CN101959665B - 聚烯烃组合物 - Google Patents
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Abstract
聚烯烃组合物,包含重量百分数:1)75-85%丙烯共聚物,所述共聚物包含至多15%重量的乙烯和/或C4-C10α-烯烃,在室温下可溶于Xilene中的流分低于6%重量,和2)15-25%乙烯与一种或多种C4-C10α-烯烃的共聚物,包含10-25%重量的所述C4-C10α-烯烃;所述组合物具有在230℃、2.16kg测量小于2.5g/10min的MFR值,14-22%重量的乙烯总量,小于4.5%重量的C4-C10α-烯烃总量,等于或高于4的乙烯总量与C4-C10α-烯烃总量的比值,在室温下可溶于二甲苯中的总流分等于或小于1.5dl/g的固有粘度值,和等于或高于0.80的组分2)的量与C4-C10α-烯烃在组分2)中的量的比值。
Description
本发明涉及聚烯烃组合物,所述组合物包含含有乙烯和/或其它α-烯烃作为共聚单体的丙烯无规共聚物,和乙烯与C4-C10α-烯烃的共聚物。
本发明的组合物可以很容易转化为各种成品或半成品。具体来讲,它们适合用于制备挤出吹塑物品。
本领域众所周知丙烯共聚物可以方便地用于挤出法,特别是获得挤出吹塑物品,因为它们具有良好的物理-机械性质平衡。常用于挤出法的丙烯共聚物具有合适的劲度和冲击性和良好的光学特性即低浊度值的优势。
长期以来已知通过机械混合或相继聚合可通过加入足量丙烯-乙烯弹性体共聚物改良聚丙烯的抗冲击性;但是,这种共聚物通常损失其透明度。
本领域已知通过乙烯与α-烯烃的弹性体共聚物形成的包含结晶聚丙烯基体和橡胶相的低MFR组合物,具体来讲描述于欧洲专利0373660。公开的组合物在低温下具有改良的抗冲击性和良好的透明度;只有当共聚单体在结晶和橡胶组分中的含量和固有粘度达到某些临界值时才实现性质的平衡。
但是,仍然需要性质平衡改良特别是在低温下具有良好透明度和抗冲击性的具有低MFR的组合物,用于例如片板挤出(sheet extrusion)/热压成形、制袋-充填-封合(form-fill-seal)和吹塑成形,已知所述应用,特别是在使用异相组合物时,可在模制品成型和/或再加热/退火后表现不利的透明度损失。
因此,仍继续需要具有为特殊的目标用途而平衡的改良性质的这类组合物。
现在通过本发明的聚烯烃组合物已获得新的和有价值的性质平衡,所述组合物包含重量(指组合物的重量)百分数:
1)75-85%,优选77-83%丙烯共聚物,所述共聚物包含至多15%、优选2.5-5%、更优选2.5-3.5%重量的乙烯和/或C4-C10α-烯烃,在室温下可溶于Xilene中的流分(Xsm)低于6%,优选3-5.5%,更优选3.5-5.5%重量(指组分1的重量),和
2)15-25%,优选17-23%乙烯与一种或多种C4-C10α-烯烃的共聚物,包含10-25%、优选12-20%重量(指组分2的重量)所述C4-C10α-烯烃;
所述组合物具有
-在230℃和2.16kg测量小于2.5g/10min、优选1.5-2g/10min的MFR值,
-14-22%重量的乙烯总量,
-小于4.5%、优选2.5-4%、更优选3-4%重量的C4-C10α-烯烃总量,
-等于或高于4、优选高于5的乙烯总量与C4-C10α-烯烃总量的比值,
-在室温下可溶于二甲苯中的总流分等于或小于1.5dl/g、优选1.1-1.5dl/g的固有粘度值,和
-等于或高于0.80、优选高于0.9、更优选高于1的组分2)的量(Split2)与组分2)中C4-C10α-烯烃量(即Split 2/组分2)中共聚单体)的比值。
本发明组合物的其它优选特征是:
-参考组合物的重量,在室温下可溶于二甲苯的组合物总流分(Xstot)为18%重量或更低;
-参考组分2)的重量,在室温下可溶于二甲苯的组分2)流分为至少40%重量或更多;
-在室温下可溶于二甲苯的组合物总流分与可溶于xilene的组分1)流分的比值(Xstot/Xsm)为2-4,优选2.5-3.5;
-弯曲模量高于700MPa。
韧/脆转变温度通常等于或低于-20℃,预计下限为约-60℃。
从以上定义清楚用于本说明书的术语“共聚物”包括含有不止一种共聚单体的聚合物。
如上文限定的共聚物组分2),优选在室温下在二甲苯中的溶解度大于40%重量,包括低晶至无定形材料,通常表现弹性特征,由此可用“弹性体”或“橡胶样”组分表示。
本发明的组合物提供有价值的性质组合,特别是根据本说明书指定的方法在瓶上测量的抗冲击性(根据韧/脆转变温度和Izod抗冲击性)和顶负荷、冲击和透明度的组合。
所述C4-C10α-烯烃,作为或可作为共聚单体存在于本发明的组分和流分中,用式CH2=CHR表示,其中R是具有2-8个碳原子的直链或支链烷基,或者芳基(特别是苯基)。
所述C4-C10α-烯烃的实例是1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯和1-辛烯。特别优选1-丁烯。
本发明的组合物可通过相继聚合制备,包括至少两个相继步骤,其中组分1)和2)在单独相继进行的步骤中制备,除了第一步之外,每一步都在形成的聚合物和用于前一步的催化剂的存在下操作。虽然只在第一步加入催化剂,但其活性在所有后续步骤中仍然有效。
优选在组分2)之前制备组分1)。
因此,本发明还涉及制备如上所述聚烯烃组合物的方法,所述方法包括至少两个相继聚合阶段,每个后续聚合阶段都在前面刚进行的聚合反应中形成的聚合材料的存在下进行,其中丙烯与共聚物组分1)的聚合阶段在至少一个阶段进行,然后进行乙烯和一种或多种C4-C10α-烯烃混合物与弹性体聚合物组分2)的至少一个共聚阶段。聚合阶段可在立体特异性Ziegler-Natta催化剂的存在下进行。
根据优选实施方案,所有聚合阶段都在催化剂的存在下进行,包括三烷基铝化合物,任选电子供体,和固体催化剂组分,包括Ti的卤化物或卤素-醇化物和支持在无水氯化镁上的电子供体化合物。具有上述特征的催化剂在专利文献中众所周知;特别有利的是描述于USP4,399,054和EP-A-45977的催化剂。其它实例可参阅USP 4,472,524。
优选聚合催化剂是Ziegler-Natta催化剂,所述催化剂包括含有下列的固体催化剂组分:
a)Mg、Ti和卤素和电子供体(内部供体),
b)烷基铝化合物,和任选(但优选),
c)一种或多种电子供体化合物(外部供体)。
内部供体优选选自单或二羧酸有机酸的酯如苯甲酸酯、丙二酸酯、邻苯二甲酸酯和某些琥珀酸酯。它们描述于例如美国专利4522930、欧洲专利45977和国际专利申请WO 00/63261和WO 01/57099。特别合适的是邻苯二甲酸酯和琥珀酸酯。优选邻苯二甲酸烷基酯,如邻苯二甲酸二异丁酯、二辛酯和二苯酯和邻苯二甲酸苄酯-丁酯。
在琥珀酸酯中,优选选自下式(I)的琥珀酸酯:
其中基团R1和R2相互之间相同或不同,是C1-C20直链或支链烷基、烯基、环烷基、芳基、芳基烷基或烷基芳基,任选包含杂原子;基团R3-R6相互之间相同或不同,是氢或C1-C20直链或支链烷基、烯基、环烷基、芳基、芳基烷基或烷基芳基,任选包含杂原子,与同一个碳原子连接的基团R3-R6可连接一起以形成环;前提是当R3-R5同时是氢时,R6基团选自具有3-20个碳原子的伯分支、仲或叔烷基、环烷基、芳基、芳基烷基或烷基芳基。
用作共催化剂的Al-烷基化合物包含Al-三烷基,如Al-三乙基、Al-三异丁基、Al-三正丁基,和直链或环状Al-烷基化合物,包含通过O或N原子或者SO4或SO3基团相互结合的两个或多个Al原子。通常使用使Al/Ti比值为1-1000的量的Al-烷基化合物。
外部供体(c)可与式(I)的琥珀酸酯为同一类型或不同。合适的外部电子供体化合物包括硅化合物、醚、酯如邻苯二甲酸酯、苯甲酸酯、还具有与式(I)不同的结构的琥珀酸酯、胺、杂环化合物,特别是2,2,6,6-四甲基哌啶、酮和通式(II)的1,3-二醚:
其中RI和RII相同或不同,是C1-C18烷基、C3-C18环烷基或C7-C18芳基;RIII和RIV相同或不同,是C1-C4烷基;或者1,3-二醚,其中2位的碳原子属于由5、6或7个碳原子组成并含有2或3个不饱和态的环状或多环结构。
这种类型的醚描述于公开的欧洲专利申请361493和728769。
可用作外部供体的优选电子供体化合物包括含有至少一个Si-OR键的芳族硅化合物,其中R是烃基。特别优选的外部供体化合物是式Ra 7Rb 8Si(OR9)c的硅化合物,其中a和b是整数0-2,c是整数1-3,总数(a+b+c)是4;R7、R8和R9是任选包含杂原子的C1-C18烃基。特别优选硅化合物,其中a是1,b是1,c是2,R7和R8中至少一个选自任选包含杂原子的具有3-10个碳原子的支链烷基、烯基、亚烷基、环烷基或芳基,R9是C1-C10烷基,特别是甲基。此类优选硅化合物的实例是环己基三甲氧基甲硅烷、叔丁基三甲氧基甲硅烷、叔己基三甲氧基甲硅烷、环己基甲基二甲氧基甲硅烷、3,3,3-三氟丙基-2-乙基哌啶基-二甲氧基甲硅烷、二苯基二甲氧基甲硅烷、甲基-叔丁基二甲氧基甲硅烷、二环戊基二甲氧基甲硅烷、2-乙基哌啶基-2-叔丁基二甲氧基甲硅烷、(1,1,1-三氟代-2-丙基)-甲基二甲氧基甲硅烷和(1,1,1-三氟代-2-丙基)-2-乙基哌啶基二甲氧基甲硅烷。另外,还优选硅化合物,其中a是0,c是3,R8是支链烷基或环烷基,任选含有杂原子,R9是甲基。特别优选硅化合物的具体实例是(叔丁基)2Si(OCH3)2、(环己基)(甲基)Si(OCH3)2、(苯基)2Si(OCH3)2、(环戊基)2Si(OCH3)2和二异丙基二甲氧基甲硅烷。
优选使用一定量的电子供体化合物(c)以便有机铝化合物与所述电子供体化合物(c)的摩尔比为0.1-500、更优选1-300、特别是3-30。
如上所述,除了以上电子供体之外,固体催化剂组分包含Ti、Mg和卤素。具体来讲,催化剂组分包含具有至少一个Ti-卤素键的钛化合物和支持在Mg卤化物上的上述电子供体化合物。镁卤化物优选是活化型MgCl2,这在专利文献中众所周知是Ziegler-Natta催化剂的支持物。专利USP 4,298,718和USP 4,495,338首先描述这些化合物在Ziegler-Natta催化剂中的用途。从这些专利中已知用作烯烃聚合的催化剂组分中的支持物或共支持物的镁二卤化物的特征在于X线谱,其中出现在无活性卤化物谱内的最强衍射线的强度减小,被卤素代替,该卤素的最大强度与更强线的相比向更低角度移位。
优选钛化合物是TiCl4和TiCl3;此外,还可以使用式Ti(OR)n-yXy的Ti-卤代醇化物,其中n是钛的化学价,y是1-n的数,X是卤素,R是具有1-10个碳原子的烃基。
可按照本领域众所周知和描述的几种方法制备固体催化剂组分。
根据优选方法,可通过使式Ti(OR)n-yXy(其中n是钛的化学价,y是1-n,优选TiCl4)的钛化合物与用从式MgCl2·pROH(其中p是0.1-6,优选2-3.5,R是具有1-18个碳原子的烃基)加合物衍生的氯化镁反应制备固体催化剂组分。可在加合物熔化温度(100-130℃)下在搅拌条件下操作,通过在与加合物不混溶的惰性烃的存在下使醇与氯化镁混合,适当制备球形加合物。然后,将乳液快速猝灭,从而导致球形颗粒形式的加合物固化。
根据这种方法制备的球形加合物实例描述于USP 4,399,054和USP 4,469,648。可将由此所得加合物直接与Ti化合物反应,或者可将其事先进行热控制脱醇(80-130℃)以便获得加合物,其中醇的摩尔数通常低于3,优选0.1-2.5。可通过使加合物(脱醇或诸如此类)悬浮于冷TiCl4(通常为0℃)中进行与Ti化合物的反应;将混合物加热至80-130℃,在该温度下保持0.5-2小时。可以一次或多次用TiCl4处理。可在用TiCl4处理过程中加入电子供体化合物。
无论使用何种制备方法,优选电子供体化合物的最终量与MgCl2的摩尔比为0.01-1,更优选0.05-0.5。
所述催化剂组分和催化剂描述于WO 00/63261和WO 01/57099。
可将催化剂与小量烯烃预接触(预聚合),使催化剂保持在烃溶剂中的混悬液内,在环境温度至60℃的温度下聚合,由此产生与催化剂重量相比0.5-3倍量的聚合物。操作还可在液体单体中进行,在这种情况下,得到与催化剂重量相比1000倍量的聚合物。
通过使用上述催化剂,获得球形颗粒形式的聚烯烃组合物,颗粒的平均直径为约250-7,000μm,流动性小于30秒,堆密度(压紧的)大于0.4g/ml。
聚合阶段可在液相、气相或液-气相进行。优选共聚物组分1)的聚合在液体单体(如用液体丙烯作为稀释剂)中进行,而弹性体共聚物组分2)的共聚阶段在气相进行。或者,所有相继聚合阶段都可在气相进行。
制备聚合物组分1)和制备弹性体共聚物组分2)的聚合阶段的反应温度可以相同或不同,优选40-100℃;更优选制备聚合物组分1)的反应温度为50-80℃,制备聚合物组分2)的反应温度为70-100℃。
如果在液体单体中进行,制备聚合物组分1)的聚合阶段的压力是可对抗所用操作温度下液体丙烯的蒸气压的压力,并且其可被用于输送催化剂混合物的小量惰性稀释剂的蒸气压、被任选单体的过压和被用作分子量调节剂的氢修饰。
如果在液相进行,聚合压力优选33-43bar,如果在气相进行,优选5-30bar。与阶段相比的保留时间取决于聚合物组分1)与2)之间的所需比值,可通常为15分钟-8小时。可使用本领域已知的常规分子量调节剂,如链转移剂(如氢或ZnEt2)。
还可通过单独制备所述组分1)和2)获得本发明的组合物,通过用与前面描述相同的催化剂和在基本相同(但将不进行整个相继聚合过程,而是将在单独聚合步骤钟制备所述组分)的聚合条件下操作,然后使熔化或软化状态的所述组分机械共混。可使用常规混合装置,如螺杆挤出机,特别是双螺杆挤出机。
本发明的组合物还可包含本领域常用的添加剂,如抗氧化剂、光稳定剂、热稳定剂、成核剂、着色剂和填充剂。
具体来讲,加入成核剂可明显改善重要的物理-机械性质,如弯曲模量、热变形温度(HDT)、所得拉伸强度和透明度。
成核剂的代表性实例是苯甲酸钠、滑石粉和1,3-和2,4-二亚苄基山梨醇。
与总重量相比,优选加入本发明组合物中的成核剂的量为0.01-2%重量,更优选0.05-1%重量。
加入无机填充剂如滑石粉、碳酸钙和矿物纤维还可改善一些机械性质,如弯曲模量和HDT。
本发明的细节在以下实施例中给出,这些实施例用于解释本发明,并非限制本发明。
通过用以下测试方法获得表中显示的数据。
-进料气体的摩尔比
通过气相层析测定。
-聚合物的乙烯和1-丁烯含量
通过I.R.波谱测定。
-熔体流动速率(MFR)
在230℃和2.16Kg根据ISO 1133测定;符合ASTM D 1238,条件L(MFR“L”)。
-二甲苯可溶性和不溶性流分
如下测定:
将2.5g聚合物和250ml二甲苯引入配备冷冻器和磁搅拌器的玻璃烧瓶内。30分钟内使温度上升至溶剂沸点。然后将由此所得透明溶液保持回流,再搅拌30分钟。将闭合的烧瓶在100℃保持10-15分钟,在25℃恒温水浴中保持30分钟。将由此形成的固体在快速滤纸上过滤。将100ml滤液倒在事前称重的铝容器中,该容器在氮气流下在加热板上加热,以蒸发除去溶剂。然后将容器在80℃烘箱中真空放置直至达到恒重。然后计算在室温下可溶于二甲苯中的聚合物重量百分数。
-固有粘度(I.V.)
在135℃下在四氢萘中测定。
-弯曲模量
根据ISO 178调节24小时后测定。
-Izod冲击强度(缺口)
在根据ISO 1873制备的T-bar样品上,根据ISO180/1A调节24小时后测定。
-斑样本的制备
用于D/B测量的斑:
用具有90吨夹紧力的Negri BossiTM型(NB 90)注射压机制备具有127×127×1.5mm尺度的用于测量D/B的斑。形成矩形斑(127×127×1.5mm)。
主要加工参数报道如下:
反压(bar):20
注射时间(s):3
最大注射压(MPa):14
水注射压(MPa):6-3
第一保持水压(MPa):4±2
第一保持时间(s):3
第二保持水压(MPa):3±2
第二保持时间(s):7
冷却时间(s):20
成型温度(℃):60
熔化温度是220-280℃。
用于浊度测量的斑
用1秒注射时间、230℃温度和40℃成型温度通过注射成型制备1mm厚的用于浊度测量的斑。
注射压机是具有50吨夹紧力的BattenfeldTM type BA 500CD。插入铸件导致形成两个斑(各55×60×1mm)。
-瓶样本的制备
用吹塑机AUTOMA SPEED 3M-Extrusion continuous InclineShuttle,由实施例的组合物制备圆筒形1L瓶(35g)。
主要加工参数报道如下:
螺杆直径 70mm
长度/直径(L/D)比 24
熔化温度 180℃,
成型温度 25℃
根据下文描述的方法测试瓶的抗冲击(在4℃和23℃)、浊度和顶负荷性质。
-韧/脆转变温度(D/B)
根据下文指定的方法测定。
用自动、电脑化打击的锤通过冲击测定双轴抗冲击性。
通过用圆形手动穿孔机(38mm直径)切割,由如上文描述制备的斑获得圆形测试样本。将它们在23℃和50RH下调节至少12小时,然后在测试温度恒温浴中放置1小时。
在用锤(5.3kg,具有1.27cm直径的半球形冲)击打放在环支持物上的圆形样品的冲击过程中检测力量-时间曲线。所用机器是CEAST6758/000 type model No.2。
D/B转变温度指接受所述冲击测试时50%样品发生脆性断裂的温度。
-斑的浊度
按照下文指定的方法测定。
将斑在50±5%相对湿度和23±1℃温度下调节12-48小时。
用于测试的仪器是具有配备G.E.1209灯和滤器C的Haze-meterUX-10的Gardner光度计。通过在没有样品的情况下测量(0%Haze)和阻断光束测量(100%Haze)进行仪器校准。
规范ASTM-D1003给出测量和计算原则。
在5个斑上进行浊度测量。
-熔化和结晶温度(Tm和Tc):
以每分钟20℃的温度变化,根据ISO 11357/3测定DSC。
-瓶的顶负荷
使用Instron测力计,配备0.2gr平衡精度和0.01mm精度测微计。在23°±1℃和50%相对湿度条件下至少12小时后,将瓶放在测力计的两个板之间,用5cm/min的板应力速度压缩。记录瓶塌陷的应力,数值以N表示。顶负荷值是在10个瓶上测量的平均值。
-对瓶的冲击
在装满7/8水的样品瓶上测量冲击。在测试温度(23℃和4℃)下调节2小时后,让瓶从渐增的高度(至多280cm)落下。表2报道的参数是50%瓶破裂的高度。
-瓶的浊度
使用与测量斑浊度的相同方法和仪器。从瓶壁上切下0.5mm平均厚度的样品以获得样品架可抓紧的平坦样品,根据以上规范ASTM-D1003。
在5个样品上进行浊度测量。
实施例1-5和对比1C
在根据混合液-气聚合技术连续操作的设备中,在表1指定的条件下运行。
在一系列的两个反应器中在催化剂系统的存在下进行聚合,所述反应器配备将产物从一个反应器转移至紧接着的另一个反应器的装置。
固体催化剂组分的制备
按照欧洲专利EP728769实施例5第48-55行制备Ziegler-Natta催化剂。用三乙基铝(TEAL)作为共催化剂,二环戊基二甲氧基甲硅烷作为外部供体,重量比如表1显示。
催化剂系统和预聚合处理
使上文描述的固体催化剂组分在12℃与三乙基铝(TEAL)接触24分钟,二环戊基二甲氧基甲硅烷(DCPMS)作为外电子供体组分。TEAL与固体催化剂组分的重量比和TEAL与DCPMS的重量比在表1中指明。
通过在20℃使催化剂系统在液体丙烯的混悬液中保持约5分钟使其预聚合,然后将其引入第一聚合反应器内。
聚合
在一系列的两个反应器中连续进行聚合,所述反应器配备将产物从一个反应器转移至紧接着的另一个反应器的装置。第一反应器是液相反应器,第二反应器是流化床气相反应器。在第一反应器中制备聚合物组分1),而在第二反应器中制备聚合物组分2)。
在反应过程中保持温度和压力不变。用氢作为分子量调节剂。
通过气相层析连续分析气相(丙烯、乙烯和氢)。
在运行结束时排出粉状物,在氮气流下干燥。
从由此所得聚合物中测量获得表1和2报道的与终聚合物组合物中Xilene可溶性和共聚单体含量有关的数据,必要时加以稳定。
然后将聚合物颗粒引入挤出机中,其中使它们与1500ppm以Irganox B 215名称购自Ciba-Geigy的商品添加剂(由1份季戊四醇四3-(3,5-二叔丁基-4-羟基苯基)丙酸酯和2份三(2,4-二叔丁基苯基)亚磷酸酯组成)、500ppm硬脂酸钙和1800ppm以Millad 3988名称购自Milliken的1,3:2,4-双(3,4-二甲基亚苄基)山梨醇透明剂混合。在双螺杆挤出机中在氮气气氛下挤出聚合物颗粒,转速为220rpm,熔化温度为200-250℃。
从由此挤出的聚合物和根据所述方法所得瓶上测量获得表2报道的与终聚合物组合物物理-机械性质有关的数据。
参考实施例(1R)
用于注射吹塑成型应用的丙烯共聚单体的量和市售获得的无规共聚物的性质作为参考实施例报道。
表1-聚合过程
注解:H2量=在液体单体中的氢浓度;C2 -=乙烯;C3 -=丙烯;C4 -=丁-烯-1
表2
*50%装满7/8水的瓶破裂的下落高度
Claims (6)
1.一种聚烯烃组合物,包含以重量百分数计的下列组分:
1)77-83%的丙烯共聚物,所述共聚物包含至多15%重量的乙烯和/或C4-C10α-烯烃,在室温下可溶于二甲苯中的级分低于6%重量,和
2)17-23%的乙烯与一种或多种C4-C10α-烯烃的共聚物,包含10-25%重量的所述C4-C10α-烯烃;
所述组合物具有
-小于2.5g/10min的MFR值,其中所述MFR在230℃和2.16Kg根据ISO1133符合ASTM D1238条件L测定,
-14-22%重量的乙烯总量,
-2.5-4%重量的C4-C10α-烯烃总量,
-等于或高于4的乙烯总量与C4-C10α-烯烃总量的比值,
-等于或小于1.5dl/g的在室温下可溶于二甲苯中的总级分的特性粘度值,其中所述特性粘度在135℃下在四氢萘中测定,和
-等于或高于0.80的组分2)的量与C4-C10α-烯烃在组分2)中的量的比值。
2.权利要求1的聚烯烃组合物,其中根据ISO178调节24小时后测定的弯曲模量大于700MPa。
3.权利要求1的聚烯烃组合物,具有等于或低于-20℃的韧/脆转变温度。
4.一种通过相继聚合制备权利要求1的聚烯烃组合物的方法,该方法在至少两个相继聚合阶段进行,每个后续聚合阶段都在前一聚合阶段刚形成的聚合材料的存在下进行。
5.包含权利要求1的聚烯烃组合物的挤出吹塑成型物品。
6.含权利要求1的聚烯烃组合物的采用瓶形式的挤出吹塑成型物品。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08152134 | 2008-02-29 | ||
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US61/068197 | 2008-03-05 | ||
PCT/EP2009/051269 WO2009106411A1 (en) | 2008-02-29 | 2009-02-04 | Polyolefin compositions |
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CN107805349B (zh) * | 2016-09-09 | 2020-10-23 | 中国石油化工股份有限公司 | 一种聚烯烃组合物及其制备方法和聚烯烃材料 |
CN107805340B (zh) * | 2016-09-09 | 2021-07-02 | 中国石油化工股份有限公司 | 一种聚烯烃组合物和聚烯烃材料 |
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- 2009-02-04 JP JP2010548058A patent/JP5263845B2/ja active Active
- 2009-02-04 US US12/735,705 patent/US8378028B2/en active Active
- 2009-02-04 BR BRPI0908411A patent/BRPI0908411B1/pt active IP Right Grant
- 2009-02-04 CN CN200980107285.6A patent/CN101959665B/zh active Active
- 2009-02-04 RU RU2010139855/05A patent/RU2010139855A/ru not_active Application Discontinuation
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JP5263845B2 (ja) | 2013-08-14 |
JP2011513528A (ja) | 2011-04-28 |
EP2247424B1 (en) | 2012-07-04 |
CN101959665A (zh) | 2011-01-26 |
WO2009106411A1 (en) | 2009-09-03 |
KR20100126709A (ko) | 2010-12-02 |
EP2247424A1 (en) | 2010-11-10 |
KR101580849B1 (ko) | 2015-12-30 |
RU2010139855A (ru) | 2012-04-10 |
US20100308007A1 (en) | 2010-12-09 |
BRPI0908411A2 (pt) | 2016-10-18 |
BRPI0908411B1 (pt) | 2018-10-30 |
US8378028B2 (en) | 2013-02-19 |
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