CN102971373B - 用于管道系统和片材的聚烯烃组合物 - Google Patents
用于管道系统和片材的聚烯烃组合物 Download PDFInfo
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- CN102971373B CN102971373B CN201180030463.7A CN201180030463A CN102971373B CN 102971373 B CN102971373 B CN 102971373B CN 201180030463 A CN201180030463 A CN 201180030463A CN 102971373 B CN102971373 B CN 102971373B
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- polyolefin compositions
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Classifications
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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Abstract
聚烯烃组合物，其包含（按重量计）：A)7%至19%的丙烯/1-己烯共聚物，其中所述共聚物含有少于1%的衍生自己烯-1的重复单元；B)81%至93%的多相聚丙烯组合物，其包含：B1)86%至95%的丙烯均聚物，所述丙烯聚合物以超过85%的量在室温下不溶于二甲苯，具有3至10的多分散性指数；和0.5至10dg/min的熔体指数；B2)5%至14%的具有50%至65%的乙烯衍生单元含量的乙烯/丙烯共聚物；所述聚合组合物具有0.05至10dg/min的熔体指数。
Description
本发明涉及适合制造管道系统和片材的聚烯烃组合物。
在术语管道系统内意在包括管材、管道和配件。
术语片材包括热成型片材和要用于制备半成品的板材，如化学工业中所用的那些。
片材或板材主要用于制造制品如家居用品和食品的容器，例如果汁容器、酸奶杯、人造黄油桶等。所述片材或板材也可用于制造汽车部件。
本发明的管道系统特别适合在室外和室内传输在高压和/或重力排水系统下的流体，且它们在安装过程中的装卸非常容易。
在耐压管用途中，在建筑物内外的热水和冷水分配系统中和/或在需要高耐化学性时，聚丙烯是受欢迎的。
由于聚丙烯材料的机械性质的平衡不足，特别是耐液压性和耐冲击性之间的平衡不足（尤其是在低温下），迄今通常不使用以聚丙烯塑料代替当前使用的塑料的管材。
专利申请WO2006/002778公开了单或多层管道系统，其中至少一层包含丙烯和1-己烯和任选地，衍生自选自乙烯和C4-C10α-烯烃的烯烃的另一重复单元的半结晶共聚物，其中所述共聚物含有0.2至5重量%，优选0.5至5重量%的衍生自己烯-1的重复单元。根据上述发明的管道系统表现出极高耐液压性，这提供具有高耐用性的管材。与所述系统相关的缺点是如IZOD试验的低值所示的低耐冲击性，特别是在低温下。这一方面是重要的，因为这一性质与管材在安装过程中的可施工性和装卸相关。在温度低于10℃时（这在大多数国家的寒季非常常见），基于具有低耐冲击值的材料的管材变得不可施工且它们的装卸困难。
专利申请WO2005/014713公开了适合非耐压管道用途，如用于室内用途和优选室外用途的废水管道的多相聚丙烯组合物。所述组合物提供具有良好冲击性质的管道系统。但是，我们已经发现，由所述组合物制成的管道系统具有极低的耐液压值，因此所述组合物无法用于在高压下长时间传输流体的管道系统。
WO2008/077773公开了聚合组合物，其包含（按重量计）：
1)10-60%的丙烯/1-己烯共聚物，其中所述共聚物包含0.2至10%，优选0.5至8%，更优选1至6%的衍生自己烯-1的重复单元；和
2)10-85%的丙烯聚合物，其选自丙烯均聚物和丙烯与0.1-10%的选自乙烯、C4-C10α-烯烃（不包括1-己烯）及其混合物的α-烯烃的聚合物，所述丙烯聚合物以超过85%的量在室温下不溶于二甲苯，并具有3至20的多分散性指数；和
3)5-30%的乙烯与C3-C10α-烯烃和任选二烯的共聚物，其具有15至60%的乙烯含量和至少1g/ml的特性粘度值。
申请人发现，通过选择要用的聚合物的特定特征，可以改进抗爆裂性，提高刚度和同时保持含有1-己烯的聚烯烃管道系统的良好耐冲击值。
因此，本发明的一个目标是聚烯烃组合物，其包含（按重量计）：
A)7%至19%；优选8%至15%，更优选9%至13%的丙烯/1-己烯共聚物，其中所述共聚物含有少于1.0%的衍生自己烯-1，优选0.3至0.9%，更优选0.3至0.7%的重复单元；和
B)81%至93%，优选92%至85%，更优选91%至87%的多相聚丙烯组合物，其包含：
B1)86%至95%，优选87%至92%，再更优选89%至91%的丙烯均聚物，所述丙烯聚合物以超过85.0%的量在室温下不溶于二甲苯，具有3至10；优选4至8的多分散性指数和0.5至10dg/min，优选0.6至5dg/min，再更优选0.6至2dg/min的根据ISO方法1133的熔体指数；
B2)5%至14%，优选8%至13%，再更优选9%至11%的具有50%至65.0%，优选50.0%至60.0%，更优选51%至55.0%的乙烯衍生单元含量的乙烯/丙烯共聚物；
所述聚合组合物具有0.05至10dg/min，优选0.1至3dg/min，更优选0.2至1dg/min的根据ISO方法1133的熔体指数。
所述聚合组合物和由其制成的制品具有机械性质的最佳平衡。特别在用于管道系统时，本发明的聚合组合物具有高的耐液压值，尤其在低温下保持高的冲击强度值。这归因于各种组分之间的特定平衡，特别可以使用低量的具有低1-己烯含量的组分A)并同时通过细调“软”组分(组分B2)改进整个组合物的性能。
组分A)中多分散性指数(P.I.)的值可以为3至15，优选4至10，再更优选4至7。
关于多分散性指数，是指如下所述测定的分子量分布的流变测量结果。
本发明中所用的丙烯-1-己烯共聚物具有如二甲苯不溶性的高值所示的丙烯序列的全同立构类型的立构规整性，二甲苯可溶性优选低于4重量%，更优选低于2重量%，再更优选低于1.5重量%。
丙烯-1-己烯共聚物组分A)优选具有至少一种下列特征：
-等于或高于135℃，优选等于或高于140℃，如140至160℃的熔融温度；和
-占该丙烯-1-己烯共聚物总重量的低于12重量%，优选低于9重量%的在室温（即大约25℃）下在二甲苯中的溶解度。
本发明中所用的丙烯-1-己烯共聚物可通过在一个或多个聚合步骤中的聚合制备。可以在齐格勒-纳塔催化剂存在下进行这样的聚合。所述催化剂的基本组分是包含都负载在活性形式的卤化镁上的具有至少一个钛-卤素键的钛化合物和给电子体化合物的固体催化剂组分。另一基本组分（助催化剂）是有机铝化合物，如烷基铝化合物。
任选添加外给电子体。
通常用于制造本发明的丙烯-1-己烯共聚物的催化剂能够提供具有大于90%，优选大于95%的在室温下的二甲苯不溶性值的聚丙烯。
具有上述特征的催化剂是专利文献中公知的；特别有利的是美国专利No.4,399,054、欧洲专利Nos.45977和395083中描述的催化剂中所用的固体催化剂组分。
所述催化剂中所用的固体催化剂组分包含选自醚、酮、内酯、含有N、P和/或S原子的化合物和单-和二羧酸的酯的化合物作为给电子体化合物（内给电子体化合物）。特别合适的给电子体化合物是邻苯二甲酸酯，如邻苯二甲酸二异丁酯、二辛酯、二苯酯和苄基丁基酯，和琥珀酸酯。在邻苯二甲酸酯中，邻苯二甲酸二异丁酯特别优选。
特别合适的内给电子体化合物选自国际专利申请WO00/63261中公开的琥珀酸酯。
特别合适的其它给电子体是EP361493和EP728769中描述的1,3-二醚。
所述二醚的代表性实例如下：2-甲基-2-异丙基-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2-异丙基-2-环戊基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷和9,9-双(甲氧基甲基)芴。根据各种方法进行上述催化剂组分的制备。例如，使MgCl2·nROH加合物（特别是球形颗粒形式）（其中n通常为1至6，且ROH是乙醇、丁醇或异丁醇）与过量的含有给电子体化合物的TiCl4反应。反应温度通常为80至120℃。随后分离固体并在存在或不存在给电子体化合物的情况下与TiCl4再反应一次，此后将其分离并用烃等分试样洗涤直至所有氯离子消失。在该固体催化剂组分中，作为Ti表示的钛化合物通常以0.5至10重量%的量存在。保持固定在固体催化剂组分上的给电子体化合物的量通常为二卤化镁的5至20摩尔%。可用于制备该固体催化剂组分的钛化合物是钛的卤化物和卤素醇化物（halogenalcoholates）。四氯化钛是优选化合物。
用作助催化剂的烷基铝化合物包含三烷基铝，如三乙基铝、三异丁基铝、三丁基铝，和含有两个或更多个经由O或N原子相互键合的Al原子或SO4或SO3基团的线型或环状烷基铝化合物。烷基铝化合物通常以使得Al/Ti比为1至1000的量使用。
可用作外给电子体的给电子体化合物包括芳族酸酯，如苯甲酸烷基酯，特别是含有至少一个Si-OR键的硅化合物，其中R是烃基。优选的硅化合物的实例是(叔丁基)2Si(OCH3)2、(环戊基)2Si(OCH3)2、(环己基)(甲基)Si(OCH3)2和(异丙基)2Si(OCH3)2。
在聚合法之前，可以使催化剂与少量烯烃预接触（预聚），由此改进催化剂的性能和聚合物的形态。如下进行预聚：使催化剂保持悬浮在烃溶剂（例如己烷或庚烷）中并在环境温度至60℃的温度下聚合足以产生固体催化剂组分重量的0.5至3倍的量的聚合物。其也可以在液体丙烯中在上述温度条件下进行，以产生可达到每克催化剂组分1000克量的聚合物。
特别地，即使前述催化剂组分的许多其它组合能够获得本发明的丙烯-1-己烯共聚物组合物，但优选使用含有邻苯二甲酸酯作为内给体和(环戊基)2Si(OCH3)2作为外给体的催化剂制备该共聚物。
所述丙烯-1-己烯共聚物通常通过公知聚合法，如在液相（本体或淤浆）或气相中制造。根据该优选聚合法，通过在至少两个互连聚合区中进行的气相聚合法制造这样的共聚物。
在EP申请782587中阐述了根据该优选方法的方法。
详细地，所述方法包括将单体进给到在催化剂存在下的在反应条件下的所述聚合区，并从所述聚合区收集聚合物产物。在所述方法中，生长的聚合物颗粒向上流经在快速流化条件下的一个（第一）所述聚合区（提升管），离开所述提升管并进入另一（第二）聚合区（下降管），它们在重力作用下以致密化形式向下流经所述下降管，离开所述下降管并再引入提升管，由此建立提升管和下降管之间的聚合物循环。
在下降管中，达到固体的高密度值，这接近该聚合物的堆积密度。由此可沿流向获得正增压，以致无需借助特殊机械手段就可将该聚合物再引入提升管中。由此，建立“回路”循环，这通过两个聚合区之间的压力平衡和通过引入该系统中的压头损失确定。
通常，通过将包含相关单体的气体混合物进给到所述提升管，建立提升管中的快速流化条件。该气体混合物的进给优选在聚合物再引入所述提升管的位置下方进行，如果适当，借助气体分配器。气体输入提升管中的速度高于在运行条件下的传输速度，并优选为2至15m/s。
通常，将离开提升管的聚合物和气体混合物传送至固体/气体分离区。可以使用常规分离方式进行固体/气体分离。聚合物从分离区进入下降管。将离开分离区的气体混合物压缩，冷却和传输（如果适当，添加补充单体和/或分子量调节剂）至提升管。可以借助该气体混合物的再循环管路实现该传输。
可以通过使用适合控制固体流量的装置，如机械阀计量加入离开下降管的聚合物量来控制在两个聚合区之间的聚合物循环。
运行参数，如温度是烯烃聚合法中常见的那些，例如50至120℃之间。
可以在0.5至10MPa，优选1.5至6MPa的运行压力下进行这种第一阶段方法。
有利地，一种或多种惰性气体以使得惰性气体分压总和优选为气体总压力的5至80%的量保持在聚合区中。该惰性气体可以是例如氮气或丙烷。
各种催化剂组分在所述提升管的任何位置进给到提升管中。但是，它们也可以在下降管的任何位置进给。
如二甲苯不溶性的高值所示，丙烯聚合物(B1)的立构规整性是全同立构类型的。特别地，丙烯聚合物(B1)优选以超过90重量%,更优选超过95重量%的量在室温下不溶于二甲苯。
可通过在如上文对组分(A)所述的齐格勒-纳塔催化剂存在下聚合单体来获得丙烯聚合物(B1)。
乙烯共聚物(B2)可包含二烯（共轭或非共轭），如丁二烯、1,4-己二烯、1,5-己二烯和亚乙基-降冰片烯-1。二烯在存在时通常为乙烯共聚物(B2)总重量的0.5至10重量%的量。
可通过在如上文对组分(A)和(B1)所述的齐格勒-纳塔催化剂存在下聚合单体来获得所述乙烯共聚物(B2)。
本发明的聚合组合物可通过共混组分(A)、(B1)和(B2)或通过相继聚合法获得。在相继聚合法中，聚合阶段的次序不是关键的工艺特征，但优选在制备乙烯共聚物(B2)之前制备具有较高二甲苯不溶性的聚合物，如组分(A)和(B1)。
根据一个优选实施方案，可通过合并组分(A)与多相组合物(B)获得本发明的组合物。
制备多相聚烯烃组合物(B)的方法通过包含至少两个相继步骤的相继聚合进行，其中组分(B1)和(B2)在分开的相继步骤中制备，在除第一步骤外的各步骤中在前一步骤中形成的聚合物和使用的催化剂存在下操作。优选仅在第一步骤中添加催化剂，但其活性使其在所有后继步骤中仍为活性。组分(B1)优选在单聚合阶段中制备。
聚合阶段的次序不是关键的工艺特征；但优选在组分(B2)之前制备组分(B1)。
该聚合可以在液相、气相或液-气相中进行。
例如，可以使用液体丙烯作为稀释剂进行丙烯聚合阶段，和随后在气相中进行共聚阶段，除丙烯的部分脱气外没有中间阶段。
合适的反应器的实例是连续运行的搅拌反应器、回路反应器、流化床反应器或水平或垂直搅拌的粉末床反应器。当然，该反应也可以在串联的多个反应器中进行。
可以在串联连接的搅拌气相反应器级联中进行聚合，其中借助垂直搅拌器使粉末反应床保持运动。该反应床通常包含在各自的反应器中聚合的聚合物。
与聚合步骤相关的反应时间、压力和温度不重要，但温度最好为20至150℃，特别是50至100℃。压力可以为大气压或更高。
使用已知调节剂，特别是氢气进行分子量的调节。
或者，可以通过在至少两个互连聚合区中进行并如上详述的气相聚合法制造多相聚烯烃组合物(B)。
本发明的聚合组合物可进一步包含相对于100重量份所述聚合组合物0.5至60重量份的量的无机填料剂。这样的填料剂的若干实例是碳酸钙、硫酸钡、二氧化钛和滑石。滑石和碳酸钙是优选的。许多填料剂也可具有成核作用，如滑石也是成核剂。成核剂的量通常为聚合物量的0.5至5重量%。
本发明的管道系统和片材可以是单层或多层，其中这些层可具有相同或不同的厚度。片材厚度通常可以为0.25毫米至10毫米，优选0.3毫米至7毫米不等。在多层管中，所有层可以由相同聚烯烃组合物制成。或者，至少一层由上述聚烯烃组合物制成，其它层由R-CH=CH2的非晶或结晶聚合物（其中R基团是氢或C1-C6烷基）或它们的混合物或氟化聚合物，如聚偏二氟乙烯制成。所述聚合物的实例是全同立构或主要全同立构的丙烯均聚物、聚乙烯、聚烯烃共聚物或其它多相聚烯烃组合物。
以本身已知的方式，例如通过聚烯烃组合物的挤出或注射成型制造本发明的管道系统和片材。也通过共挤或其它方法制造多层管道。
可以用聚烯烃的不同类型的挤出机，例如单或双螺杆挤出机进行制品的挤出。
借助本发明的聚合组合物，可以获得具有高弯曲模量和同时高抗蠕变性的材料。这归因于组分A)的特征，如1-己烯衍生单元的量、该组分本身的多分散性和量的特别平衡，和多相组合物B)的特征，如组分B2)中所用B1和B2的量和乙烯单元的量的平衡。
给出下列实施例以例示而非限制本发明。
通过下面报道的方法测定与实施例的管道系统和片材相关的数据。试验结果显示在表1中。
-二甲苯可溶级分:如下测定
在配有制冷器和磁搅拌器的玻璃烧瓶中引入2.5克聚合物和250毫升二甲苯。温度在30分钟内升至溶剂的沸点。由此获得的清澈溶液随后在回流和搅拌下再保持30分钟。该封闭的烧瓶随后在冰水浴中保持30分钟和在25℃恒温水浴中保持30分钟。由此形成的固体在快速滤纸上过滤。将100毫升滤液倒在预先称重的铝容器中，其在加热板上在氮气流下加热，以通过蒸发除去溶剂。该容器随后在真空下保存在80℃下的炉中直至获得恒重。然后计算在室温下的二甲苯可溶聚合物的重量百分比。
-多分散性指数:使用RHEOMETRICS(USA)出售的平行板流变仪型号RMS-800在200℃的温度下测定，其以从0.1rad/sec提高至100rad/sec的振荡频率运行。由交叉模量借助公式P.I.=105/Gc推导P.I.：
其中Gc是交叉模量，其是指在该值（以Pa表示）下，G’=G”，其中G'是储能模量，G''是损耗模量。
-熔体流动速率(MFR):根据ISO方法1133(5Kg,230℃)。
-1-己烯的含量:通过IR光谱学测定。
以吸光度vs.波数(cm-1)记录该聚合物的压膜的红外光谱。在4482和3950cm-1之间的组合谱带的面积用于膜厚度的光谱标准化。对范围790-760cm-1施以偏最小二乘法（PLS）校准以测定乙烯和己烯重量%。
-乙烯的含量:通过IR光谱学测定
以吸光度vs.波数(cm-1)记录该聚合物的压膜的红外光谱。在4482和3950cm-1之间的组合谱带的面积用于膜厚度的光谱标准化。对范围790-760cm-1施以偏最小二乘法（PLS）校准以测定乙烯和己烯重量%。
-耐液压性:根据ISO方法1167-1，在95℃的温度下和在2.5MPa的周向应力下进行试验。
-弯曲弹性模量:根据ISO方法178。
-悬臂梁式抗冲击性（缺口）:根据ISO方法180/1A。
组分A
根据专利申请EP10150735.8的实施例1中公开的方法，通过改变添加的1-己烯的量以获得具有0.4重量%的1-己烯衍生单元含量的丙烯/1-己烯共聚物来制备组分(A)。该共聚物的数据报道在表1中。
表1
| 1-己烯含量,重量% | 0.4 |
| 多分散性指数 | 4.2 |
| 二甲苯可溶含量, 重量% | 1.3 |
组分B)
固体催化剂组分的制备
在0℃下向氮气吹扫的500毫升四颈圆底烧瓶中引入250毫升TiCl4。在搅拌的同时，加入10.0克微球MgCl2·1.8C2H5OH（根据USP4,399,054的实施例2中描述的方法制备，但以3000rpm而非10000rpm操作）和9.1毫摩尔2,3-(二异丙基)琥珀酸二乙酯。将温度升至100℃并保持120分钟。然后，停止搅拌，使固体产物沉降并虹吸抽出上清液。然后重复下列操作两次：加入250毫升新鲜TiCl4，使该混合物在120℃下反应60分钟，虹吸抽出上清液。该固体用无水己烷（6×100mL）在60℃下洗涤六次。
聚合
通过如上所述制成的催化剂组分、作为助催化剂的三乙基铝（TEAL）和作为外给电子体的二环戊基二甲氧基硅烷以下表中所示的重量比形成催化剂体系。
在两步聚合法中制备实施例的丙烯聚合物组合物，其中在第一聚合步骤中通过将单体和催化剂体系进给到如欧洲专利EP-A1-782587中所述的包含两个互连聚合区——提升管和下降管的气相聚合反应器中来制备均聚物A)。从所述反应器中排出聚合混合物，传送至气体-固体分离器并将聚合材料送入常规气相流化床反应器，在此制造共聚物B)。运行条件显示在表2中。
对离开第二聚合步骤的聚合物颗粒施以蒸汽处理以除去未反应的单体并干燥。所得聚合物的特征报道在表3中。
表2
| 组分B | 1 | |
| 组分B1 | ||
| TEAL/外给电子体 | wt/wt | 4 |
| TEAL/催化剂 | wt/wt | 5 |
| 温度 | ℃ | 80 |
| 压力 | barg | 27 |
| 分流滞留量（Split holdup） | ||
| 提升管 | 重量% | 40 |
| 下降管 | 重量% | 60 |
| H2/C3提升管/下降管 | mol/mol | 0.003 |
| Tm | ℃ | 163 |
| 组分B2 | ||
| 温度 | ℃ | 80 |
| 压力 | MPa | 1.7 |
| C2/C2+C3 | 0,43 | |
| H2/C2 | 0,009 |
C2=乙烯；C3=丙烯；C6=1-己烯；H2=氢气。
表3
| 组分B | ||
| 组分B1 | ||
| MFR (熔体指数) | g/10' | 1.1 |
| 多分散性 | 4.3 | |
| 二甲苯可溶物 | % | 1.8 |
| 组分B2 | ||
| 乙烯含量 | 重量% | 50-53 |
| 分流 | % | 10 |
| 组分B (总计) | ||
| 乙烯含量 | 重量% | 4.8-5.5 |
| MFR | g/10' | 0.8-1.3 |
| 二甲苯可溶物 | % | 12 |
| IV XS | dl/g | 4 |
表4报道对比例1和实施例1的配方的特征。
表4
| 实施例 | 对比例1 | 实施例1 | |
| 配方 | |||
| DSTDP | % | 0.33 | 0.33 |
| TALC | % | 1.0 | 1.0 |
| 组分B | % | - | 10 |
| 硬脂酸钙 - M | % | 0.05 | 0.05 |
| IRGAFOS 168 | % | 0.11 | 0.11 |
| IRGANOX 1010 | % | 0.2 | 0.2 |
| IRGANOX 1330 | % | 0.11 | 0.11 |
| 表征 | |||
| MFR 5Kg | g/10' | 1.3 | 1.3 |
| C2 | % | 4.7 | - |
| 黄色指数 | nr. | 2.7 | 3.3 |
| XS | % | 9.3 | 8.7 |
| 在23 ℃下的Izod 24h | kJ/m2 | 50.8 | 51.4 |
| 屈服拉伸强度24h | MPa | 32.7 | 33 |
| 屈服伸长24h | % | 7.4 | 7 |
| 致断拉伸强度24h | MPa | 29.8 | 29.5 |
| ℃ | 163.9 | 162.7 | |
| Tc | ℃ | 116.1 | 116.1 |
从表4中清楚得出，本发明的实施例1的组合物保持对比例1的基本所有特征。
耐液压性:根据ISO方法1167-1，在95℃的温度下和在2.5MPa的周向应力下测试实施例1和对比例1。此外，使用来自WO2008/077773的实施例1的材料的管材作为另一对比例2。这种聚合材料含有20%的具有2%wt的1-己烯衍生单元含量的丙烯/1-己烯共聚物和80%的多相丙烯组合物——其含有85%的丙烯均聚物和15%的含有15重量%乙烯衍生单元的丙烯/乙烯共聚物。挤出管材具有32毫米外径和2.9毫米壁厚。结果报道在表5中。
表5
| 对比例1 | 实施例1 | 对比例2 | ||
| 耐液压性 | 小时 | 497 | >8000* | 6231 |
*实施例1的试验在8000小时停止，无破裂。
在表5中显示，与单独的组分B)相比和与含有更高含量的组分A)（其含有高1-己烯衍生单元）的组合物相比，本发明的组合物表现出更优异的抗爆裂性。
Claims (6)
1.聚烯烃组合物，其包含，以%重量计：
A)7%至19%的丙烯/1-己烯共聚物，其中所述共聚物含有少于1%的衍生自1-己烯的重复单元；
B)81%至93%的多相聚丙烯组合物，其包含：
B1)87%至92%的丙烯均聚物，所述丙烯均聚物以超过85%的量在室温下不溶于二甲苯，多分散性指数为3至10；和熔体指数为0.5至10dg/min；
B2)8%至13%的具有51%至55%的乙烯衍生单元含量的乙烯/丙烯共聚物；
所述聚烯烃组合物具有0.05至10dg/min的熔体指数，根据MFRISO方法1133。
2.根据权利要求1的聚烯烃组合物，其具有高于1500MPa的弯曲模量。
3.根据权利要求1或2的聚烯烃组合物，其包含，以%重量计：
A)8%至15%的权利要求1中所述的丙烯/1-己烯共聚物；和
B)85%至92%的权利要求1中所述的多相聚丙烯。
4.根据权利要求1或2的聚烯烃组合物，其中丙烯/1-己烯组分A含有0.3至0.9%衍生自1-己烯的重复单元。
5.包含根据权利要求1至4任一项的聚烯烃组合物的管道系统和片材。
6.单或多层管道和片材，其中至少一层包含根据权利要求1的聚烯烃组合物。
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| CN102549062B (zh) * | 2009-09-22 | 2013-11-20 | 巴塞尔聚烯烃意大利有限责任公司 | 丙烯聚合物组合物 |
| WO2011160945A1 (en) | 2010-06-23 | 2011-12-29 | Basell Poliolefine Italia Srl | Pipes and polyolefin composition for the manufacture thereof |
| RU2567546C2 (ru) | 2010-06-23 | 2015-11-10 | Базелль Полиолефин Италия Срл | Полиолефиновая композиция для систем труб и листов |
| US8809461B2 (en) * | 2011-04-28 | 2014-08-19 | Braskem America, Inc. | Multimodal heterophasic copolymer and thermoformed articles from same |
| WO2014052173A1 (en) * | 2012-09-28 | 2014-04-03 | Dow Global Technologies Llc | A composition, tape and composite pipe made therefrom and a method of producing composite pipe |
| US9738761B2 (en) | 2013-01-29 | 2017-08-22 | Ineos Europe Ag | Injection moulded polypropylene articles |
| ES2707968T3 (es) * | 2014-10-01 | 2019-04-08 | Basell Poliolefine Italia Srl | Composición de copolímero en base a propileno para tuberías |
| US10501616B2 (en) | 2016-10-06 | 2019-12-10 | Basell Poliolefine Italia S.R.L. | Propylene-based composition for pipes |
| US10730238B2 (en) * | 2016-10-06 | 2020-08-04 | Basell Poliolefine Italia S.R.L. | Plate comprising a polyolefin composition for 3D printer |
| WO2019002294A1 (en) * | 2017-06-30 | 2019-01-03 | Borealis Ag | POLYPROPYLENE COMPOSITION HAVING EXCELLENT SURFACE APPEARANCE |
| PL3456776T3 (pl) * | 2017-09-13 | 2020-09-21 | Borealis Ag | Kompozycja polipropylenowa |
| CN112469746A (zh) * | 2018-07-27 | 2021-03-09 | Sabic环球技术有限责任公司 | 用于管道的基于丙烯的三元共聚物组合物 |
| CN113454158B (zh) * | 2019-03-12 | 2023-08-08 | 巴塞尔聚烯烃意大利有限公司 | 由回收的聚烯烃获得的组合物 |
| WO2021053154A1 (en) * | 2019-09-20 | 2021-03-25 | Borealis Ag | Heterophasic propylene polymer composition with improved property profile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1582317A (zh) * | 2001-10-30 | 2005-02-16 | 巴塞尔聚烯烃意大利有限公司 | 聚丙烯组合物的管系统 |
| CN1973160A (zh) * | 2004-06-25 | 2007-05-30 | 巴塞尔聚烯烃意大利有限责任公司 | 由丙烯和α－烯烃的无规共聚物制造的管道系统 |
| CN101675104A (zh) * | 2006-12-22 | 2010-03-17 | 巴塞尔聚烯烃意大利有限责任公司 | 用于管道系统和片材的聚烯烃组合物 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1098272B (it) | 1978-08-22 | 1985-09-07 | Montedison Spa | Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine |
| IT1209255B (it) | 1980-08-13 | 1989-07-16 | Montedison Spa | Catalizzatori per la polimerizzazione di olefine. |
| IT1227260B (it) | 1988-09-30 | 1991-03-28 | Himont Inc | Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta |
| IT1230134B (it) | 1989-04-28 | 1991-10-14 | Himont Inc | Componenti e catalizzatori per la polimerizzazione di olefine. |
| IL117114A (en) | 1995-02-21 | 2000-02-17 | Montell North America Inc | Components and catalysts for the polymerization ofolefins |
| IT1275573B (it) | 1995-07-20 | 1997-08-07 | Spherilene Spa | Processo ed apparecchiatura per la pomimerizzazione in fase gas delle alfa-olefine |
| JP4717219B2 (ja) | 1999-04-15 | 2011-07-06 | バセル テクノロジー カンパニー ビー．ブイ． | オレフィン重合用の成分および触媒 |
| AU2004262661A1 (en) | 2003-08-05 | 2005-02-17 | Basell Poliolefine Italia S.R.L. | Polyolefin articles |
| GB0324837D0 (en) * | 2003-10-24 | 2003-11-26 | Polypropylene Belgium Nv | Polypropylene pipe |
| EP1874530A2 (en) | 2005-04-28 | 2008-01-09 | Basell Poliolefine Italia S.r.l. | Reinforced polypropylene pipe |
| EP2022824A1 (en) | 2007-08-08 | 2009-02-11 | Borealis Technology Oy | Sterilisable and Tough Impact Polypropylene Composition |
| BRPI0923586B1 (pt) | 2008-12-24 | 2019-09-10 | Basell Poliolefine Italia Srl | composição de poliolefina heterofásica |
| RU2567546C2 (ru) | 2010-06-23 | 2015-11-10 | Базелль Полиолефин Италия Срл | Полиолефиновая композиция для систем труб и листов |
| WO2011160945A1 (en) | 2010-06-23 | 2011-12-29 | Basell Poliolefine Italia Srl | Pipes and polyolefin composition for the manufacture thereof |
-
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- 2011-06-08 US US13/805,779 patent/US8709564B2/en active Active
- 2011-06-08 CN CN201180030463.7A patent/CN102971373B/zh active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1582317A (zh) * | 2001-10-30 | 2005-02-16 | 巴塞尔聚烯烃意大利有限公司 | 聚丙烯组合物的管系统 |
| CN1973160A (zh) * | 2004-06-25 | 2007-05-30 | 巴塞尔聚烯烃意大利有限责任公司 | 由丙烯和α－烯烃的无规共聚物制造的管道系统 |
| CN101675104A (zh) * | 2006-12-22 | 2010-03-17 | 巴塞尔聚烯烃意大利有限责任公司 | 用于管道系统和片材的聚烯烃组合物 |
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| Publication number | Publication date |
|---|---|
| US20130108818A1 (en) | 2013-05-02 |
| US8709564B2 (en) | 2014-04-29 |
| BR112012032731B1 (pt) | 2020-05-26 |
| EP2585528A1 (en) | 2013-05-01 |
| CN102971373A (zh) | 2013-03-13 |
| BR112012032731A2 (pt) | 2016-11-08 |
| EP2585528B1 (en) | 2014-12-03 |
| WO2011160953A1 (en) | 2011-12-29 |
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