CN1094138C - 电缆护套组合物 - Google Patents
电缆护套组合物 Download PDFInfo
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Abstract
本文公开了一种电缆护套组合物及其作为电力电缆或电信电缆外护套的用途。该电缆护套组合物是一种多模态(优选双模态)烯烃聚合物(优选乙烯塑料)混合物,其密度为约0.915-0.955克/厘米3、熔体流动速率为约0.1-0.3克/10分钟,所述烯烃聚合物混合物包含至少有第一种烯烃聚合物与第二种烯烃聚合物,其中第一种烯烃聚合物的密度与熔体流动速率选自(a)约0.930-0.975克/厘米3与约50-2000克/10分钟及(b)约0.88-0.93克/厘米3与约0.1-0.8克/10分钟。优选的是,烯烃聚合物混合物是由至少一种α-烯烃以几个聚合反应步骤,优选由环管反应器/气相反应器或气相反应器/气相反应器组成的两个聚合步骤,通过乙烯在第一聚合步骤中的配位催化聚合及共聚合以及乙烯与丁烯、4-甲基-1-戊烯、1-己烯或1-辛烯在第二聚合步骤中的配位催化共聚合而制成的。
Description
本发明涉及电缆护套组合物及其用作电力电缆或电信电缆的外护套的用途。
所谓电缆,是指电力电缆如高压、中压或低压电力电缆和电信电缆,如光纤电缆、共芯电缆及双股电缆。电缆通常包含一条芯线并在芯线周围包有由一层或多层护层构成的护套。最外层被称为外护套或外护套层,现今外护套层是由聚合物材料,优选乙烯塑料制成的。对于各种不同的应用领域有不同种类的电缆,如电信通讯电缆(包括常规的铜电缆和光纤电缆)以及电力电缆,不同的应用领域要求护套材料必须符合各种性能要求,而这些性能要求在某些方面是相互矛盾的。因此,电缆护套材料的重要性能是加工性能好,即材料易于在宽的温度范围内加工,收缩率低力学强度高、表面光洁度高以及耐环境应力开裂(ESCR)性能好。因为,直至今日,要满足所有这些性能要求仍是困难的或甚至是不可能的,因此,先有技术护套材料的性能是各种性能折衷的结果,实际上是以降低某些性能为代价才使其在另一方面获得良好的性能。
因此,如果关于电缆护套材料性能的这种折衷能被降低或甚至被消除的话,这会是十分有利的。具体地说,我们如果在保持给定的加工性能下能够提高材料的ESCR和降低收缩率的话,这是很有益的。
本发明是通过由具有某种指定密度值和熔体流动速率值的多模态分布烯烃聚合物的混合物组成的电缆护套组合物以代替用于常规电缆护套中的单模态分布聚乙烯塑料来达到这一目标的,其中仅聚合物的混合物而且组成混合物的各聚合物都要具有指定的密度和熔体流动速率值。
于是,本发明提供了一种电缆护套组合物,其特征在于该组合物是由密度为约0.915-0.955克/厘米3、熔体流动速率为约0.1-3.0克/10分钟的多模态分布烯烃聚合物的混合物组成的,所述烯烃聚合物的混合物包含至少有第一种与第二种烯烃聚合物,其中第一种聚合物的密度与熔体流动速率选自(a)约0.930-0.975克/厘米3与约50-2000克/10分钟和(b)约0.88-0.93克/厘米3与约0.01-0.8克/10分钟。
本发明还涉及这种电缆护套组合物作为电力电缆或电信电缆的外护套的用途。
从以下说明和附后的权利要求书会清楚地看到本发明与众不同的特征和优点。
然而,在对本发明进行更详细的说明之前,应对几个关键术语作出规定。
所谓聚合物的“模态”是指聚合物分子量分布的结构,即指聚合物分子数作为分子量的函数所呈现的曲线形状。如果该曲线呈现一个最大峰,则该聚合物称为“单模态”聚合物,如果该曲线呈现一个很宽最大峰或两个或两个以上最大峰以及聚合物是由两个或多个组分组成的话,则该聚合物称为“双模态”聚合物、“多模态”聚合物等。在下文中,所有分子量分布曲线很宽或呈现一个以上最大峰的聚合物都称为“多模态”聚合物。
聚合物的“熔体流动速率”(MFR)是按照ISO 1133,条款4测定的,相当于以前采用的术语“熔体流动指数”。熔体流动速率(以克/10分钟表示)是聚合物的流动性的表征,因此也是聚合物加工性的一种指示。聚合物的熔体流动速率越高粘度就越低。
所谓“耐环境应力开裂”(ESCR)是指聚合物在机械应力和以表面活性剂形态的试剂作用下的耐开裂性能。ESCR是按照ASTM D1693A测定的,所用试剂是Igepal CO-630。
所谓“乙烯塑料”是指以聚乙烯或乙烯共聚物(其中乙烯单体构成主体)为主要成分的塑料。
如前所述,根据本发明的电缆护套组合物的区别之处在于该组合物是由具有特定密度和熔体流动速率的呈多模态分布的烯烃聚合物混合物所组成的。
用两个或两个以上反应器以串联方式连接来制备多模态(尤其是双模态)烯烃聚合物,优选多模态乙烯塑料,是早已熟知的。作为该先有技术的实例,欧洲专利040 992、041796、022 376及WO 92/12182已作了介绍,这些内容在此列入本文作为制备多模态聚合物时的参考。根据这些文献,各聚合物的每一聚合步骤能以液相、淤浆或气相聚合来实施。
根据本发明,主要聚合步骤优选以淤浆聚合/气相聚合或气相聚合/气相聚合相组合的方法来实施。淤浆聚合优选在所谓环管反应器中进行。在本发明中最好不要在带搅拌的槽式反应器中进行淤浆聚合,因为这种方法不能完全适应本发明组合物的制备,而且有溶解度问题。为了制备具有高性能的本发明组合物,需要一种适应性强的方法。为此,以环管反应器/气相反应器或气相反应器/气相反应器相组合的方式,以两个主要聚合步骤制备该组合物是优选的。将该组合物的制备分为两个主要聚合步骤,其中第一步是在环管反应器中实施淤浆聚合,第二步在气相反应器中实施气相聚合,是特别优选的。任选的是,主聚合步骤可进行预聚合,预聚合量可达到20(重量)%,优选1-10(重量)%(以制备的聚合物总重量计)。通常,该技术借助铬、茂金属或齐格勒-纳塔催化剂在几个连续聚合反应器中通过聚合作用制得一种呈多模态分布的聚合物混合物。比方说,对于双模态乙烯塑料(这是根据本发明优选的聚合物)的制备来说,第一种乙烯聚合物是在关于单体组成、氢气压力、温度、压力等确定条件下,在第一个反应器中制备的。在第一个反应器中聚合后,将含制得的聚合物的反应混合物供入第二个反应器中,在其它条件下再进行聚合反应。通常,在第一个反应器中制备高熔体流动速率(低分子量)的、具有中等或少量附加的共聚单体或者完全没有这种共聚单体的第一种聚合物,而在第二个反应器中制备低熔体流动速率(高分子量)的,具有大量的附加共聚单体的第二种聚合物。常可采用的共聚单体是含达12个碳原子的其它烯烃,如含3-12个碳原子的α-烯烃,例如丙烯、丁烯、4-甲基-1-戊烯、己烯、辛烯、癸烯等可作为共聚单体与乙烯共聚合。制得的最终产物是一种由两个反应器聚合而成的均匀的聚合物混合物,这两种聚合物的不同分子量分布曲线叠合在一起构成具有宽最大峰或两个最大峰的分子量分布曲线,即最终产物是一种呈双模态分布的聚合物混合物。因为多模态,特别是双模态聚合物(优选乙烯聚合物)以及它们的制备方法都属于先有技术,因此本文不再详述,但可参阅上述说明。
这里应当指出,以相应数量的反应器串联制备两种或两种以上聚合物组分时,只有在第一反应器步骤中制备的组分和最终产物的熔体流动速率、密度及其它性能可直接从反应器中提取的物料进行测定。在第一步骤之后的各反应器步骤中制备的聚合物组分的相应性能只能根据供入各自反应器步骤和从各自反应器步骤排放的物料的相应性能值间接地加以确定。
虽然,从本质上说,多模态聚合物及它们的制备方法是已知的,然而,以前并不知道将这类多模态聚合物混合物用于电缆护套组合物。尤其是,关于采用具有本发明要求的特定密度和熔体流动速率值的多模态聚合物混合物这一点以前是不为所知的。
如上提及的,用于本发明电缆护套组合物的多模态烯烃聚合物混合物,优选的是双模态聚合物混合物。通过如上所述的在两个或两个以上串联的聚合反应器中、在不同聚合条件下来聚合制备这种双模态聚合物混合物也是优选的。由于这种方式可以灵活地改变反应条件,因此,当有一种、两种或多种烯烃单体,不同聚合步骤涉及不同的共聚单体含量进行聚合反应时,将这种聚合反应在环管反应器/气相反应器、气相反应器/气相反应器或环管反应器/环管反应器中进行是最优选的。优选的是,在优选的两步法中所选择的聚合条件要使在一个聚合步骤,优选在第一步中制备出共聚单体含量中等、低的或优选不含共聚单体的、较低分子量的聚合物(因高含量链转移剂(氢气)的存在),而具有较高含量共聚单体的高分子量聚合物是在另一步骤,优选在第二步骤中制备的。然而,这些聚合步骤的次序是可以颠倒的。
优选的是,根据本发明的多模态烯烃聚合物混合物是一种丙烯塑料的混合物,或者是最优选的乙烯塑料混合物。用于本发明的共聚单体或多种共聚单体选自含多达12个碳原子的α-烯烃,对于乙烯塑料来说,共聚单体或多种共聚单体选自含3-12个碳原子的α-烯烃。特别优选的共聚单体是丁烯、4-甲基-1-戊烯、1-己烯及1-辛烯。
鉴于上述,根据本发明的一种优选乙烯塑料混合物是由低分子量乙烯均聚物与高分子量的乙烯与丁烯、4-甲基-1-戊烯、1-己烯或1-辛烯的共聚物相混合形成的。
本发明烯烃聚合物混合物中各个聚合物的性能的选择应使最终烯烃聚合物混合物的密度为约0.915-0.955克/厘米3,优选约0.920-0.950克/厘米3,熔体流动速率为约0.1-3.0克/10分钟,优选约0.2-2.0克/10分钟。本发明优选通过由含约0.930-0.975克/厘米3,优选约0.955-0.975克/厘米3和熔体流动速率约50-2000克/10分钟,优选约100-1000克/10分钟,最优选约200-600克/10分钟的第一种烯烃聚合物与至少有第二种烯烃聚合物的烯烃聚合物混合物来实现,而这种第二种烯烃聚合物的密度和熔体流动速率应使所得烯烃聚合物混合物具有如上所述的密度和熔体流动速率。
如果多模态烯烃聚合物混合物是呈双模态分布的,即是两种烯烃聚合物(第一种烯烃聚合物和第二种烯烃聚合物)的混合物,第一种烯烃聚合物是在第一反应器中制备的,具有如上所述的密度和熔体流动速率,在第二个反应器步骤制备的第二种烯烃聚合物的密度和熔体流动速率,可如前所述,根据供入第二反应器的物料和从第二反应器步骤排放的物料的相应性能值间接地加以确定。
在烯烃聚合物混合物和第一种烯烃聚合物具有上述密度和熔体流动速率的情况下,计算表明,在第二反应器步骤制备的第二种烯烃聚合物的密度应在约0.88-0.93克/厘米3,优选0.91-0.93克/厘米3,熔体流动速率在约0.01-0.8克/10分钟,优选约0.05-0.3克/10分钟。
如上所述,反应步骤的次序是可以颠倒的,这就是说,如果最终烯烃聚合物混合物的密度为约0.915-0.955克/厘米3,优选约0.920-0.950克/厘米3,熔体流动速率约0.1-3.0克/10分钟,优选约0.2-2.0克/10分钟,以及在第一步制备的第一种烯烃聚合物的密度为约0.88-0.93克/厘米3,优选约0.91-0.93克/厘米3,熔体流动速率为0.01-0.8克/10分钟,优选约0.05-0.3克/10分钟,则在两步法的第二步中制备的第二种烯烃聚合物的密度和熔体流动速率,按上述计算,应当为约0.93-0.975克/厘米3,优选约0.955-0.975克/厘米3和50-2000克/10分钟,优选约100-1000克/10分钟,最优选约200-600克/10分钟。然而,这种反应次序对本发明烯烃聚合物混合物的制备步骤来说,是不大优选的。
为了优化本发明电缆护套组合物的性能,烯烃聚合物混合物中各个聚合物的重量比应该使最终烯烃聚合物混合物的性能达到由各个聚合物贡献的目标性能。因此,各个聚合物的含量不能低到如约10(重量)%或以下,以致使该聚合物不能对烯烃聚合物混合物的性能产生影响。更具体地说,具有高熔体流动速率(低分子量)的烯烃聚合物含量至少25(重量)%,但不超75(重量)%(以聚合物总重量计),优选35-55(重量)%(以聚合物总重量计),从而优化最终产物的性能,这是优选的。
采用上述类型的多模态烯烃聚合物混合物可制得较常规电缆护套组合物性能,特别是收缩率、ESCR及加工性好得多的本发明电缆护套组合物。特别是,本发明电缆护套组合物的低收缩率是一大优点。
如前所述,根据本发明的电缆护套组合物可用来生产包括电力电缆和电信电缆在内的电缆外护套。在那些外护套可由本发明电缆护套组合物制造的电力电缆中,可提及的有:高压电缆、中压电缆及低压电缆。在那些外护套可由本发明电缆护套组合物制造的电信电缆中,可提及的有双股电缆、共芯电缆及光纤电缆。
下面将以几个非限制性实施例来进一步阐明本发明及其优点。
实施例1
设有由环管反应器与气相反应器相串连构成的聚合反应器的车间中,利用齐格勒-纳塔催化剂并在下述条件下进行双模态乙烯塑料的聚合。
第一反应器(环管反应器)
在该反应器中,乙烯在氢气(氢气与乙烯的摩尔比=0.38∶1)存在下聚合成第一种聚合物(聚合物1)。所得乙烯均聚物的MFR值为492克/10分钟,密度为0.975克/厘米3。
第二反应器(气相反应器)
在该反应器中,乙烯与丁烯(气相丁烯与乙烯的摩尔比=0.22∶1,氢气与乙烯的摩尔比=0.03∶1)聚合成第二种聚合物(聚合物2)。所得的乙烯与丁烯共聚物与由第一反应器制得的乙烯均聚物形成均匀混合物,聚合物1与聚合物2的重量比为45∶55。
聚合物1和聚合物2形成的双模态混合物的密度为0.941克/厘米3,MFR值为0.4克/10分钟。该混合物与碳黑配混后,得到含碳黑为2.5(重量)%的最终产物,其最终密度为0.951克/厘米3。这一成品在下文中称为双模态乙烯塑料1。
将双模态乙烯塑料1用作电缆护套组合物,对该组合物的性能进行测定并与那些常规的单模态乙烯塑料电缆护套组合物(参比1)进行比较。参比1的密度为0.941克/厘米3(与2.5(重量)%碳黑配混后,其密度为0.951克/厘米3),MFR值为0.24克/10分钟。
在这一实施例以及下面实施例中,制得组合物的收缩率按照为评价护套材料的收缩倾向而开发的方法(下文中称为UNI-5079)进行测定。收缩率按下述方法测定。
评价用电缆试样按下列条件挤塑:
导线 3.0毫米实心,铝导线
护层厚度 1.0毫米
温度,模头: +210℃或+180℃
模头与水浴间距离 35厘米
温度,水浴: +23℃
线速度 75米/分钟
模头类型: 半-芯管
嘴管 3.65毫米
模头 5.9毫米
螺杆设计: Elise
破料板
在室温(+23℃)下放24小时后以及在+100℃放置24小时后测定收缩百分比。
量取约40厘米电缆试样进行测定。为方便起见,在电缆试样上作标记,以便在经调理后,可在电缆试样的同一点进行测定。
为了在测定过程中测出试样的收缩率,首先,必须在约40厘米处作一记号,然后切出该长度并再次测量。每一受试电缆取两份试样。将试样置于室内常温下24小时后测定并计算出收缩率(以百分比计)。
其后,将所有试样置于+100℃的滑石粉床上24小时后,对试样进行测量并计算出以初始长度为基准的总收缩率(以百分比计)。
测定结果如下表1所示。
表1
材料性能 双模态1 参比1拉伸断裂强度(兆帕)1 34 38断裂伸长(%)1 800 900ESCR2 0/2000小时 F20/550小时收缩率(%)23℃/24小时3 0.0 0.723℃/24小时4 0.0 0.7收缩率(%)100℃/24小时3 1.0 2.0100℃/24小时4 0.9 2.3表面光洁度5180℃挤塑,挤塑速度15米/分钟 0-1 035米/分钟 0-1 075米/分钟 0 0140米/分钟 0 1210℃挤塑,挤塑速度15米/分钟 - 035米/分钟 0-1 075米/分钟 0-1 0140米/分钟 0 0-1
1:按ISO 527-2 1993/5A测定电缆试样。
2:按ASTM D 1693/A,10% Igepal试剂中测定。结果表示试样在给定时间内开裂的百分比。F20指在所示时间后试样开裂为20%。
3:按UNI-5079,在180℃挤塑后测定。
4:按UNI-5079,在210℃挤塑后测定。
5:分级:0=优良至4=很不平滑。
根据表1所示数据,本发明护套材料在收缩率,尤其是室温收缩率和耐环境应力开裂(ESCR)方面具有良好的性能,这是显而易见的。本发明护套材料的拉伸强度性能与参比1的性能在同等水平。根据本发明的护套材料的加工性(可由MFR值推测的)实际上也与参比1一样好。应当着重指出,参比1护套材料的良好加工性是以降低收缩性能,特别是降低室温收缩性能为代价的,而本发明护套材料既具有良好的加工性又具有良好(低)的收缩性能。这是一个相当好的优点,由于根据本发明护套材料具有高的ESCR性能而使这些性能得以增强。
实施例2
在实施例1的聚合车间中,在下列条件下制备双模态乙烯塑料。
第一反应器(环管反应器)
在该反应器中,乙烯在氢气(氢气与乙烯的摩尔比=0.38∶1)存在下聚合成第一种聚合物(聚合物1)。制成的乙烯均聚物的MFR值为444克/10分钟,密度为0.975克/厘米3。
第二反应器(气相反应器)
在该反应器中乙烯与丁烯(丁烯与乙烯的摩尔比=0.23∶1;氢气与乙烯的摩尔比=0.09∶1)聚合成第二种聚合物(聚合物2)。制成的乙烯与丁烯共聚物与由第一反应器制得的乙烯均聚物形成均匀混合物,聚合物1与聚合物2的重量比为40∶60。
构成最终产物的聚合物1与聚合物2双模态混合物的密度为0.941克/厘米3(添加2.5(重量)%碳黑后的密度为0.951克/厘米3),MFR值为1.4克/10分钟。在下文中该最终产物被称为双模态乙烯塑料2。
用类似方式,还制备了另一种双模态乙烯塑料(在下文称为双模态乙烯塑料3),在第一反应器中氢气对乙烯的摩尔比为0.39∶1,并且第一反应器中制得的乙烯均聚物(聚合物1)的MFR值为468克/10分钟,密度为0.962克/厘米3。在第二反应器中,制备乙烯与丁烯共聚物(聚合物2),丁烯与乙烯的摩尔比为0.24∶1,氢气与乙烯的摩尔比为0.07∶1。聚合物1与聚合物2的重量比为45∶55。最终产物(双模态乙烯塑料4)的密度为0.941克/厘米3(混合2.5(重量)%碳黑后密度为0.951(克/厘米3),MFR值为1.3克/10分钟。
双模态乙烯塑料2与双模态乙烯塑料3用作电缆护套组合物,测定这些组合物的性能并与先有技术护套组合物(参比2)作比较。参比2是一种在要求收缩率特别低的环境中使用如光纤用途的专用组合物,该组合物由一种由密度为0.960克/厘米3、MFR值3.0克/10分钟的聚乙烯组分与另一种密度为0.920克/厘米3、MFR值为1.0克/10分钟的聚乙烯组分组成的熔体共混物构成。最终产物的密度为0.943克/厘米3(添加2.5(重量)%碳黑后的密度为0.953克/厘米3,MFR值为1.7克/10分钟。
三种电缆护套组合物的性能测定结果列于下表2。
表2
材料性能 双模态乙烯塑料 参比2
2 3拉伸断裂强度(兆帕)1 32 30 32断裂伸长(%)1 900 890 1150ESCR2 /2000小时 0/2000小时 F20/190小时收缩率(%)23°/24小时4 0.0 0.0 0.1收缩率(%)100℃/24小时4 0.8 1.0 0.8表面光洁度5210℃挤塑,挤塑速度15米/分钟 2 2 335米/分钟 1-2 1 475米/分钟 0-1 0 4140米/分钟 0-1 0 4
1:按ISO 527-2 1993/5A测定电缆试样。
2:按ASTM D 1693/A,10%Igepal试剂中测定。结果表示试样在给定时间内开裂的百分比。F20指在所示时间后试样开裂为20%。
4:按UNI-5079,在210℃挤塑后测定。
5:分级:0=优良至4=很不平滑。
根据表2数据,先有技术专用护套材料(参比2)在室温下具有良好的收缩性能,这是显而易见的。然而,参比2已达到的收缩性能是以降低加工性能为代价的,这尤其表现在不良的表面光洁度值上。通常,参比2护套材料只能在窄的“加工窗口”内加工,即在加工参数范围很窄的条件下加工。与参比2不同,根据本发明的护套材料(双模态乙烯塑料2和3)具有如参比2同样好的收缩性能,同时呈现包括较好的电缆护套表面光洁度在内的较好加工性能(较宽的加工窗口)。此外,根据本发明的护套材料具有很好的环境应力开裂(ESCR)性能和良好的拉伸断裂强度。
实施例3
在实施例1和2中所采用的聚合车间中,在下述条件下制备双模态聚乙烯塑料(乙烯塑料4)。
第一反应器(环管反应器)
在该反应器中,在1-丁烯和氢气存在下(1-丁烯∶氢气∶乙烯=1.74∶0.22∶1),乙烯聚合成第一聚合物(聚合物1)。聚合物1的MFR值为310克/10分钟,密度为0.939克/厘米3。
第二反应器(气相反应器)
将环管反应器制成的聚合物转移到气相反应器中,在气相反应器中,在氢气存在下再进行乙烯与1-丁烯的聚合(1-丁烯∶氢∶乙烯的摩尔比=0.80∶0.02∶1),得到一种新的聚合物组分(聚合物2)。聚合物1与聚合物2的重量比为42∶58。制得最终产物的MFR值为0.3克/10分钟,密度为0.922克/厘米3。
在两种聚合物都含1-丁烯作为共聚单体的情况下,也能得到优良的力学性能、好的ESCR性能以及良好的收缩性能,这可从下表3清楚地看出。
表3材料性能 乙烯塑料4拉伸断裂强度 25.9兆帕断裂伸长 905%ESCR 0/2000小时收缩率%23℃/24小时 0%
100℃/24小时 0%
15米/分钟 2
35米/分钟 0-1
75米/分钟 0
140米/分钟 0
由此可见,这种挤塑混合物(乙烯塑料5)的力学性能值、收缩率、ESCR和表面光洁度与在串联反应器中制备的双模态材料的那些性能相当。
Claims (10)
1.一种电缆护套组合物,其特征在于a)该组合物包括由乙烯经至少两步聚合和在至少所述步骤之一中与一种具有3-12碳原子的α-烯烃共聚单体聚合而成的多模态分子量分布乙烯聚合物混合物,b)所述乙烯聚合物混合物的密度为0.915-0.955克/厘米3和熔体流动速率为0.1-3.0克/10分钟,c)所述的乙烯聚合物混合物包含至少两种乙烯聚合物,其中i)一种是密度为0.955-0.975克/厘米3和熔体流动速率为100-1000克/10分钟的第一种烯烃聚合物,和ii)另一种是密度为0.88-0.93克/厘米3和熔体流动速率为0.01-0.8克/10分钟的第二种烯烃聚合物,以及d)该乙烯聚合物混合物中乙烯聚合物的各自含量不低于10重量%。
2.根据权利要求1的电缆护套组合物,其特征在于在第二种烯烃聚合物聚合之前在一聚合步骤中已聚合了所述第一种烯烃聚合物。
3.根据权利要求1或2的电缆护套组合物,其特征在于该烯烃聚合物混合物的密度为0.920-0.950克/厘米3和熔体流动速率为0.2-2.0克/10分钟。
4.根据权利要求1的电缆护套组合物,其特征在于以淤浆聚合、气相聚合或两者组合实施那些聚合步骤。
5.根据权利要求4的电缆护套组合物,其特征在于淤浆聚合是在一环管反应器中实施的。
6.根据权利要求5的电缆护套组合物,其特征在于聚合反应是在至少一个环管反应器接着至少一个气相反应器中以环管反应器/气相反应器工艺来实施的。
7.根据权利要求1所述的电缆护套组合物,其特征在于该组合物是一种双模态乙烯塑料混合物。
8.根据权利要求7的电缆护套组合物,其特征在于该组合物中第一种烯烃聚合物的含量为25-75重量%,以聚合物总量计。
9.根据上述权利要求中任一项的电缆护套组合物作为电力电缆的外护套的用途。
10.根据权利要求1-8中任一项的电缆护套组合物作为电信电缆外护套的用途。
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1995
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1996
- 1996-07-03 JP JP09505747A patent/JP3088467B2/ja not_active Expired - Lifetime
- 1996-07-03 EP EP96923157A patent/EP0837905B2/en not_active Expired - Lifetime
- 1996-07-03 CZ CZ199865A patent/CZ291053B6/cs not_active IP Right Cessation
- 1996-07-03 RU RU98102358A patent/RU2137788C1/ru active
- 1996-07-03 ES ES96923157T patent/ES2138357T5/es not_active Expired - Lifetime
- 1996-07-03 US US08/983,273 patent/US6329054B1/en not_active Expired - Lifetime
- 1996-07-03 KR KR1019980700128A patent/KR100294397B1/ko not_active IP Right Cessation
- 1996-07-03 PL PL96324435A patent/PL185886B1/pl unknown
- 1996-07-03 BR BR9609621A patent/BR9609621A/pt not_active IP Right Cessation
- 1996-07-03 HU HU9802544A patent/HU218740B/hu not_active IP Right Cessation
- 1996-07-03 DE DE69604296T patent/DE69604296T3/de not_active Expired - Lifetime
- 1996-07-03 WO PCT/SE1996/000900 patent/WO1997003124A1/en active IP Right Grant
- 1996-07-03 CA CA002225858A patent/CA2225858C/en not_active Expired - Lifetime
- 1996-07-03 CN CN96195417A patent/CN1094138C/zh not_active Expired - Lifetime
- 1996-07-03 AU AU63748/96A patent/AU693784B2/en not_active Ceased
- 1996-07-04 IN IN1227CA1996 patent/IN187867B/en unknown
- 1996-07-08 MY MYPI96002815A patent/MY138666A/en unknown
- 1996-07-08 TW TW085108225A patent/TW411353B/zh not_active IP Right Cessation
- 1996-07-10 ZA ZA965857A patent/ZA965857B/xx unknown
- 1996-07-10 AR ARP960103510A patent/AR002792A1/es unknown
- 1996-10-07 UA UA98020615A patent/UA68329C2/uk unknown
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