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Publication numberCN1878799 A
Publication typeApplication
Application numberCN 200480033441
PCT numberPCT/US2004/037875
Publication date13 Dec 2006
Filing date12 Nov 2004
Priority date14 Nov 2003
Also published asCA2545203A1, CA2545203C, CA2546075A1, CA2546075C, CN1878799B, CN1890276A, CN1890276B, EP1687345A1, EP1687345B1, EP1687346A1, EP1687346B1, US7390866, US7605217, US7928165, US8013093, US20050107529, US20050107530, US20050107534, US20050131142, WO2005049670A1, WO2005049671A1, WO2005049672A1
Publication number200480033441.6, CN 1878799 A, CN 1878799A, CN 200480033441, CN-A-1878799, CN1878799 A, CN1878799A, CN200480033441, CN200480033441.6, PCT/2004/37875, PCT/US/2004/037875, PCT/US/2004/37875, PCT/US/4/037875, PCT/US/4/37875, PCT/US2004/037875, PCT/US2004/37875, PCT/US2004037875, PCT/US200437875, PCT/US4/037875, PCT/US4/37875, PCT/US4037875, PCT/US437875
InventorsS达塔, A萨努内
Applicant埃克森美孚化学专利公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Transparent and translucent crosslinked propylenebased elastomers, and their production and use
CN 1878799 A
Abstract
The present invention provides a crosslinked propylene-based elastomer having an isotactic propylene triad tacticity of from 65 to 95%, a melting point by DSC equal to or less than 110 DEG C, a heat of fusion of from 5 J/g to 50 J/g, and a haze% per 100 mil thickness of 95 or less, and comprising at least 75 wt% propylene-derived units, at least 5 wt% ethylene-derived units, and optionally 10 wt% or less of dime-derived units. In an embodiment, the present invention is a blend of a continuous phase of the crosslinked propylene-based elastomer and a dispersed phase of a crystalline polymeric compound. The present invention also provides elastomeric compositions comprising a crosslinked propylene-based elastomer as described herein and 100 parts by weight or less of a pigment per 100 parts of polymer. The present invention also provides films, fibers, nonwovens, molded objects, and extruded forms which include any of the inventive compositions described herein.
Claims(14)  translated from Chinese
1.一种交联的弹性体,其包含:(a)丙烯衍生的单元,其量为至少75wt%,基于组分(a)、(b)和(c)的总重量;(b)乙烯衍生的单元,其量为至少5wt%,基于组分(a)、(b)和(c)的总重量;和(c)任选地,10wt%或更少的二烯衍生的单元,基于组分(a)、(b)和(c)的总重量;其中所述弹性体具有65-95%的等规丙烯三单元组立构规整度,等于或低于110℃的DSC所测熔点,5J/g至50J/g的熔化热,和95或更低,优选60或更低,更优选40或更低,特别是20或更低的雾度%/100密耳厚度。 A crosslinked elastomer, comprising: (a) propylene-derived units in an amount of at least 75wt%, based on the total weight of components (a), (b) and (c) of; (b) Ethylene derived units in an amount of at least 5wt%, based on component (a), (b) and (c) of the total weight; and (c) optionally, 10wt% or less of diene-derived units, based on component (a), (b) and (c) of the total weight; wherein the isotactic propylene elastomer having 65-95% of the triad tacticity, is equal to or lower than 110 ℃ a DSC measured melting point , 5J / g to 50J / g heat of fusion, and 95 or less, preferably 60 or less, more preferably 40 or less, particularly 20% or less haze / 100 mil thickness.
2.权利要求1的交联的弹性体,其中权利要求1的交联的弹性体,其中所述弹性体在交联前具有0.1至400,优选5至150的MFR@230℃。 Crosslinked elastomer of claim 1, a crosslinked elastomer of claim 1 wherein, wherein the elastomer before crosslinking has from 0.1 to 400, preferably 5 to 150 MFR @ 230 ℃.
3.权利要求1或2的交联的弹性体,其中所述交联的弹性体具有0.5MPa或更大的极限拉伸强度。 Elastomer crosslinked 1 or claim 2, wherein said crosslinked elastomer has 0.5MPa or greater ultimate tensile strength.
4.前述权利要求任一项的交联的弹性体,其中所述交联的弹性体以MPa度量的极限拉伸强度(TS)为0.5MPa或更大。 Crosslinked elastomer according to any one of the preceding claims, wherein said crosslinked elastomeric limit MPa to measure tensile strength (TS) of 0.5MPa or more.
5.前述权利要求任一项的交联的弹性体,其中所述弹性体包含二烯衍生的单元,其量基于组分(a)、(b)和(c)的总重量为0.3至10wt%。 Crosslinked elastomer according to any one of the preceding claims, wherein the elastomer comprises a diene-derived units in an amount based on the component (a), (b) and (c) the total weight of 0.3 to 10wt %.
6.前述权利要求任一项的交联的弹性体,其中在交联前的所述弹性体的肖氏A硬度与MFR@230℃之比与所述交联的弹性体的以MPa度量的极限拉伸强度(TS)之间满足以下方程式:(肖氏A硬度/MFR@230℃)≤1.66*TS-B1,其中B1为0,优选3.33,更优选6.66,特别是10。 Any one crosslinked elastomeric preceding claims, wherein the Shore A hardness in MPa and MFR @ 230 ℃ ratio with the crosslinked elastomer of the elastomer before crosslinking metrics satisfies the following equation :( Shore A hardness /MFR@230℃)≤1.66*TS-B1 between ultimate tensile strength (TS), wherein B1 is 0, preferably 3.33, more preferably 6.66, especially 10.
7.前述权利要求任一项的交联的弹性体,其中所述交联的弹性体以磅力/英寸度量的口型C撕裂强度(口型C)为50或更大。 Crosslinked elastomer according to any one of the preceding claims, wherein said crosslinked elastomer in pounds-force / inch metric Die C tear strength (port type C) of 50 or greater.
8.前述权利要求任一项的交联的弹性体,其中交联前的所述弹性体的肖氏A硬度与MFR@230℃之比与所述交联的弹性体的以磅力/英寸度量的口型C撕裂强度(口型C)满足以下方程式:(肖氏A硬度/MFR@230℃)≤0.2*口型C-B2,其中B2为0,优选10,更优选20,特别是30。 Crosslinked elastomer according to any one of the preceding claims, wherein the force in pounds and a Shore A hardness than the elastomeric MFR @ before crosslinking of 230 ℃ of the elastomer crosslinked / inch metric Die C tear strength (mouth C) satisfies the following equation :( Shore A hardness /MFR@230℃)≤0.2* lip C-B2, wherein B2 is 0, preferably 10, more preferably 20, particularly 30.
9.一种共混组合物,其包括由前述权利要求任一项的交联的弹性体形成的连续相和结晶聚合物组分的分散相,所述结晶聚合物组分具有115℃或更高的DSC所测熔点和50J/g或更高的熔化热,并选自下组:丙烯均聚物、丙烯接枝共聚物、丙烯嵌段共聚物、丙烯无规共聚物及它们的混合物,并且优选为等规聚丙烯。 A blend composition, comprising a dispersed phase by any one of the preceding claims crosslinked elastomer formed of a continuous phase and a crystalline polymer component, the crystalline polymer component has 115 ℃ or more high melting point measured by DSC and 50J / g or higher heat of fusion, and is selected from the group consisting of: propylene homopolymer, propylene graft copolymers, propylene block copolymers, propylene random copolymers, and mixtures thereof, and is preferably isotactic polypropylene.
10.一种弹性体组合物,其包括前述权利要求任一项的组合物,及相对于每100份聚合物100重量份或更少的颜料,优选着色颜料。 10. An elastomeric composition, comprising the composition according to any one of the preceding claims, and with respect to 100 parts by weight per 100 parts of polymer or less of a pigment, preferably a coloring pigment.
11.一种包含前述权利要求任一项的组合物的制品,其中所述制品具有95或更低,优选80或更低,更优选50或更低,特别是30或更低的雾度%/100密耳厚度。 11. A composition comprising the preceding claims An article according to any one of, wherein the article has a 95 or less, preferably 80 or less, more preferably 50 or less, particularly 30% or less haze / 100 mil thickness.
12.权利要求11的制品,其中所述制品为挤出制品或模制物件。 12. The article of claim 11, wherein the article is an extruded article or molded articles.
13.权利要求9所述的共混组合物,其中所述共混组合物已被加热至足以熔化基本上全部结晶聚合物组分的水平。 Blend composition of claim 9, wherein, wherein the blend composition has been heated to a level sufficient to melt substantially all of the crystalline polymer component.
14.权利要求9所述的共混组合物,其中所述结晶聚合物组分是等规聚丙烯,并且其中所述共混物已被加热到至少150℃。 Blend composition of claim 9, wherein, wherein said crystalline polymer component is isotactic polypropylene, and wherein the blend has been heated to at least 150 ℃.
Description  translated from Chinese
透明及半透明的交联的基于丙烯的弹性体及它们的制备和用途 Propylene-based elastomers and their preparation and use of transparent and translucent crosslinked

技术领域 FIELD

[0001]本发明总体上涉及交联的基于丙烯的弹性体,所述弹性体具有65-95%的等规丙烯三单元组立构规整度,等于或低于110℃的通过DSC测定的熔点,5J/g至50J/g的熔化热,和95或更低的雾度%/100密耳厚度。 [0001] relates to crosslinked propylene-based elastomer, said elastomer having 65-95% of an isotactic propylene triad tacticity of the present invention is generally equal to or lower than 110 ℃ melting point measured by DSC , 5J / g to 50J / g heat of fusion, and a haze of 95% or less / 100 mil thickness. 本发明的基于丙烯的弹性体包含至少75wt%的丙烯衍生的单元、至少5wt%的乙烯衍生的单元及任选地10wt%或更少的二烯衍生的单元。 Propylene-based elastomer of the invention comprises at least 75wt% of propylene-derived units, at least 5wt% of ethylene-derived units and, optionally, 10wt% or less of diene derived units. 本发明还涉及包含这种交联的基于丙烯的弹性体和100重量份或更少的颜料/100份聚合物的弹性体组合物。 The present invention further relates to compositions comprising such propylene-based elastomer and 100 parts by weight or less of a pigment elastomer / 100 parts of polymer composition crosslinked. 本发明的实施方案还包括含这样的组合物的薄膜、纤维、无纺布、模制物件及挤出成型物(form)。 Embodiments of the invention also include a composition containing such a film, fiber, nonwoven fabric, and the molded article extruded material (form). 本发明的特别优选的实施方案和应用是其中需要一定程度的透明性或半透明性的那些。 Particularly preferred embodiments and applications of the present invention are those in which transparency is required or translucency of those certain degree.

背景技术 BACKGROUND

[0002]无定型和部分结晶的(通常称为半结晶的)聚合物可以提供例如ASTM D1566中所定义的弹性体性质。 [0002] The amorphous and partially crystalline (typically referred to as semi-crystalline) polymer may provide, for example elastomeric properties as defined in ASTM D1566. 一类重要的弹性体衍生自聚烯烃,通常使用采用齐格勒-纳塔型催化剂体系的加成聚合。 An important class of elastomers derived from polyolefins, generally used Ziegler - Natta addition polymerization catalyst system. 通常地,聚烯烃弹性体是乙烯、提供短支链的破坏结晶性的α-烯烃如丙烯及任选地小量的多烯如二烯的共聚体,所述多烯用于提供可用于提供不同链之间的交联的不饱和短支链。 Typically, the polyolefin elastomer is ethylene, to provide short chain branches destruction crystalline α- olefins such as propylene and, optionally, a small amount of polyene such as diene interpolymer, the polyene may be used to provide for providing crosslinked unsaturated short branched chains of different chain. 这些共聚体可以是不含二烯衍生的单元的乙烯-丙烯共聚物(EP),或乙烯-丙烯-二烯三元共聚物(EPDM)。 These interpolymers can be free of diene-derived units of ethylene - propylene copolymer (EP), or ethylene - propylene - diene terpolymers (EPDM).

[0003]存在不同的技术用于硫化EP和EPDM共聚体。 [0003] There are different techniques for vulcanization EP and EPDM copolymers. 硫化可以逐渐地进行,从最初的产生长链支化(其中大分子单体或聚合物链本身插入到已经形成的聚合物链中),到中间形式(其中硫化的聚合物部分是可溶的和部分是不可溶的),再到全硫化的形式(其中聚合物的整体是不可溶的,并且基本上全部聚合物链都连接到网络中,没有孤立的聚合物链残留下来可供单独萃取)。 Curing can be carried out gradually, from the initial generation of long chain branching (wherein macromer or polymer chain itself is inserted into the polymer chain has formed), the intermediate form (which is part of the polymer soluble sulfurized and separate extraction portion is insoluble), to form a full-vulcanized (wherein the polymer as a whole is insoluble, and substantially all of the polymer chains are connected to the network, there is no isolation of the polymer chains are left behind for ).

[0004]本领域的技术人员选择所述共聚体、硫化/交联体系及其它配制成分,以平衡最终产品的可加工性及物理性能,例如老化、硬度、延展性(extensibility)、压缩永久变形、拉伸强度及冷的时候的性能。 [0004] Those skilled in the art to select the interpolymer, vulcanization / cross-linking system and other formulation ingredients, in order to balance the processability and physical properties of the final product, such as aging, hardness, ductility (extensibility), compression set tensile strength and performance when cold.

[0005]EP 964641、EP 946640、EP 1003814、US 6,245,856及US6,525,157及其它专利公开了聚烯烃共聚体,它们是弹性体,并且具有得自聚合物链中等规排列的丙烯衍生序列的结晶性。 [0005] EP 964641, EP 946640, EP 1003814, US 6,245,856 and US6,525,157 and other patents disclose a polyolefin copolymer, which is an elastic body, and having a polymer chain derived from propylene derived sequences medium gauge arrangement crystalline . 这与目前商业应用中的结晶性源自乙烯衍生的序列的EP和EPDM共聚体相反。 This is the current commercial applications crystalline ethylene-derived opposite from EP and EPDM interpolymers sequence. 这类基于丙烯的弹性体的性质在很多方面不同于已知的EP和EPDM共聚体弹性体。 Such propylene based elastomeric properties different from the known EP and EPDM elastomeric copolymers in many aspects. 二烯在这些新的基于丙烯的弹性体中的应用已经被想到。 Diene in these new propylene-based elastomer application has been thought of. 参见例如WO 00/69964,包括第15页18至25行。 See, for example WO 00/69964, including page 15 lines 18-25.

发明概述 Summary of the Invention

[0006]在一个方面,本发明提供了基于丙烯的弹性体,其被硫化至不同程度以进一步扩大所述弹性体的弹性体性能范围并允许进行方便的加工。 [0006] In one aspect, the present invention provides a propylene-based elastomer which is cured to different degrees in order to further expand the range of elastomeric properties of the elastic body and allow for easy processing.

[0007]在另一个方面,所述改进的基于丙烯的弹性体包括二烯,以有利于硫化和在复配及加工的各种选择中的最佳的最终应用性能。 [0007] In another aspect, the modified propylene-based elastomer comprises a diene, to facilitate the compounding and vulcanization and processing of various options in the best performance of the final application.

[0008]在另一个方面,本发明提供了改进的复配物,其含有这种基于丙烯的弹性体,以提供使用EP和EPDM共聚体弹性体所不能够实现的外观及最终应用性能特性。 [0008] In another aspect, the present invention provides an improved compound thereof, comprising such propylene-based elastomer to provide the appearance and performance characteristics of the final application using the EP and EPDM interpolymers resilient body can not be achieved.

[0009]现已惊奇地发现,可以制备出新颖的交联的基于丙烯的弹性体,该弹性体是透明或半透明的,并具有高的极限拉伸强度和撕裂强度。 [0009] It has now surprisingly been found possible to prepare novel crosslinked propylene-based elastomer, the elastomer is transparent or translucent, and has a high ultimate tensile strength and tear strength. 在一个特别的实施方案中,与从商购的EPDM制得的交联组合物相比,这些交联的基于丙烯的弹性体具有改进的极限拉伸强度和口型C撕裂强度。 In a particular embodiment, as compared with the commercially available EPDM crosslinked composition was prepared, and these crosslinked propylene-based elastomer having improved ultimate tensile strength, and Die C tear strength.

[0010]在一个实施方案中,本发明提供了一种交联的弹性体,所述弹性体具有65-95%的等规丙烯三单元组立构规整度,等于或低于110℃的通过DSC测定的熔点,5J/g至50J/g的熔化热,和95或更低的雾度%/100密耳厚度。 [0010] In one embodiment, the present invention provides a crosslinked elastomer, said elastomer having 65-95% of an isotactic propylene triad tacticity, is equal to or lower than the via 110 ℃ DSC melting point measured, 5J / g to 50J / g heat of fusion, and a haze of 95% or less / 100 mil thickness. 所述交联的弹性体包含至少75wt%的丙烯衍生的单元、至少5wt%的乙烯衍生的单元及任选地10wt%或更少的二烯衍生的单元。 Said crosslinked elastomer comprises at least 75wt% of propylene-derived units, at least 5wt% of ethylene-derived units and, optionally, 10wt% or less of diene derived units.

[0011]在另一个实施方案中,本发明提供了一种弹性体组合物,其包含这里所描述的交联的基于丙烯的弹性体及100重量份或更少的颜料/100份聚合物。 [0011] In another embodiment, the present invention provides an elastomer composition comprising a propylene-based elastomer and 100 parts by weight or less of a pigment / 100 parts of the crosslinked polymer described herein.

[0012]在另一个实施方案中,本发明提供了一种制品,例如薄膜、纤维、无纺布、模制物件或挤出成型物,其包括以上所述的任何本发明组合物。 [0012] In another embodiment, the present invention provides an article, such as films, fibers, nonwoven fabrics, molded article or extrusion molded article comprising the above composition according to any of the present invention.

详细描述 Detailed Description

[0013]光学性质 [0013] Optical properties

[0014]在优选的实施方案中,本发明涉及具有好的强度及撕裂性质、同时还具有显著的透明性或半透明性的弹性体材料。 [0014] In a preferred embodiment, the present invention relates to having good strength and tear properties, but also has remarkable transparency or translucency of the elastomeric material. 优选的实施方案包括一种或多种基于丙烯的弹性体与最优选为等规聚丙烯的第二聚合物的共混物,其中至少一种基于丙烯的弹性体和所述第二聚合物被交联。 Preferred embodiments include one or more elastomeric propylene-based polymer of the second and most preferably isotactic polypropylene blend, wherein the at least one propylene-based elastomer and the second polymer is crosslinking. 透明性由按照以下“试验方法”中更全面叙述的方式测量的每100密耳材料样品厚度的雾度%最大值来度量。 Haze% of maximum transparency by more fully in accordance with the following "test" in the way described in the measurement of every 100 mils to measure the thickness of the sample material. 本发明的交联的基于丙烯的弹性体及包含这种基于丙烯的弹性体的本发明组合物的雾度%/100密耳厚度优选为95或更低、或80或更低、或60或更低、或50或更低、或40或更低、或30或更低、或20或更低。 Crosslinking of the present invention and the propylene-based elastomer comprising such a composition based on the haze of the propylene elastomer of the present invention% / 100 mil thickness is preferably 95 or less, or 80 or less, or 60 or less, or 50 or less, or 40 or less, or 30 or less, or 20 or less.

[0015]在本发明的一个实施方案中,所述组合物还包含非黑颜料。 [0015] In one embodiment of the present invention, the composition further comprises a non-black pigment. 所述颜料虽然不显著影响交联制品的透明性,但是可以赋予色调或颜色。 Although the pigment does not significantly affect the transparency of the crosslinked product, but can impart hue or color. 所述颜料可以是任何颜色或色调,例如白色、红色、绿色、蓝色或黄色。 The pigment can be any color or hue, such as white, red, green, blue or yellow.

[0016]交联 [0016] crosslinking

[0017]在一个实施方案中,所述基于丙烯的弹性体的强度、耐撕裂性及其它性能通过将弹性体交联至预先选定的程度而得到改进。 [0017] In one embodiment, the strength of the propylene-based elastomer, tear resistance and other properties will be improved by crosslinking the elastomer to a preselected degree. 在另一个实施方案中,所述基于丙烯的弹性体被交联至不同程度,以允许进行方便的加工。 In another embodiment, the propylene-based elastomer is crosslinked to varying degrees, to allow easy processing. 在某些实施方案中,所述基于丙烯的弹性体包括二烯,以有利于交联和在配制及加工的各种选择中的最佳最终应用性能。 In certain embodiments, the propylene-based elastomer comprises a diene, to facilitate crosslinking and optimum performance in the formulation of the final application and processing of a variety of selection. 在其它的实施方案中,例如当使用辐射来诱导交联时,基于丙烯的弹性体中二烯的存在是任选的。 In other embodiments, such as when using radiation to induce cross-linking, the presence of the elastomeric propylene-diene-based is optional.

[0018]这里所使用的术语“交联的”涉及一种组合物,其中聚合物链已经被通过一种或多种常规的交联方法所连接,以提供具有以组合物总重量计至少2wt%不溶物的组合物和/或粘度比为1至10的组合物。 [0018] As used herein, the term "cross-linked" relates to a composition, wherein the polymer chain has been connected via one or more conventional cross-linking methods, to provide a total composition weight, at least 2wt The composition and / or viscosity% insolubles composition ratio of 1 to 10. 在一个特别的实施方案中,所述基于丙烯的弹性体被交联至一定程度,以提供在交联前能溶解所述组合物的任何溶剂中有至少2wt%、或至少5wt%、或至少10wt%、或至少20wt%、或至少35wt%、或至少45wt%、或至少65wt%、或至少75wt%、或至少85wt%、或少于95wt%不溶物的组合物。 In a particular embodiment, the propylene-based elastomer is crosslinked to a certain extent, in order to provide crosslinking before any solvent capable of dissolving the composition in at least 2wt%, or at least 5wt%, or at least 10wt%, or at least 20wt%, or at least 35wt%, or at least 45wt%, or at least 65wt%, or at least 75wt%, or at least 85wt%, or less than the composition 95wt% insolubles. 在另一个具体的实施方案中,所述基于丙烯的弹性体被交联至一定程度,以提供粘度比为1.1至100、或1.2至50、或还更优选2.0至20、并且最优选为5.0至10的组合物。 In another specific embodiment, the propylene-based elastomer is crosslinked to a certain extent, in order to provide a viscosity ratio of 1.1 to 100, or 1.2 to 50, or still more preferably from 2.0 to 20, and most preferably 5.0 10 to the composition.

[0019]通常,一种特定材料的极限拉伸强度受未交联化合物的MFR影响;例如,具有较低起始粘度(即较高MFR)的那些材料通常具有较低的极限拉伸强度。 [0019] Typically, the ultimate tensile strength of a particular material uncrosslinked compound MFR affected; e.g., those having low initial viscosity (i.e., high MFR) usually have a lower ultimate tensile strength. 因此,本发明的交联的基于丙烯的弹性体具有高的极限拉伸强度,但是在交联之前不具有高的粘度是令人惊奇的。 Therefore, the cross-linking of the present invention the propylene-based elastomer has a high ultimate tensile strength, but does not have high viscosity prior to crosslinking is surprising. 例如,在一个特别的实施方案中,本发明的交联的基于丙烯的弹性体具有0.5MPa或更大的极限拉伸强度(TS),同时具有25MFR的起始粘度。 For example, in one particular embodiment, the present invention is crosslinked propylene-based elastomer having 0.5MPa or greater ultimate tensile strength (TS), while having the initial viscosity 25MFR. 在该实施方案的一个特定方面中,交联前所述基于丙烯的弹性体的肖氏A硬度与MFR@230℃之比与以MPa为单位的交联的基于丙烯的弹性体的极限拉伸强度(TS)之间满足以下方程式:(肖氏A硬度/MFR@230℃)≤1.66*TS-B1,其中B1为0,或3.33,或6.66,或10。 In one particular aspect of this embodiment, the front of the crosslinked propylene-based elastomer has a Shore A hardness MFR @ propylene based elastomer limit draw ratio of 230 ℃ and in MPa between crosslinked satisfies the following equation :( a Shore A hardness between /MFR@230℃)≤1.66*TS-B1 strength (TS), wherein B1 is 0, or 3.33, or 6.66, or 10.

[0020]通常,一种材料的口型C撕裂强度受未交联化合物的MFR影响;例如,具有较低粘度(即较高MFR)的那些材料通常具有较低的口型C撕裂强度。 [0020] Typically, a material Die C tear strength of the uncrosslinked compound MFR affected; e.g., those materials having a lower viscosity (i.e., high MFR) usually has a lower tear strength Die C . 相反地,具有高肖氏A硬度的那些材料也固有地具有高的口型C撕裂强度。 Conversely, a high Shore A hardness of those materials inherently have high Die C tear strength. 因此,本发明的交联的基于丙烯的弹性体具有高的口型C撕裂强度却没有高粘度是令人惊奇的。 Accordingly, the present invention is crosslinked propylene-based elastomer has a high Die C tear strength was not high viscosity is surprising. 例如,在一个特别的实施方案中,本发明的交联的基于丙烯的弹性体具有50磅力/英寸或更大的口型撕裂强度(口型C)。 For example, in one particular embodiment, the present invention is crosslinked propylene-based elastomer having 50 pounds-force / inch or greater tear strength mouth (lip-C). 在该实施方案的一个具体方面中,交联前所述基于丙烯的弹性体的肖氏A硬度与MFR@230℃之比与以磅力/英寸为单位的交联的基于丙烯的弹性体的口型C撕裂强度满足以下方程式:(肖氏A硬度/MFR@230℃)≤0.2*口型C-B2,其中B2为0,或10,或20,或30。 In a particular aspect of this embodiment, the propylene-based elastomeric body has a Shore A hardness before crosslinking the propylene-based elastomer with MFR @ 230 ℃ ratio and force in pounds / inch units crosslinked Die C tear strength satisfying the following equation :( Shore A hardness /MFR@230℃)≤0.2* port type C-B2, wherein B2 is 0, or 10, or 20, or 30.

[0021]这里所描述的组合物可以通过提供聚合物组分的紧密混合物的任何方法制备。 [0021] The composition described herein can be prepared by any method providing an intimate mixture of the polymeric components. 通常,本发明方法的第一步骤为混合聚合物组分与任选的添加剂,例如加工油、填料、着色剂、抗氧剂、成核剂以及流动改进剂,使用设备例如但不限于用于熔融压制所述组分在一起的Carver压机,用于各组分的溶液或熔体共混的密闭式混合机如班伯里密炼机或Brabender混炼机,以及用于连续混合方法的设备,包括单和双螺杆挤出机、静态混合器、撞击式混合器以及设计成使各组分分散以紧密接触的其它机器和工艺。 Typically, the first step of the present invention is the method for mixing the polymer components and optional additives, such as process oils, fillers, colorants, antioxidants, nucleating agents and flow improvers using equipment such as, but not limited to, for melt pressing the components together in a Carver press, the components of the solution or melt blending mixer such as a Banbury mixer or a Brabender mixer, and a continuous mixing method used for equipment, including single and twin screw extruders, static mixers, impact mixers, and other machines and processes designed to disperse the components are in intimate contact. 聚合物组分的完全混合由组合物形态的均匀性来指示。 Complete mixing of the polymer components from a homogeneous composition morphology indicated. 这样的方法对本领域技术人员来说是众所周知的。 Such methods of the skilled artisan is well known. 在一个实施方案中,下一步是将化学硫化剂如过氧化物或硫化合物与所述紧密混合物混合,然后将包括所述化学硫化剂的所述紧密混合物制造成最终形状的制品,并升高温度一段时间,以允许所述基于丙烯的弹性体交联。 In one embodiment, the next step is a chemical curing agent such as a peroxide or a sulfur compound is mixed with the intimate mixture, and then the chemical vulcanizing agent comprising the intimate mixture into the final shape of the manufactured article, and elevated temperature for a time to allow the propylene-based elastomer is crosslinked. 在另一个实施方案中,下一步是将所述紧密混合物制成最终形状的制品,然后使所述成形的混合物暴露于外硫化剂如高能辐射,以引起所述基于丙烯的弹性体的交联。 In another embodiment, the next step is the intimate mixture into the final shape of the article, and then the mixture is exposed to the outside of the shaped high-energy radiation, such as a vulcanizing agent to cause cross-linking of the propylene-based elastomer .

[0022]可用于本发明实践中的硫化体系包括硫基硫化剂、过氧化物硫化剂、树脂硫化、氢化硅烷化(hydrosilation)、不稳定或迁移的硫化体系和高能辐射中的一种或多种。 [0022] The cure system may be used in the practice of the present invention the vulcanization system comprises sulfur-based vulcanizing agent, a peroxide curing agent, a resin cure, hydrosilylation (hydrosilation), migration and unstable or high-energy radiation in one or more of species. 这些硫化体系是本领域中所熟知的。 These cure systems are well known in the art.

[0023]当使用化学硫化剂如硫、硫给体、过氧化物及树脂以诱导反应时,所述硫化剂通常在制造最终形状的待制备制品之前混合到所述基于丙烯的弹性体中或包含所述弹性体的共混物中。 [0023] When using a chemical vulcanizing agents such as sulfur, sulfur donors, peroxides, and the resin to induce the reaction, the curing agent is generally manufactured prior to the final shape of the article to be produced is mixed into the propylene-based elastomer, or comprising the blend elastomer. 在一个优选的实施方案中,所述硫化过程可以在制品制造后通过加热或其它硫化引发步骤来引发,如本领域技术人员所熟知的那样。 In one preferred embodiment, the curing process can be triggered after a product making step is performed by heating or other curing is initiated, as the skilled artisan as. 当使用外交联剂如高能辐射诱导反应时,将所述基于丙烯的弹性体或包含所述弹性体的共混物在与外交联剂接触前制造成最终形状的待制备制品。 When using external crosslinking agents such as high-energy radiation-induced reactions, the propylene-based elastomer or a blend comprising the elastic body in contact with the outer cross-linking agent prior to manufacturing into the final shape of the article to be prepared.

[0024]基于丙烯的弹性体 [0024] propylene-based elastomer

[0025]本发明的基于丙烯的弹性体是无规的丙烯均聚物,或具有被非结晶区干扰的结晶区的共聚物。 Propylene-based elastomer is a random propylene [0025] The present invention is a homopolymer or copolymer of a non-crystalline regions is disturbed crystalline region having. 所述非结晶区可以源自不可结晶的聚丙烯链段的区域和/或包含共聚单体单元。 Region of the amorphous region may be derived from non-crystalline polypropylene segments and / or containing comonomer units. 通过引入丙烯插入错误和/或通过存在共聚单体,所述基于丙烯的弹性体的结晶度和熔点与高等规的聚丙烯相比被降低。 Compared propylene insertions is reduced by the introduction of errors and / by the presence of comonomer, the propylene-based elastomer of crystallinity and melting point and highly isotactic polypropylene or.

[0026]所述基于丙烯的弹性体的结晶度可以以熔化热表示。 [0026] Based on the degree of crystallinity of the propylene elastomer can be expressed as the heat of fusion. 在特别的实施方案中,所述基于丙烯的弹性体具有在下限为1.0J/g、或1.5J/g、或3.0J/g、或4.0J/g、或6.0J/g、或7.0J/g,上限为30J/g、或40J/g、或50J/g、或60J/g、或75J/g的范围内的由DSC测定的熔化热。 In a particular embodiment, the propylene-based elastomer having a lower limit of 1.0J / g, or 1.5J / g, or 3.0J / g, or 4.0J / g, or 6.0J / g, or 7.0J / g, an upper limit of 30J / g, or 40J / g, or 50J / g, or 60J / g, or 75J / heat of fusion measured by DSC within the range g.

[0027]所述基于丙烯的弹性体的结晶度也可以用结晶度百分数表示。 [0027] The crystallinity of the propylene elastomer can be expressed in percentage of crystallinity. 最高等级的聚丙烯的热能据估计为189J/g,即100%结晶度等于189J/g。 It is estimated that the highest level of thermal energy of polypropylene is 189J / g, i.e., 100% crystallinity is equal to 189J / g. 因此,在特别的实施方案中,所述基于丙烯的弹性体具有在上限为65%、或40%、或30%、或25%、或20%,下限为1%、或3%、或5%、或7%、或8%的范围内的丙烯结晶度。 Thus, in particular embodiments, the propylene-based elastomer has an upper limit of 65%, or 40%, or 30%, or 25%, or 20%, the lower limit is 1%, or 3%, or 5 %, or 7%, or propylene crystallinity in the range of 8%.

[0028]结晶度的水平还反映在熔点上。 [0028] The level of crystallinity is also reflected in the melting point. 这里所用的术语“熔点”是通过DSC测定的、主熔融峰和次熔融峰中的最高峰。 As used herein, the term "melting point" is measured by DSC, the main melting peak and a secondary peak of the melting peak. 在特别的实施方案中,所述基于丙烯的弹性体的由DSC测定的熔点在上限为110℃、或105℃、或90℃、或80℃、或70℃,下限为0℃、或20℃、或25℃、或30℃、或35℃、或40℃、或45℃的范围内。 In a particular embodiment, the melting point measured by DSC of the propylene-based elastomer in the upper limit is 110 ℃, or 105 ℃, or 90 ℃, or 80 ℃, or 70 ℃, the lower limit is 0 ℃, or 20 ℃ within the range or 25 ℃, or 30 ℃, or 35 ℃, or 40 ℃, or 45 ℃ for.

[0029]所述基于丙烯的弹性体通常包含至少60wt%的丙烯衍生的单元,并且在特别的实施方案中,所述基于丙烯的弹性体包含至少75wt%、或至少80wt%、或至少90wt%的丙烯衍生的单元。 [0029] The propylene-based elastomers typically contain at least 60wt% of propylene-derived units, and in particular embodiments, the propylene-based elastomer comprises at least 75wt%, or at least 80wt%, or at least 90wt% of propylene-derived units.

[0030]适合于本发明的基于丙烯的弹性体的等规丙烯三单元组立构规整度在下限为65%、或70%、或75%,上限为95%、或97%、或98%、或99%的范围内。 [0030] Suitable propylene-based elastomer isotactic propylene triad tacticity of the present invention is configured in a lower limit of 65%, or 70%, or 75% and up to 95%, or 97%, or 98% , or in the range of 99%. 聚合物的等规丙烯三单元组立构规整度是由头-尾键组成、表示为m和r序列的二元组合的三个相邻丙烯单元序列即链的相对立构规整度。 Isotactic propylene triad tacticity of the polymer is from head - tail bonds, expressed in three binary combination of m and r sequences adjacent relative tacticity of the propylene unit sequences i.e. chain. 这里所公开的聚合物的等规丙烯三单元组立构规整度使用C13NMR和在US 5,504,172中阐述的计算方法测定。 Isotactic propylene triad tacticity of the polymer disclosed herein, and measured using C13NMR calculation method set forth in US 5,504,172.

[0031]在特别的实施方案中,本发明的基于丙烯的弹性体的全同立构规整度指数大于0%,或者在上限为50%或25%,下限为3%或10%的范围内。 [0031] In a particular embodiment, the present invention is based on isotactic tacticity index of the elastomer is greater than 0% of propylene, or the upper limit is 50% or 25%, the lower limit of the range of 3% or 10% of the .

[0032]在特别的实施方案中,本发明的基于丙烯的弹性体的立构规整度指数(m/r)在上限为8、或10、或12,下限为4或6的范围内。 [0032] In a particular embodiment, the present invention is based on tacticity index of the propylene elastomer (m / r) at the upper limit of 8, or 10, or 12, a lower limit of a range of 4 or 6.

[0033]在特别的实施方案中,本发明的基于丙烯的弹性体在交联前具有0.1至400,或3至200,或5至150的在230℃下的熔体流动速率(MFR)。 [0033] In a particular embodiment, the present invention is the propylene-based elastomer before crosslinking has from 0.1 to 400, or 3-200, or at 230 ℃ melt flow rate of 5-150 (MFR).

[0034]在特别的实施方案中,所述基于丙烯的弹性体在200%伸长率后的拉伸永久变形小于50%。 [0034] In a particular embodiment, the propylene-based elastomer is stretched after 200% elongation of less than 50% permanent deformation. 在本实施方案的一个具体方面,所述基于丙烯的弹性体的极限拉伸强度为1500psi(10.4MPa)或更大、或1000psi(6.9MPa)或更大、或500psi(3.5MPa)或更大。 In a particular aspect of this embodiment, the limit of the propylene-based elastomer has a tensile strength 1500psi (10.4MPa) or greater, or 1000psi (6.9MPa) or more, or 500psi (3.5MPa) or more .

[0035]在某些实施方案中,通过丙烯与有限量的一种或多种选自乙烯、C4-C20α-烯烃及多烯的共聚单体的共聚合来控制所述基于丙烯的弹性体的结晶度。 [0035] In certain embodiments, by a limited amount of propylene with one or more selected from ethylene, copolymerization of olefins and C4-C20α- polyene comonomer controlling said propylene-based elastomeric body crystallinity. 在这些共聚物中,以所述基于丙烯的弹性体的总重量计,在所述基于丙烯的弹性体中存在的丙烯衍生单元的量上限为99.9wt%、或97wt%、或95wt%、或94wt%、或92wt%、或90wt%、或85wt%,下限为60wt%、68wt%、或70wt%、或71wt%或75wt%或76wt%或80wt%。 In these copolymers, based on the total weight of the propylene-based elastomer, the upper limit on the amount of the propylene-based elastomer in the presence of propylene-derived units is 99.9wt%, or 97wt%, or 95wt%, or 94wt%, or 92wt%, or 90wt%, or 85wt%, the lower limit is 60wt%, 68wt%, or 70wt%, or 71wt% or 75wt% or 76wt% or 80wt%. 以所述基于丙烯的弹性体的总重量计,所述基于丙烯的弹性体中存在的衍生自乙烯和/或C4-C20α-烯烃的任选单元的量上限为40wt%、或35wt%、或30wt%、或28wt%、或25wt%、或20wt%、或15wt%,下限为0wt%、或0.5wt%、或1wt%、或2wt%、或3wt%、或5wt%、或6wt%、或8wt%或10wt%。 In the elastomer based on the total weight of the propylene, the propylene-based elastomer is present in an amount derived from the upper limit of ethylene and / or C4-C20α- optionally olefin units is 40wt%, or 35wt%, or 30wt%, or 28wt%, or 25wt%, or 20wt%, or 15wt%, the lower limit is 0wt%, or 0.5wt%, or 1wt%, or 2wt%, or 3wt%, or 5wt%, or 6wt%, or 8wt% or 10wt%. 以所述基于丙烯的弹性体的总重量计,所述基于丙烯的弹性体中存在的任选的多烯衍生单元的量上限为25wt%、或20wt%、或15wt%、或10wt%、或7wt%、或6wt%、或5wt%、或4.5wt%、或3wt%、或2.5wt%,下限为0wt%、或0.1wt%、或0.2wt%、或0.3wt%、或0.5wt%、或1wt%、或1.5wt%。 In the elastomer based on the total weight of propylene, based on the upper limit of the amount of elastomeric propylene optionally in the presence of the polyene derived units is 25wt%, or 20wt%, or 15wt%, or 10wt%, or 7wt%, or 6wt%, or 5wt%, or 4.5wt%, or 3wt%, or 2.5wt%, the lower limit is 0wt%, or 0.1wt%, or 0.2wt%, or 0.3wt%, or 0.5wt%, or 1wt%, or 1.5wt%.

[0036]任选存在于所述基于丙烯的弹性体中的优选α-烯烃的非限制性实例包括丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和1-癸烯。 [0036] optionally present in the non-limiting examples based on the propylene elastomer is preferably α- olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1- decene. 任选存在于所述基于丙烯的弹性体中的多烯衍生单元可以衍生自具有至少两个不饱和键的任何烃结构,其中至少一个不饱和键可以被引入聚合物中。 Optionally present in the propylene-based elastomer of polyene derived units may be derived from having at least two unsaturated bonds any hydrocarbon structure, wherein the at least one unsaturated bond may be introduced into the polymer. 优选的多烯的非限制性实例包括5-乙叉-2-降冰片烯(″ENB″)、5-乙烯基-2-降冰片烯(″VNB″)、二乙烯基苯(″DVB″)以及双环戊二烯(″DCPD″)。 Preferred polyene Non-limiting examples include 5-ethylidene-2-norbornene ("ENB"), 5- vinyl-2-norbornene ("VNB"), divinyl benzene ("DVB" ) and dicyclopentadiene ("DCPD").

[0037]在一个特别的实施方案中,所述基于丙烯的弹性体的在125℃的门尼粘度ML(1+4)为0.5至100、或5至40、或10至40。 [0037] In a particular embodiment, the propylene-based elastomer at 125 ℃ Mooney viscosity ML (1 + 4) of from 0.5 to 100, or 5-40, or 10-40.

[0038]本发明的基于丙烯的弹性体的重均分子量(Mw)在上限为5,000,000g/mol、或1,000,000g/mol、或500,000g/mol,下限为10,000g/mol、或15,000g/mol、或20,000g/mol、或80,000g/mol的范围内,并且有时被称为“多分散指数”(PDI)的分子量分布Mw/Mn(MWD)在上限为40、或20、或10、或5、或4.5、或4.0、或3.2、或3.0,下限为1.5、或1.8、或2.0的范围内。 [0038] The present invention is based on the weight of the propylene elastomer-average molecular weight (Mw) upper limit of 5,000,000g / mol, or 1,000,000g / mol, or 500,000g / mol, a lower limit of 10,000g / mol, or 15,000g / mol , or in the range of 20,000g / mol, or 80,000g / mol, and is sometimes referred to as "polydispersity index" (PDI) of a molecular weight distribution Mw / Mn (MWD) at the upper limit of 40, or 20, or 10, or 5, or 4.5, or 4.0, or 3.2, or 3.0, the lower limit of 1.5, or 1.8, or in the range of 2.0.

[0039]合适的基于丙烯的弹性体以及用于制备它们的方法的示例性非限制实例包括:在未决的美国临时专利申请号60/519,975中所公开的″FPC″;在美国专利申请公布号2003/0204017中所公开的″等规的丙烯共聚物″;在US 6,525,157中所公开的″丙烯乙烯共聚物″;以及在PCT公布号WO 02/083754中所公开的″丙烯乙烯共聚物″,其公开内容通过引用全部结合在此。 [0039] Suitable elastomeric propylene and an exemplary method for their preparation is based on non-limiting examples include: U.S. Provisional Patent Application No. 60 pending / 519,975 disclosed "FPC"; published in U.S. Patent Application No. 2003/0204017 disclosed "isotactic propylene copolymer"; in US 6,525,157 as disclosed in "propylene ethylene copolymer"; and in PCT Publication No. WO 02/083754 disclosed "propylene ethylene copolymer" , the disclosure of which is incorporated herein by reference in its entirety.

[0040]与前述分开地或相组合地,所述基于丙烯的弹性体的结晶度也可以通过立体不规则地引入丙烯衍生的单元来降低,这可能被例如催化剂和聚合温度的选择所影响。 [0040] the aforementioned separately or in combination, the crystallinity of the propylene elastomer can also be introduced irregularly propylene-derived units to reduce by three-dimensional, which may be for example the choice of catalyst and the polymerization temperature affected.

[0041]本发明的基于丙烯的弹性体不受任何具体的制备聚合方法限制,并且这里所描述的聚合方法不受任何具体类型的反应容器限制。 [0041] The present invention is a propylene-based elastomer is not any particular polymerization method for preparing limit, and the polymerization methods described herein without any specific type of reaction vessel limits.

[0042]在一个特别的实施方案中,用于生产基于丙烯的弹性体的催化剂体系包括一种或多种过渡金属化合物及一种或多种活化剂。 [0042] In a particular embodiment, the catalyst system for the production of elastomers based on propylene comprising one or more transition metal compounds and one or more activators. 当使用铝氧烷或烷基铝活化剂时,结合的前催化剂-活化剂摩尔比通常为1∶5000至10∶1。 When alumoxane or aluminum alkyl activators, bound catalyst precursor - activator molar ratio is usually 1:5000 to 10:1. 当使用离子化活化剂时,结合的前催化剂-活化剂摩尔比通常为10∶1至1∶10。 When using ionizing activators, bound catalyst precursor - activator molar ratio is usually 10:1 to 1:10. 可以使用多重活化剂,包括使用铝氧烷或烷基铝与离子化活化剂的混合物。 Multiple activators may be used, including the use of alkyl alumoxane or a mixture of aluminum and ionizing activators.

[0043]在另一个特别的实施方案中,所述催化剂体系包括双(环戊二烯基)金属化合物,和(1)非配位的相容的阴离子活化剂,或(2)铝氧烷活化剂。 [0043] In another particular embodiment, the catalyst system comprises a bis (cyclopentadienyl) metal compound, and (1) a non-coordinating compatible anion activator, or (2) an aluminoxane activator. 可以使用的催化剂体系的非限制性实例描述在US5,198,401和5,391,629中,通过引用将其结合在此。 Non-limiting examples of catalyst system can be used is described in US5,198,401 and in 5,391,629, which is incorporated by reference herein.

[0044]在另一个实施方案中,所述基于丙烯的弹性体是在活化助催化剂存在下制得的,该助催化剂是包含卤化的四芳基取代的第13族阴离子的母体离子化合物,其中每个芳基取代基含至少两个环芳环。 [0044] In another embodiment, the propylene-based elastomer in the presence of activating co-catalyst, the cocatalyst is a precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion wherein each aryl substituent contains at least two aromatic rings. 在该实施方案的一个具体方面,所述基于丙烯的弹性体含有大于0.2ppm、或大于0.5ppm、或大于1ppm、或大于5ppm的所述活化助催化剂的残余物。 In a particular aspect of this embodiment, the propylene-based elastomer comprises greater than 0.2ppm, or greater than 0.5ppm, or greater than 1ppm, or greater than the activating cocatalyst residue of 5ppm.

[0045]在另一个特别的实施方案中,用于生产基于丙烯的弹性体的催化剂体系包括含Hf的茂金属催化剂,例如但不限于二甲基二甲基甲硅烷基双(茚基)合铪,和非配位阴离子活化剂,例如但不限于二甲基苯铵四(七氟萘基)硼酸盐。 [0045] In another particular embodiment, the catalyst system for the production of elastomers based on propylene containing Hf metallocene catalysts include, for example, but not limited to, di methyl dimethylsilyl bis (indenyl) hafnium, and non-coordinating anion activator, such as, but not limited to, dimethylanilinium tetrakis (heptafluoronaphthyl) borate.

[0046]在又一个特别的实施方案中,使用在美国专利申请公布2004/0024146中所公开的任何催化剂体系及聚合方法制备所述基于丙烯的弹性体,该文件公开的内容通过引用结合在此。 [0046] In yet another particular embodiment, using any in U.S. Patent Application Publication 2004/0024146 catalyst system and polymerization process as disclosed for preparing the propylene-based elastomer, the disclosure of which document is incorporated herein by reference .

[0047]在另一个特别的实施方案中,使用催化剂体系,例如在美国专利申请公布2003/0204017中描述的非茂金属的、金属中心的、杂芳基配体的催化剂体系之一来制备所述基于丙烯的弹性体,该文件公开的内容通过引用结合在此。 [0047] In another particular embodiment, the catalyst system used, e.g., be prepared as reported by the non-metallocene catalyst systems, metal-centered 2003/0204017 described, heteroaryl ligand in U.S. Patent Application said propylene-based elastomer, the disclosure of which document is incorporated herein by reference.

[0048]适合用于制备所述基于丙烯的弹性体的其它一般工艺条件信息可以在包括但不限于US 5,001,205及PCT公布WO 96/33227和WO 97/22639的公开内容中找到。 [0048] Suitable for the preparation of the general process conditions based on other information propylene elastomers may include, but are not limited to, US 5,001,205 and PCT Publication WO 96/33227 and WO 97/22639 the disclosures found in. 关于气相聚合工艺的进一步的信息可以在包括但不限于以下的公开内容中找到:US 4,543,399;4,588,790;5,028,670;5,317,036;5,352,749;5,405,922;5,436,304;5,453,471;5,462,999;5,616,661;5,627,242;5,665,818;5,668,228及5,677,375,以及欧洲公布EP-A-0 794 200;EP-A-0 802 202;及EP-B-634 421。 For further information on gas phase polymerization process may include, but are not limited to, the following disclosure is found in: US 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; 5,627,242; 5,665,818; 5,668,228 and 5,677,375, and European publications EP-A-0 794 200; EP-A-0 802 202; and EP-B-634 421. 涉及将液体催化剂引入到流化床聚合中贫粒子区(particle lean zone)中的方法的信息可在包括但不限于US 5,693,727的公开内容中找到。 Relates to a liquid catalyst is introduced into the particle lean zone in a fluidized bed polymerization (particle lean zone) method information may include, but are not limited to US 5,693,727 the disclosure of which is found in. 关于淤浆聚合工艺的进一步的信息可以在包括但不限于US 3,248,179和4,613,484的公开内容中找到。 Further information on slurry polymerization process may include, but are not limited to, US 3,248,179 and 4,613,484 the disclosures found in. PCT公布WO 96/08520及US 5,712,352是描述在不存在或基本不存在任何清除剂下操作的聚合方法的公开内容的非限制性实例。 PCT Publication WO 96/08520 US 5,712,352 is described in the absence or substantial absence of a polymerization method of the disclosure in any scavenger operation and non-limiting examples.

[0049]在本发明包括含基于丙烯的弹性体的组合物的实施方案中,所述基于丙烯的弹性体的存在量为至少50wt%、或至少60wt%、或至少70wt%、或至少75wt%、或至少80wt%、或至少95wt%,基于所述组合物的总重量。 [0049] In the present embodiment of the invention comprises a composition containing based on the propylene elastomer, the elastomer is present in an amount based on propylene is at least 50wt%, or at least 60wt%, or at least 70wt%, or at least 75wt% , or at least 80wt%, or at least 95wt%, based on the total weight of the composition.

[0050]在本发明包括含基于丙烯的弹性体的组合物的另一个实施方案中,结晶聚合物组分、填料、颜料及增塑剂等的总重量(即除基于丙烯的弹性体之外的材料的总重量)与所述基于丙烯的弹性体的重量之比为2或更小、或1.5或更小、或1.3或更小、或1或更小、或0.5或更小、或0.3或更小、或0.2或更小。 [0050] In the present invention comprises a containing based on another embodiment of the composition of elastomers of propylene, the crystalline polymer component, a filler, a pigment, and the total weight of the plasticizer, etc. (i.e., in addition to the propylene-based elastomer other than ratio by weight of the total weight of the material) and the propylene-based elastomer is 2 or less, or 1.5 or less, or 1.3 or less, or 1 or less, or 0.5 or less, or 0.3 or less, or 0.2 or less.

[0051]结晶聚合物组分 [0051] crystalline polymer component

[0052]本发明的一些实施方案包括结晶的丙烯聚合物组分。 [0052] Some embodiments of the present invention comprises a crystalline propylene polymer component. 所述结晶聚合物组分可以选自:丙烯均聚物、丙烯共聚物及通常被称为反应器共聚物或抗冲共聚物的其混合物。 The crystalline polymer component may be selected from: propylene homopolymers, propylene copolymers, and commonly referred to a reactor copolymer or an impact copolymer of a mixture thereof. 在其中结晶聚合物组分包括丙烯共聚物的实施方案中,所述丙烯共聚物可以是接枝共聚物、嵌段共聚物或无规共聚物。 In which the crystalline polymer component comprises a propylene copolymer embodiments, the propylene copolymer may be a graft copolymer, block copolymer or random copolymer.

[0053]存在于结晶聚合物组分中的丙烯衍生单元的量为90wt%或更高,或92wt%或更高,或95wt%或更高,或97wt%或更高,或100wt%,基于所述结晶聚合物组分的总重量。 [0053] The crystalline polymer component present in the amount of propylene-derived units is 90wt% or more, or 92wt% or more, or 95wt% or more, or 97wt% or more, or 100wt%, based on The total weight of the crystalline polymer component.

[0054]在一个实施方案中,所述结晶聚合物组分包括丙烯和至少一种共聚单体的无规共聚物,所述至少一种共聚单体选自乙烯和C4-C12α-烯烃中的一种或多种。 [0054] In one embodiment, the crystalline polymer component comprises propylene and at least one comonomer of the random copolymer, said at least one comonomer selected from ethylene and C4-C12α- olefins one or more. 在该实施方案的一个具体方面,共聚单体的量的上限为9wt%、或8wt%、或6wt%,下限为2wt%,以所述结晶聚合物组分的总重量计。 In a particular aspect of this embodiment, the upper limit of the amount of comonomer is 9wt%, or 8wt%, or 6wt%, the lower limit of 2wt%, of the crystalline polymer component to the total weight.

[0055]本发明的结晶聚合物组分具有至少110℃、或至少115℃、或至少130℃的DSC熔点,和至少60J/g、或至少70J/g、或至少80J/g的由DSC测定的熔化热。 [0055] The crystalline polymer component of the present invention has at least 110 ℃, or at least 115 ℃, or a DSC melting point of at least 130 ℃ and at least 60J / g, or at least 70J / g, or at least 80J / g measured by DSC heat of fusion.

[0056]本发明的结晶聚合物组分的重均分子量(Mw)在上限为5,000,000g/mol或500,000g/mol,下限为10,000g/mol或50,000g/mol的范围内,并且有时被称为“多分散指数”(PDI)的分子量分布Mw/Mn(MWD)在上限为40,下限为1.5的范围内。 [0056] Recrystallization polymer component of the present invention average molecular weight (Mw) within a maximum of 5,000,000g / mol or 500,000g / mol, a lower limit of 10,000g / mol or 50,000g / mol range, and are sometimes referred to distribution Mw / Mn (MWD) as "polydispersity index" (PDI) of a molecular weight in the upper limit is 40, the lower limit is in the range of 1.5.

[0057]本发明不受任何制备结晶聚合物组分的具体方法的限制。 Limiting the invention without any preparation of the crystalline polymer component of the specific method of [0057] the present. 在一个实施方案中,所述结晶聚合物组分可以是通过众所周知的在单段或多段反应器中的丙烯均聚方法得到的丙烯均聚物。 In one embodiment, the crystalline polymer component may be known by one or more pieces of propylene in single stage reactor is homopolymerization of propylene homopolymer obtained. 在另一个实施方案中,所述结晶聚物组分可以是通过众所周知的在单段或多段反应器中共聚合丙烯与一种或多种共聚单体的方法得到的丙烯共聚物。 In another embodiment, the prepolymer component may be crystallized by a known segment in a single section of the reactor or copolymerizing propylene with one or more comonomers of the propylene copolymer obtained by the method.

[0058]制备所述结晶聚合物组分的聚合方法包括高压法、淤浆法、气相法、本体法、溶液相法及它们的组合。 [0058] The polymerization process for preparing the crystalline polymer component comprises a high pressure, slurry, gas phase, bulk, solution phase method and a combination thereof. 可以使用的催化剂体系包括传统的齐格勒-纳塔催化剂及单中心茂金属催化剂体系。 The catalyst system can be used include conventional Ziegler - Natta catalysts and single-site metallocene catalyst system. 在一个实施方案中,所使用的催化剂具有高的立体专一性(isospecificity)。 In one embodiment, the catalyst used has a high stereospecificity (isospecificity).

[0059]结晶聚合物组分的聚合可以通过连续或间歇法进行,并可以使用链转移剂、清除剂或本领域技术人员所熟知的其它的这样的添加剂。 Polymerization [0059] of the crystalline polymer component can be produced by a continuous or batch process and may be used chain transfer agents, scavengers, or the skilled artisan of other such additives. 所述结晶聚合物组分可以还含有诸如流动改进剂、成核剂及抗氧剂的添加剂,所述添加剂通常被添加到等规聚丙烯中以改进或保持性能。 The crystalline polymer component may further contain as flow improvers, nucleating agents and antioxidant additives which are usually added to isotactic polypropylene to improve or maintain performance.

[0060]共混 [0060] Blends

[0061]在一个实施方案中,本发明提供了包含至少一种基于丙烯的弹性体及至少一种结晶聚合物组分的共混组合物。 [0061] In one embodiment, the present invention provides a composition comprising at least one propylene-based elastomer and at least one crystalline polymer component of the blend compositions. 这样的共混组合物具有由不同结晶性的区域所组成的多相形态。 Such blend compositions having multiphase morphology different crystalline region thereof. 这些不同结晶性的区域将本发明组合物与通常可以获得的具有单一晶相的丙烯反应器共聚物(即,等规聚丙烯与丙烯和乙烯共聚物的共混物)区分开。 These different crystalline region and the compositions of the invention can generally be obtained as reactor copolymers of propylene having a single crystalline phase (i.e., a blend of isotactic polypropylene and copolymers of propylene and ethylene) on the other.

[0062]在优选的实施方案中,所述多相共混组合物的连续相具有无定型或可结晶的形态,并含有基于丙烯的弹性体和可以含有少量的结晶聚合物组分。 [0062] In a preferred embodiment, the continuous phase of the heterogeneous blend composition having an amorphous or crystalline form, and containing elastomeric propylene and may contain a small amount of a crystalline polymer component based. 分散相具有结晶形态,并含有结晶聚合物组分、任选的填料,并且可以以比所述连续相少的量含有所述基于丙烯的弹性体。 A dispersed phase having a crystal form, and comprising a crystalline polymer component, optional filler, and may be less than the amount of the continuous phase containing the propylene-based elastomer. 所述基于丙烯的弹性体相对于所述结晶聚合物组分具有低的结晶度;因此,相对于分散相,本发明组合物的连续相具有低的结晶度。 The propylene-based elastomer with respect to the crystalline polymer component having a low crystallinity; therefore, with respect to the dispersed phase, the continuous phase composition of the present invention has a low degree of crystallinity. 所述低结晶度的连续相使得本发明组合物最优选的实施方案区别于具有高结晶连续相的通常可获得的丙烯抗冲共聚物、热塑性弹性体、热塑性硫化橡胶和热塑性聚烯烃。 The continuous phase of low crystallinity such that the composition of the present invention is most distinguished from the preferred embodiment has a generally available highly crystalline propylene impact copolymer continuous phase, a thermoplastic elastomer, thermoplastic vulcanizates, and thermoplastic polyolefins.

[0063]所述共混组合物的组分应被选择是相容的,优选相容至不需要加入预形成的或原位形成的增容剂来得到和保持优良的共混形态的程度。 [0063] The components of the blend compositions should be selected to be compatible, preferably compatible compatibilizing agent is not required to join a pre-formed or formed in situ to obtain and maintain an excellent degree of blend morphology.

[0064]这里所描述的优选的多相共混组合物的分散相的区域较小,平均最小轴小于5微米。 Region [0064] The preferred heterogeneous blend described herein composition dispersed phase is small, the average minor axis of less than 5 microns. 分散相的较大的轴可以大至100微米。 The larger axis of the dispersed phase can be as large as 100 microns.

[0065]添加剂 [0065] Additives

[0066]本领域技术人员将明白,除聚合物组分以外,本发明的组合物可以包含添加剂。 [0066] Those skilled in the art will appreciate, in addition to the polymer component, the compositions of the present invention may contain additives. 可以存在各种添加剂以提高具体的性能,或者各种添加剂可以由于对各组分的加工而存在。 Various additives may be present to improve specific properties, or various additives may be due to processing of the components exists. 可以加入的添加剂包括但不限于加工油、防火剂、抗氧剂、增塑剂、颜料、硫化剂或固化剂、硫化或固化促进剂、硫化延迟剂、加工助剂、阻燃剂、增粘剂、流动改进剂等。 The additives may be added include, but are not limited to, processing oils, fire retardants, antioxidants, plasticizers, pigments, vulcanizing or curing agents, vulcanizing or curative accelerators, cure retarders, processing aids, flame retardants, tackifying agents, flow improvers, and the like. 还可以使用防粘连剂、着色剂、润滑剂、脱模剂、成核剂、增强剂及填料(包括粒状的、纤维的或粉状的)。 You can also use anti-blocking agents, colorants, lubricants, mold release agents, nucleating agents, reinforcing agents and fillers (including granular, fibrous or powdered). 成核剂和填料可以改进制品的刚性。 Nucleating agents and fillers may improve the rigidity of the article. 这里所述的名单并不是意图包括可用于本发明中的所有类型的添加剂。 The list described herein is not intended to be included in the present invention can be used in all types of additives. 本领域的技术人员将明白,可以采用其它添加剂来提高所述组合物的性能。 Those skilled in the art will appreciate that other additives may be employed to improve the performance of the composition. 如本领域技术人员所理解的,本发明的组合物可以被改性,以按照所希望的方式调节共混物的特性。 As the skilled artisan will appreciate, the compositions of the present invention may be modified, to adjust the blend according to the characteristics desired manner.

[0067]这里描述的组合物可以还含有无机颗粒填料,所述填料可以改进所述组合物的机械及耐磨损性能,尤其是在包括硫化的组分的组合物中。 [0067] The composition described herein may further contain an inorganic particulate filler, the filler can improve the mechanical and wear properties of the composition, especially in a composition comprising components vulcanization. 使用的无机填料的量通常为1至100重量份无机填料/100份聚合物材料。 Amount of the inorganic filler used is generally 1 to 100 parts by weight of an inorganic filler / 100 parts of polymer material. 所述无机填料包括直径小于1mm的颗粒,长度小于1cm的棒状物及表面积小于0.2cm2的片状物。 The inorganic filler comprises particles smaller than 1mm in diameter, the length of the rods is less than 1cm and a surface area of less than 0.2cm2 sheet. 示例性的颗粒填料包括滑石、粘土、钛和镁的氧化物,以及硅石。 Exemplary particulate fillers include talc, clay, titanium and magnesium oxide, and silica. 炭黑通常不是优选的,因为它干扰希望的光学性质。 Carbon black is generally not preferred, because it interferes with the desired optical properties. 此外,也可以使用其它颗粒填料如碳酸钙、氧化锌、白粉及氧化镁。 In addition, other particulate fillers may also be used such as calcium carbonate, zinc oxide, whiting, and magnesium oxide. 棒状填料的一个实例是玻璃纤维。 One example of a rod-like filler is glass fiber. 片状填料的一个实例是云母。 An example of the sheet-like filler is mica. 添加通常称为纳米复合材料的非常小的颗粒填料也是可以想到的。 Add commonly referred to as very small particulate filler nanocomposites also conceivable. 填料的添加可以改变这里所描述的组合物的性质。 Adding filler may alter the properties of the composition described herein. 例如,包括无机填料的组合物可以产生改进的热稳定性和耐磨性。 For example, a composition comprising an inorganic filler can produce improved thermal stability and wear resistance.

[0068]填料的量及选择限于不损害所述交联制品的透明性的那些组合。 [0068] The amount of filler and the selection is limited to those compositions without impairing the crosslinked article transparency. 通常,添加填料导致透明度的损失,原因在于穿过包括填料的聚合物样品的光线通路受阻。 Typically, adding a filler results in a loss of transparency, because the light path through the sample comprises a polymer filler hindered. 有几种方法可以用于在填料存在下提高透明性,包括:(a)使用其线性尺寸与可见光波长相当或比可见光波长更小的填料,(b)使用折光指数与基于丙烯的弹性体相似的透明填料,和(c)使用最小可允许量的填料或颜料。 There are several methods that can be used to improve transparency in a filler is present, comprising: (a) using the wavelength of visible light and its linear dimension comparable to or smaller than the wavelength of visible light filler, (b) using a refractive index similar to the propylene-based elastomer transparent filler material, and (c) using the minimum allowable amount of filler or pigment. 在本发明的各种实施方案中,可以使用这些方法中的一种或多种来维持本发明组合物的透明性。 In various embodiments of the present invention, these methods may be used one or more of the compositions of the present invention to maintain the transparency.

[0069]这里所描述的组合物可以含有0至500重量份、或2至200重量份、或5至150重量份、或10至100重量份、或20至50重量份的加工油,相对于每100份总聚合物。 [0069] The composition described herein may contain from 0 to 500 parts by weight, or from 2 to 200 parts by weight, or from 5 to 150 parts by weight, or 10 to 100 parts by weight, or 20 to 50 parts by weight of processing oil, with respect to per 100 parts of total polymer. 适宜量加工油的加入可以降低共混物的粘度和挠曲性,同时改进所述共混物在接近和低于0℃的温度下的性能。 Adding suitable amounts of processing oil may reduce blend viscosity and flexibility, while improving the properties of the blend at temperatures near and below 0 ℃ temperature. 据信这些潜在的好处源自所述共混物玻璃化转变温度(Tg)的降低。 According to these potential benefits letter from the blend glass transition temperature (Tg) is reduced. 向共混物中加入加工油也可以改进可加工性,并提供更好的弹性与拉伸强度的平衡。 Blend was added to the processing oil can also improve processability and provide a better balance of elastic and tensile strength. 所述加工油在橡胶应用中通常被称为增量油。 The processing oil in rubber applications commonly referred extender oil. 加工油包括具有(a)痕量杂原子如氧或(b)至少一个杂原子的烃,例如邻苯二甲酸二辛酯、醚及聚醚。 Processing oils include those having (a) trace amounts of hetero atoms such as oxygen or (b) at least one hetero atom of a hydrocarbon, such as dioctyl phthalate, ethers and polyethers. 加工油的沸点使得其在200℃基本上是不挥发的。 Process oil having a boiling point such that it is substantially at 200 ℃ non-volatile. 这些加工油通常可以以净的固体、液体的形式,或以这些材料吸附在惰性载体(例如粘土、硅石)上以形成自由流动粉末的物理吸收混合物的形式获得。 These processing oils may generally be net form of solid, liquid, or any of these materials adsorbed on an inert support (e.g. clays, silica) to form a physical absorbent in the form of a free flowing powder mixture is obtained. 加工油通常包括很多化合物的混合物,所述化合物可以由线性的、无环但支化的、环状的及芳族的含碳结构组成。 Process oils usually include a mixture of many compounds, the compound may be formed of linear, acyclic but branched, cyclic and aromatic carbonaceous structures family composition. 另一类加工油是分子量(Mn)低于10,000的某些有机酯及烷基醚酯。 Another class of processing oil having a molecular weight (Mn) is less than certain organic esters and alkyl ether esters 10,000. 加工油的组合也可以用于本发明的实践中。 Combination of processing oil can also be used in the practice of the present invention. 所述加工油应该与呈熔体的聚合物共混组合物相容或混溶,并且在室温下可以基本上混溶在所述基于丙烯的弹性体中。 The process oil should be compatible or miscible with the polymer showed a melt blend composition, and at room temperature can be substantially miscible in the propylene-based elastomer in. 加工油可以用本领域中已知的任何常规方法加入共混组合物中,包括在回收聚合物之前添加全部或部分的加工油,和添加全部或部分加工油至聚合物中作为用于基于丙烯的弹性体相互掺混的配混操作的一部分。 Processing oil may be any conventional method known in the art by the addition of the blend composition, comprising, prior to recovering the polymer add all or part of process oil, and add all or part of process oil to be used as the propylene-based polymer elastomers blended with each other compounding part of the operation. 配混步骤可以在间歇混合机中进行,例如在开炼机中或在密闭式混合机如班伯里密炼机中进行。 Compounding step may be carried out in a batch mixer, e.g., carried out in an open roll mill or in a mixer such as a Banbury mixer. 配混操作也可以在连续工艺中进行,例如在双螺杆挤出机中进行。 Compounding operation may be carried out in a continuous process, for example in a twin-screw extruder. 加入加工油以降低等规聚丙烯和乙烯-丙烯-二烯橡胶的共混物的玻璃化转变温度描述在US 5,290,886和5,397,832中,其公开内容通过引用结合在此。 Added process oil to reduce isotactic polypropylene and ethylene - propylene - diene rubber blends glass transition temperature are described in US 5,290,886 and 5,397,832, the disclosure of which is incorporated by reference herein.

[0070]这里所使用的术语“加工油”也包括某些烃树脂,其被选择为可与所述聚合物混溶。 [0070] As used herein, the term "process oil" also includes some hydrocarbon resin, which is selected to be miscible with the polymer. 如果所述树脂满足以下标准,则它们是可混溶的。 If the resin satisfies the following criteria, they are miscible. 在差示扫描量热法(DSC)试验中,聚合物组合物表现出在20℃至-50℃之间的单一的玻璃化转变温度(Tg1);相应的含有所述聚合物组合物和烃树脂的聚合物共混物也表现出单一的玻璃化转变温度(Tg2);Tg2高于Tg1至少1℃。 In Differential scanning calorimetry (DSC) test, the polymer composition exhibits between 20 ℃ to -50 ℃ single glass transition temperature (Tg1); the corresponding compositions containing the polymer and a hydrocarbon polymer blend resins also exhibit a single glass transition temperature (Tg2); Tg2 higher than Tg1 at least 1 ℃. 可在本发明中用作加工油的树脂优选具有20℃或更高的由DSC测定的玻璃化转变温度。 Can be used as a processing oil in the present invention, the resin preferably has 20 ℃ or higher as measured by DSC, the glass transition temperature.

[0071]可用于本发明实施方案中的烃树脂的软化点在上限为180℃、或150℃、或140℃,下限为80℃、或120℃、或125℃的范围内。 The softening point of the [0071] embodiments of the invention may be used in the hydrocarbon resin in the upper limit is 180 ℃, or 150 ℃, or 140 ℃, the lower limit is 80 ℃, or 120 ℃, or 125 ℃ range. 软化点(℃)是按照ASTM E-28(1996修订)测定的环球软化点。 Softening point (℃) is Ball softening point according to ASTM E-28 (1996 Revision) assay.

[0072]在一个特别的实施方案中,本发明的共混物包括烃树脂,烃树脂量的下限为1%、或5%、或10%重量,上限为30%、或25%、或20%重量,以所述共混物的总重量计。 [0072] In a particular embodiment, the blends of the present invention comprises a lower limit of a hydrocarbon resin, the hydrocarbon resin amount is 1% or 5%, or 10% by weight, the upper limit of 30%, or 25%, or 20 % by weight, based on the total weight of the blend meter.

[0073]各种类型的天然和合成树脂可单独或彼此混合地用于制备这里所描述的组合物。 [0073] Various types of natural and synthetic resins may be used alone or mixed with each other used in the preparation of the compositions described herein. 适宜的树脂包括但不限于天然松香和松香酯、氢化松香和氢化松香酯、苯并呋喃-茚树脂、石油树脂、多萜烯树脂及萜烯-酚醛树脂。 Suitable resins include, but are not limited to, natural rosins and rosin esters, hydrogenated rosins and hydrogenated rosin esters, coumarone - indene resin, petroleum resin, terpene resin and terpene - phenolic resin. 适宜的石油树脂的具体实例包括但不限于脂族烃树脂、氢化的脂族烃树脂、混合的脂族和芳族烃树脂、氢化的混合的脂族和芳族烃树脂、脂环族烃树脂、氢化的脂环族树脂、混合的脂环族和芳族烃树脂、氢化的混合的脂环族和芳族烃树脂、芳族烃树脂、取代的芳族烃树脂、氢化的芳族烃树脂。 Specific examples of suitable petroleum resins include, but are not limited to, aliphatic hydrocarbon resins, aliphatic hydrocarbon resins, hydrogenated mixed aliphatic and aromatic hydrocarbon resins, hydrogenated mixed aliphatic and aromatic hydrocarbon resins, alicyclic hydrocarbon resins , hydrogenated cycloaliphatic resins, mixed cycloaliphatic and aromatic hydrocarbon resins, hydrogenated mixed cycloaliphatic and aromatic hydrocarbon resins, aromatic hydrocarbon resins, substituted aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins . 这里所使用的氢化的树脂包括完全氢化、基本上氢化和至少部分氢化的树脂。 Hydrogenated resins used herein include fully hydrogenated, substantially hydrogenated resin and at least partially hydrogenated. 适宜的芳族树脂包括芳族改性的脂族树脂、芳族改性的脂环族树脂和氢化的芳族烃树脂,其芳族含量为1-30%、优选1-20%、更优选1-5%、甚至更优选小于1wt%。 Suitable aromatic resins include aromatic modified aliphatic resins, aromatic modified cycloaliphatic resin, and hydrogenated aromatic hydrocarbon resins, which aromatic content of 1-30%, preferably 1-20%, more preferably 1-5%, even more preferably less than 1wt%. 上述树脂的任何一种可以用不饱和酯或酸酐接枝,以便为树脂提供提高的性能。 Any of the above resins can be used an unsaturated ester or anhydride grafted to the resin to provide improved performance. 接枝树脂及其制造的实例描述在PCT申请PCT/EP02/10794、PCT/EP02/10795、PCT/EP02/10796和PCT/EP02/10686中,所述文件为了美国的目的通过引用结合在此。 Examples of graft resin and fabrication are described in PCT application PCT / EP02 / 10794, PCT / EP02 / 10795, PCT / EP02 / 10796 and PCT / EP02 / 10686, the file for the purpose of the United States are incorporated herein by reference. 为了获得另外的对所述树脂的描述,可以参考技术文献如HydrocarbonResins,Kirk-Othmer,Encyclopedia of Chemical Technology,第4版第13卷,717-743页(J.Wiley & Sons,1995)。 In order to obtain an additional description of the resin, and can refer to the technical literature as HydrocarbonResins, Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition, Vol. 13, pages 717-743 (J.Wiley & amp; Sons, 1995).

[0074]合适树脂的示例性的、非限制性的实例包括可以从ExxonMobil Chemical Company得到的EMPR 100、101、102、103、104、105、106、107、108、109、110、116、117和118树脂,以及EMFR树脂。 [0074] Non-limiting examples of exemplary suitable resins which may be obtained from ExxonMobil Chemical Company EMPR 100,101,102,103,104,105,106,107,108,109,110,116,117 and 118 resins, and EMFR resins. 前述实例仅是示例性的,绝不意味是限制的。 The foregoing examples are merely illustrative, and not meant to be limiting. 本发明的实施方案包括分子量(Mn)小于所述聚合物的分子量的树脂。 Embodiments of the present invention comprises a resin molecular weight of the polymer molecular weight (Mn) of less than. 优选地,所述树脂的分子量(Mn)在上限为1000,下限为500的范围内。 Preferably, the molecular weight (Mn) of the resin in the upper limit is 1000, the lower limit is in the range of 500.

[0075]将加工助剂,例如脂肪酸酯混合物或结合在矿物填料上的脂肪酸皂钙加入这里所描述的组合物中,可有助于所述组合物的混合和将所述组合物注射到模具中。 [0075] The processing aids, such as fatty acid ester mixture or bound to the mineral filler added to the composition of fatty acid soaps of calcium described herein, can help to the mixed composition and the composition is injected into mold. 加工助剂的其它实例是低分子量聚乙烯共聚物蜡和石蜡。 Other examples of processing aids are low molecular weight polyethylene copolymer wax and paraffin. 使用的加工助剂的量可以在0.5至5重量份/100份聚合物的范围内。 Amounts of processing aids may be used within a weight of 0.5 to 5 parts / 100 parts of polymer ranges.

[0076]向这里所描述的组合物中加入抗氧剂可以改进长期老化性。 [0076] to the composition described herein is added antioxidants may improve long-term aging. 抗氧剂的实例包括但不限于喹啉(quinolein),例如三甲基羟基喹啉(TMQ);咪唑,例如巯基甲苯甲酰基咪唑锌(ZMTI);和常规的抗氧剂,例如受阻酚、内酯及亚磷酸酯。 Examples of antioxidants include, but are not limited to quinoline (quinolein), e.g. trimethyl-hydroxy quinoline (TMQ); imidazole, e.g., mercapto zinc toluyl imidazole (ZMTI); and conventional antioxidants, such as hindered phenols, lactone and phosphite. 抗氧剂的用量可以在0.001至5重量份/100份聚合物的范围内。 The amount of the antioxidant can be within 0.001 to 5 weight parts / 100 parts of polymer ranges.

[0077]共混物的处理及用途 [0077] Blends processing and use

[0078]我们已发现,所述共混物的光学性质可以通过后共混处理来改进。 [0078] We have found that the optical properties of the blend can be improved by post-blending processing. 在很多实施方案中,加热所述共混物可以显著地改进透明度。 In many embodiments, heating the blend can be significantly improved transparency. 这种加热可以作为共混过程的一部分来进行,或者在共混过程后进行。 Such heating may be used as part of the blending process is performed, or after the blending process. 优选地,当使用热活化的交联剂时,它可以作为交联步骤的一部分进行。 Preferably, when using a heat activated crosslinking agent, it can be used as part of the crosslinking step. 例如,当结晶聚丙烯被用作共混物的结晶聚合物组分时(优选地,例如可得自ExxonMobil Chemical Company,Houston,Texas的Achieve 3854),我们发现在交联步骤期间或之后加热共混物到至少170℃可以极大地改进透明度。 For example, when the crystalline polypropylene is used as the crystalline polymer when the components of the blend (preferably, e.g., available from ExxonMobil Chemical Company, Houston, Texas the Achieve 3854), we found that in the crosslinking step, during or after heating co blend to greatly improve the transparency of at least 170 ℃. 更具体而言,我们发现,升高温度至使结晶聚合物组分基本上完全熔融的水平是有利的。 More specifically, we have discovered that by raising the temperature to the crystalline polymer component is substantially completely melted level is advantageous. 优选地,所述温度至少升高到在DSC热分析图中99%的熔化已经发生的温度。 Preferably, the temperature was raised at least to a temperature in the DSC thermograms of 99% of the melt has occurred. 本领域技术人员可以理解,较低的温度可以被用于可忽略或适度降低透明度的某些应用中。 Skilled in the art will be appreciated, lower temperatures may be used or may be ignored in some applications a modest decrease in transparency. 在某些情况下,95%或90%的熔化就足够了。 In some cases, 95% or 90% of the melt is sufficient.

[0079]尽管不希望被理论所束缚,我们相信,升高共混物的温度至大约所述结晶聚合物的熔点或高于所述结晶聚合物的熔点可以导致在基于丙烯的弹性体基质内结晶聚丙烯的晶体尺寸的显著减小,由此带来透明度的大大增加。 [0079] While not wishing to be bound by theory, we believe that the elevated temperature of the blend to about the melting point of the crystalline polymer or higher than the crystalline melting point of the polymer can result in the propylene-based elastomer matrix of significantly reduced the size of the crystalline polypropylene crystals, resulting in greatly increased transparency. 在某些应用中,该加热步骤最好在形成最终制品的过程中进行。 Process in some applications, this heating step is preferably carried out to form the final product. 在其它应用中,形成制品并然后在制品形成后进行该加热步骤可能是理想的。 In other applications, to form an article after the article is formed and then to carry out the heating step may be desirable. 我们还相信,某些添加剂,尤其是多环聚合物,例如可以得自ExxonMobil Chemical Company,Houston,Texas的EMPR 100或103,可以改进最终共混物的透明度性能。 We also believe that certain additives, especially polycyclic polymers, for example, available from ExxonMobil Chemical Company, Houston, Texas the EMPR 100 or 103, can improve the transparency properties of the final blend. 它们可以以等于结晶聚合物组分的10至500wt%、最优选结晶聚合物组分的10至50wt%的量使用。 They may be equal to 10 to 500wt% crystalline polymer component, 10 to 50wt% and most preferably an amount of the crystalline polymer component used.

[0080]定义和测试方法 [0080] Definitions and test methods

[0081]共聚单体含量:聚合物的共聚单体含量和序列分布可以通过本领域技术人员所熟知的方法,使用13C核磁共振(NMR)测定。 [0081] The comonomer content: comonomer content and sequence distribution of the polymer by the skilled artisan, a method using 13C nuclear magnetic resonance (NMR) measurement. 离散的分子量范围的共聚单体含量可以使用本领域技术人员熟知的方法测定,包括对样品进行GPC分析结合傅立叶变换红外光谱法(FTIR),如Wheeler和Willis,Applied Spectroscopy,1993,第47卷第1128-1130页中所描述的。 Comonomer content of discrete molecular weight ranges can be performed using methods well known to those skilled measured, comprising combining the sample was analyzed by GPC Fourier transform infrared spectroscopy (FTIR), as Wheeler and Willis, Applied Spectroscopy, 1993, vol. 47 1128-1130 page described.

[0082]在含有大于75wt%丙烯的丙烯-乙烯共聚物的特定情况中,共聚单体含量可以如下测定:在约150℃或更高的温度下压制薄的均匀的薄膜,并固定在Perkin Elmer PE 1760红外光谱仪上。 [0082] In the propylene containing more than 75wt% of a propylene - ethylene copolymer in specific cases, the comonomer content can be determined as follows: at a temperature of about or higher 150 ℃ pressing a thin uniform film, and fixed Perkin Elmer PE 1760 infrared spectrometer. 记录从600cm-1至4000cm-1的样品的全光谱,乙烯的单体重量百分数可以按照以下方程式计算:乙烯wt%=82.585-111.987X+30.045X2,其中X是1155cm-1的峰高与722cm-1或732cm-1中较高峰的峰高之比。 Recording the full spectrum of the sample from the 600cm-1 to 4000cm-1, and the monomer weight percent of ethylene can be calculated according to the following equation: Ethylene wt% = 82.585-111.987X + 30.045X2, wherein X is the peak height of 1155cm-1 and 722cm -1 or the peak height of the more than 732cm-1 peak.

[0083]多烯含量:聚合物中存在的多烯的量可以通过定量测量聚合后聚合物中存在的侧挂的游离烯烃的量来推断。 [0083] polyene content: the amount of polyene present in the polymer can measure the amount present in the polymer after the polymerization of the pendant free-olefins by quantitative inferred. 已经建立了几种方法,例如碘值及通过H1或13C核磁共振(NMR)测定烯烃含量。 Several methods have been established, such as iodine number and olefin content determined by H1 or 13C nuclear magnetic resonance (NMR). 在这里所描述的其中所述多烯是ENB的实施方案中,聚合物中存在的多烯的量可以使用ASTM D3900测定。 Described herein in which the polyene is ENB embodiment, the amount of polyene present in the polymer can be determined using ASTM D3900.

[0084]全同立构:术语“全同立构”在这里定义为这样的聚合物序列,其中在位于以区域规则的1,2方式插入到所述链中的相邻丙烯单元上并且不是骨架结构部分的侧挂甲基对中的50%以上位于主链中的原子以上或以下,当主链中的这种原子全部在一个平面中时。 [0084] isotactic: The term "isotactic" is defined herein as a sequence of such a polymer, wherein the rule is located in the region of 1,2 inserted into the chain and is not adjacent propylene units above skeletal structure portion side hanging methyl 50% in the main-chain atoms or more or less, when the main chain atoms of this all in one plane. 在共混物中的聚合物或单一聚合物内的聚合物序列的某些组合被描述为具有“基本上相同的立构规整度”,这里它意味着两种聚合物都是按照以上定义的全同立构的。 In certain combinations of polymer blend or polymer sequences within a single polymer is described as having "substantially the same tacticity", it means that the two polymers herein are defined in accordance with the above isotactic's.

[0085]立构规整度:术语“立构规整度”是指聚合物中源自丙烯的甲基残基的取向的立体规整性。 [0085] The tacticity: The term "tacticity" refers to a polymer derived from propylene methyl residues orientation stereoregularity. 相对于聚合物骨架具有相同取向的、来自相邻的等同地插入的丙烯单元的甲基残基对被称为“内消旋的”(m)。 With respect to the polymer backbone having the same orientation, from the adjacent equally-methyl residues inserted propylene units to be referred to as "meso" (m). 相反构型的那些甲基残基对被称为“外消旋的”(r)。 Opposite configuration to those of methyl residues is called "racemic" (r). 当三个相邻的丙烯基团具有采取相同取向的甲基时,所述三单元组的立构规整性为“mm”。 When the group of three adjacent propylene having to take the same orientation methyl, the triad of stereoregularity is "mm". 如果在一个三单体序列中的两个相邻单体具有相同的取向,且所述取向与第三单元的相对构型不同,所述三单元组的立构规整性为“mr”。 If a three-monomer sequence two adjacent monomers having the same orientation, and the different orientations of the relative configuration of the third unit, the triad of stereoregularity as "mr". 当中间的单体单元具有与任一相邻单体单元相反的构型时,所述三单元组具有“rr”立构规整性。 When the middle monomer unit having monomer units with any adjacent opposite configuration, said triads having "rr" stereoregularity. 聚合物中各类型的三单元组的分数可以确定,并且当乘以100时表示在聚合物中发现的该类型的百分数。 Polymer triad fraction of each type can be determined, and indicates the percentage of that type found in the polymer, when multiplied by 100.

[0086]这里所描述聚合物的三单元组立构规整度可以从所述聚合物的13C核磁共振(NMR)谱测定,如以下所描述的和在US 5,504,172中所描述的,其公开内容通过引用结合在此。 [0086] The triad tacticity of a polymer can be determined from the spectrum of the polymer is 13C nuclear magnetic resonance (NMR), as described below and as described in US 5,504,172, the disclosure of which is herein described by reference herein.

[0087]立构规整度指数:这里表示为“m/r”的立构规整度指数通过13C核磁共振(NMR)测定。 [0087] The tacticity index: here represented 13C nuclear magnetic resonance (NMR) was determined to be "m / r" stereoregularity index through. 立构规整度指数m/r按照HNCheng,Macromolecules,17,1950(1984)中所描述的进行计算。 The tacticity index m / r in accordance HNCheng, Macromolecules, 17,1950 (1984) as described in the calculation. 1.0的m/r比通常描述间规聚合物,2.0的m/r比通常描述无规的材料。 1.0 m / r ratio between generally described syndiotactic polymer, 2.0 m / r ratio described generally random material. 等规材料理论上可具有接近无穷大的比,并且很多副产物无规聚合物具有足够大的全同立构含量,从而导致大于50的比。 Isotactic material theoretically may have a ratio approaching infinity, and many by-product atactic polymers have sufficient isotactic content, resulting in greater than 50 ratio.

[0088]熔点及熔化热:这里所描述的聚合物的熔点(Tm)及熔化热可以通过差示扫描量热法(DSC),采用ASTM E-794-95的程序确定。 [0088] Melting point and heat of fusion: polymer melting point (Tm) as described herein and a heat of fusion by Differential scanning calorimetry (DSC), using ASTM E-794-95 procedure determined. 将在约200℃至230℃下压制的约6至10mg的聚合物片从冲压模具中取出,并在室温下退火48小时。 Will be at about 200 ℃ to 230 ℃ pressed from about 6 to 10mg of the polymer sheet is removed from the stamping die and annealed at room temperature for 48 hours. 在该时间结束时,将样品置于差示扫描量热仪(Perkin Elmer Pyris Analysis System)上,并冷却至约-50℃至-70℃。 At the end of that time, the samples were placed in a differential scanning calorimeter (Perkin Elmer Pyris Analysis System) on, and cooled to about -50 ℃ to -70 ℃. 以约20℃/min的速率加热样品达到约180℃至200℃的最终温度。 To about 20 ℃ / min heating rate of the sample to a final temperature of about 180 ℃ to 200 ℃ of. 这里所使用的术语“熔点”是通过以上所讨论的DSC测定的、主熔融峰和次熔融峰中的最高峰。 As used herein, the term "melting point" is measured by DSC measurement discussed above, the main melting peak and a secondary peak of the melting peak. 热输出记录为样品的熔融峰下的面积,其通常在约30℃至约175℃的最大峰处,并发生在约0℃至约200℃的温度之间。 Thermal output is recorded as the area under the melting peak of the sample, which is typically at about 30 ℃ to about 175 ℃ the maximum peak position, and occurs at a temperature between about 0 ℃ to about 200 ℃ of. 热输出以焦耳测量,作为熔化热的量度。 Joule heat output to measure, as a measure of the heat of fusion. 熔点记录为样品熔化范围内最大吸热的温度。 Melting point of the sample is recorded as the maximum endothermic melting temperature range.

[0089]分子量和分子量分布:这里所描述的聚合物的分子量和分子量分布可如下测量。 [0089] Molecular weight and molecular weight distribution: polymers described herein the molecular weight and molecular weight distribution can be measured as follows. 分子量分布(MWD)是在给定的聚合物样品内分子量范围的量度。 The molecular weight distribution (MWD) is a measure of a given polymer sample in the molecular weight range. 众所周知,MWD的宽度可以通过各种分子量平均值的比,例如重均分子量与数均分子量之比Mw/Mn,或Z均分子量与重均分子量之比Mz/Mw表征。 Known, MWD width by various molecular weight averages than, for example, the weight average molecular weight to number average molecular weight ratio Mw / Mn, or Z-average molecular weight and weight-average molecular weight ratio Mz / Mw characterization.

[0090]Mz、Mw和Mn可以使用还称为尺寸排阻色谱法(SEC)的凝胶渗透色谱法(GPC)测定。 [0090] Mz, Mw and Mn can be determined using size exclusion chromatography, also known as (SEC) by gel permeation chromatography (GPC). 该技术利用包括装填有多孔珠粒的柱、洗提溶剂及检测器的仪器,以分离不同大小的聚合物分子。 The technique includes the use of porous beads filled with a column elution solvent, and detector devices to separate polymer molecules of different sizes. 在典型的测量中,所使用的GPC仪器是装有在145℃下运行的ultrastyro凝胶柱的Waters色谱仪。 In a typical measurement, GPC instrument used is a Waters chromatograph equipped at 145 ℃ running ultrastyro gel columns. 使用的洗提溶剂是三氯苯。 Elution solvent used is trichlorobenzene. 所述柱子用16个具有准确已知分子量的聚苯乙烯标准样品进行校准。 The column was calibrated using 16 polystyrene standard samples with accurately known molecular weight. 从标准样品得到的聚苯乙烯保留体积与测试聚合物的保留体积之间的相互关系给出所述聚合物的分子量。 Reserved Reserved volume as the relationship between a given test the polymer molecular weight of the polymer obtained from a standard sample of polystyrene.

[0091]平均分子量M可以从以下表达式计算:M=ΣiNiMin+1ΣiNiMin]]>其中Ni是具有分子量Mi的分子的数目。 [0091] The average molecular weight M is calculated from the following expression: M = & Sigma; iNiMin + 1 & Sigma; iNiMin]]> where Ni is the number of molecules having a molecular weight Mi. 当n=0时,M是数均分子量Mn。 When n = 0,, M is the number average molecular weight Mn. 当n=1时,M是重均分子量Mw。 When when n = 1, M is the weight average molecular weight Mw. 当n=2时,M是Z均分子量Mz。 When n = 2 时, M is the Z average molecular weight Mz. 希望的MWD函数(例如Mw/Mn或Mz/Mw)是相应的M值的比值。 Desired MWD function (e.g., Mw / Mn or Mz / Mw) is the ratio of the corresponding M values. M及MWD的测量是本领域中熟知的,并更详细地描述在例如Slade,PEEd.,Polymer Molecular Weights第II部分,MarcelDekker,Inc.,NY,(1975)287-368;Rodriguez,F.,Principles ofPolymer Systems第3版,Hemisphere Pub.Corp.,NY,(1989)155-160;US 4,540,753;Verstrate等,Macromolecules,第21卷,(1988)3360;以及其中所引用的参考文件中。 Measurement of M and MWD is well known in the art, and described in more detail in e.g. Slade, PEEd, Polymer Molecular Weights Part II, MarcelDekker, Inc., NY, (1975) 287-368;.. Rodriguez, F, Principles ofPolymer Systems 3rd Edition, Hemisphere Pub.Corp, NY, (1989) 155-160;. US 4,540,753; Verstrate etc., Macromolecules, vol. 21 (1988) 3360; and references cited therein.

[0092]拉伸永久变形:拉伸永久变形可以按照一般的ASTM D790程序,通过单轴向地使样品变形至不同的伸长率来测量。 [0092] tensile set: tensile set ASTM D790 can follow the usual procedures, by uniaxial deformation of the sample to a different Gravitropism elongation measured.

[0093]应力松弛:应力松弛可以使用以下程序测量:将样品固定在Instron 4465试验机上,并伸长至200%的伸长率。 [0093] Stress relaxation: Stress relaxation may be measured using the following procedure: The sample was fixed on a Instron 4465 testing machine and elongated to 200% elongation. 在此伸长率下的负荷测定为L1。 Load measured at this elongation for L1. 将样品保持在该伸长下30秒钟,并在该30秒钟结束时测量新的负荷,为L130。 The sample was held at that elongation for 30 seconds, and measure the new load at the end of 30 seconds, for L130. 薄膜的松弛率(R1)测定为100(L1-L130)/L1,并以百分数表示。 Film at a relaxation rate (R1) was determined to be 100 (L1-L130) / L1, and expressed as a percentage. 使样品回复到0%的初始伸长率。 The samples were returned to 0% of the initial elongation. 然后将样品伸长至200%的伸长率。 The sample was then elongated to 200% elongation. 在此伸长率下的负荷测定为L2。 Load measured at this elongation for L2. 将样品保持在该伸长下30秒钟,并在该30秒钟结束时测量新的负荷,为L230。 The sample was held at that elongation for 30 seconds, and measure the new load at the end of 30 seconds, for L230. 薄膜的松弛率(R2)测定为100(L2-L230)/L2,并以百分数表示。 Film at a relaxation rate (R2) was determined to be 100 (L2-L230) / L2, and expressed as a percentage. 使样品回复到0%的初始伸长率。 The samples were returned to 0% of the initial elongation. 在第二循环中样品上负荷为0时的伸长率称为永久变形%。 In the second cycle the sample load of elongation of 0% is referred to permanent deformation. 样品中的滞后作用指定为100(L1-L2)/L1,并以百分数表示。 Samples designated as hysteresis 100 (L1-L2) / L1, and expressed as a percentage.

[0094]应力应变测量:这里所描述的硫化的混合物的应力应变伸长性能可以按照下面描述的ASTM D790方法测量。 [0094] Stress Strain Measurement: a mixture of sulfide stress described herein strain elongation properties can be measured according to ASTM D790 method described below. 将哑铃型样品制成模制成6英寸6英寸尺寸的硫化片(pad),并用冲模取出。 The dumbbell-shaped sample made of molded 6 inches 6-inch form vulcanized sheet (pad), and remove with a die. 样品的应力应变评价在Instron Corporation,Canton,MA制造的Instron4465型试验机上对共混物以20英寸/分钟进行。 Stress strain evaluation of the samples in the Instron Corporation, Canton, MA-type testing machine manufactured Instron4465 blends at 20 inches / min. 数位式数据收集在通过由Instron Corporation得到的Series IX Material Testing System收集的文件中,并用得自WA Redmond的微软公司的Excel(一种电子数据表程序)进行分析。 Digital data collection by the Instron Corporation in the resulting Series IX Material Testing System files collected and used from WA Redmond's Microsoft Excel (an electronic spreadsheet program) for analysis.

[0095]PHR:这里所使用的术语“phr”是指份数/百份橡胶或份数/百份弹性体聚合物。 [0095] PHR: As used herein, the term "phr" refers to parts / hundred parts of rubber or parts / hundred parts of elastomeric polymer.

[0096]回流二甲苯中的萃取:在回流二甲苯中的溶解度是在含有硫化的基于丙烯的弹性体及硫化的基于乙烯的聚合物(如果存在)的组合物中,不可溶解的和不可萃取的基于丙烯的弹性体及任选的基于乙烯的聚合物的量的量度。 [0096] was refluxed in xylene extraction: solubility in xylene at reflux is based vulcanization containing ethylene-based polymer (if present) in the composition, insoluble and non-extractable propylene elastomers and vulcanizable The propylene-based elastomer, and optionally the amount of ethylene-based polymer of the measure. 测定二甲苯中的溶解度的方法如下:称量具有薄的截面即小于0.5英寸和重约2g的样品,重量记录为W1。 Method for determining the solubility in xylene as follows: weighing the sample with a thin cross section that is less than 0.5 inches and weighing about 2g, and the weight recorded as W1. 使样品在萃取装置中暴露于50ml回流的二甲苯中。 Exposing the sample to 50ml refluxing xylene in the extraction apparatus. 通过回流的溶剂使样品的温度维持在140℃或接近140℃。 Refluxing the solvent through the sample temperature is maintained at 140 ℃ or near 140 ℃. 萃取24小时后,倾析掉溶剂并加入50ml新的溶剂,并在相同条件下再进行24小时萃取。 Extraction After 24 hours, the solvent was decanted off and added to 50ml of fresh solvent, and under the same conditions for 24 hours and then extracted. 在该段时间结束后,取出样品并在真空烘箱中在100℃下干燥24小时。 At the end of that period, a sample was taken in a vacuum oven at 100 ℃ dried for 24 hours. 然后冷却样品并称量最终的重量,记录为W2。 The sample was then cooled and weighed a final weight is recorded as W2. 在回流二甲苯中不溶的聚合物的分数通过下式确定:通过萃取测定的交联物%=100[W2(1-FFi)]/[W1(1-Fs-Fp-FFi)],其中Fs是组合物中存在的结晶聚合物组分的重量分数,Fp是组合物中存在的在回流二甲苯中可萃取的增塑剂、加工油及其它低分子量材料的重量分数,FFi是组合物中存在的在回流二甲苯中通常不可萃取的填料和其它无机材料的重量分数。 In refluxing xylene insoluble fraction of the polymer is determined by the following equation: Determination by extraction crosslinked% = 100 [W2 (1-FFi)] / [W1 (1-Fs-Fp-FFi)], wherein Fs is present in the composition of the crystalline polymer component weight fraction, Fp is a plasticizer in refluxing xylene extractables present in the composition, processing oil, and other low molecular weight material weight fraction, FFi is a composition in refluxing xylene is not normally present in the extraction of the filler and other inorganic materials weight fraction.

[0097]口型C撕裂强度:口型C撕裂性能按照ASTM D624的00版程序以磅力/英寸报告。 [0097] Die C tear strength: Die C tear resistance in accordance with ASTM D624 version 00 program to lbf / in the report. 这里的数据是峰值力,并且三个样品的平均值报告为平均数据。 The data here is the peak force, and the average value reported is the average of three samples of data. 原始数据可以乘以0.175,以将单位从磅力/英寸转换成千牛顿/米。 The original data can be multiplied by 0.175 to convert thousands of units of N / m from lbf / inch.

[0098]裤形撕裂:裤形撕裂性能按照ASTM D624的00版程序以磅力/英寸报告。 [0098] Trouser Tear: Trouser tear resistance in accordance with ASTM D624 version 00 program to lbf / in the report. 这里的数据是峰值力,并且三个样品的平均值报告为平均数据。 The data here is the peak force, and the average value reported is the average of three samples of data. 原始数据可以乘以0.175,以将单位从磅力/英寸转换成千牛顿/米。 The original data can be multiplied by 0.175 to convert thousands of units of N / m from lbf / inch.

[0099]门尼粘度:这里所使用的门尼粘度按照ASTM D1646测量,为ML(1+4)@125℃。 [0099] Mooney viscosity: As used herein, Mooney viscosity measured in accordance with ASTM D1646, is ML (1 + 4) @ 125 ℃.

[00100]熔体流动速率和熔融指数:聚合物的熔体流动速率(MFR)和熔融指数按照ASTM D1238,使用2.16kg负荷的改进1确定。 [00100] The melt flow rate and melt index: Melt flow rate of the polymer (MFR) and the melt index, using a load of 2.16kg of improvement is determined in accordance with ASTM D1238. 在所述方法的该版本中,一部分在试验期间被挤出的样品被收集并称重。 In this version of the method, a portion of the sample extruded during the test was collected and weighed. 样品分析在230℃下进行,采用1分钟的样品预热,以提供测试期间稳定的温度。 Samples were analyzed at 230 ℃, a 1-minute sample was preheated, in order to provide a stable temperature during the test. 表示为每分钟挤出的样品的dg的该数据被称为MFR。 Is expressed as a sample extruded dg per minute the data is referred to MFR. 在备选的方法中,所述测试以相同的方式进行,除了温度为190℃。 In an alternative method, the test in the same manner, except that the temperature was 190 ℃. 该数据被称为MI@190℃。 This data is referred MI @ 190 ℃. 这里所使用的MFR@230℃是指包含基于丙烯的弹性体、任选的结晶聚合物组分及除硫化剂以外的任选添加剂的组合物交联之前的MFR。 Used herein means a MFR @ 230 ℃ comprising propylene based elastomers, crosslinked composition of the crystalline polymer component and, optionally, other than a vulcanizing agent before the optional additives MFR.

[00101]肖氏A硬度和肖氏D硬度:聚合物的肖氏A硬度和肖氏D硬度按照ASTM D2240确定。 [00101] Shore A hardness and Shore D hardness: Shore A hardness of the polymer and a Shore D hardness is determined in accordance with ASTM D2240. 在所述方法的该版本中,在室温下测试一部分样品。 In this version of the method, the test portion of the sample at room temperature. 在样品中产生压痕15秒钟后记录数据。 Indentation in the sample after 15 seconds of recorded data. 这里所使用的肖氏A硬度是交联组合物的肖氏A硬度。 Shore A hardness used herein is a crosslinked composition of a Shore A hardness.

[00102]全同立构指数:全同立构指数按照EP 0374695A2中描述的方法进行计算。 [00102] Isotactic index: isotactic index is calculated according to the method described in EP 0374695A2. 记录所述材料的薄膜的IR光谱,并确定在997cm-1和973cm-1的吸光度。 IR spectra were recorded of the material of the film, and determining the absorbance at 997cm-1 and 973cm-1's. 将997cm-1的吸光度与973cm-1的吸光度之商乘以100,得到全同立构指数。 The absorbance at 997cm-1 and 973cm-1 absorbance of the quotient multiplied by 100 to obtain isotactic index. 在确定这两个位置的吸光度时,0吸光度的位置是当在样品光束(beam)中没有分析样品存在时的吸光度。 Absorbance was determined at these two positions, the position is 0 when the absorbance did not exist when the absorbance of the sample in the analysis sample beam (beam) in.

[00103]粘度比:在辐射前和辐射后的样品上进行流变试验。 [00103] The viscosity ratio: rheological tests conducted on the samples before and after irradiation of radiation. 试验在Rheomterics ARES流变仪上使用25mm直径的平行板几何形状的板进行。 Test using 25mm diameter parallel plate geometry plate on Rheomterics ARES rheometer. 在190℃和20%的应变下从0.1至100rad/s进行小振幅振荡剪切测量。 At 190 ℃ and 20% strain were measured from small amplitude oscillatory shear 0.1 to 100rad / s. 在辐射后在0.1rad/s下的样品粘度与辐射之前的样品粘度之比取为所述粘度比。 After the irradiation the sample viscosity than sample viscosity in 0.1rad / s under the radiation prior to the viscosity ratio is taken.

[00104]雾度:雾度在约千分之50至千分之90英寸厚的所述混合物的压模薄片上进行测量。 [00104] Haze: Haze over the approximately thousandths 50-1000 per 90 inches thick mixture of die sheet were measured. 雾度以百分数表示,并按照ASTMD1003-00的方法,用CIE Illuminant C光源在Hazegard Plus雾度仪上测量。 The haze in percent, and in accordance with ASTMD1003-00 method, measured using CIE Illuminant C source on Hazegard Plus haze meter.

[00105]厚度:厚度用手持式千分尺测量,并表示为密耳或千分之英寸。 [00105] Thickness: Thickness with handheld micrometer measurements and expressed as mils or thousandths of an inch.

[00106]RPA测量:硫化特性(扭矩及损耗因数)使用得自OhioAkron的Alpha Technologies的RPA 2000(橡胶加工分析仪)进行测量。 [00106] RPA measurements: curing characteristics (torque and dissipation factor) obtained from the use of Alpha Technologies OhioAkron the RPA 2000 (Rubber Process Analyzer) measurement. 称量约5.5g的混合物并置于两块薄的Mylar膜之间,并置于RPA模板之间。 Said mixture is about 5.5g and placed between two thin Mylar film and placed between RPA template. 测量在步进为10℃的数个恒定的温度下作为时间函数进行。 Measured at step is 10 ℃ several constant temperature as a function of time. 温度范围从140至210℃,取决于使用的硫化包(cure package)。 Temperature range from 140C 至 210 ℃, depending on the package used vulcanization (cure package). 应变设定为13.95%,频率为1Hz。 Strain is set to 13.95%, a frequency of 1Hz. 样品首先在选择的温度下调理1分钟,数据收集持续1小时。 Sample was first condition for one minute at a selected temperature, the data collection for 1 hour. 测量结果的输出包括作为时间函数的所述混合物的扭矩(S′)、模量及损耗因数(tanδ),数据然后被存储以供进一步处理和分析。 The output includes the measurement result of the mixture as a function of time of the torque (S '), modulus and loss factor (tanδ), the data is then stored for further processing and analysis.

实施例[00107]Sunpar 150为可以从Sunoco Inc,Philadelphia,PA得到的加工油。 Example [00107] Sunpar 150 that can be obtained from Sunoco Inc, Philadelphia, PA processing oils.

[00108]Translink 37为得自Engelhard Corporation,Iselin,NJ的表面处理的高岭土。 [00108] Translink 37 is available from Engelhard Corporation, Iselin, NJ surface treatment of kaolin.

[00109]EMPR 103和EMPR 100是可商购自TX Houston的ExxonMobil Chemical Co.的烃树脂。 [00109] EMPR 103 and EMPR 100 are commercially available from ExxonMobil Chemical Co. TX Houston of hydrocarbon resin.

[00110]过氧化二枯基(DiCup R)及氰脲酸三烯丙基酯(TAC)可商购自WI Milwaukee的Aldrich Chemical Co.。 [00110] dicumyl peroxide (DiCup R) and triallyl cyanurate (TAC) commercially available from WI Milwaukee the Aldrich Chemical Co ..

[00111]ESC PP 4292(3MFR)、ESC Achieve 3854(34MFR)、ESCPP 3155(35MFR)、ESC 100MFR(100MFR)、ESC PP 3505(400MFR)及PP Achieve 3936(100MFR)是具有给定MFR的等规聚丙烯,可得自TX Houston的ExxonMobil Chemical Co. [00111] ESC PP 4292 (3MFR), ESC Achieve 3854 (34MFR), ESCPP 3155 (35MFR), ESC 100MFR (100MFR), ESC PP 3505 (400MFR) and PP Achieve 3936 (100MFR) is a given MFR isotactic polypropylene, available from TX Houston of ExxonMobil Chemical Co.

[00112]V2504、V3666和V404是可商购自TX Houston的ExxonMobil Chemical Co.的乙烯-丙烯共聚物。 [00112] V2504, V3666 and V404 are commercially available from ExxonMobil Chemical Co. TX Houston of ethylene - propylene copolymers.

[00113]Irganox 1076是可得自Novartis Corporation的抗氧剂。 [00113] Irganox 1076 is available from Novartis Corporation antioxidant.

[00114]HVA-2是可从DE Wilmington的EIDuPont deNemours获得的硫化助剂。 [00114] HVA-2 is a vulcanization aid available from DE Wilmington of EIDuPont deNemours.

[00115]SHF 101是可从TX Houston的ExxonMobil Chemical Co.得到的合成油。 [00115] SHF 101 is available from the ExxonMobil Chemical Co. TX Houston synthetic oils.

[00116]以下实施例中的基于丙烯的弹性体可以按照以下方法制备:在装配有双倾斜(pitch)桨叶涡轮搅拌器的27升连续流搅拌釜反应器中,每小时加入92kg干燥己烷、34kg丙烯、1.8kg乙烯、1.1kg的5-乙叉-2-降冰片烯(ENB)。 [00116] The following examples of the propylene elastomer can be prepared based on the following: In the assembly a double tilt (pitch) turbine agitator blades 27 l continuous flow stirred tank reactor, 92kg per hour of dry hexane was added , 34kg propylene, 1.8kg ethylene, 1.1kg 5-ethylidene-2-norbornene (ENB). 反应器在反应过程中以650rpm的速度搅动,并在1600psi压力(表压)下保持液体是满的,以使聚合区中的所有区域在整个聚合过程中都具有相同的组成。 Reactor during the reaction at a rate of 650rpm stirring, and the liquid is maintained at 1600psi full pressure (gauge pressure), so that all regions in the polymerization zone in the entire polymerization process have the same composition. 将1.5610-3g二甲基二甲基甲硅烷基茚基合铪及2.4210-3g二甲基苯铵四(七氟萘基)硼酸盐的在甲苯中的催化剂溶液以6.35ml/min的速度加入以引发聚合。 The catalyst solution 1.5610-3g dimethyl dimethylsilyl indenyl hafnium and 2.4210-3g dimethylanilinium tetrakis (heptafluoronaphthyl) borate in toluene to 6.35ml / min speed was added to initiate polymerization. 在聚合过程中加入另外的三正辛基铝(TNOA)溶液以除去外来的水分。 An additional tri-n-octyl aluminum (TNOA) solution in the polymerization process to remove extraneous moisture. 聚合在约59℃下进行,并且在聚合期间通过加入温度为-3℃至2℃的预冷的己烷来维持所述温度。 Polymerization carried out at about 59 ℃, and to maintain the temperature during the polymerization by the addition of a temperature of -3 ℃ to 2 ℃ precooled hexane. 所述聚合通常导致形成9.5kg的聚合物/小时。 The polymerization is generally result in the formation of polymer 9.5kg / hr. 聚合物通过两段式溶剂脱除来回收,首先使用如WO 0234795A1中所述的低临界溶液方法除去70%的溶剂,然后在LIST脱挥发分挤出机中除掉剩余溶剂。 Removal of the solvent by a two-stage polymer was recovered, 70% was removed first using a solvent such as a lower critical solution method described in WO 0234795A1, then LIST devolatilizing extruder remove residual solvent. 聚合物以主轴为约1/8至1/4英寸的颗粒形式回收。 Polymer spindle is about 1/8 to 1/4 inch particles recovered in the form.

[00117]实施例1[00118]按照以上方法制备含有13.5wt%乙烯、2.1wt%5-乙叉-2-降冰片烯(ENB),并且MFR@230℃为25的基于丙烯的弹性体,然后该基于丙烯的弹性体与表1中所示的组分在Brabender密炼机中共混,所述Brabender密炼机在约50rpm和约100℃的温度下操作。 [00117] Example 1 [00118] The above methods containing 13.5wt% ethylene, 2.1wt% 5- ethylidene-2-norbornene (ENB), and MFR @ 230 ℃ propylene-based elastomer 25, Then the elastomer component shown in Table 1 with the propylene-based blended in a Brabender mixer, the Brabender mixer at a temperature of about 50rpm about 100 ℃ operation. 然后将所述混合物卷成平滑的片材。 The mixture is then rolled into a smooth sheet. 所述掺混的材料随后以厚度为0.125″的8″8″的模压片的形式在150℃下硫化100分钟。从所述硫化的片取下适宜几何形状的样品并进行分析。分析结果在下表1中给出。 The blended material is then in a thickness of 0.125 "8" form 8 "of the molded sheet was vulcanized at 150 ℃ 100 minutes. Remove the sample from a suitable geometry of the vulcanized sheet and analyzed. The results in Table 1 below.

表1 Table 1

[00119]实施例2[00120]按照以上方法制备具有表2中所给出的性能的各种基于丙烯的弹性体。 [00119] Example 2 [00120] was prepared according to the above method having various properties given in Table 2. The propylene-based elastomers.

表2 Table 2

*未测量**在对于熔点给出两个数值时,第一个数值表示主要的或最大的熔融峰,第二个数值表示次熔融峰。 * Not measured ** When the melting point is given for the two values, the first value represents major or maximum melting peak, the second value indicates the second melting peak.

[00121]实施例3[00122]将得自实施例2的某些基于丙烯的弹性体按照表3-1和3-2中所给的配方使用以下程序进行硫化。 [00121] Example 3 [00122] Example 2 obtained from certain propylene-based elastomer is vulcanized in accordance with Tables 3-1 and 3-2 given in the recipe using the following procedure. 在内容积为约280ml的Brabender密炼机中,将聚合物首先与增塑剂及填料在约135至145℃的温度下混合10分钟。 Internal volume of about 280ml in a Brabender mixer, the polymer is first mixed with a plasticizer and a filler at a temperature of about 135 至 145 ℃ for 10 minutes. 取出40g聚合物与增塑剂的混合物,用于测定MFR。 Remove 40g mixture of the polymer and plasticizer, for the determination of MFR. 将其余混合物冷却,并与硫化剂在不超过105℃的温度下混合10分钟。 The remaining mixture was cooled, and mixed with vulcanizing agent at a temperature not exceeding 105 ℃ temperature for 10 minutes. 然后所述材料以厚度为0.125″的8″8″压模片的形式在20吨压力下在150℃硫化100分钟。从所述硫化的片上取下适宜几何形状的样品并进行分析。分析结果在下表3-1和3-2中给出。 Then the material having a thickness of 0.125 "of 8" 8 "in the form of a pressed sheet at 20 tons of pressure. Remove the sample from the appropriate geometry of the vulcanized sheet cured at 150 ℃ 100 minutes and analyzed. Analysis results are shown in Table 3-1 and 3-2 below.

表3-1 Table 3-1

表3-2 Table 3-2

[00123]实施例4[00124]将得自实施例2的某些基于丙烯的弹性体按照表4中所给出的配方与等规聚丙烯共混。 [00123] Example 4 [00124] Certain embodiments obtained from elastomeric propylene-based formulation according to Table 4 given isotactic polypropylene blended with 2. 所述聚合物组分在L/D为30∶1的双螺杆挤出机中在200℃的温度下沿机筒长度共混。 The polymer component in L / D of 30:1 twin screw extruder barrel along the length of the blend at a temperature of 200 ℃. 除聚合物组分外,实施例4的组合物各自含有500ppm的抗氧剂Irganox 1076。 In addition to the polymer components, the composition of Example 4 embodiment each containing 500ppm of an antioxidant Irganox 1076.

表4 Table 4

[00125]实施例5[00126]将得自实施例4的某些样品按照表5-1和5-2中所给的配方使用以下方法进行硫化。 [00125] Example 5 [00126] The sample obtained from Example 4 in accordance with certain Tables 5-1 and 5-2 given in the following methods Formulation Example vulcanization. 在内容积为约280ml的Brabender密炼机中,将聚合物材料首先与增塑剂及填料在约135至145℃的温度下混合10分钟。 Internal volume of about 280ml in a Brabender mixer, the polymer material is first mixed with a plasticizer and a filler at a temperature of about 135 至 145 ℃ for 10 minutes. 取出40g聚合物与增塑剂的混合物,用于测定MFR。 Remove 40g mixture of the polymer and plasticizer, for the determination of MFR. 将其余混合物冷却,并与硫化剂在不超过105℃的温度下混合10分钟。 The remaining mixture was cooled, and mixed with vulcanizing agent at a temperature not exceeding 105 ℃ temperature for 10 minutes. 然后所述材料以厚度为0.125″的8″8″压模片的形式在20吨压力下在150℃硫化100分钟。从所述硫化的片上取下适宜几何形状的样品并进行分析。分析结果在下表5-3和5-4中给出。 Then the material having a thickness of 0.125 "of 8" 8 "in the form of a pressed sheet at 20 tons of pressure. Remove the sample from the appropriate geometry of the vulcanized sheet cured at 150 ℃ 100 minutes and analyzed. Analysis The results below are given in Table 5-3 and 5-4.

表5-1 Table 5-1

表5-2 Table 5-2

表5-3 Table 5-3

表5-4 Table 5-4

[00127]包括优先权文件的所有专利、测试方法及其它在此所引的文件全部通过引用而结合,至这种公开内容与本发明不矛盾的程度和为了其中这种结合被允许的所有权限。 [00127] All patents, test methods including priority documents and other documents cited herein all incorporated by reference to this disclosure is not inconsistent with the present invention, and all rights to the degree in which such incorporation is permitted in .

[00128]尽管本发明的示例性实施方案已被具体地描述,应该指出,各种其它改变对本领域技术人员来说是明显的,并且可以被本领域技术人员在不背离本发明精神和范围的情况下容易地做出。 [00128] Although the exemplary embodiments of the invention have been specifically described, it should be noted that various other changes to the skilled artisan is apparent, and may be skilled in the art without departing from the spirit and scope of the invention readily made case. 因此,所附权利要求书的范围不打算局限于实施例及这里所做的说明,相反,所述权利要求书应被理解为包括了本发明中存在的可取得专利权新颖性的全部特征,包括那些被本发明所属领域技术人员视为其等同物的全部特征。 Accordingly, the scope of the appended claims are not intended to Examples and limited to the embodiment described herein made, on the contrary, the book of the claims should be understood to include the present invention may be present in all the patentable novelty characteristics, including all features that are considered the present invention to those skilled in the equivalents thereof.

[00129]当在此列出数字的低限和数字的高限时,从任何低限至任何高限的范围都被想到。 [00129] When the numbers listed in this low limit and high limit numbers from any lower limit to any upper limit of the range have been thought of.

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Classifications
International ClassificationC08F210/18, C08F8/00, C08L23/16, C08F210/06, C08F4/659
Cooperative ClassificationY10T442/678, A43B13/04, C08F4/65908, C08F210/18, C08F210/06
European ClassificationC08F210/18, C08F210/06
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