CN101808800A - 用于注坯拉伸吹塑的丙烯基聚合物 - Google Patents
用于注坯拉伸吹塑的丙烯基聚合物 Download PDFInfo
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- CN101808800A CN101808800A CN200880110493.7A CN200880110493A CN101808800A CN 101808800 A CN101808800 A CN 101808800A CN 200880110493 A CN200880110493 A CN 200880110493A CN 101808800 A CN101808800 A CN 101808800A
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Images
Classifications
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- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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Abstract
在此本发明提供注坯拉伸吹塑(ISBM)的制品和其制造方法。在一个实施方式中，ISBM制品一般包括分子量分布约为9-20的丙烯基无规共聚物。在另一个实施方式中，ISBM制品一般包含由含琥珀酸酯内给体的齐格勒纳塔催化剂形成的丙烯基无规共聚物。
Description
技术领域
本发明的实施方式一般涉及适合用于注坯拉伸吹塑的聚合物。具体地，本发明的实施方式涉及适合用于注坯拉伸吹塑的丙烯聚合物。
背景技术
历史上，聚对苯二甲酸酯(PET)已经用于注坯拉伸吹塑型坯(preform)，所述型坯用于形成注坯拉伸吹塑(ISBM)的制品，例如，瓶子和广口瓶。虽然曾经尝试利用聚丙烯制备预制件，但是基于丙烯的预制件倾向于显示窄的加工窗，主要是在再加热、拉伸和吹塑步骤期间。特别是，丙烯聚合物一般产生窄的温度范围，导致不能确保生产无缺陷的容器。虽然使用无规共聚物能稍微增大该范围，但是以前尝试使用无规共聚物产生的聚合物，对的ISBM方法而言刚性太高。
因此，需要制造能够用于注坯拉伸吹塑的丙烯基聚合物(包括共聚物)。
发明概述
本发明的实施方式包括注坯拉伸吹塑(ISBM)制品。在一个实施方式中，ISBM制品一般包括分子量分布约为9-20的丙烯基无规共聚物。在另一个实施方式中，ISBM制品一般包含由含琥珀酸酯内给体的齐格勒纳塔催化剂形成的丙烯基无规共聚物。
实施方式还包括形成ISBM制品的方法。这类方法通常包括提供丙烯基无规共聚物，将该丙烯基无规共聚物注塑成型坯，并将该型坯拉伸吹塑成瓶子。
附图简述
图1图示聚合物样品的拉伸屈服应力。
图2图示成形的样品的堆载(top load)强度。
图3图示形成的样品的光泽。
图4图示形成的样品的雾度。
图5图示形成的样品的重量分布。
发明详述
介绍和定义
现在给出详细说明。所附各权利要求确定一独立发明，为了防止侵权，应认为本发明包括权利要求中规定的各要素或限制的等同项。根据上下文，以下所有提到“发明”，在一些情况下都可以仅指某些具体的实施方式。在其他情况下，可以认为所提到的“发明”是指一项或多项权利要求中叙述的主题，但是不一定是所有权利要求中叙述的主题。以下将更详细地描述各发明，包括具体实施方式、形式和实施例，但是各发明并不限于这些实施方式、形式和实施例，说明书中包括这些实施方式、形式和实施例是使本领域普通技术人员能够结合本专利中的信息和可用的信息与技术来进行和应用各发明。
本文使用的各种术语如下文所示。对于权利要求中使用但是下文中没有定义的术语，应给予相关领域技术人员通过印刷出版物和已授权专利了解到的最宽泛的定义。此外，除非另有说明，否则，本文所述所有化合物都可以是取代或未取代的，列出的化合物包括其衍生物。
催化剂体系
用于聚合烯烃单体的催化剂体系包括本领域技术人员已知的任何催化剂体系。例如，该催化剂体系包含茂金属催化剂体系，单中心(single site)催化剂体系，齐格勒-纳塔催化剂体系，或它们的组合。下面包括了对这些催化剂体系的简要讨论，但是这些简要讨论决不用来将本发明的范围限于这些催化剂。
齐格勒-纳塔催化剂体系一般由金属组分(如潜在活性催化剂位点)与一种或多种其他组分例如催化剂载体、助催化剂和/或例如一种或多种电子给体的组合形成。
齐格勒-纳塔催化剂的具体例子包括一般由以下通式表示的金属组分：
MRx；
其中M是过渡金属，R是卤素、烷氧基、氢羧基，x是过渡金属的价数。例如，x可以是1-4。
例如，过渡金属可选自第IV族至第VIB族(如钛、铬或钒)。在一个实施方式中，R可选自氯、溴、碳酸酯、酯或烷氧基。催化剂组分的例子包括：例如TiCl4、TiBr4、Ti(OC2H5)3Cl、Ti(OC3H7)2Cl2、Ti(OC6H13)2Cl2、Ti(OC2H5)2Br2和Ti(OC12H25)Cl3。
本领域的技术人员应认识到，催化剂在用于促进聚合反应之前可以某种方式进行“活化”。如下面进一步讨论的，通过使催化剂与活化剂接触完成活化，所述活化剂在一些情况下也称作“助催化剂”。这种Z-N活化剂的实施方式包括有机铝化合物，例如三甲基铝(TMA)、三乙基铝(TEAl)和三丁基铝(TiBAl)。
齐格勒-纳塔催化剂体系还可以包含一种或多种电子给体，例如内电子给体和/或外电子给体。可以使用内电子给体来减少形成的聚合物的无规形式，因此减少聚合物中二甲苯可溶物的量。内电子给体可以包括：例如，胺、酰胺、酯、酮、腈、醚、硫醚、硫酯、醛、醇盐、盐、有机酸、膦、二醚、琥珀酸酯、邻苯二甲酸酯、丙二酸酯、马来酸衍生物、二烷氧基苯，以及它们的组合。(参见美国专利第5,945,366号和第6,399,837号，这些专利通过参考结合于此。)
在一个具体的非限制性实施方式中，电子给体是琥珀酸酯。琥珀酸酯的非限制性的具体例子包括：琥珀酸二乙酯、琥珀酸二丁酯、甲基琥珀酸二乙酯、琥珀酸二丙酯、琥珀酸二戊酯、琥珀酸二己酯、琥珀酸二辛酯、琥珀酸二癸酯、琥珀酸丁辛酯、琥珀酸二(十二烷基)酯、仲丁基琥珀酸二乙酯、己基(thexyl)琥珀酸二乙酯、三甲基甲硅烷基琥珀酸二乙酯、环己基琥珀酸二乙酯、苄基琥珀酸二乙酯、环己基(甲基)琥珀酸二乙酯、叔丁基琥珀酸二乙酯、异丁基琥珀酸二乙酯、异丙基琥珀酸二乙酯、新戊基琥珀酸二乙酯、、异戊基琥珀酸二乙酯、2-苄基-2-异丙基琥珀酸二乙酯、2，2-环戊基琥珀酸二乙酯、2，2-二异丁基琥珀酸二乙酯、2-异丙基-2-甲基琥珀酸二乙酯、2，2-二异丙基琥珀酸二乙酯、2-异丁基-2-乙基琥珀酸二乙酯、2-异戊基-2-异丁基琥珀酸二乙酯、2，2-环己基琥珀酸二乙酯、2，3-二异丙基琥珀酸二乙酯、2，3-二环己基琥珀酸二乙酯、2，3-二(环己基甲基)琥珀酸二乙酯、2，3-二叔丁基琥珀酸二乙酯、2，3-二异丁基琥珀酸二乙酯、2，3-二新戊基琥珀酸二乙酯、2，3-二异戊基琥珀酸二乙酯、2-异丙基-3-异丁基琥珀酸二乙酯、2-叔丁基-3-异丙基琥珀酸二乙酯、2-异丙基-3-环己基琥珀酸二乙酯和2-异戊基-3-环己基琥珀酸二乙酯。
琥珀酸酯基催化剂体系一般生成的聚合物具有宽分子量分布，将在下面更详细论述。以前用丙烯聚合物制备ISBM制品的尝试都未能认识到应用宽分子量分布聚合物作为对聚合物的窄加工范围和刚性的一种解决方案。如本文所用，术语“加工范围”表示聚合物对加热温度与预定理想温度的变化的敏感性。例如，加工范围越窄，聚合物对温度变化的敏感性越高，反之亦然。实际上，以前用丙烯基聚合物的尝试实际上包括进一步降低使用的聚合物的分子量分布(变窄)的方法。出乎意料地，本发明的实施方式能够在可接受的加工范围(如，对温度变化的敏感性较低)制备ISBM制品，制得的制品很少(如，小于10％或小于5％)存在缺陷。如本文使用，“缺陷”通过肉眼检查来测量。肉眼可见的缺陷一般是因集中在制品的任意区域中(拉伸太大或太小)的结果。缺陷还可以通过机械性能测试来测量。
可以使用外电子给体进一步控制制得的无规聚合物的量。外电子给体可以包括单官能或多官能的羧酸、羧酸酐、羧酸酯、酮、醚、醇、内酯、有机磷化合物和/或有机硅化合物。在一个实施方式中，外给体可以包括二苯基二甲氧基硅烷(DPMS)、环己基甲基二甲氧基硅烷(CMDS)、二异丙基二甲氧基硅烷(DIDS)和/或二环戊基二甲氧基硅烷(CPDS)。外给体可以与使用的内给体相同或不同。
齐格勒-纳塔催化剂体系的组分(如，催化剂、活化剂和/或电子给体)可以与载体结合或者不结合，它们可以相互组合或者分离。Z-N的载体材料可以包括二卤化镁，例如，二氯化镁、二溴化镁，或者二氧化硅。
可采用本领域技术人员已知的任何方法形成齐格勒-纳塔催化剂。例如，齐格勒-纳塔催化剂可通过使过渡金属卤化物与金属烷基化物或金属氢化物接触而形成。(参见美国专利第4,298,718号，美国专利第4,298,718号，美国专利第4,544,717号，美国专利第4,767,735号和美国专利第4,544,717号，这些专利通过参考结合于此。)
聚合方法
如本文其它地方说明的，可以采用催化剂体系形成聚烯烃组合物。制备催化剂体系后，如上所述和/或本领域技术人员已知的，就可以使用该组合物进行各种方法。在聚合方法中使用的设备、工艺条件、反应物、添加剂和其他材料在指定的方法中将依据所需的组合物和形成的聚合物的性质变化。这些方法可包括，例如溶液相法，气相法、淤浆相法、本体相法、高压法或者它们的组合。(参见，美国专利第5,525,678号；美国专利第6,420,580号；美国专利第6,380,328号；美国专利第6,359,072号；美国专利第6,346,586号；美国专利第6,340,730号；美国专利第6,339,134号；美国专利第6,300,436号；美国专利第6,274,684号；美国专利第6,271,323号；美国专利第6,248,845号；美国专利第6,245,868号；美国专利第6,245,705号；美国专利第6,242,545号；美国专利第6,211,105号；美国专利第6,207,606号；美国专利第6,180,735号和美国专利第6,147,173号，这些专利通过参考结合于此。)
在一些实施方式中，上述方法一般包括聚合一种或多种烯烃单体形成聚合物。烯烃单体包括，例如C2-C30烯烃单体，或者C2-C12烯烃单体(例如，乙烯、丙烯、丁烯、戊烯、甲基戊烯、己烯、辛烯和癸烯)。单体可包括烯键式不饱和单体，例如C4-C18二烯烃，共轭或非共轭的二烯，多烯，乙烯基单体和环烯烃。其他单体的非限制性例子包括，例如，降冰片烯、降冰片二烯(nobornadiene)、异丁烯、异戊二烯、乙烯基苯并环丁烷、苯乙烯、烷基取代的苯乙烯、亚乙基降冰片烯、二环戊二烯和环戊烯。形成的聚合物可包括，例如均聚物、共聚物或三元共聚物。
溶液法例子在美国专利第4,271,060号，美国专利第5,001,205号，美国专利第5,236,998号，美国专利第5,589,555号中描述，这些专利通过参考结合于此。
气相聚合法的一个例子包括连续循环系统，该系统中在反应器中通过聚合反应热加热循环气流(或者称作再循环物流或流化介质)。在该循环的另一部分通过在反应器的外部冷却系统从该循环气流除去热量。在反应条件下在催化剂存在下，含一种或多种单体的循环气流可以连续循环通过流化床。循环气流一般从流化床排出并再循环回到反应器。同时，聚合物产物可以从反应器排出，并且可加入新鲜单体以取代聚合的单体。气相法中反应器的压力可以在例如约100-500psig范围变化，或者约200-400psig，或者约250-350psig范围变化。气相法中反应器温度可以在例如约30-120℃范围变化，或者约60-115℃，或者约70-110℃范围，或者约70-95℃范围变化。(参见，例如，美国专利第4,543,399号；美国专利第4,588,790号；美国专利第5,028,670号；美国专利第5,317,036号；美国专利第5,352,749号；美国专利第5,405,922号；美国专利第5,436,304号；美国专利第5,456,471号；美国专利第5,462,999号；美国专利第5,616,661号；美国专利第5,627,242号；美国专利第5,665,818号；美国专利第5,677,375号；美国专利第5,668,228号，这些专利通过参考结合于此。)
淤浆相法一般包括形成固体、颗粒聚合物在液体聚合介质中的悬浮液，在该悬浮液中加入单体和任选的氢，以及催化剂。该悬浮液(其可包含稀释剂)可以以间歇或连续方式从反应器中排出，然后可以将其中的挥发性组分与聚合物分离，并任选在蒸馏之后将该挥发性组分再循环至该反应器。在聚合介质中使用的液化稀释剂可包括，例如，C3-C7链烷(如，己烷或异丁烷)。使用的介质一般在聚合反应条件下是液体，并且是相对惰性的。本体相法与淤浆法类似，但是在本体相法中液体介质也是反应物(如单体)。然而，一个方法可以是例如本体法、淤浆法或者本体淤浆法。
在具体的实施方式中，淤浆法或本体法可以在一个或多个环管反应器中连续进行。催化剂以淤浆或自由流动的干粉形式规则地注入反应器环管，反应器环管本身中充满生长的聚合物颗粒在稀释剂中的循环淤浆。任选地，可以将氢加入该聚合过程，例如用于控制制成的聚合物的分子量。环管反应器中的压力例如可保持在约27-50巴，或者约35-45巴，温度例如在约38-121℃。可通过本领域技术人员已知的任何方法通过环管壁去除反应热，例如通过双夹套管或者热交换器。
或者，可以采用其他类型的聚合反应方法，例如串联、并联或者它们的组合形式的搅拌反应器。聚合物从反应器排出后，聚合物可以通入聚合物回收系统进行进一步的加工，例如添加添加剂和/或挤出。
添加剂可包括本领域技术人员已知的添加剂。例如，非限制性添加剂可包括：抗氧化剂如位阻酚，稳定剂如磷酸盐，中和剂如硬脂酸盐，润滑剂，脱模剂，填充剂如滑石和白垩，抗静电剂，增塑剂，染料，颜料，阻燃剂，成核剂如滑石、二氧化硅、高岭土、苯甲酸钠和2，2’-亚甲基二(4，6-二叔丁基苯基)磷酸钠，或者它们的组合。
聚合物产物
通过本文所述方法形成的聚合物(和其掺混物)可以包括丙烯基无规共聚物。除非另外规定，否则术语“丙烯基”表示聚合物的主要组分是丙烯(如，至少约50重量％，或至少约75重量％，或者至少约80重量％，或至少约89重量％)。术语“丙烯基无规共聚物”表示主要由丙烯和一定量的其他共聚单体构成的共聚物，所述其他共聚单体例如是乙烯，共聚单体占聚合物重量的至少约0.2重量％，或者至少约0.8重量％，或者至少约2重量％。此外，术语“无规共聚物”表示由大分子形成的共聚物，其中，指定单体单元在链中任何指定位置的可能性与相邻单元的特性无关。
在一个实施方式中，聚合物包括丙烯基无规共聚物。所述共聚物选自C2-C10链烯。例如，共聚单体可选自：乙烯、丙烯、1-丁烯、1-戊烯、l-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、4-甲基-1-戊烯，和它们的组合。在一个特定实施方式中，所述共聚单体包括乙烯。在这种实施方式中，乙烯的含量例如约为0.2-10重量％，或者约0.6-4重量％。
除非在本文中另外指出，所有测试方法是提交本申请时的通用方法。
虽然常规齐格勒-纳塔形成的聚丙烯一般显示分子量分布约为5-7，但是，例如，将聚丙烯用于ISBM的先前的尝试包括通过一些方法例如过氧化物降解来进一步减小聚合物的分子量分布，以缩短循环时间。不幸的是，这些方法导致损害机械性能。但是，如采用GPC测定的，在此使用的丙烯基无规共聚物一般显示宽分子量分布(Mw/Mn)。例如，丙烯基无规共聚物一般显示分子量分布例如至少为9，或者至少为10，或者至少为11。在一个实施方式中，丙烯基无规共聚物显示分子量分布例如约为10-20，或者约为10-18，或者约10-15。
丙烯基无规共聚物的熔体流动速率(采用ASTM D1238测定)，至少约为2分克/10分钟，或者约为5-30分克/10分钟，或者约为10-20分克/10分钟。
产物应用
所述聚合物和其掺混物可用于本领域技术人员已知的应用，例如，成形操作(例如，薄膜、片材、管材和纤维的挤出和共挤出，以及吹塑，注塑和旋转式模塑)。薄膜包括通过共挤出或者层压形成的吹塑薄膜或流延薄膜，可用作收缩薄膜、食品包鲜薄膜、拉伸薄膜、密封薄膜、取向薄膜、快餐包装、重型袋、杂货大口袋、烤制食品和冷冻食品包装、医药包装、工业衬料和膜，例如与食品接触和与非食品接触的应用。纤维包括用于织造形式或非织造形式的熔融纺丝、溶液纺丝和熔喷纤维操作，以制造过滤器、尿布织物、医疗手术服和土工用织物(geotextiles)。挤出制品包括，例如，医用软管、电线和电缆涂层，土工用膜(geomembrane)和池塘衬料。成型制品包括单层结构和多层结构，其形式例如为瓶子、槽、大型中空制品、刚性食品容器和玩具。
在一个实施方式中，聚合物可用于注坯拉伸吹塑(ISBM)。ISBM可用于制备薄壁高透明性的瓶子。这些方法为本领域技术人员公知。例如，ISBM方法可包括将聚合物注塑成型坯，然后将该型坯拉伸吹塑成瓶子。
如本文前面所述，本发明的实施方式一般导致能在比常规齐格勒-纳塔聚合物经历的更宽的加工范围的条件下形成ISBM制品。例如，本发明的实施方式的结果是加工范围约为115-140℃(与预定理想温度的偏差)。
出乎意料地，本文所述的实施方式产生用于ISBM方法的有成本效益的PET的成功的替代品。
实施例
由各种聚合物形成注坯拉伸吹塑(ISBM)的制品。如本文所用，聚合物“A”指由常规齐格勒-纳塔催化剂形成的无规共聚物(可以7525MZ，从美国总石油化学品公司(TOTAL Petrochemicals USA，Inc.)购得)，其包含3.1重量％C2(通过NMR分析)，分子量分布为6.4，熔体流动速率为11克/10分钟。聚合物“A”还包含500ppm的Irganox 1010，1000ppm的Irganox 168，1000ppm硬脂酸钙，250ppm的DHT-4A和500ppm的Atmer 129。聚合物“B”指由琥珀酸酯基齐格勒-纳塔催化剂形成的无规共聚物，其包含3.2重量％C2(通过NMR分析)，分子量分布为10，熔体流动速率为15克/10分钟。聚合物“B”还包含500ppm的Irganox 1010，1000ppm的Irganox 168，1000ppm硬脂酸钙，250ppm的DHT-4A和500ppm的Atmer129。聚合物“C”指由琥珀酸酯基齐格勒-纳塔催化剂形成的无规共聚物，其包含3.3重量％C2(通过NMR分析)，分子量分布为10，熔体流动速率为14克/10分钟。聚合物“C”还包含560ppm的Irganox 1010，1090ppm的Irganox 168，1010ppm硬脂酸钙，260ppm的DHT-4A和10400ppm的Atmer 129。
将聚合物样品浇铸成16密耳的片材，然后在Bruckner拉伸机上，自105℃起双轴向拉伸至拉伸破坏温度。结果示于图1(观察到B和C的线性拟合线的斜率小于A的线的斜率)。观察到聚合物B和C受温度的影响较小，表明在随后ISBM过程中的加工范围比聚合物A的加工范围宽。
将各聚合物样品成型为21克瓶子型坯。聚合物和相应型坯的性质示于表1。
表1
观察到在型坯和聚合物之间接近的结果，表明注塑方法不会明显改变聚合物的形态。
将各型坯老化至少24小时，然后使用线性注坯拉伸吹塑机(生产线速度为1000个瓶子/小时/模腔)，吹塑成瓶子。
观察到，虽然所有瓶子能够经受四分之一英寸的挠曲，但是由聚合物A形成的瓶子具有的堆载性能略好于由聚合物B和C形成的瓶子。参见图2。所有瓶子具有类似的光泽和雾度性能。参见图3和4。
但是，观察到聚合物A产生的瓶子缺陷多于聚合物B和C。特别是，观察到每制造40个制品，聚合物C产生1个底部区域瓶子缺陷，聚合物B产生1个瓶肩区域和1个底部区域瓶子缺陷，而聚合物A产生21个瓶肩区域和2个底部区域瓶子缺陷。
特定瓶子部分重量的分析显示，对于不同瓶子部分的重量，聚合物A样品的标准偏差显著大于聚合物B和C样品，特别是在瓶肩和底部区域。参见图5。
还对瓶子进行坠落冲击试验。该测量包括将瓶子充满水，使瓶子在20℃调节24小时，在2个不同方向从不同高度对瓶子进行坠落试验。虽然观察到从4英尺的高度的坠落冲击性能无差别，但是由聚合物A制成的40个瓶子中有3个开裂，由聚合物B制成的4个瓶子中有1个开裂，由聚合物C制成的瓶子均未开裂。
虽然上述内容涉及本发明的实施方式，但是，可以在不偏离本发明的基本范围条件下，对本发明的其他和进一步的实施方式进行设计，并且本发明的范围由所附权利要求书确定。
Claims (19)
1.一种注坯拉伸吹塑(ISBM)的制品，该制品包括：
分子量分布约为9-20的丙烯基无规共聚物。
2.如权利要求1所述的制品，其特征在于，所述无规共聚物包含乙烯。
3.如权利要求2所述的制品，其特征在于，所述无规共聚物包含约0.2-10重量％乙烯。
4.如权利要求1所述的制品，其特征在于，所述无规共聚物包含至少约89重量％丙烯。
5.如权利要求1所述的制品，其特征在于，所述丙烯基无规共聚物用齐格勒-纳塔催化剂形成。
6.如权利要求5所述的制品，其特征在于，所述齐格勒-纳塔催化剂包含琥珀酸酯电子给体。
7.如权利要求1所述的制品，其特征在于，所述丙烯基无规共聚物的熔体流动速率约为2-30分克/10分钟。
8.如权利要求1所述的制品，其显示，每制得的100个制品中的缺陷小于5个。
9.一种形成注坯拉伸吹塑制品的方法，该方法包括：
提供分子量分布约为9-20的丙烯基无规共聚物；
将该丙烯基无规共聚物注塑成型坯；和
将该型坯拉伸吹塑成制品。
10.如权利要求9所述的方法，其特征在于，所述无规共聚物包含乙烯。
11.如权利要求9所述的方法，其特征在于，所述无规共聚物包含约0.2-10重量％乙烯。
12.如权利要求9所述的方法，其特征在于，所述无规共聚物包含至少约89重量％丙烯。
13.如权利要求9所述的方法，其特征在于，所述丙烯基无规共聚物用齐格勒-纳塔催化剂形成。
14.如权利要求13所述的方法，其特征在于，所述齐格勒-纳塔催化剂包含琥珀酸酯电子给体。
15.如权利要求9所述的方法，其特征在于，所述丙烯基无规共聚物的熔体流动速率约为2-30分克/10分钟。
16.一种注坯拉伸吹塑(ISBM)的制品，该制品包括：
由包含琥珀酸酯内给体的齐格勒—塔催化剂形成的丙烯基无规共聚物。
17.如权利要求16所述的制品，其特征在于，所述无规共聚物的分子量分布约为9-20。
18.如权利要求16所述的制品，其特征在于，所述无规共聚物包含乙烯。
19.如权利要求16所述的方法，其特征在于，所述丙烯基无规共聚物的熔体流动速率约为2-30分克/10分钟。
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| CA1334841C (en) | 1988-09-13 | 1995-03-21 | Mamoru Kioka | Olefin polymerization catalyst component, process for production thereof, olefin polymerization catalysts, and process for polymerizing olefins |
| US7074871B2 (en) * | 1992-05-29 | 2006-07-11 | Basell Poliolefine Italia S.R.L. | Crystalline polymers of propylene having improved processability in the molten state and process for their preparation |
| US5641848A (en) * | 1995-07-24 | 1997-06-24 | Montell North America Inc. | Polypropylene blown film |
| WO1999007752A1 (fr) * | 1997-08-05 | 1999-02-18 | Grand Polymer Co., Ltd. | Composition de resine de polypropylene et utilisation de celle-ci |
| DE19805329A1 (de) * | 1998-02-11 | 1999-08-12 | Basf Ag | Spritzstreckgeblasene Behälter aus Olefinpolymerisaten |
| KR100700957B1 (ko) | 1999-04-15 | 2007-03-28 | 바셀 테크놀로지 컴퍼니 비.브이. | 올레핀 중합반응을 위한 성분 및 촉매 |
| US6630538B1 (en) * | 1999-05-13 | 2003-10-07 | Maria D. Ellul | Polypropylene thermoplastic elastomer compositions having improved processing properties and physical property balance |
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| JP4964396B2 (ja) | 2000-10-13 | 2012-06-27 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | オレフィン重合用触媒成分 |
| EP1392638B1 (en) | 2001-06-07 | 2016-12-14 | Basell Poliolefine Italia S.r.l. | Process for preparing alkylidene substituted succinic acid esters |
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| JP4664080B2 (ja) * | 2002-09-20 | 2011-04-06 | エクソンモービル・ケミカル・パテンツ・インク | 超臨界条件でのポリマー製造 |
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| BRPI0412935B1 (pt) * | 2003-08-05 | 2014-08-05 | Basell Poliolefine Srl | Artigos preparados por extrusão, moldagem e suas combinações e seu processo de produção, tubos mono- ou multicamadas e composição poliolefínica heterofásica |
| JP2008510056A (ja) * | 2004-08-18 | 2008-04-03 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | チーグラー−ナッタプロピレンポリマー組成物からの延伸ブロー成形容器 |
| US20060279026A1 (en) * | 2005-06-09 | 2006-12-14 | Fina Technology, Inc. | Polypropylene composition for injection stretch blow molding |
| EP2097459A1 (en) * | 2006-12-29 | 2009-09-09 | Fina Technology, Inc. | Succinate-containing polymerization catalyst system using n-butylmethyldimethoxysilane for preparation of polypropylene film grade resins |
-
2007
- 2007-10-02 US US11/906,605 patent/US8507628B2/en not_active Expired - Fee Related
-
2008
- 2008-09-30 CN CN200880110493.7A patent/CN101808800A/zh active Pending
- 2008-09-30 WO PCT/US2008/078231 patent/WO2009045987A1/en active Application Filing
- 2008-09-30 JP JP2010528064A patent/JP2010540298A/ja active Pending
- 2008-09-30 KR KR1020107005398A patent/KR20100071039A/ko not_active Application Discontinuation
- 2008-09-30 EP EP08835798A patent/EP2205424A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010540298A (ja) | 2010-12-24 |
| KR20100071039A (ko) | 2010-06-28 |
| WO2009045987A1 (en) | 2009-04-09 |
| EP2205424A1 (en) | 2010-07-14 |
| US8507628B2 (en) | 2013-08-13 |
| US20090087602A1 (en) | 2009-04-02 |
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