CN1675298A - 增塑聚烯烃组合物 - Google Patents
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Abstract
本发明涉及含有聚烯烃和非官能化增塑剂的增塑聚烯烃组合物;其中非官能化增塑剂可以包括具有低于-5℃的倾点的C6-C200链烷烃(包括支化和正链烷烃)。在一个实施方案中,非官能化增塑剂是包括C6-C25异链烷烃的异链烷烃。在另一个实施方案中,非官能化增塑剂是包括C10-C100正链烷烃的聚α-烯烃。该聚烯烃可以是聚丙烯均聚物,共聚物,耐冲击共聚物,或它们的共混物,并且可以包括塑性体。由本发明的组合物制备的合乎需要的制品的非限制性实例包括薄膜,软管,管道,片材,纤维,纺织和无纺织物,汽车组件,家具,运动器材,食品储存容器,透明和半透明制品,玩具,胶管和管材,以及医疗器材。
Description
发明领域
本发明涉及包括聚烯烃和非官能化增塑剂比如C6-C200链烷烃的增塑聚烯烃。更具体地说,本发明涉及增塑聚烯烃比如具有改进加工性能和诸如柔性和耐冲击性之类的性能的丙烯聚合物。
背景技术
聚烯烃可用于大量的日用制品。然而,许多聚烯烃,尤其聚丙烯均聚物和共聚物的一个缺陷是相对高的玻璃化转变温度。该特性使这些聚烯烃变脆,尤其在低温下。如果希望制备能够耐受宽范围温度的制品,那么需要提供能够保持其理想的特性比如高温性能等,同时改进冲击强度和韧性的聚烯烃。尤其,有利的是,提供拥有改进的韧性,但不损害它的韧性和其它理想的性能的丙烯聚合物。
将增塑剂或其它物质加入到聚烯烃中是改进诸如冲击强度和韧性之类的性能的一种选择。有一些公开物就是为了这种目的,比如US4,960,820;US 4,132,698;US 3,201,364;WO 02/31044;WO01/18109A1;和EP 0 300 689A2。这些公开物涉及与官能化增塑剂共混的聚烯烃和弹性体。官能化增塑剂是诸如含有芳族基团的矿物油之类的材料,以及高倾点(高于-20℃)化合物。这些化合物的使用一般没有保持聚烯烃的透明性,以及冲击强度常常没有被改进。
其它背景参考文献包括EP 0 448 259A,EP 1 028 145A,US专利Nos.4,073,782和3,415,925。
所需要的是具有改进的柔软度,更好的柔性(低挠曲模量),降低的玻璃化转变温度,和在低温(0℃以下)下的改进冲击强度(改进的加德纳冲击强度),同时不影响聚烯烃的熔融温度,聚烯烃结晶速率,它的透明度,并且具有最低程度的增塑剂至由此制备的制品的表面的迁移的增塑聚烯烃。此外,需要能够在诸如食品容器和玩具之类的应用中使用的增塑聚丙烯。
尤其希望通过使用简单的非反应性化合物比如链烷烃来增塑聚烯烃。然而,我们被教导,脂族或链烷烃类化合物会损害聚烯烃的性能,因此不被推荐。(例如参阅CHEMICAL ADDITIVES FOR PLASTICSINDUSTRY 107-116(Radian Corp.,Noyes Data Corporation,NJ1987);WO 01/18109 A1)。本发明的发明人已经令人惊奇地发现,链烷烃化合物是聚烯烃的有效增塑剂。本发明涉及此类增塑聚烯烃。
本发明的概述
本发明涉及含有聚烯烃和非官能化增塑剂的增塑聚烯烃组合物;其中非官能化增塑剂可以包括具有低于-5℃的倾点的C6-C200链烷烃(包括支化和正链烷烃)。在一个实施方案中,非官能化增塑剂是包括C6-C25异链烷烃的异链烷烃。在另一个实施方案中,非官能化增塑剂是包括C10-C100正链烷烃的聚α-烯烃。该聚烯烃可以是聚丙烯均聚物,共聚物,耐冲击共聚物,或它们的共混物,并且可以包括塑性体。由本发明的组合物制备的合乎需要的制品的非限制性实例包括薄膜,片材,纤维,纺织和无纺织物,软管,管道,汽车组件,家具,运动器材,食品储存容器,透明和半透明制品,玩具,胶管和管材,以及医疗器材。本发明的组合物特征在于具有改进(降低)的Tg,与起始聚烯烃相比,同时保持了其它理想的性能。
附图简述
图1是本文列举的各种增塑丙烯均聚物实例的随温度而变的储能模量(E′)的图解表示;
图2是本文列举的各种增塑丙烯均聚物实例的随温度而变的Tanδ的图解表示;
图3是本文列举的各种增塑丙烯共聚物实例的随温度而变的Tanδ的图解表示;
图4是本文列举的各种增塑丙烯抗冲共聚物实例的随温度而变的Tanδ的图解表示;
图5是说明本发明的各种增塑丙烯均聚物样品的随温度而变的由DSC得到的熔化热流的图解表示;
图6是说明本发明的各种样品-增塑丙烯均聚物样品的随温度而变的由DSC得到的结晶热流的图解表示;
图7是说明本发明的各种增塑丙烯共聚物样品的随温度而变的由DSC得到的熔化热流的图解表示;
图8是说明本发明的各种增塑丙烯共聚物样品的随温度而变的由DSC得到的结晶热流的图解表示;
图9是说明本发明的各种增塑丙烯抗冲共聚物样品的随温度而变的由DSC获得的熔化热流的图解表示;
图10是说明本发明的各种增塑丙烯抗冲共聚物样品的随温度而变的由DSC得到的结晶热流的图解表示;
图11是说明本发明的各种增塑丙烯均聚物样品的随剪切速率而变的剪切粘度的图解表示;
图12是说明本发明的各种增塑丙烯共聚物样品的随剪切速率而变的剪切粘度的图解表示;
图13是说明本发明的各种增塑丙烯抗冲共聚物样品的随剪切速率而变的剪切粘度的图解表示;和
图14是说明本发明的各种增塑丙烯均聚物样品的分子量分布的图解表示。
本发明的详细描述
本发明是包括聚烯烃和非官能化增塑剂(NFP)的增塑聚烯烃组合物。NFP可以是脂族烃,或链烷烃,通常包括C6-C200链烷烃。本文所使用的术语“链烷烃”包括C6-C200链烷烃的所有异构体,包括支化和线性结构,以及它们的共混物。各链烷烃可以包括饱和环烃类。理想地,NFP具有低于0℃的倾点,0.1-3000cSt的100℃粘度(ASTMD445-97)。有用的NFP可以包括所谓的聚α-烯烃(PAO)和异链烷烃。
本发明的某些组合物的特征能够在于,在一个实施方案中,对于存在于组合物中的每4wt%的NFP,组合物的玻璃化转变温度(Tg)降低至少2℃;在另一个实施方案中,对于存在于组合物中的每4wt%的NFP,Tg降低至少3℃;和在又一个实施方案中,对于存在于组合物中的每4wt%的NFP,组合物的玻璃化转变温度(Tg)降低至少4-10℃,同时聚烯烃的熔融温度和结晶温度保持恒定(±1-2℃)。此外,本发明的组合物特征在于NFP与丙烯聚合物相容和混溶,不形成单独的相。这例如通过用DMTA(动态机械热分析)对组合物观测到的Tg分布来证明。
聚烯烃和NFP能够通过任何适合的方式来共混。例如,它们可以在转鼓、挤出机或它们的结合物中共混。性能增强的本文所述的增塑聚烯烃组合物可用于许多应用,包括透明组件,比如炊具和储存用具,其它制品,比如家具,汽车组件,玩具,运动装,医疗器材,可灭菌的医疗器材和灭菌容器,无纺纤维和织物以及由此获得的制品比如窗帘,睡衣,过滤器,卫生保健制品,尿布,以及膜,取向膜,片材,软管,管和其中柔软度、高冲击强度和冷冻温度之下的冲击强度很重要的其它制品。许多技术能够用于加工本发明的增塑聚烯烃以形成这些制品,包括注塑,挤出,热成形,吹塑,滚塑,纺粘,熔体喷射,纤维纺丝,吹塑薄膜,用于取向薄膜的拉伸,以及其它普通加工方法。
以下就聚烯烃,NFP和其中的实施方案来进一步描述本发明。
聚烯烃
聚烯烃可以用本发明的NFP增塑,或与本发明的NFP共混,以便形成柔性更高,但仍耐冲击的组合物。在本发明的一个方面,聚烯烃选自聚丙烯均聚物,聚丙烯共聚物,和它们的共混物。均聚物可以是无规立构聚丙烯,全同立构聚丙烯,间同立构聚丙烯和它们的共混物。共聚物可以是无规共聚物,嵌段共聚物,和它们的共混物。尤其,聚合物共混物包括所谓的耐冲击共聚物,弹性体和塑性体,它们的任何一种可以是聚丙烯和聚丙烯共聚物的物理共混物或就地共混物。制备聚丙烯的方法不是关键的,因为它能够通过淤浆、溶液或气相方法,以及通过使用齐格勒-纳塔类催化剂,金属茂类催化剂,或它们的结合物来制备。此类催化剂在本领域中是众所周知的,并且例如描述在ZIEGLER CATALYSTS(Gerhard Fink,Rolf Mulhaupt and Hans H.Brintzinger,eds.,Springer-Verlag 1995);Resconi等人,Selectivity in Propene Polymerization with MetalloceneCatalysts,100 CHEM.REV.1253-1345(2000);和I,IIMETALLOCENE-BASED POLYOLEFINS(Wiey & Sons 2000)中。
聚烯烃可以是丙烯均聚物。理想的丙烯均聚物具有1.5-10,或在另一个实施方案中2.0-7,或在仍然另一个实施方案中2.0-5,或在再一个实施方案中2.0-4的分子量分布(Mw/Mn)。丙烯均聚物的在23℃下用0.125英寸圆盘测试的加德纳冲击强度在一个实施方案中可以是20in-lb到1000in-lb,在另一个实施方案中是30in-lb到500in-lb,以及在又一个实施方案中是40in-lb到400in-lb。在又一个实施方案中,丙烯均聚物的1%正割挠曲模量在一个实施方案中是100MPa到2300MPa,在另一个实施方案中是200MPa到2100MPa,以及在又一个实施方案中是300MPa到2000MPa,其中合乎需要的聚烯烃可以具有任何挠曲模量上限与任何挠曲模量下限的任意组合。丙烯均聚物的熔体流动速率(MFR)(ASTM D 1238,230℃,2.16kg)在一个实施方案中是0.1dg/min到2500dg/min,而在另一个实施方案中是0.3-500dg/min。
可用于本发明的丙烯均聚物或共聚物可以具有一定水平的全同立构规整度。因此,在一个实施方案中,全同立构聚丙烯是有用的聚丙烯,在另一个实施方案中,高度全同立构聚丙烯是有用的聚丙烯。本文所使用的“全同立构”被定义为具有根据13C-NMR分析的至少10%全同立构五价物。本文所使用的“高度全同立构”被定义为具有根据13C-NMR分析的至少60%全同立构五价物。在一个期望的实施方案中,具有至少85%全同立构规整度的聚丙烯均聚物是聚烯烃,而在另一个实施方案中,具有至少90%的全同立构规整度的聚丙烯均聚物是聚烯烃。
在本发明的另一个实施方案中,聚烯烃是丙烯衍生的单元和选自乙烯和C4-C20α-烯烃衍生的单元,或乙烯和C4-C10α-烯烃衍生的单元中的单元的无规或嵌段丙烯共聚物。乙烯或C4-C20α-烯烃衍生的单元在一个实施方案中以共聚物的0.1-50wt%存在,在另一个实施方案中以0.5-30wt%存在,在又一个实施方案中以1-15wt%存在,以及在再一个实施方案中以0.1-5wt%存在,其中合乎需要的共聚物包括这里所述的任何wt%上限与任何wt%下限的任意组合的乙烯和C4-C20α-烯烃衍生的单元。丙烯共聚物具有在一个实施方案中高于8,000g/mol,在另一个实施方案中高于10,000g/mol,在又一个实施方案中高于12,000g/mol,在再一个实施方案中高于200,000g/mol,以及在另一个实施方案中低于1,000,000g/mol,在又一个实施方案中低于800,000g/mol的重均分子量,其中合乎需要的共聚物可以包括这里所述的任何分子量上限与任何分子量下限。
在另一个实施方案中,丙烯共聚物的在23℃下用0.125英寸圆盘测试的加德纳冲击强度在一个实施方案中是20in-lb到1000in-lb,在另一个实施方案中是30in-lb到500in-lb,以及在又一个实施方案中是40in-lb到400in-lb。此外,丙烯共聚物可以具有在一个实施方案中100MPa到2300MPa,在另一个实施方案中200MPa到2100MPa,和在又一个实施方案中300MPa到2000MPa的1%正割挠曲模量,其中合乎需要的聚烯烃可以具有任何挠曲模量上限与任何挠曲模量下限的任意组合。合乎需要的共聚物的熔体流动速率(MFR)(ASTM D 1238,230℃)在一个实施方案中是0.1dg/min到2500dg/min,而在另一个实施方案中是0.1-500dg/min。
在另一个实施方案中,聚烯烃可以是所谓的“耐冲击共聚物”或嵌段共聚物。该耐冲击共聚物可以是反应器共混物(就地共混物)或物理共混物。在一个实施方案中,按耐冲击共聚物的总重量为基准计,适合的耐冲击共聚物包含40-95wt%的组分A和5-60wt%的组分B;其中组分A包括丙烯均聚物或共聚物,该共聚物含有≤10wt%乙烯,丁烯,己烯或辛烯共聚单体;和其中组分B包括丙烯共聚物,其中该共聚物含有5-70wt%乙烯,丁烯,己烯和/或辛烯共聚单体,以及大约95到大约30wt%丙烯。在耐冲击共聚物的一个实施方案中,组分B基本上由丙烯和大约30到大约65wt%乙烯组成。在另一个实施方案中,组分B包括乙烯-丙烯共聚物,乙烯-丙烯-二烯三元共聚物,乙烯-丙烯酸酯共聚物,乙烯-乙酸乙烯酯共聚物,苯乙烯-丁二烯共聚物,乙烯-丙烯酸酯共聚物,聚丁二烯,聚异戊二烯,天然橡胶,异丁烯,烃树脂(特征在于低于5000的分子量,大约50-100℃的Tg和低于大约140℃的软化点),松香,和它们的混合物。在另一个实施方案中,组分B具有低于3.5的分子量分布。在又一个实施方案中,组分B具有至少20,000的重均分子量。有用的耐冲击共聚物例如公开在US6,342,566和US 6,384,142中。
在又一个实施方案中,丙烯抗冲共聚物的在-29℃下用0.125英寸圆盘测试的加德纳冲击强度在一个实施方案中是20in-lb到1000in-lb,在另一个实施方案中是30in-lb到500in-lb,以及在又一个实施方案中是40in-lb到400in-lb。此外,丙烯抗冲共聚物可以具有在一个实施方案中100MPa到2300MPa,在另一个实施方案中200MPa到2100MPa,和在又一个实施方案中300MPa到2000MPa的1%正割挠曲模量,其中合乎需要的聚烯烃可以具有任何挠曲模量上限与任何挠曲模量下限的任意组合。合乎需要的均聚物的熔体流动速率(MFR)(ASTM D 1238,230℃,2.16kg)在一个实施方案中是0.1dg/min到2500dg/min,而在另一个实施方案中是0.3-500dg/min。
另一适合的聚烯烃包括聚丙烯均聚物或共聚物与所谓的“塑性体”的共混物。可用于本发明的塑性体可以被描述为具有0.85-0.915g/cm3和0.10-30dg/min(ASTM D1238;190℃,2.1kg)的熔体指数(MI)的聚烯烃共聚物。在一个实施方案中,有用的塑性体是乙烯衍生的单元和至少一种C3-C10α-烯烃衍生的单元的共聚物,该共聚物具有低于0.915g/cm3的密度。存在于塑性体中的共聚单体(C3-C10α-烯烃衍生的单元)的量在一个实施方案中是2-35wt%,在另一个实施方案中是5-30wt%,在又一个实施方案中是15-25wt%,以及在再一个实施方案中是20-30wt%。
可用于本发明的塑性体具有在一个实施方案中0.10-20dg/min,在另一个实施方案中0.2-10dg/min,和在又一个实施方案中0.3-8dg/min的熔体指数(MI)。有用的塑性体的平均分子量在一个实施方案中是10,000-800,000,而在另一个实施方案中是20,000-70,000。有用的塑性体的1%正割挠曲模量(ASTM D790)在一个实施方案中是10MPa到150MPa,而在另一个实施方案中是20MPa到100MPa。此外,可用于本发明的组合物的塑性体具有在一个实施方案中30-80℃(第一熔融峰)和50-125℃(第二熔融峰),以及在另一个实施方案中40-70℃(第一熔融峰)和50-100℃(第二熔融峰)的熔融温度(Tm)。
可用于本发明的塑性体是乙烯衍生的单元和高级α-烯烃衍生的单元,比如丙烯,1-丁烯,1-己烯和1-辛烯的金属茂催化的共聚物,它在一个实施方案中含有足够的一种或多种的这些共聚单体,以便获得0.860-0.900g/cm3的密度。合乎需要的塑性体的分子量分布(Mw/Mn)在一个实施方案中是1.5-5,而在另一个实施方案中是2.0-4。商购塑性体的实例是EXACT 4150,乙烯和1-己烯的共聚物,1-己烯衍生的单元占塑性体的18-22wt%,并具有0.895g/cm3的密度和3.5dg/min的MI(ExxonMobil Chemical Company,Houston,TX);和EXACT 8201,乙烯和1-辛烯的共聚物,1-辛烯衍生的单元占塑性体的26-30wt%,并具有0.882g/cm3的密度和1.0dg/min的MI(ExxonMobil ChemicalCompany,Houston,TX)。
当用于与本发明的NFP共混时,适合用于本发明的聚烯烃能够为任何物理形式。在一个实施方案中,反应器粒料(定义为在任何加工工序之前从聚合反应器中分离出来的聚合物的颗粒)用来与本发明的NFP共混。反应器粒料具有在一个实施方案中50μm-10mm,在另一个实施方案中10μm-5mm的平均直径。在另一个实施方案中,聚烯烃以切粒(pellet)的形式存在,例如具有由反应器粒料的熔体挤出所形成的1mm-10mm的平均直径,
在本发明的一个实施方案中,适于该组合物的聚烯烃不包括聚丙烯与其它聚烯烃的物理共混物,尤其不包括聚丙烯与低分子量(500-10,000g/mol)聚乙烯或聚乙烯共聚物的物理共混物,即,低分子量聚乙烯或聚乙烯共聚物不有意地以任何量加入到本发明的聚烯烃(例如聚丙烯均聚物或共聚物)组合物中,比如象在WO 01/18109A1中的情况那样。
聚烯烃在一个实施方案中以40-99.9wt%,在另一个实施方案中以50-99wt%,在又一个实施方案中以60-98wt%,在又一个实施方案中以70-97wt%,在再一个实施方案中以80-97wt%,以及在还一个实施方案中以90-98wt%的量存在于本发明的组合物中,其中合乎需要的范围可以是这里所述的任何wt%上限与任何wt%下限的任意组合。
用于本发明的合乎需要的聚烯烃因此可以用这里的任何实施方案,或这里所述的实施方案的任何组合来描述。
非官能化增塑剂
本发明的聚烯烃组合物包括非官能化增塑剂(“NFP”)。本发明的NFP是含有碳和氢的化合物,但不包括相当量的选自羟基,芳基和取代芳基,卤素,烷氧基,羧酸根,酯,碳不饱和键,丙烯酸酯,氧,氮和羧基中的官能团。所谓“相当量”是指不故意地将这些基团和含有这些基团的化合物加入到NFP中,如果存在的话,在一个实施方案中以低于NFP的5wt%,在另一个实施方案中低于1wt%,以及在又一个实施方案中以低于0.5wt%的量存在。
在一个实施方案中,NFP由C6-C200链烷烃,或C8-C100链烷烃组成。在另一个实施方案中,NFP主要由C6-C200链烷烃,或由C8-C100链烷烃组成。对于本发明和这里的说明来说,术语“链烷烃”包括所有异构体,比如正链烷烃,支化链烷烃,异链烷烃,还可以包括脂环族物质,和它们的共混物,并且可以由本领域已知的方式合成,或者以使得满足对于这里合乎需要的NFP所述的要求的这种方式由精炼原油获得。应该认识到,可用作NFP的这里所述的材料类型能够单独使用,或与本文所述的其它NFP混合,以便获得所需的性能。
NFP在一个实施方案中以0.1到60wt%,在另一个实施方案中以0.5-40wt%,在又一个实施方案中以1-20wt%,以及在还一个实施方案中以2-10wt%的量存在于本发明的聚烯烃组合物中,其中合乎需要的范围可以包括这里所述的任何wt%上限与任何wt%下限。
NFP还可以通过许多或任意组合的这里所述的参数来描述。在一个实施方案中,本发明的NFP具有在一个实施方案中低于0℃,在另一个实施方案中低于-5℃,在另一个实施方案中低于-10℃,在又一个实施方案中低于-20℃,在再一个实施方案中低于-40℃,在另一个实施方案中低于-50℃,在还一个实施方案中低于-60℃,在另一个实施方案中高于-120℃,以及在又一个实施方案中高于-200℃的倾点(ASTMD97),其中合乎需要的范围可以包括这里所述的任何倾点上限与任何倾点下限。在一个实施方案中,NFP是在0.5-200cSt(40℃)的粘度范围内(ASTM D445-97)具有低于-30℃,或-30℃到-90℃的倾点的链烷烃或其它化合物。大多数矿物油(通常含有芳族结构部分和其它官能团)在相同的粘度范围内具有10℃到-20℃的倾点。
NFP可以具有在一个实施方案中低于3.0,在另一个实施方案中低于2.8,在另一个实施方案中低于2.5,在又一个实施方案中低于2.3,以及在再一个实施方案中低于2.1的介电常数(20℃)。聚乙烯和聚丙烯各自具有至少2.3的介电常数(1kHz,23℃)(CRC HANDBOOKOF CHEMISTRY AND PHYSICS(David R.Lide,ed.82d ed.CRC Press2001))。
NFP具有在一个实施方案中0.1-3000cSt(100℃),在另一个实施方案中0.5-1000cSt(100℃),在又一个实施方案中1-250cSt(100℃),在再一个实施方案中1-200cSt(100℃),以及在还一个实施方案中10-500cSt(100℃)的粘度(ASTM D445-97),其中合乎需要的范围包括这里所述的任何粘度上限与任何粘度下限。
NFP具有在一个实施方案中低于0.920g/cm3,在另一个实施方案中低于0.910g/cm3,在另一个实施方案中0.650-0.900g/cm3,在另一个实施方案中0.700-0.860g/cm3,在另一个实施方案中0.750-0.855g/cm3,在另一个实施方案中0.790-0.850g/cm3,在又一个实施方案中0.800-0.840g/cm3的比重(ASTM D 4052,15.6/15.6℃),其中合乎需要的范围可以包括这里所述的任何比重上限与任何比重下限。NFP具有在一个实施方案中100-800℃,在另一个实施方案中200-600℃,在又一个实施方案中250-500℃的沸点。此外,NFP具有在一个实施方案中低于20,000g/mol,在另一个实施方案中低于10,000g/mol,在又一个实施方案中低于5,000g/mol,在另一个实施方案中低于4,000g/mol,在又一个实施方案中低于2,000g/mol,在再一个实施方案中低于500g/mol,以及在还一个实施方案中低于100g/mol的重均分子量(GPC或GC),其中合乎需要的分子量范围能够是这里所述的任何分子量上限与任何分子量下限的任意组合。
适合作为用于本发明的聚烯烃的NFP的化合物可以选自商购化合物,比如所谓的“异链烷烃”,“聚α-烯烃”(PAO)和“聚丁烯类”(PAO的亚类)。这三类化合物能够被描述为含有支化、环状和直链结构的链烷烃,和它们的共混物。这些NFP能够被描述为在一个实施方案中包括C6-C200链烷烃,而在另一个实施方案中包括C8-C100链烷烃。
所谓的“异链烷烃”描述如下。这些链烷烃理想地是异链烷烃,是指链烷烃链具有沿各链烷烃链的至少一部分分布的C1-C10烷基支化。C6-C200链烷烃可以在一个实施方案中包括C6-C25异链烷烃,在另一个实施方案中包括C8-C20异链烷烃。
更具体地说,异链烷烃是其分子具有键接于至少其它三个碳原子的至少一个碳原子或至少一条侧链的饱和脂族烃类(即具有一个或多个叔或季碳原子的分子),优选其中每分子的碳原子总数在一个实施方案中是6-50,在另一个实施方案中是10-24,在又一个实施方案中是10-15。一般存在各碳数的各种异构体。异链烷烃还可以包括具有支化侧链的环烷烃,一般作为异链烷烃的次要组分。这些异链烷烃的密度(ASTM 4052,15.6/15.6℃)是0.70-0.83g/cm3;在一个实施方案中低于-40℃,而在另一个实施方案中低于-50℃的倾点;0.5-20cSt(25℃)的粘度(ASTM 445,25℃);和100-300g/mol的平均分子量。异链烷烃可以ISOPAR的商品名从市场上买到(ExxonMobil Chemical Company,Houston TX),例如描述在US6,197,285,3,818,105和3,439,088中,并且作为异链烷烃的ISOPAR系列出售,它们的一些在以下表1中总结:
表1 ISOPAR系列异链烷烃
名称 | 馏程(℃) | 倾点(℃) | 平均比重(g/cm3) | 粘度@25℃(cSt) | 饱和物和芳族化合物(wt%) |
ISOPAR EISOPAR GISOPAR HISOPAR KISOPAR LISOPAR MISOPAR V | 117-136161-176178-188179-196188-207223-254272-311 | -63-57-63-60-57-57-63 | 0.720.750.760.760.770.790.82 | 0.851.461.81.851.993.814.8 | <0.01<0.01<0.01<0.01<0.01<0.01<0.01 |
在另一个实施方案中,异链烷烃是在分子中具有6-50个碳原子或10-24个碳原子的支化和正链烷烃的混合物。异链烷烃组合物具有在一个实施方案中0.5∶1-9∶1,在另一个实施方案中1∶1-4∶1的支化链烷烃∶正链烷烃比率。在该实施方案中,异链烷烃混合物含有高于50wt%(基于异链烷烃组合物的总重量)单-甲基物质,例如2-甲基,3-甲基,4-甲基,5-甲基等,其中最低限度地形成了具有碳数大于1的取代基的分支,例如乙基,丙基,丁基等,以混合物中的异链烷烃的总重量为基准计。在一个实施方案中,混合物的异链烷烃含有高于70wt%的单-甲基物质,以混合物中的异链烷烃的总重量为基准计。该异链烷烃混合物在一个实施方案中在100-350℃,而在另一个实施方案中在110-320℃沸腾。在不同等级的制备中,一般将链烷烃混合物分馏为具有窄沸程,例如35℃沸程的馏分。这些支化链烷烃/正链烷烃共混物例如描述在US 5,906,727中。
其它适合的异链烷烃还可以商品名SHELLSOL(Shell),SOLTROL(Chevron Phillips)和SASOL(Sasol Limited)购买。SHELLSOL是Royal Dutch/Shell Group of Companies的产品,例如ShellsolTM(沸点=215-260℃),SOLTROL是Chevron Phillips Chemical Co.LP的产品,例如SOLTROL 220(沸点=233-280℃)。SASOL是Sasol Limited的产品(Johannesburg,South Africa),例如SASOL LPA-210,SASOL-47(沸点=238-274℃)。
适合作为本发明的NFP的链烷烃还包括如下描述的所谓PAO。可用于本发明的PAO包括C6-C200链烷烃,在另一个实施方案中,C10-C100正链烷烃。PAO在一个实施方案中是C4-C12α-烯烃,在另一个实施方案中C5-C12α-烯烃的二聚体,三聚体,四聚体,五聚体等。适合的烯烃包括1-丁烯,1-戊烯,1-己烯,1-庚烯,1-辛烯,1-壬烯,1-癸烯,1-十一碳烯和1-十二碳烯。在一个实施方案中,烯烃是1-癸烯,以及NFP是1-癸烯的二聚体、三聚体、四聚体和五聚体(和五聚体以上)的混合物。PAO更具体地描述在例如US 5,171,908,和US5,783,531,以及SYNTHETIC LUBRICANNTS AND HIGH-PERFORMANCEFUNCTIONAL FLUIDS 1-52(Leslie R.Rudnick & Ronald L.Shubkin,ed.Marcel Dekker,Inc.1999)。
本发明的PA0具有在一个实施方案中100-20,000,在另一个实施方案中200-10,000,在又一个实施方案中200-7,000,在仍然又一个实施方案200-2,000,以及在再一个实施方案中200-500的重均分子量。一般,PAO具有0.1-150cSt(100℃),或0.1-3000cSt(100℃)的粘度(ASTM 445)。可用于本发明的PAO具有在一个实施方案中低于0℃,在另一个实施方案中低于-10℃,在又一个实施方案中低于-20℃,以及在再一个实施方案中低于-40℃的倾点。合乎需要的PAO可以作为SHF和SuperSyn PAO(ExxonMobil Chemical Company,Houston TX)购买到,它们的一些在以下表2中总结。
表2 SHF和SuperSyn系列聚α-烯烃
PAO | 比重(g/cm3;15.6/15.6℃) | 粘度@100℃,cSt | VI | 倾点,℃ |
SHF-20SHF-21SHF-23SHF-41SHF-61/63SHF-82/83SHF-101SHF-403SHF-1003SuperSyn 2150SuperSyn 2300SuperSyn 21000SuperSyn 23000 | 0.7980.8000.8020.8180.8260.8330.8350.8500.8550.8500.8520.8560.857 | 1.681.701.804.005.807.9010.040.01071503001,0003,000 | ---123133135136152179214235305388 | -63-57-54-57-57-54-54-39-33-42-30-18-9 |
聚丁烯类(PAO的子集)是本发明的另一有用的NFP,并描述如下。在本发明的一个实施方案中,聚丁烯操作油是在一个实施方案中具有3-8个碳原子,在另一个实施方案中优选具有4-6个碳原子的烯烃衍生的单元的低分子量(低于15,000数均分子量;低于60,000重均分子量)均聚物或共聚物。在又一个实施方案中,聚丁烯是C4残液的均聚物或共聚物。称为“聚丁烯”聚合物的这种低分子量聚合物的实例例如描述在SYNTHETIC LUBRICANNTS AND HIGH-PERFORMANCEFUNCTIONAL FLUIDS 357-392(Leslie R.Rudnick & Ronald L.Shubkin,ed.,Marcel Dekker 1999)(下文“聚丁烯操作油”或“聚丁烯”)。
用另一种方式来描述,聚丁烯是至少一种异丁烯衍生的单元,1-丁烯衍生的单元,和2-丁烯衍生的单元的共聚物。在一个实施方案中,聚丁烯是该三种单元的均聚物、共聚物或三元共聚物,其中异丁烯衍生的单元是共聚物的40-100wt%,1-丁烯衍生的单元是共聚物的0-40wt%,和2-丁烯衍生的单元是共聚物的0-40wt%。在另一个实施方案中,聚丁烯是该三种单元的共聚物或三元共聚物,其中异丁烯衍生的单元是共聚物的40-99wt%,1-丁烯衍生的单元是共聚物的2-40wt%,以及2-丁烯衍生的单元是共聚物的0-30wt%。在又一个实施方案中,聚丁烯是该三种单元的三元共聚物,其中异丁烯衍生的单元是共聚物的40-96wt%,1-丁烯衍生的单元是共聚物的2-40wt%,以及2-丁烯衍生的单元是共聚物的2-20wt%。在还一个实施方案中,聚丁烯是异丁烯和1-丁烯的均聚物或共聚物,其中异丁烯衍生的单元是均聚物或共聚物的65-100wt%,和1-丁烯衍生的单元是共聚物的0-35wt%。
用于本发明的聚丁烯操作油一般具有在一个实施方案中低于10,000g/mol,在另一个实施方案中低于8000g/mol,和在又一个实施方案中低于6000g/mol的数均分子量(Mn)。聚丁烯油具有在一个实施方案中高于400g/mol,在另一个实施方案中高于700g/mol,以及在又一个实施方案中高于900g/mol的数均分子量。一个优选的实施方案能够是这里所述的任何分子量下限与任何分子量上限的组合。例如,在本发明的聚丁烯的一个实施方案中,聚丁烯具有400g/mol到10,000g/mol,在另一个实施方案中700g/mol到8000g/mol,以及在又一个实施方案中900g/mol到3000g/mol的数均分子量。聚丁烯操作油的有用粘度在一个实施方案中是10-6000cSt(厘沲)(100℃),在另一个实施方案中是35-5000cSt(100℃),在又一个实施方案中高于35cSt(100℃),以及在再一个实施方案中高于100cSt(100℃)。
聚丁烯的商品实例是PARAPOLTM系列的操作油(Infineum,Linden,NJ),比如PARAPOLTM 450,700,950,1300,2400和2500。聚丁烯操作油的商购PARAPOLTM系列是合成液体聚丁烯,各配制料具有一定的分子量,所有配制料能够在本发明的组合物中使用。PARAPOLTM油的分子量是420Mn(PARAPOLTM 450)到2700Mn(PARAPOLTM 2500),通过凝胶渗透色谱法测定。PARAPOLTM油的MWD在一个实施方案中是1.8-3,而在另一个实施方案中是2-2.8;这些聚丁烯的倾点在一个实施方案中低于25℃,在另一个实施方案中低于0℃,在又一个实施方案中低于-10℃,以及在还一个实施方案中为-80℃到25℃;和密度(IP 190/86,20℃)在一个实施方案中是0.79-0.92g/cm3,而在另一个实施方案中是0.81-0.90g/cm3。
在以下,表3示出了可用于本发明的实施方案的PARAPOLTM油的某些性能,其中粘度按照ASTM D445-97测定,以及数均分子量(Mn)通过凝胶渗透色谱法测定。
表3 聚丁烯的PARAPOLTM等级
等级 | Mn | 粘度@100℃,cSt |
450700950130024002500 | 420700950130023502700 | 10.67823063032004400 |
用于本发明的合乎需要的NFP因此可以通过这里所述的任何实施方案,或这里所述的实施方案的任何组合来描述。例如,在一个实施方案中,NFP是具有低于25℃的倾点的C6-C200链烷烃。换句话说,NFP包括具有0.1-1000cSt(100℃)的粘度的脂族烃。换句话说,NFP选自具有8-25个碳原子的正链烷烃,支化异链烷烃,和它们的共混物。NFP在一个实施方案中的特征在于,当与聚烯烃混合成增塑组合物时,NFP与丙烯聚合物相容和混溶,不形成单独的相。
在本发明的组合物的一个实施方案中,基本不含普通增塑剂比如通常用于聚(氯乙烯)的那些。尤其,基本不含增塑剂比如邻苯二甲酸酯,己二酸酯,偏苯三酸酯,聚酯和例如在US 3,318,835;US4,409,345;WO 02/31044 A1;和PLASTICS ADDITIVES499-504(Geoffrey Pritchard,ed.,Chapman & Hall 1998)中公开的其它官能化增塑剂。所谓“基本不含”是指这些化合物不被有意地加入到组合物中。
在另一个实施方案中,油如环烷油和其它含芳基的油类以低于本发明的组合物的0.5wt%存在。还有,在又一个实施方案中,用于本发明的非官能化增塑剂基本不含芳族结构部分和碳-碳不饱和键。芳族结构部分包括其分子具有苯、萘、菲、蒽等的环结构特性的化合物。所谓“基本不含”是指不有意地将这些芳族化合物或结构部分加入到组合物中,如果存在的话,以低于NFP的组合物的0.5wt%存在。因此,本发明的组合物基本不含大多数“矿物油”。
在本发明的组合物的另一个实施方案中,基本不含普通增塑剂,弹性体或“相容剂”比如低分子量聚乙烯。尤其,基本不含具有500-10,000的重均分子量的聚乙烯均聚物和共聚物。这种聚乙烯相容剂例如公开在WO 01/18109A1中。所谓“基本不含”是指不有意地将这些化合物加入到组合物中。
共混和制品
本发明的聚烯烃组合物还可以含有其它添加剂。这些添加剂包括抗氧化剂,成核剂,除酸剂,稳定剂,防腐蚀剂,发泡剂,其它UV吸收剂比如断链抗氧化剂等,猝灭剂,抗静电剂,滑爽剂,颜料,染料和填料以及固化剂比如过氧化物。工业上常用的染料和其它着色剂在一个实施方案中以0.01-10wt%存在,而在另一个实施方案中以0.1-6wt%存在。适合的成核剂例如由H.N.Beck公开在HeterogeneousNucleating Agents for Polypropylene Crystallization,11 J.APPLIED POLY.SCI.673-685(1967)和Heterogeneous NucleationStudies on Polypropylene,21 J.POLY.SCI.:POLY.LETTERS347-351(1983)中。适合的成核剂的实例是苯甲酸钠,2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯,2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸铝,二苄叉基山梨醇,二(对-甲苯叉基)山梨醇,二(对-乙基苄叉基)山梨醇,双(3,4-二甲基苄叉基)山梨醇,和N’,N’-二环己基-2,6-萘二羧酰胺,以及歧化松香酯的盐。以上名单用来举例说明包含在主题聚丙烯配制料中的成核剂的适合选择。
尤其,抗氧化剂和稳定剂比如有机亚磷酸酯,位阻胺和酚类抗氧化剂可以在一个实施方案中0.001-2wt%,在另一个实施方案中0.01-0.8wt%,和在又一个实施方案中0.02-0.5wt%存在于本发明的聚烯烃组合物中。适合的有机亚磷酸酯的非限制性实例是三(2,4-二叔丁基苯基)亚磷酸酯(IRGAFOS 168)和二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯(ULTRANOX 626)。位阻胺的非限制性实例包括聚[2-N,N’-二(2,2,6,6-四甲基-4-哌啶基)-己烷二胺-4-(1-氨基-1,1,3,3-四甲基丁烷)-对称-三嗪](CHIMASORB 944);双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(TINUVIN 770)。酚类抗氧化剂的非限制性实例包括四(3,5-二叔丁基-4-羟苯基)丙酸季戊四醇酯(IRGANOX 1010);和1,3,5-三(3,5-二叔丁基-4-羟基苄基-异氰脲酸酯(IRGANOX 3114)。
填料在一个实施方案中可以组合物的0.1-50wt%存在,在另一个实施方案中以0.1-25wt%存在,以及在又一个实施方案中以0.2-10wt%存在。合乎需要的填料包括、但不限于二氧化钛,碳化硅,硅石(和沉淀或非沉淀的硅的其它氧化物),氧化锑,碳酸铅,锌白,锌钡白,锆石,金刚砂,尖晶石,磷灰石,重晶石粉,硫酸钡,菱镁矿,炭黑,白云石,碳酸钙,水合或非水合的离子Mg、Ca、或Zn与Al、Cr或Fe和CO3和/或HPO4的滑石和水滑石化合物;石英粉,盐酸碳酸镁,玻璃纤维,粘土,氧化铝,和其它金属氧化物和碳酸盐,金属氢氧化物,铬,磷和溴化阻燃剂,三氧化二锑,硅石,聚硅氧烷,和它们的共混物。这些填料尤其可以包括本领域已知的任何其它填料和多孔填料及载体,并且在一个实施方案中可以具有在添加到聚烯烃中之前预接触,或预吸附到填料中的本发明的NFP。
更具体地说,在本发明的一个实施方案中,NFP或NFP的某些部分可以与填料,最好多孔填料共混。NFP和填料例如可以通过转鼓或其它湿法共混装置来共混。在该实施方案中NFP和填料共混达适于形成NFP和填料的均匀组合物的时间,理想地,在一个实施方案中,是1分钟到5小时。该NFP/填料共混物然后可以与在本发明中使用的聚烯烃共混,以便进行聚烯烃的增塑。在另一个实施方案中,在将填料与聚烯烃接触之前,可以将多孔填料与NFP或它的某些部分接触。在另一个实施方案中,多孔填料、聚烯烃和NFP同时接触(或在同一共混装置中)。在任何情况下,NFP可以以组合物的0.1-60wt%,或0.2-40wt%,或0.3-20wt%的量存在。
脂肪酸盐还可以存在于本发明的聚烯烃组合物中。此类盐可以在一个实施方案中以组合物的0.001-1wt%存在,而在另一个实施方案中以0.01-0.8wt%存在。脂肪酸金属盐的实例包括月桂酸,硬脂酸,丁二酸,硬脂基乳酸,乳酸,邻苯二甲酸,苯甲酸,羟基硬脂酸,蓖麻油酸,环烷酸,油酸,棕榈酸,和芥酸,适合的金属包括Li,Na,Mg,Ca,Sr,Ba,Zn,Cd,Al,Sn,Pb等。优选的脂肪酸盐选自硬脂酸镁,硬脂酸钙,硬脂酸钠,硬脂酸锌,油酸钙,油酸锌和油酸镁。
本发明的所得增塑聚烯烃可以通过任何适合的方式,比如通过压延,浇铸,涂层,配混,挤出,发泡,层压,吹塑,压塑,注塑,热成型,压铸模塑,浇铸成型,滚塑,流延(比如用于薄膜),纺粘或熔粘(比如用于纤维),或其它加工形式,例如在PLASTICS PROCESSING(Radian Corporation,Noyes Data Corp.1986)中所述的那些。更具体地说,对于生产共混物的物理方法,应该进行充分的混合以确保在转换为成品之前形成均匀的共混物。
更具体地说,本发明的聚烯烃组合物的各组分可以通过任何适合的方式共混,以形成增塑聚烯烃,后者然后适合于加工成有用的制品。在本发明的一个方面,在诸如挤出机或布拉本德混合机的设备内将聚烯烃和NFP共混,或熔体混合。聚烯烃还可以使用转鼓、双锥形混合机、螺带式掺混机或其它适合的掺混机与NFP共混。在又一个实施方案中,聚烯烃和NFP通过例如转鼓和后续的在挤出机中的熔体混合的组合来共混。聚丙烯的挤出技术例如更详细地描述在PLASTICSEXTRUSION TECHNOLOGY 26-27(Friedhelm Hensen,ed.HanserPublishers 1988)和POLYPROPYLENE HANDBOOK 304-308(Edward P.Moore,Jr.ed.,Hanser Publishers 1996)中。
当用于与本发明的NFP共混时,适合用于本发明的聚烯烃能够为任何物理形式。在一个实施方案中,反应器粒料(定义为从聚合反应器中分离出来的聚合物的颗粒)用来与本发明的NFP共混。反应器粒料具有在一个实施方案中10μm-5mm,在另一个实施方案中50μm-10mm的平均直径。另外,聚烯烃以切粒的形式存在,例如具有由反应器粒料的熔体挤出所形成的lmm-6mm的平均直径,
将NFP与聚烯烃共混的一种方法是将各组分在转鼓中接触,聚烯烃以反应器粒料形式存在。这对于聚丙烯均聚物是特别有效的。如果需要,这然后能够在挤出机内熔体混合。将各组分共混的另一种方法是将聚烯烃切粒与NFP在挤出机或布拉本德混合机中直接熔体混合。
因此,在注塑各种制品的情况下,切粒的简单固态共混物与原料聚合物颗粒,颗粒与切粒,或两种组分的切粒的造粒熔态共混物,因为成型工艺包括原材料的再熔融和混合。在医疗器材的压塑工艺中,然而,熔融组分发生了很小的混合,以及造粒熔体共混物比成分切粒和/或粒料的简单固态共混物优选。本领域的那些技术人员能够确定用于共混聚合物的适当工序,以平衡对组分的均匀混合的需要与对工艺经济性的期望。
本发明的聚烯烃组合物适合于制品如汽车部件,电线和电缆外壳,管道,农膜,土工膜,玩具,运动设备,医疗器材,包装薄膜的流延和吹塑,胶管、管道和型材的挤出,运动设备,户外家具(例如园林设施)和运动场设备,船和小艇部件,和其它此类制品。尤其,该组合物适合于汽车部件,比如减震器,护栅,装饰部件,仪表板和仪表盘,外门和发动机罩部件,阻流板,挡风板,毂盖,反射镜外罩,车身镶板,防护性侧面模塑体,以及与汽车、卡车、船和其它交通工具有关的其它内部和外部部件。
其它有用的制品和物品可以经济地通过实施本发明来形成,包括:板条箱,容器,包装物,实验室器皿,如用于培养物生长的滚瓶和培养瓶,办公室地毯,仪器试样夹和采样窗口;液体贮藏容器如用于血液或溶液的储存和IV输注的袋,小包,和瓶子;包装材料,包括用于任何医疗器材或药物的那些,包括单位剂量容器,或其它的型罩或泡罩包装,以及用于包封或贮存在光照下保藏的食品。其它有用的制品包括用于任何医疗设备的医用管料和阀门,包括输注用具,导管,和呼吸性治疗设备,以及用于被照射的医疗设备或食品的包装材料,包括托盘,以及储存液体,尤其水、牛奶或果汁的容器,包括单份食品容器和大容量储存容器以及输送工具如胶管,管道等等。
这些器材可以通过用于成型聚烯烃的任何有用的成型方式来制备或成型。这至少涵盖了模塑,包括压塑,注塑,吹塑和压铸模塑;薄膜吹塑或流延;挤出和热成型;以及层压,拉挤成型,推出成型,拉伸变形(draw reduction),滚塑,纺粘,熔体纺丝,熔体喷射;或它们的结合。至少热成型或成膜法的使用使来自耐辐射材料的单轴或双轴取向的益处成为可能并产生。
在一个实施方案中,本发明是包含99.9wt%-60wt%聚烯烃;和0.1-40wt%的NFP的增塑聚烯烃组合物;其中NFP包括具有低于-5℃的倾点的C6-C200链烷烃。在另一个实施方案中,非官能化增塑剂包括C8-C100链烷烃。在又一个实施方案中,NFP包括C6-C50异链烷烃,而在再一个实施方案中包括C10-C100正链烷烃。
换句话说,本发明的增塑聚烯烃是聚烯烃和非官能化增塑剂的共混物,其中非官能化增塑剂是在一个实施方案中在0.5-200cSt(40℃)(ASTM D445-97)的粘度范围内具有低于-30℃的倾点,或在另一个实施方案中,在0.5-200cSt(40℃)(ASTM D445-97)的粘度范围内具有-30℃到-90℃的倾点的化合物。
该组合物还能够通过许多物理和化学性能来描述。例如,在一个实施方案中,本发明的组合物特征在于,对于加入到组合物中的每4wt%的NFP,聚烯烃的Tg下降4-10℃,同时Tm保持±1-2℃。
本发明的NFP能够通过这里所述的许多物理和化学性能来描述。例如,在一个实施方案中,非官能化增塑剂具有低于-30℃的倾点;在另一个实施方案中,具有0.1-3000cSt(100℃)的粘度;在又一个实施方案中,具有低于2.1的介电常数(20℃);以及在还一个实施方案中,具有低于0.91g/cm3的比重。在NFP的又一个实施方案中,基本不含芳族结构部分。
此外,NFP具有100-25,000g/mol;在另一个实施方案中,200-10,000g/mol的重均分子量。
适于本发明的组合物的聚烯烃能够用许多实施方案来描述。在一个实施方案中,聚烯烃包括全同立构链段。在另一个实施方案中,聚烯烃选自丙烯均聚物,丙烯共聚物,和丙烯抗冲共聚物,和它们的混合物。在又一个实施方案中,聚烯烃是全同立构聚丙烯。在再一个实施方案中,聚烯烃是包括丙烯衍生的单元和选自乙烯衍生的单元和C4-C20α-烯烃衍生的单元中的单元的共聚物。
在又一个实施方案中,按共聚物的总重量计,聚烯烃是包括40-95wt%的组分A和5-60wt%的组分B的丙烯抗冲共聚物;其中组分A包括丙烯均聚物或共聚物,该共聚物包括≤10wt%乙烯,丁烯,己烯或辛烯共聚单体;和其中组分B包括丙烯共聚物,其中该共聚物包括5-70wt%乙烯,丁烯,己烯和/或辛烯共聚单体,和95-30wt%丙烯。
该聚烯烃可以进一步包括塑性体。
本发明的组合物可以用其中基本不含具有500-10,000的重均分子量的聚乙烯的另一个实施方案来描述。
本发明还包括增塑聚烯烃的方法,包括将聚烯烃与非官能化增塑剂共混;其中非官能化增塑剂包括具有低于-5℃的倾点的C6-C200链烷烃。在一个实施方案中,共混包括熔体混合。熔体混合在一个实施方案中在挤出机中进行。
在一个实施方案中,共混包括固体聚烯烃的湿掺合。在一个实施方案中,聚烯烃以反应器粒料的形式存在,而在另一个实施方案中以挤出切粒的形式存在,或以它们的共混物存在。如果使用反应器粒料,在一个实施方案中,反应器粒料具有10μm到5mm的平均直径。
能够由本发明的组合物形成制品,此类制品的非限制性实例包括薄膜,片材,纤维,纺织和无纺织物,软管,管道,汽车部件,家具,运动设备,食品储存容器,透明和半透明制品,玩具,胶管和管材,和医用器材。
实施例
参考以下实施例和表格可以更好地理解本发明,但本发明不受它们的限制。
如下所示通过动态机械热分析(“DMTA”)来测定玻璃化转变温度(Tg)和储能模量(E′)。动态机械试验通过振动在一端以任意偏转角度固定的实体矩形梁来进行。使用该力和偏转角度来分别计算应力和应变。应力与应变的比率得到了模量。改变试验过程中的温度获得了关于随温度而变的材料的特性的信息。试验参数包括单一悬臂梁,1Hz的频率,-130℃的起始温度,60℃的最高温度。温度以2℃/min的速率增加。Tanδ是E″/E′的比率,其中E″是损耗模量和E′是储能模量或弹性模量。玻璃化转变温度通过当Tanδ达到其最大值时的温度来测定。
结晶温度(Tc)和熔融温度(Tm)如下测量:差示扫描量热法(DSC,以10℃/min的加热速率)。例如,大约6-10mg的聚合物或增塑聚合物的片材在大约150-200℃下用冲模压制。将样品放置在差示扫描量热仪(Perkin Elmer 7 Series Thermal Analysis System)中,加热到200℃,再保持10分钟。该样品以10℃/min冷却,以获得25℃的最终温度。记录热输出,指示热容变化的热输出数据中的拐点通过用电子仪器辨别热输出数据来测定。差示热输出数据的最大值对应于样品的结晶温度。样品在25℃下保持10分钟,以10℃/min加热到200℃。记录热输入,指示热容变化的热输入数据中的拐点通过用电子仪器辨别热输入数据来测定。差示热输入数据的最大值对应于样品的熔融温度。
分子量分布使用凝胶渗透色谱法测定。
随剪切速率而变的剪切粘度通过双筒毛细管流变仪测定。毛细管流变仪(Rosand Model RAH7/2,Bohum Instruments)安装30∶1长度与直径比毛细管。将总质量25-30g的切粒装入到毛细管柱中,并在试验之前在230℃下预热10分钟以除去任何夹带的空气。各试验在230℃下在30-3000s-1的剪切速率范围内进行。对进口压力损失的数据的校准(即Bagley校准)经由同时测量通过安装到流变仪的第二根柱体中的孔口的材料流的压力损失而在线进行。
本领域已知的纺粘无纺织物的柔软度或“手感”使用Thwing-Albert Handle-O-Meter(Model 211-10-B/America)测量。“手感”的质量被认为是由于表面摩擦所产生的阻力和织物材料的柔性的结合。Hand-O-Meter用LVDT(线性差动变换器)测量以上两个系数,以检测当迫使材料样品进入平行边缘的槽缝时叶片遇到的阻力。3位数数字电压表(DVM)直接以克表示阻力。任何给定片材的“总手感”是在试样的两面和两个方向取得的四个读数的平均值,并以克/标准宽度的样品材料来报道。“总手感”的降低表示织物柔软度的改进。
其它试验方法如在以下表格的正文中所述。
本发明的各组分能够通过任何适合的方式来共混。以下的实施例举例说明了共混各组分的一种方法。对于样品1-5,金属茂生产的丙烯均聚物的反应器粒料首先在转鼓掺混机内与添加的抗氧化剂,即600ppm的Irganox 1076,以及260ppm的硬脂酸钙和4wt%的用于增塑样品的NFP共混,以均匀混合共混物组分。共混的聚合物使用57mm双螺杆挤出机在230℃的挤出温度下配混和造粒。对于实施例10-14,丙烯无规共聚物的反应器粒料首先在转鼓掺混机中与反应器粒料和添加的抗氧化剂,即825ppm的硬脂酸钙,800ppm的Ultranox 626,500ppm的TINUVIN 622和2500ppm的Millad 3940,以及5wt%的用于增塑样品的NFP共混,以均匀混合共混物组分。共混的聚合物使用30mm双螺杆挤出机在216℃的挤出温度下配混和造粒。对于样品15-19,丙烯抗冲共聚物的反应器粒料首先在转鼓掺混机中与反应器粒料和添加的抗氧化剂,即800ppm的硬脂酸钙,1500ppm的IRGANOX 1010,500ppm的ULTRANOX 626和675ppm的苯甲酸钠以及5wt%的用于增塑样品的NFP共混,以均匀混合共混物组分。共混的聚合物使用30mm单螺杆挤出机在205℃的挤出温度下配混和造粒。对于样品6-9,10wt%增塑金属茂型丙烯均聚物以与以上对于样品1-5所述相同的方式制备。对于样品21-24,以与以上对于样品6-9所述相同方式制备的10wt%增塑金属茂生产的丙烯均聚物与纯丙烯聚合物(AchieveTM 3854)以切粒形式干混,从而获得在共混物中的4wt%活性增塑样品。
使用120吨注塑设备制备标准ASTM拉伸和HDT棒及加德纳冲击圆盘。所制备的样品的物理性能在下表中示出。由在4wt%PAO或异链烷烃的加料量下的本发明增塑聚丙烯均聚物获得的模塑件显示了显著降低的挠曲模量和拉伸模量,同时保持了它们的拉伸强度,室温艾佐德抗冲击性和热挠曲温度。为了对比,还用芥酰胺(表11),设计用于降低4wt%浓度的模塑件表面摩擦的普通润滑剂制备模塑样品。芥酰胺对挠曲模量的作用是不明显的。
典型纺粘工艺包括连续长丝挤出,随后拉伸,使用某些类型的喷射器成网,再粘结该网。首先将聚合物切粒进给到挤出机中。在挤出机中,通过加热熔化螺杆使切粒同时被熔融和强制通过该系统。在螺杆的末端,纺丝泵通过过滤器将熔融聚合物计量给喷丝板,其中熔融聚合物在压力下通过毛细管以0.4g/孔/分钟的速率挤出。喷丝板含有直径为0.4mm的几百个毛细管。聚合物在其熔点以上大约30-50℃下熔化,以获得用于挤出的充分低的熔体粘度。从喷丝板排出的纤维被骤冷和拉伸成直径大约16微米的细纤维。固化纤维无规地堆放在运送带上,形成本领域称为纤维网的无规网状结构。通过控制皮带运送速度获得25基重(g/m2)的纤维网。在纤维网形成之后,使用本领域已知的加热纺织品压延机作为热粘结压延机将纤维网粘结,以获得其最终强度。压延机由两个加热钢辊组成;一个辊是平的和另一个辊带有凸点图案。将纤维网输送到压延机,其中织物通过在大约138℃的粘结温度下将纤维网在辊之间压缩来形成。
流延薄膜使用以下操作来制备。流延单层薄膜用Killion流延薄膜生产线制造。该生产线具有三个24∶1 L/D 2.54cm直径挤出机,它将聚合物进给到进料区中。进料区将熔融聚合物从挤出机转移到20.32cm宽Cloeren模头。熔融聚合物在230℃的温度下从模头排出,在21℃的冷却辊(20.3cm直径,25.4cm辊面)上流延。流延装置配备可调卷绕速度,以便获得目标厚度的薄膜。
在表5-7中分别列举了增塑丙烯均聚物、丙烯共聚物和丙烯抗冲共聚物的树脂性能。如熔体流动速率的显著增加所示,在丙烯聚合物中添加NFP改进了熔体流动性。如在图11-13中所示,熔体流动性的改进能够通过随剪切速率范围而变的剪切粘度的降低来表征。与过氧化物降解,或所谓的“减粘裂化”过程相反,在本发明中的熔体流动性的增高主要归因于NFP的增塑效果,该聚合物分子量没有改变。如图14所示,这在分子量分布的比较中是显而易见的。鉴于更好的拉细、更低的挤出机扭矩、薄壁注射和更快的周期时间,熔体流动性的改进通常有利于制造工艺,即纤维纺丝,薄膜流延,挤出,注塑。
在本发明中的NFP提供了聚丙烯聚合物的储能模量的显著降低。如在图1中所示,与未增塑的聚烯烃相比,增塑丙烯聚合物的储能模量随温度而急剧降低。具有在任何特定温度范围内的较低储能模量(或“弹性模量”)的丙烯聚合物显示了在该特定温度条件下提供用于终用途的更好的柔性的能力。
如图5-10所示,在本发明中的NFP证明了降低Tg,但不改变丙烯聚合物的熔融温度和结晶温度的能力。降低Tg的传统方法包括引入共聚单体,比如在丙烯共聚物的情况下,它还降低了聚合物的熔融温度和结晶温度。具有较低Tg,但不损害熔融特性的聚合物是非常理想的,并且能够提供更好的抗冲击性,尤其冷冻温度以下的抗冲击性,同时保持了高温应用的能力。本发明的增塑聚烯烃提供了这样的能力。
本发明中的NFP与丙烯聚合物相容和混溶,例如由增塑丙烯均聚物和丙烯共聚物的单一Tg分布所确定。这在图2-3中示出。本发明中的NFP还与丙烯抗冲共聚物相容和混溶,例如由增塑丙烯抗冲共聚物的两个Tg分布(乙烯-丙烯橡胶相的较低Tg分布和丙烯聚合物相的较高Tg分布)所确定。这在图4中示出。
丙烯均聚物、丙烯共聚物和丙烯抗冲共聚物的注塑性能的概述分别在表8-10中提供。NFP的添加大大改进了模塑件的抗冲击性,没有显著降低热挠曲温度。例如,由于添加了4-5wt%的NFP,丙烯均聚物的在室温和冷冻温度下的加德纳冲击强度改进了350-400%,丙烯共聚物改进了140-165%,以及丙烯抗冲共聚物改进了20-40%。据估计,通过增加丙烯聚合物中的NFP浓度可以进一步提高抗冲击性。抗冲击性的其它衡量标准,包括在室温和冷冻温度下的艾佐德冲击强度也显著改进。
本发明的另一个优点是,增塑聚烯烃的热挠曲温度没有受损(要么保持,要么仅仅稍微降低),这对于要求在高温下维持模塑制品尺寸的应用来说是关键的。韧性改进的其它指标是屈服伸长率和断裂伸长率的显著增加。许多应用要求在终用途期间的良好顺应性。较高的伸长率有利于模塑制品对在转化过程中或在终用途中的变形的顺应性。
NFP还证明了对纺粘无纺织物提供显著的柔软度改进的能力,如在表12中以较低的“总手感”所提供的那样。在许多应用中,尤其在个人卫生和护理中,柔软的无纺织物对于皮肤接触舒适感是非常理想的。本发明不仅提供了柔软度的改进,而且保持了必要的拉伸强度、抗撕裂性和织物均匀性。
在表13中列举了薄膜性能的比较。如由在纵向(MD)和横向(TD)中的相对高(相对于未增塑的聚烯烃)埃尔曼多夫撕裂以及在室温和冷冻温度下的落镖冲击强度所示,NFP,尤其Isopar-V增塑丙烯均聚物(样品2)提供了抗撕裂性和抗冲击性的改进。另外,光学性能(即浊度和光泽)也被改进。该改进在许多薄膜应用,例如食品包装,文具盒,带材,医用包装和电子封装中提供了优点。
虽然已经参照特定实施方案描述和举例说明了本发明,但本领域的那些普通技术人员清楚,本发明本身提供了本文没有举例说明的许多不同变型。为此,那么,应该仅仅参照所附权利要求书来决定本发明的范围。此外,就一组数字上限和一组数字下限描述了本发明的某些特征。应该清楚的是,由这些界限值的任意组合形成的范围在本发明的范围内,除非另有规定。
所有优先权文件在这里以其中这种引入被允许的所有权限全面引入供参考。此外,本文引用的所有文件,包括测试工序在这里以其中这种引入被允许的所有权限全面引入供参考。
表4在实施例中的组分的目录
组分 | 说明 | 商品来源 |
芥酰胺 | 顺式-13-二十二烯酸酰胺 | Crompton Corporation |
ISOPAR V | 异链烷烃;0.82g/cm3 | ExxonMobil ChemicalCompany(Houston,TX) |
金属茂型聚丙烯均聚物 | 金属茂制备的均聚物,24MFR;Mw/Mn<2.3,Tm 152℃ | AchieveTM3854,ExxonMobilChemical Company(Houston,TX) |
丙烯共聚物 | Z-N制备的共聚物,12MFR;Tm 152℃ | Clarified PP9054,ExxonMobilChemical Company(Houston,TX) |
丙烯抗冲共聚物 | Z-N制备的共聚物,21MFR;Tm 163℃ | PP7684E2,ExxonMobil ChemicalCompany(Houston,TX) |
SHF-101 | PAO;0.835g/cm3 | ExxonMobil ChemicalCompany(Houston,TX) |
SHF-403 | PAO;0.850g/cm3 | ExxonMobil ChemicalCompany(Houston,TX) |
SuperSyn 2150 | PAO;0.850g/cm3 | ExxonMobil ChemicalCompany(Houston,TX) |
SuperSyn 23000 | PAO;0.857g/cm3 | ExxonMobil ChemicalCompany(Houston,TX) |
表5 增塑金属茂型丙烯均聚物的树脂性能
样品No. | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
NFP | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | Isopar-V | SHF-403 | SuperSyn-2150 | SuperSyn-23000 |
NFP的浓度(wt%) | 0 | 4 | 4 | 4 | 4 | 10 | 10 | 10 | 10 |
树脂性能熔体流动速率(230℃/2.16kg)熔融温度(℃)结晶温度(℃)玻璃化转变温度(℃) | 231521154 | 32151115-1 | 29153118-1 | 291521180 | 291531182 | 51152115-11 | 45151116-5 | 39152115-3 | 371521151 |
表6 增塑丙烯无规共聚物的树脂性能
样品No. | 10 | 11 | 12 | 13 | 14 |
NFP | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 |
NFP的浓度(wt%) | 0 | 5 | 5 | 5 | 5 |
树脂性能熔体流动速率(230℃/2.16kg)熔融温度(℃)结晶温度(℃)玻璃化转变温度(℃) | 121521221 | 16152121-7 | 16152121-5 | 15152121-3 | 15152121-1 |
表7 增塑丙烯抗冲共聚物的树脂性能
样品No. | 15 | 16 | 17 | 18 | 19 |
NFP | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 |
NFP的浓度(wt%) | 0 | 5 | 5 | 5 | 5 |
树脂性能熔体流动速率(230℃/2.16kg)熔融温度(℃)结晶温度(℃)玻璃化转变温度(℃) | 23163119-53和5.2 | 32162120-55和-3 | 29162120-56和-4 | 29162120-50和-1 | 29162121-52和1 |
表8金属茂型丙烯均聚物的模塑件性能
样品No. | 1 | 2 | 3 | 4 | 5 | |
NFP: | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | |
NFP的浓度(wt%) | 0 | 4 | 4 | 4 | 4 | |
光学性能浊度(0.04英寸注塑板)(%)光泽@45° | ASTM方法D1003D2457 | 6585 | 6287 | 6586 | 6185 | 6486 |
机械性能拉伸强度@屈服(kpsi)屈服伸长率(%)1%正割挠曲模量(kpsi)热挠曲温度@66psi(℃)洛氏硬度(R-标度) | D638D638D790AD648D785 | 4.99200105104 | 4.41215510197 | 4.51117510899 | 4.51117710799 | 4.61017910499 |
冲击性能缺口艾佐德冲击强度@23℃(ft-lb/in)加德纳冲击强度0.125英寸厚圆盘@23℃(in-lb)加德纳冲击强度0.125英寸厚圆盘@0℃(in-lb) | D256AD5420D5420 | 0.431注a | 0.715314 | 0.6166<8b | 0.6164<8b | 0.5141<8b |
a.样品太脆,不能进行该试验。b.样品在最低锤击重量下破坏。
表9丙烯无规共聚物的模塑件性能
样品No. | 10 | 11 | 12 | 13 | 14 | |
NFP: | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | |
NFP的浓度(wt%) | 0 | 5 | 5 | 5 | 5 | |
光学性能浊度(0.04英寸注塑板)(%)光泽@45° | ASTM方法D1003D2457 | 8.280 | 10.381 | 8.779 | 11.775 | 11.676 |
机械性能拉伸强度@屈服(kpsi)屈服伸长率(%)断裂伸长率(%)1%正割挠曲模量(kpsi)热挠曲温度@66psi(℃) | D638D638D638D790AD648D256AD256AD5420 | 5.09185205870.93.983 | 4.414754141842.012.6203 | 4.413559158851.212.4207 | 4.411259166771.210.5201 | 4.411196173771.29.0219 |
冲击性能缺口艾佐德冲击强度@23℃(ft-lb/in)无缺口艾佐德冲击强度@-18℃(ft-lb/in)加德纳冲击强度0.125英寸厚圆盘@23℃(in-1b) |
表10丙烯抗冲共聚物的模塑件性能
样品No. | 15 | 16 | 17 | 18 | 19 | |
NFP: | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | |
NFP的浓度(wt%) | 0 | 5 | 5 | 5 | 5 | |
机械性能拉伸强度@屈服(kpsi)屈服伸长率(%)断裂伸长率(%)1%正割挠曲模量(kpsi)热挠曲温度@66psi(℃) | ASTM方法D638D638D638D790AD648 | 3.3512516395 | 3.01223011281 | 3.01018512488 | 3.0812013284 | 3.0811013586 |
冲击性能缺口艾佐德冲击强度@23℃(ft-lb/in)加德纳冲击强度0.125英寸厚圆盘@-29℃(in-lb) | D256AD5420 | 4.8123 | 6.5170 | 6.0165 | 3.9159 | 3.5148 |
表11金属茂型丙烯均聚物的模塑件性能
样品No. | 20 | 21 | 22 | 23 | 24 | |
NFP: | 无 | Isopar-V | SHF-403 | SuperSyn-23000 | 芥酰胺 | |
NFP的浓度(wt%) | 0 | 4 | 4 | 4 | 4 | |
树脂性能熔体流动速率(230℃/2.16kg) | ASTM方法D1238 | 24 | 35 | 33 | 30 | 23 |
机械性能拉伸强度@屈服(kpsi)屈服伸长率(%)1%正割挠曲模量(kpsi)热挠曲温度@66psi(℃) | D638D638D790AD648 | 4.7919092 | 4.51115594 | 4.41117090 | 4.51018090 | 4.51118889 |
冲击性能缺口艾佐德冲击强度@23℃(ft-lb/in)无缺口艾佐德冲击强度@-18℃(ft-lb/in) | D256AD256A | 0.42.7 | 0.53.1 | 0.33.0 | 0.4n/a | 0.4n/a |
表12 由金属茂型丙烯均聚物制备的纺粘无纺织物的柔软度性能/总手感
样品No. | 1 | 2 | 3 | 4 | 5 | |
NFP: | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | |
NFP的浓度(wt%) | 0 | 4 | 4 | 4 | 4 | |
织物性能峰值负荷(lbs)MD/TD断裂伸长率(%)MD/TD埃尔曼多夫撕裂(g/基重)TD总手感(g) | ASTM方法D882D882D1922 | 9.4/4.876/771731 | 8.0/4.465/761932 | 7.8/4.158/671524 | 8.3/4.172/731821 | 7.5/3.964/732015 |
总手感以对25gsm(克/平方米)的织物的测试量为基础。
表13金属茂型丙烯均聚物的流延薄膜性能
样品No. | 1 | 2 | 3 | 4 | 5 | |
NFP: | 无 | Isopar-V | SHF-101 | SHF-403 | SuperSyn-2150 | |
NFP的浓度(wt%) | 0 | 4 | 4 | 4 | 4 | |
光学性能浊度(%)光泽 | ASTM方法D1003D2457 | 8.868 | 6.270 | 16.757 | 14.758 | 10.565 |
机械性能1%正切模量(kpsi)MD/TD断裂拉伸强度(kpsi)MD/TD断裂伸长率(%)MD/TD埃尔曼多夫撕裂(g/mil)/MD穿刺(lb/mil)穿刺能量(in.lb/mil)落镖冲击总能量(ft.lb)@23℃@-15℃ | D882D882D882D1922D3420D3420D4272 | 140/1307.6/7.8730/72829/329.0180.40.04 | 84/867.5/7.1725/68054/588.1211.90.07 | 119/1207.1/7.5770/79217/198.6190.60.09 | 133/1217.2/7.0785/76517/188.6170.70.09 | 120/1157.0/6.9738/73922/249.2200.60.05 |
薄膜性能以2mil厚度为基础。
Claims (31)
1、增塑聚烯烃组合物,包括99.9-60wt%丙烯均聚物或共聚物;和0.1-40wt%的非官能化增塑剂;其中非官能化增塑剂包括具有低于-5℃的倾点的C6-C200链烷烃。
2、权利要求1的组合物,其中非官能化增塑剂包括C8-C100链烷烃。
3、权利要求1的组合物,其中非官能化增塑剂包括C6-C50异链烷烃。
4、权利要求1的组合物,其中非官能化增塑剂包括C10-C100正链烷烃。
5、前述权利要求的任一项的组合物,其中对于加入到组合物中的每4wt%的非官能化增塑剂,聚烯烃的Tg降低至少2℃,同时Tm保持不变。
6、权利要求5的组合物,其中对于加入到组合物中的每4wt%的非官能化增塑剂,聚烯烃的Tg降低4-10℃,同时Tm保持不变。
7、前述权利要求的任一项的组合物,其中非官能化增塑剂具有低于-30℃的倾点。
8、前述权利要求的任一项的组合物,其中非官能化增塑剂具有在100℃下的0.1-3000cSt的粘度。
9、前述权利要求的任一项的组合物,其中非官能化增塑剂具有在100℃下的1-3000cSt的粘度。
10、前述权利要求的任一项的组合物,其中非官能化增塑剂具有在100℃下的2-300cSt的粘度。
11、前述权利要求的任一项的组合物,其中非官能化增塑剂具有在20℃下的低于2.1的介电常数。
12、前述权利要求的任一项的组合物,其中非官能化增塑剂具有低于0.91g/cm3的比重。
13、前述权利要求的任一项的组合物,其中非官能化增塑剂基本上不含芳族结构部分。
14、前述权利要求的任一项的组合物,其中基本不存在增塑剂如邻苯二甲酸酯,己二酸酯,偏苯三酸酯,和聚酯。
15、前述权利要求的任一项的组合物,其中非官能化增塑剂的重均分子量是100-25,000g/mol。
16、权利要求15的组合物,其中非官能化增塑剂的重均分子量是200-25,000g/mol。
17、权利要求16的组合物,其中非官能化增塑剂的重均分子量是200-10,000g/mol。
18、前述权利要求的任一项的组合物,其中聚烯烃包括全同立构链段。
19、前述权利要求的任一项的组合物,其中聚烯烃选自丙烯均聚物,丙烯共聚物,丙烯无规共聚物,丙烯嵌段共聚物,丙烯抗冲共聚物,和它们的混合物。
20、权利要求19的组合物,其中丙烯均聚物是全同立构聚丙烯。
21、权利要求1-17的任一项的组合物,其中聚烯烃是包括丙烯衍生的单元和选自乙烯衍生的单元和C4-C20α-烯烃衍生的单元中的单元的共聚物。
22、权利要求1-17的任一项的组合物,其中聚烯烃是包含40-95wt%的组分A和5-60wt%的组分B的丙烯抗冲共聚物,以共聚物的总重量为基准计;其中组分A包括丙烯均聚物或共聚物,该共聚物含有≤10wt%乙烯,丁烯,己烯或辛烯共聚单体;和其中组分B包括丙烯共聚物,其中该共聚物含有5-70wt%乙烯,丁烯,己烯和/或辛烯共聚单体,以及大约95到30wt%丙烯。
23、前述权利要求的任一项的组合物,进一步包括塑性体。
24、前述权利要求的任一项的组合物,其中基本不含具有500-10,000的重均分子量的聚乙烯。
25、增塑聚烯烃的方法,包括将聚烯烃与非官能化增塑剂共混,其中聚烯烃和非官能化增塑剂如权利要求1-24的任一项所定义。
26、权利要求25的方法,其中共混包括熔体混合。
27、权利要求26的方法,其中熔体混合在挤出机中进行。
28、权利要求25的方法,其中共混包括固体聚烯烃的湿掺合。
29、权利要求25-28的任一项的方法,其中聚烯烃是以反应器粒料或挤出切粒的形式存在。
30、权利要求29的方法,其中反应器粒料具有10μm到5mm的平均直径。
31、包括权利要求1-24的任一项的组合物,或通过权利要求25-30的任一项的方法制备的选自薄膜,片材,纤维,纺织和无纺织物,软管,管道,汽车组件,家具,运动器材,食品储存容器,透明和半透明制品,玩具,胶管和管材,以及医疗器材中的制品。
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- 2003-08-04 EP EP03754386.5A patent/EP1530611B1/en not_active Expired - Lifetime
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- 2003-08-04 BR BR0313398-2A patent/BR0313398A/pt not_active Application Discontinuation
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CN104277325A (zh) * | 2013-07-12 | 2015-01-14 | 住友化学株式会社 | 丙烯树脂组合物 |
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CN107250237B (zh) * | 2015-02-25 | 2018-09-14 | 博里利斯股份公司 | 具有改进的长期机械性能的丙烯共聚物组合物 |
US10227473B2 (en) | 2015-02-25 | 2019-03-12 | Borealis Ag | Propylene copolymer composition with improved long-term mechanical properties |
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