A propylene polymer composition comprising a propylene polymer having: 1) an MFR ranging from 10 dg/min to 21.5 dg/min; and 2) a) from 1.2 to 4.5 at 190 ° C The dimensionless stress ratio index R ₁ ; or b) the dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 1.5 to 28; or c) from 6 to 13 at 190 ° C The secondary shear thinning index R ₃ ; or d) the dimensionless loss tangent / elastic index R ₄ at 190 ° C from 1.5 to 20; or e) from 14 to 70 at 190 ° C at 0.1 Loss tangent (tan δ) of the angular frequency of rad/s; or f) stress ratio (SR) at a shear rate of 500 s ^-1 at 190 ° C from 3.1 to 6.1; and 3) a) at least 131 ° C Or higher starting temperature Tc of flowing crystals with 0% nucleating agent _{, rheo} (via SAOS rheology, 1 ° C / min); or b) 0% of at least 125 ° C or higher T _{cp of the} nucleating agent (measured at a cooling rate of 1 ° C per minute by DSC); or c) T _cp with a 0% nucleating agent of at least 117 ° C or higher (cooling at 10 ° C per minute as measured by DSC) Speed); or d) subcooling parameter SCP with 0% nucleating agent less than -2 °C (measured by DSC) Heating and cooling rate at 10 ° C / min); or e) subcooling parameter SCP with 0% nucleating agent less than -13 ° C (heating and cooling rate measured at 1 ° C / min by DSC); and 4) a) an average meso run length measured by ¹³ C NMR of at least 97 or higher; or b) a total number of defects (stereo and region) of less than 103 per 10,000 monomers.

P18.如申請專利範圍第17項之丙烯聚合物組成物，其中該丙烯聚合物具有：1)在從14dg/分鐘至19dg/分鐘之範圍的MFR；及2)a)從2.0至3.0之在190℃下的無因次應力比指數R₁ ；或b)從2.5至6.5之在190℃下的無因次應力比/損耗角正切指數R₂ ；或c)從7.0至10.0之在190℃下的無因次剪切稀化指數R₃ ；或d)從2.0至6.0之在190℃下的無因次損耗角正切/彈性指數R₄ ；或e)從35至65之在190℃下的於0.1rad/s之角頻率的損耗角正切(tanδ)；或f)從3.3至4.0之在190℃下的於500s^-1 之剪切速度的應力比(SR)；及3)a)具有0%成核劑的至少134℃或更高之在流動下的結晶之起始溫度T_c,rheol (經由SAOS流變學，1℃/分鐘)；或b)具有0%成核劑的至少133℃或更高之 T_cp (以DSC測量於每分鐘1℃之冷卻速度)；或c)至少123℃或更高之具有0%成核劑的T_cp (以DSC測量於10℃每分鐘之冷卻速度)；或d)小於-3.5℃之具有0%成核劑的過冷參數SCP(以DSC測量於10℃/分鐘之加熱和冷卻速度)；或e)小於-17.0℃之具有0%成核劑的過冷參數SCP(以DSC測量於1℃/分鐘之加熱和冷卻速度)；及4)a)至少100或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)；或b)每10,000個單體的小於100之缺陷總數(立體和區域)。P18. The propylene polymer composition of claim 17, wherein the propylene polymer has: 1) an MFR ranging from 14 dg/min to 19 dg/min; and 2) a) from 2.0 to 3.0 The dimensionless stress ratio index R ₁ at 190 ° C; or b) the dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 2.5 to 6.5; or c) from 7.0 to 10.0 at 190 ° C The lower dimensionless shear thinning index R ₃ ; or d) the dimensionless loss tangent / elastic index R ₄ at 190 ° C from 2.0 to 6.0; or e) from 35 to 65 at 190 ° C Loss tangent (tan δ) at an angular frequency of 0.1 rad/s; or f) stress ratio (SR) at a shear rate of 500 s ^-1 at 190 ° C from 3.3 to 4.0; and 3) a) Starting temperature T _c,rheol (via SAOS rheology, 1 ° C/min) with at least 134 ° C or higher of 0% nucleating agent at flow; or b) with 0% nucleating agent T _{cp of} at least 133 ° C or higher (cooling rate of 1 ° C per minute measured by DSC); or c) T _{cp of} 0% nucleating agent of at least 123 ° C or higher (measured by DSC at 10 ° C per Minute cooling rate); or d) subcooled ginseng with 0% nucleating agent less than -3.5 °C SCP (heating and cooling rate measured at 10 °C/min by DSC); or e) subcooling parameter SCP with 0% nucleating agent less than -17.0 °C (heating and cooling rate measured at 1 °C/min by DSC) And 4) a) an average meso run length measured by ¹³ C NMR of at least 100 or higher; or b) a total number of defects less than 100 per 10,000 monomers (stereo and region) ).

P19.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中丙烯聚合物未被減黏。P19. A propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer is not reduced in viscosity.

P20.如前述申請專利範圍中任一項之丙烯聚合物組成物，其中丙烯聚合物已被減黏。P20. A propylene polymer composition according to any one of the preceding claims, wherein the propylene polymer has been reduced in viscosity.

P21.如前述申請專利範圍中任一項之丙烯聚合物組成物，其具有190kpsi或更高之1%正割撓曲模數。P21. A propylene polymer composition according to any one of the preceding claims, which has a 1% secant flexural modulus of 190 kpsi or higher.

P22.如前述申請專利範圍中任一項之丙烯聚合物組成物，其具有4,700psi或更高之降伏抗拉強度。P22. A propylene polymer composition according to any one of the preceding claims A material having a reduced tensile strength of 4,700 psi or higher.

P23.如前述申請專利範圍中任一項之丙烯聚合物組成物，其具有95℃或更高之於66psi的熱變形溫度。P23. A propylene polymer composition according to any one of the preceding claims, which has a heat distortion temperature of from 95 ° C or higher to 66 psi.

P24.一種物件，其包含如前述申請專利範圍中任一項之組成物。P24. An article comprising the composition of any one of the preceding claims.

P25.一種模製物件，其包含如前述申請專利範圍中任一項之組成物。P25. A molded article comprising the composition of any one of the preceding claims.

P26.如申請專利範圍第17-25項中之組成物，其中丙烯聚合物未被減黏。P26. The composition of claim 17-25, wherein the propylene polymer is not reduced in viscosity.

P27.如申請專利範圍第17-26項中之組成物，其中丙烯聚合物已被減黏。P27. The composition of claim 17-26, wherein the propylene polymer has been reduced in viscosity.

P28.如申請專利範圍第17-27項中之組成物，其具有190kpsi或更高之1%正割撓曲模數。P28. The composition of claim 17-27, which has a 1% secant flexural modulus of 190 kpsi or higher.

P29.如申請專利範圍第17-28項中之組成物，其具有4,700psi或更高之降伏抗拉強度。P29. The composition of claim 17-28, which has a reduced tensile strength of 4,700 psi or higher.

P30.如申請專利範圍第17-29項中之組成物，其具有95℃或更高之於66psi的熱變形溫度。P30. The composition of claim 17-29, which has a heat distortion temperature of 95 ° C or higher and 66 psi.

P31.一種物件，其包含如申請專利範圍第17-30項之組成物。P31. An article comprising the composition as set forth in claims 17-30.

P32.一種模製物件，其包含如申請專利範圍第17-31項之組成物。P32. A molded article comprising the composition of claim 17-31.

P33.一種摻合物，其包含：1)具有22dg/分鐘或更大之MFR的均聚丙烯和2)丙烯聚合物組成物，其包含至少50莫耳%丙烯，該聚合物組成物具有：a)10dg/分鐘至21.5dg/分鐘之熔體流動速度(MFR，ASTM 1238，230℃，2.16公斤)；b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ ；c)至少131℃之在流動下的結晶之起始溫度T_c,rheol (如以SAOS流變學測定，1℃/分鐘，其中該聚合物具有0重量%成核劑存在)；及d)至少97或更高的以¹³ C NMR測定之平均內消旋運行長度(average meso run length)。P33. A blend comprising: 1) a homopolypropylene having an MFR of 22 dg/min or greater and 2) a propylene polymer composition comprising at least 50 mol% propylene, the polymer composition having: a) melt flow rate (MFR, ASTM 1238, 230 ° C, 2.16 kg) from 10 dg/min to 21.5 dg/min; b) dimensionless stress ratio/loss tangent index at 190 ° C from 1.5 to 28 R _2; c) crystallization of at least 131 ℃ the flow initiation temperature _{T c,} rheol (such as a rheological measurement in SAOS, 1 ℃ / min, wherein the polymer having 0% by weight of a nucleating agent is present); And d) an average meso run length measured by ¹³ C NMR of at least 97 or higher.

本文中所述之所有文件係以引用方式併入本文中，包括任何與本文無不一致之程度的優先權文件及/或測試步驟，但先決條件係最初提出之申請案或申請文件中未命名的任何優先權文件不以引用方式併入本文中。如從前文一般說明和特定實施態樣顯而易見，雖然已舉例說明且描述本發明的形式，但是可在不違背本發明的精神及範圍的情況下進行各種修改。因此，用意不在藉其局限本發明。All documents described herein are hereby incorporated by reference in their entirety by reference to the extent of the extent of the the the the the the the Any priority documents are not incorporated herein by reference. Various modifications may be made without departing from the spirit and scope of the inventions. Therefore, the intention is not to limit the invention.

Claims

一種丙烯聚合物組成物，其包含至少50莫耳%丙烯，該聚合物組成物具有：a)10dg/分鐘至21.5dg/分鐘之熔體流動速度(MFR，ASTM 1238，230℃，2.16公斤)；b)從1.5至28之在190℃下的無因次應力比/損耗角正切指數R₂ ；c)至少131℃之在流動下的結晶之起始溫度T_c,rheol (如以SAOS流變學測定，1℃/分鐘，其中該聚合物具有0重量%成核劑存在)；及d)至少97或更高之以¹³ C NMR測定的平均內消旋運行長度(average meso run length)。A propylene polymer composition comprising at least 50 mole % propylene having a: a) melt flow rate of 10 dg/min to 21.5 dg/min (MFR, ASTM 1238, 230 ° C, 2.16 kg) ; b) dimensionless stress ratio/loss tangent index R ₂ at 190 ° C from 1.5 to 28; c) at least 131 ° C of the initial temperature of the crystallization under flow T _c,rheol (eg with SAOS flow Variant measurement, 1 ° C / min, wherein the polymer has 0 wt % nucleating agent present; and d) at least 97 or higher average meso run length as determined by ¹³ C NMR .

如申請專利範圍第1項之丙烯聚合物組成物，其中該組成物包含二或多種丙烯聚合物之組合。 The propylene polymer composition of claim 1, wherein the composition comprises a combination of two or more propylene polymers.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有1.2至4.5之在190℃下的無因次應力比指數R₁ 及/或從14至70之在190℃下的於0.1rad/s之角頻率的損耗角正切tanδ。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a dimensionless stress ratio index R _{1 of} from 1.2 to 4.5 at 190 ° C and/or from 14 to 70 The loss tangent tan δ at an angular frequency of 0.1 rad/s at 190 °C.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有6至13之在190℃下的無因次剪切稀化指數R₃ 。The propylene polymer composition of claim 1 or 2, wherein the propylene polymer composition has a dimensionless shear thinning index R ₃ of from 6 to 13 at 190 °C.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有1.5至20之在190℃下的無因次損耗角正切/彈性指數R₄ 。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a dimensionless loss tangent/elasticity index R ₄ of from 1.5 to 20 at 190 °C.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有120℃或更高之T_mp (第二熔體，1℃/分鐘)。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a T _mp (second melt, 1 ° C/min) of 120 ° C or higher.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有20%至80%之百分比結晶度。 The propylene polymer composition of claim 1 or 2, wherein the propylene polymer composition has a percent crystallinity of from 20% to 80%.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有-50℃至120℃之玻璃轉移溫度Tg。 A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a glass transition temperature Tg of from -50 °C to 120 °C.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有15℃至150℃之結晶溫度Tc(1℃/分鐘)。 A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a crystallization temperature Tc (1 ° C/min) of from 15 ° C to 150 ° C.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有0.85或更大之分枝指數(g’_vis )。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a branching index (g' _vis ) of 0.85 or more.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物包含具有1至7之M_w /M_n 及/或1.5至2.5之M_z /M_w 的丙烯聚合物。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition comprises a propylene polymer having a M _w /M _{n of} from 1 to 7 and/or a M _z /M _{w of} from 1.5 to 2.5 .

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有135℃或更高之T_c,rhcol 。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a T _{c,rcol of} 135 ° C or higher.

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有120℃或更高之T_mp (每分鐘10℃)和125℃或更高之T_cp (每分鐘1℃)。A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a T _{mp of} 120 ° C or higher (10 ° C per minute) and a T _{cp of} 125 ° C or higher (per minute 1 ° C).

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有-10℃或更小之過冷參數SCP(每分鐘1℃)和-1℃或更小之SCP(每分鐘10℃)。 A propylene polymer composition according to claim 1 or 2, wherein the propylene polymer composition has a subcooling parameter SCP (1 ° C per minute) of -10 ° C or less and an SCP of -1 ° C or less. (10 ° C per minute).

如申請專利範圍第1或2項之丙烯聚合物組成物，其中該丙烯聚合物組成物具有140℃或更高之T_mp (每分鐘1℃)和1.2至4.5之在190℃下的無因次應力比指數R₁ 。The propylene polymer composition of claim 1 or 2, wherein the propylene polymer composition has a T _{mp of} 140 ° C or higher (1 ° C per minute) and 1.2 to 4.5 of no cause at 190 ° C. The secondary stress ratio is index R ₁ .