CN104769033A - 用于发泡的矿物填充聚丙烯组合物 - Google Patents

用于发泡的矿物填充聚丙烯组合物 Download PDF

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CN104769033A
CN104769033A CN201380026274.1A CN201380026274A CN104769033A CN 104769033 A CN104769033 A CN 104769033A CN 201380026274 A CN201380026274 A CN 201380026274A CN 104769033 A CN104769033 A CN 104769033A
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D·郎根费尔德
J·罗赫尔曼
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Abstract

本发明涉及一种新的聚丙烯组合物,其用于生产发泡成型制品,诸如,汽车行业的成品件。

Description

用于发泡的矿物填充聚丙烯组合物
本发明涉及包含滑石作为矿物填料的热塑性聚丙烯组合物,其用于生产具有光滑表面和内部泡沫结构的发泡成型制品。
通常,具有光滑的模印表面的整体发泡制品用于室内设计,例如,汽车或飞机的装饰组件。由于其自由流动特性,填充有滑石的不同共混物在这样的应用中应用至今。对于刚性成品,诸如,汽车仪表盘的整体发泡成型而言,滑石加固的共混物的潜力是有限的,这是由于其所固有的低抗弯刚度。此外,发泡过程中的相对体积增加是有限的。然而,滑石共混物,由于其出色的自由流动性,允许实现非常均匀的同质泡沫结构和泡沫细胞分离模式,没有发生泡沫内部分层或广泛的细胞分裂。
期望避开现有技术的缺点并设计一种新的复合材料,其能改进成型制品的整体发泡的容积增益同时保留用于发泡的现有技术的共混物的优点,特别是其出色的自由流动性和均匀的细胞形成特性。
因此,本发明的目的在于一种组合物,其包含:
(A)从丙烯均聚物、丙烯共聚物或多相丙烯聚合物中选出的以重量计30-85%,优选为40-80%,更优选为50-70%的一种或多种丙烯基组分,根据ISO 178确定的这样的第一丙烯基组分的弯曲模量高于800MPa;
(B)按重量计1-20%,优选为3-15%,更优选为5-10%的多相丙烯聚合物,其包含:
(B1)按重量计20-90%,优选为50-90%的结晶聚丙烯;
(B2)按重量计10-80%,优选为按重量计15-60%的乙烯和至少一个C3-C10α-烯烃的共聚物,这样的共聚物含有按重量计10-70%,优选为按重量计10-50%的乙烯,其在室温下可溶于二甲苯,并且在135℃下在四氢化萘中的特性粘度高于3.5dl/g,优选为高于4dl/g,更优选为5-8dl/g;
(C)按重量计1-30%,优选为5-25%,更优选为10-20%的乙烯基塑性体,其硬度(肖氏A,ASTM D-2240)的值等于或低于90点,优选为等于或低于85点,更优选为等于或低于80点;
(D)按重量计5-30%,优选为8-25%,更优选为10-20%的滑石。
(E)按重量计0-10%,优选为1-10%,更优选为3-8%的高密度聚乙烯(HDPE);以及
(F)按重量计0-1.5%,优选为0.1-1.5%,更优选为0.1-1.0%,再优选为0.2-0.5%的抗划伤添加剂。
组合物各组分的百分比量之和等于100%。
第一丙烯基组分(A)可以适当是含有按重量计最多5%的乙烯和可选的一个或多个C4-C10α-烯烃的丙烯均聚物或共聚物。可用作共聚单体的C4-C10α-烯烃的例子包括1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯和1-辛烯,1-丁烯是尤其优选的。
作为合适的替代方案,组分(A)可以是多相丙烯聚合物,其包含结晶均聚物或无规共聚物基质和按重量计5-25%的丙烯和乙烯的共聚物,这样的共聚物含有按重量计40-60%的乙烯。
适当地,所述组分(A)的MFR(230℃,2.16kg)的值为10-150g/10min。
也合适地,所述组分(A)具有按重量计小于7%,优选为按重量计小于5%,更优选为按重量计小于2%的二甲苯可溶部分(在25℃下)含量。
根据一个实施例,所述组分(A)在茂金属催化剂存在下获得。特别有利的是使用熔体流动速率(MFR)的值较高,优选为MFR(ISO 1133-230℃,2.16Kg)值高于100g/10min的茂金属基聚合物作为组分(A)。因此获得的组合物具有良好的流动性。
一般而言,所述组分(A)的全同立构五元组的量高于95%。
组分(B)可适当地通过连续聚合来制备,所述连续聚合包含至少两个连续的步骤,其中组分(B1)和(B2)在单独的后续步骤中制备,在所形成的聚合物和前面的步骤中所使用的催化剂存在下在每一步中操作。
在第二丙烯基组分(B)内,组分(B1)可以适当地是结晶丙烯(共)聚合物,按重量计,其至少85%,优选为按重量计至少90%,更优选为按重量计至少95%,在25℃下不溶于二甲苯。
在第二丙烯基组分(B)内,组分(B2)可以适当地是乙烯共聚物,其含有按重量计15-60%,优选为按重量计20-40%的C3-C10α-烯烃,优选为丙烯,其在室温下至少60%可溶于二甲苯。适合作为组分(B)的聚合物组合物是国际申请WO 02/28958中所公开的那些,特别是包含以下组分(重量百分比)的组合物:
A)20%-90%的结晶聚丙烯组分,其含有25%-75%的部分AI,AI的熔体流动速率MFRI为0.5-10g/10min,和75%-25%的部分AII,AII的熔体流动速率MFRII使得比率MFRII/MFRI为30-2000,优选为50-1000;且其中部分AI和AII独立地从丙烯均聚物、含有最多8%的乙烯的丙烯的无规共聚物,和含有最多8%的至少一个C4-C10α-烯烃的丙烯的无规共聚物组成的组中选出;以及
B)10%-80%的乙烯和至少一个C3-C10α-烯烃的共聚物组分,所述共聚物含有10-70%的乙烯,和可选的少量的二烯,所述共聚物在室温下可溶于二甲苯,且在135℃下在四氢化萘中的特性粘度为4-9,优选为5-8,最优选为5.5-7dl/g。
适合作为组分(B)的其他聚合物组合物是国际申请WO 2004/087805中所公开的那些,特别是包含以下组分(重量百分比)的组合物:
A)50-90%的结晶聚丙烯组分,其包含:
AI)25-75%的部分,其熔体流动速率MFRI为0.1-10g/10min;和
AII)25-75%的部分,其熔体流动速率值MFRII等于或低于100g/10min;
其中比率MFRII/MFRI为5-60,且部分(AI)和(AII)独立地从丙烯均聚物、含有最多3%的乙烯的丙烯的无规共聚物,和含有最多6%的至少一个C4-C10α-烯烃的丙烯的无规共聚物组成的组中选出;以及
B)10%-50%的乙烯和至少一个C3-C10α-烯烃的共聚物组分,所述共聚物含有15%-50%的乙烯和可选的少量二烯;
所述组合物在室温(约25℃)下可溶于二甲苯的部分的特性粘度值等于或高于3.5dl/g。
根据本发明,既没有必要也不期望通过硫化使组分(A)和(B)交联。
通常,适用于本发明的组合物的乙烯基塑性体(C)是乙烯与C3-C10α-烯烃的共聚物,其含有衍生自C3-C10α-烯烃的至少20wt%,优选为20-50wt%,的单元(13C-NMR分析)。优选的是,乙烯基塑性物(C)的密度低于0.89g/ml(根据ASTM D-792测得)。
乙烯基塑性物(C)的优选例子为:
·乙烯与1-辛烯的共聚物,其具有衍生自1-辛烯的20wt%-45wt%的单元(13C-NMR分析);
·乙烯与1-丁烯的共聚物,其具有衍生自1-丁烯的20wt%-40wt%的单元(13C-NMR分析)。
通常,适用于本发明的组合物的滑石(D)是粒子形式,平均粒径(Sedigraph ISO 13317-3)范围为(D50)0.1-20微米(μm)。
根据一个实施例,当本发明的组合物包括一定数量的高密度聚乙烯(HDPE)时,其显示出实质性的抗划伤性改进。
根据另一个实施例,通过引入少量的抗划伤添加剂,抗划伤性也得到改良。可用于本发明的组合物的抗划伤添加剂是本领域中已知的那些,其润滑作用使得划伤可见性降低。这样的化合物的例子为芥酸酰胺、油酰胺以及聚二甲基硅氧烷。
根据又一个实施例,通过引入大量的色素,抗划伤性也得到改良。
上述化合物显示出添加剂抗划伤性改良效果。
本发明的组合物优选的熔体流动速率值(ISO 1133-230℃,2.16Kg)为10-150g/10min,优选为20-120g/10min。
本发明的组合物可通过机械混合其祖分来制备。
本发明的组合物适当地显示出弯曲模量高于1000MPa,优选为高于1200MPa,更优选为高于1500MPa。本发明的组合物还适当地显示出拉伸模量高于1000MPa,优选为高于1200MPa,更优选为高于1500MPa。
本发明的组合物进一步适当地显示出C-排放值小于50g/10min,优选为小于20g/10min。
本发明的组合物,由于性质的组合(高刚度、高流动性和良好的耐冲击性),尤其适合于成型制品,诸如,汽车行业的成品件,例如,汽车仪表盘的整体发泡。
因此,本发明的另一个目的在于一种由根据本发明的组合物制备的发泡制品。不通过硫化活性改性而获得的所述发泡制品的适当的密度在0.5-1.1g/cm3。其可以是整体发泡制品,其中平均细胞大小优选为5-500μm。
一种用于成型制品的整体发泡的合适的方法是图1所示的所谓的“呼吸成型法”。将熔体注入模具中,如同传统的注射成型一样。然而,在注射之前,在熔体的熔化和挤出过程中,在压力下加入惰性气体,在熔体中物理溶解和均质化(物理发泡)。同样可以使用化学发泡剂,可以任选地使用或与这样的气体结合使用。典型的化学发泡剂是惰性的挥发性液体,诸如,举例而言,低级烃,其具有高于80℃的沸点,其膨胀是由加热模具触发的。其它例子是在加热下释放二氧化碳的碳酸氢盐。也可以添加包含在微球体中的这样的化学发泡剂,所述微球体能更容易均质化并处理且在膨胀时破裂。通常,这样的整体泡沫具有夹层结构,基本上由成型片材的膨胀衍生而来;如同在夹层中,位于泡沫层侧面的平行的大表面均保持其致密的结构,和原始片材一样。在将充气熔体注入模具后,填充有熔体聚合物的模具体积增加,从而形成泡沫。
根据本发明的发泡制品可以是,例如,汽车行业的成品件,诸如,汽车的仪表板、仪表盘或其他内饰组件。
根据另一个目的,本发明提供了一种交通工具,诸如,汽车或卡车,其包含根据本发明的发泡制品。
给出以下实施例是为了说明本发明,而没有任何限制目的。
测量方法
所述丙烯聚合物和所获得的薄膜的特性化数据根据以下方法得到:
熔体流动速率(MFR)
根据ISO 1133(230℃,2.16Kg)确定。
拉伸模量
根据ISO 527/1+2确定。
简支梁冲击强度(Chamy)
根据ISO 179/1eU和/1eA确定。
抗划伤性
根据GME 60280-10N确定,增益:Lynx/Cordwain,7日后。具有定义的几何形状的钢针用于创建在粒状表面上具有定义的速度和接触力的划伤网格。测量划伤前后亮度(dL)的差异。亮度(dL)的差异值较小表示较好的划伤性能。
二甲苯可溶物(XS)
如下确定:将2.5g聚合物和250ml的二甲苯装入配备有致冷器和磁性搅拌器的玻璃烧瓶中。将温度在30分钟内升高至溶剂的沸点。然后,将如此获得的澄清溶液保持回流,并进一步搅拌30分钟。然后将封闭的烧瓶放在25℃恒温水浴中保持30分钟。用快速过滤纸对这样形成的固体进行过滤。将100ml过滤后的液体倾倒在预先称重的铝容器中,在氮气流下在加热板上加热,以通过蒸发除去溶剂。然后将容器在真空下保持在80℃烘箱中,直到获得恒重。然后,计算聚合物在室温下可溶于二甲苯的重量百分比。
全同立构五元组含量的确定
如下确定:将50mg的每个二甲苯不溶部分溶解在0.5mL的C2D2Cl4中。用Bruker DPX-400(100.61Mhz,90°脉冲,脉冲之间有12s延迟)获得13C NMR谱。对于每一光谱,存储约3000个瞬态;mmmm五元组的峰值(21.8ppm)用作参考。进行微观结构分析,如在文献(Polymer,1984,25,1640,Inoue Y.等人和Polymer,1994,35,339,Chujo R.等人)中所述。
硬度
肖氏A-ASTM D-2240
实施例
实施例中描述的所有组合物均用双螺杆挤出机Krupp Werner&Pfleiderer/1973,ZSK 53来制造,螺杆直径:2×53,36D,螺杆转速为150rpm且熔融温度为230℃,以获得供发泡试验用的化合物。
所有化合物都在相同的加工条件下用Battenfeld BA 1500/630注射成型机来发泡,熔融温度:220℃,模具温度:35℃,注射压力:1500巴,利用物理发泡剂(0.4%的氮)。高压发泡方法用于生产发泡平板。在高压注射后,在将模具打开控制距离时,材料开始发泡。这个打开距离控制零件的最终厚度,从而控制最终密度。
实施例1(比较)-组合物
该组合物由以下组分形成:
·84%的MP EP348U,购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为70g/10min的多相共聚物;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·2%的BK MB-PE 4687(Cabot),炭黑的PE母料;
·1.3%的MP HF 500N,购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为12g/10min的均聚物。
最终的未发泡组合物的主要组分示于表1。
实施例2-组合物
该组合物由以下组分形成:
·62%的MP EP348U,购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为70g/10min的多相共聚物;
·7%的Hifax X 1956 A,购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的反应器制备的TPO(热塑性聚烯烃),在室温下可溶于二甲苯的部分在135℃下在四氢化萘中的特性粘度为7dl/g,由MFR(ISO 1133-230℃,2.16Kg)为73g/10min的35%的均聚物、MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的35%的均聚物,和具有按重量计36%的乙烯单元的30%的乙烯/丙烯共聚物形成;
·15%的Engage 8200,一种乙烯-辛烯共聚物,具有66肖氏A点的硬度和0.87g/ml的密度,由DowChemical销售;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·2%的BK MB-PE 4687(Cabot),炭黑的PE母料;
·1.3%的MP HF 500N,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为12g/10min的均聚物。
最终的未发泡组合物的主要组分示于表1。
实施例3-组合物
该组合物由以下组分形成:
·42%的MP EP348U,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为70g/10min的多相共聚物;
·20%的MC MF650Y,一种超高熔体流动速率的树脂,具有非常窄的分子量分布,购自LyondellBasell,其MFR(ISO 1133-230℃,2.16Kg)为1800g/10min;
·7%的Hifax X 1956 A,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的反应器制备的TPO(热塑性聚烯烃),在室温下可溶于二甲苯的部分在135℃下在四氢化萘中的特性粘度为7dl/g,由MFR(ISO 1133-230℃,2.16Kg)为73g/10min的35%的均聚物、MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的35%的均聚物,和具有按重量计36%的乙烯单元的30%的乙烯/丙烯共聚物形成;
·15%的Engage 8200,一种乙烯-辛烯共聚物,具有66肖氏A点的硬度和0.87g/ml的密度,由DowChemical销售;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·2%的BK MB-PE 4687(Cabot),炭黑的PE母料;
·1.3%的MP HF 500N,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为12g/10min的均聚物。
最终的未发泡组合物的主要组分示于表1。
实施例4-组合物
该组合物由以下组分形成:
·48%的MC HM2015,一种超高熔体流动速率的树脂,具有非常窄的分子量分布,购自LyondellBasell,其MFR(ISO 1133-230℃,2.16Kg)为140g/10min;
·14%的MC MF650Y,一种超高熔体流动速率的树脂,具有非常窄的分子量分布,购自LyondellBasell,其MFR(ISO 1133-230℃,2.16Kg)为1800g/10min;
·7%的Hifax X 1956 A,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的反应器制备的TPO(热塑性聚烯烃),在室温下可溶于二甲苯的部分在135℃下在四氢化萘中的特性粘度为7dl/g,由MFR(ISO 1133-230℃,2.16Kg)为73g/10min的35%的均聚物、MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的35%的均聚物,和具有按重量计36%的乙烯单元的30%的乙烯/丙烯共聚物形成;
·15%的Engage 8200,一种乙烯-辛烯共聚物,具有66肖氏A点的硬度和0.87g/ml的密度,由DowChemical销售;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·2%的BK MB-PE 4687(Cabot,炭黑的PE母料;
·1.3%的MP HF 500N,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为12g/10min的均聚物。
最终的未发泡组合物的主要组分示于表1。
实施例5-组合物
该组合物由以下组分形成:
·57%的MP EP348U,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为70g/10min的多相共聚物;
·5%的HS GC 7260,一种购自LyondellBasell,MFR(ISO 1133-190℃,2.16Kg)为8g/10min的高密度聚乙烯(HDPE);
·7%的Hifax X 1956 A,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的反应器制备的TPO(热塑性聚烯烃),在室温下可溶于二甲苯的部分在135℃下在四氢化萘中的特性粘度为7dl/g,由MFR(ISO 1133-230℃,2.16Kg)为73g/10min的35%的均聚物、MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的35%的均聚物,和具有按重量计36%的乙烯单元的30%的乙烯/丙烯共聚物形成;
·15%的Engage 8200,一种乙烯-辛烯共聚物,具有66肖氏A点的硬度和0.87 g/ml的密度,由DowChemical销售;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·0.3%的禾大芥酸酰胺(芥酸酰胺,(Z)-Docos-13-enamid);
·2%的BK MB-PE 4687(Cabot),炭黑的PE母料;
·1.0%的MP HF 500N,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为12g/10min的均聚物。
最终的未发泡组合物的主要组分示于表1。
实施例6-组合物
该组合物由以下组分形成:
·57%的MP EP348U,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16kg)为70g/10min的多相共聚物;
·5%的HS GC 7260,一种购自LyondellBasell,MFR(ISO 1133-190℃,2.16Kg)为8g/10min的高密度聚乙烯(HDPE);
·7%的Hifax X 1956 A,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的反应器制备的TPO(热塑性聚烯烃),在室温下可溶于二甲苯的部分在135℃下在四氢化萘中的特性粘度为7dl/g,由MFR(ISO 1133-230℃,2.16Kg)为73g/10min的35%的均聚物、MFR(ISO 1133-230℃,2.16Kg)为1.2g/10min的35%的均聚物,和具有按重量计36%的乙烯单元的30%的乙烯/丙烯共聚物形成;
·15%的Engage 8200,一种乙烯-辛烯共聚物,具有66肖氏A点的硬度和0.87g/ml的密度,由DowChemical销售;
·12%的滑石Jetfine 3CA(水合硅酸镁);
·0.1%的Irganox 1010(pentaerythriltetrakis(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯));
·0.1%的Irgafos 168(三(2,4-二叔丁基苯基)亚磷酸酯);
·0.1%的硬脂酸钙-LIGA CA 860;
·0.2%的Rikemal AS-005(甘油脂肪酸偏酯);
·0.2%的Chimassorb 944 FDL(空间位阻胺光稳定剂);
·2%的BK MB-PE 4687(Cabot),炭黑的PE母料;
·1.3%的MP HF 500N,一种购自LyondellBasell,MFR(ISO 1133-230℃,2.16 Kg)为12 g/10 min的均聚物。
最终的未发泡组合物的主要组分示于表1。
表1
对实施例1(比较)、2、3、4、5和6的组合物的流动性、机械性能和抗划伤性进行了研究。所获得的结果示于表2。
可以看出,相比于比较实施例1,实施例2的组合物在室温下实现了近十倍的简支梁缺口值。
相比于实施例1,实施例3的组合物的拉伸模量略有减少,而耐冲击性改良两倍以上。
相比于比较实施例1,实施例4的组合物的MFR值是相当高的。
实施例5的组合物表现出出色的抗划伤性和表面质量,加之良好的起泡性。在Lynx粒状物下,划伤值可以从4.5(实施例1)降至0.01(实施例5),且在Cordwain粒状物下,从2.8(实施例1)降至0.1(实施例5)。
实施例6的组合物也显示出抗划伤性在不使用芥酸酰胺的情况下显著提高。
这些具有出色的抗划伤性的材料被预先指定用于供用户触摸,例如,在汽车内部触摸的发泡可见零件。
表2
实施例7(比较)和8至12-发泡制品
通过打开模具(“呼吸模具”)使实施例1(比较)、2、3、4、5和6的组合物发泡,以得到2mm厚(未发泡的)且密度为0.98g/cm3的平板。用物理发泡剂(氮)使样品发泡。表3示出结果。发泡性能被描述为打开距离的函数。可以看出,通过将模具打开2mm到4mm,比较实施例7中使用的组合物显示出良好的发泡性能。在较高打开距离下,发泡方法不可行,因为泡沫会因细胞壁破裂而被破坏。发泡板的外层由于被破坏的泡沫结构而分层。最低可实现密度为0.48g/cm3。相反,实施例8-12中使用的组合物也通过打开模具最高6mm而在过程中存活,这意味着这些材料可以实现更高的密度减小。可以实现0.33g/cm3的最终密度。
表3
C=封闭,O=打开,N=否,Y=是;G=好,B=坏。

Claims (9)

1.一种组合物,其包含:
从丙烯均聚物、丙烯共聚物或多相丙烯聚合物中选出的以重量计30-85%,优选为40-80%,更优选为50-70%的一种或多种丙烯基组分,根据ISO 178确定的这样的第一丙烯基组分的弯曲模量高于800MPa;
(B)按重量计1-20%,优选为3-15%,更优选为5-10%的多相丙烯聚合物,其包含:
(B1)按重量计20-90%,优选为50-90%的结晶聚丙烯;
(B2)按重量计10-80%,优选为按重量计15-60%的乙烯和至少一个C3-C10 α-烯烃的共聚物,这样的共聚物含有按重量计10-70%,优选为按重量计10-50%的乙烯,其在室温下可溶于二甲苯,并且在135℃下在四氢化萘中的特性粘度高于3.5dl/g,优选为高于4dl/g,更优选为5-8dl/g;
(C)按重量计1-30%,优选为5-25%,更优选为10-20%的乙烯基塑性体,其硬度(肖氏A,ASTM D-2240)的值等于或低于90点,优选为等于或低于85点,更优选为等于或低于80点;
(D)按重量计5-30%,优选为8-25%,更优选为10-20%的滑石。
(E)按重量计0-10%,优选为1-10%,更优选为3-8%的高密度聚乙烯(HDPE);以及
(F)按重量计0-1.5%,优选为0.1-1.5%,更优选为0.1-1.0%,再优选为0.2-0.5%的抗划伤添加剂。
2.根据权利要求1所述的组合物,其中,共聚物(B2)在135℃下在四氢化萘中的特性粘度为5-8dl/g。
3.根据权利要求1或2所述的组合物,其中,组分(B)包含(重量百分比):
A)20%-90%的结晶聚丙烯组分,其含有25%-75%的部分AI,AI的熔体流动速率MFRI为0.5-10g/10min,和75%-25%的部分AII,AII的熔体流动速率MFRII使得比率MFRII/MFRI为30-2000,优选为50-1000;且其中部分AI和AII独立地从丙烯均聚物、含有最多8%的乙烯的丙烯的无规共聚物,和含有最多8%的至少一个C4-C10 α-烯烃的丙烯的无规共聚物组成的组中选出;以及
B)10%-80%的乙烯和至少一个C3-C10 α-烯烃的共聚物组分,所述共聚物含有10-70%的乙烯,和可选的少量的二烯,所述共聚物在室温下可溶于二甲苯,且在135℃下在四氢化萘中的特性粘度为4-9,优选为5-8,最优选为5.5-7dl/g。
4.根据权利要求1至3中任一项所述的组合物,其中,组分(B)包含(重量百分比):
A)50-90%的结晶聚丙烯组分,其包含:
AI)25-75%的部分,其熔体流动速率MFRI为0.1-10g/10min;和
AII)25-75%的部分,其熔体流动速率值MFRII等于或低于100g/10min;
其中比率MFRII/MFRI为5-60,且部分(AI)和(AII)独立地从丙烯均聚物、含有最多3%的乙烯的丙烯的无规共聚物,和含有最多6%的至少一个C4-C10 α-烯烃的丙烯的无规共聚物组成的组中选出;以及
B)10%-50%的乙烯和至少一个C3-C10 α-烯烃的共聚物组分,所述共聚物含有15%-50%的乙烯和可选的少量二烯;
所述组合物在室温(约25℃)下可溶于二甲苯的部分的特性粘度值等于或高于3.5dl/g。
5.根据权利要求1至4中任一项所述的组合物,其中,抗划伤添加剂选自芥酸酰胺、油酰胺以及聚二甲基硅氧烷。
6.根据权利要求1至5中任一项所述的组合物,其熔体流动速率值(ISO 1133-230℃,2.16Kg)为10-150g/10min,优选为20-120g/10min。
7.一种由根据前述权利要求中的任一项所述的组合物制备的发泡制品。
8.一种根据权利要求7所述的发泡制品,其是用于汽车行业的成品件。
9.一种交通工具,其包含根据权利要求8所述的发泡制品。
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