CN111410793B - 一种熔喷聚丙烯组合物及其制备和应用 - Google Patents

一种熔喷聚丙烯组合物及其制备和应用 Download PDF

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CN111410793B
CN111410793B CN202010509795.4A CN202010509795A CN111410793B CN 111410793 B CN111410793 B CN 111410793B CN 202010509795 A CN202010509795 A CN 202010509795A CN 111410793 B CN111410793 B CN 111410793B
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尹朝清
张爽爽
刘乐文
袁绍彦
王培武
杨泽
王亚南
王琦玲
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Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Abstract

本发明公开了一种熔喷聚丙烯组合物及其制备方法和应用。该熔喷聚丙烯组合物由以下组分及重量份组成:聚丙烯树脂90‑99份、成纤调节母粒0.5‑10份、自由基引发剂0.1‑1份,其中成纤调节母粒按重量份计包括组分聚丙烯树脂30‑90份、超支化缔合聚合物5‑35份、界面阻隔剂5‑35份。本发明制备的熔喷聚丙烯组合物生产的熔喷无纺布纤维具有均匀的直径,良好的手感和蓬松度,同时兼具良好的过滤率,有效提高了口罩的安全性。

Description

一种熔喷聚丙烯组合物及其制备和应用
技术领域
本发明属于高分子材料领域,具体涉及一种熔喷聚丙烯组合物及其制备方法和应用。
背景技术
2019年岁末的新冠肺炎(COVID-19)影响了210多个国家和地区,新冠病毒主要通过呼吸道飞沫传播,在高风险地区,病人、医生乃至普通民众都普遍使用一次性医用口罩。熔喷布是口罩的主要结构之一,是有效阻隔病毒、细菌的核心结构,熔喷布主要以超高流动聚丙烯为原料,采用熔喷非织造工艺,在高速热气流的牵伸作用下,迅速高倍拉伸固化成形,工艺流程短,可以直接制备无纺织物。
在熔喷布生产过程中,热风温度可达到250℃及以上,如果接收装置和喷丝头的距离(DCD)较小,纤维冷却不充分,残留热量较多,表面温度较高,易引起并丝,导致纤维较粗,纤维不均匀,直径分布较宽,熔喷布较硬,同时呼吸阻力增大。另一方面,纤维直径较粗,无法构成多弯曲通道的纤维过滤层,且表面积较小,驻极效率降低,静电吸附能力减弱,导致过滤效率降低,降低口罩的有效阻隔作用。
因此,制备一种熔喷聚丙烯组合物,以获得手感柔顺兼具高过滤效率熔喷布,具有极佳的工业应用前景。
发明内容
为了克服上述现有技术存在的不足,本发明的首要目的在于提供一种熔喷聚丙烯组合物,该材料有利于改善熔喷布微米纤维的尺寸均匀性、手感与过滤效率。
本发明的另一目的在于提供上述熔喷聚丙烯组合物的制备方法。
本发明是通过以下技术方案实现的:
为了克服上述现有技术存在的不足,本发明的首要目的在于提供一种熔喷聚丙烯组合物,该材料有利于改善熔喷布微米纤维的尺寸均匀性、手感与过滤效率。
本发明的另一目的在于提供上述熔喷聚丙烯组合物的制备方法。
本发明是通过以下技术方案实现的:
一种熔喷聚丙烯组合物,按重量份计,包括以下组份:
聚丙烯树脂 90-99份;
成纤调节母粒 0.5-10份;
自由基引发剂 0.1-1份;
抗氧剂 0-3份;
润滑剂 0-1份;
其中,所述成纤调节母粒,按重量份数计,包括组分:
聚丙烯树脂 30-90份;
超支化缔合聚合物 5-35份;
界面阻隔剂 5-35份;
抗氧剂 0-1份;
润滑剂 0-1份。
本发明通过在熔喷聚丙烯中引入成纤调节剂,可有效改善熔喷料成纤过程中纤维的均匀性,减少纤维的并丝、黏连现象,改善手感蓬松度,提高熔喷布的柔软性。同时,通过对结晶性能的调节,构筑“界面陷阱”,提高纤维的电荷捕获能力,增强静电作用,提高滤效,具有优异的细菌、病毒捕获能力。
作为本发明进一步优选的技术方案,所述成纤调节母粒,按重量份计,包括组分:
聚丙烯树脂 60-80份;
超支化缔合聚合物 10-20份;
界面阻隔剂 10-20份;
抗氧剂 0-1份;
润滑剂 0-1份。
所述聚丙烯树脂为均聚聚丙烯,在测试条件为230℃/2.16kg时,其熔体流动速率为10-200g/10min。
所述超支化缔合聚合物选自超支化含氟聚醚酰亚胺、端羧基超支化芳香族聚酯聚醚、超支化聚酯酰胺、超支化聚乙烯接枝甲基丙烯酸甲酯中的一种或多种。
本发明选用的超支化缔合聚合物,一方面,由于其自身的体型结构,可以增加分子链的自由体积,链段运动能力增强,有利于提高纤维长度,使纤维交错形成三维结构,提高过滤效率;另一方面,超支化缔合聚合物可以有效提高聚丙烯树脂的自由体积,降低垂直于分子链方向的界面自由能,促进聚丙烯分子链的折叠作用,提高聚丙烯的结晶能力,提高聚丙烯的结晶速率,有利于构筑更多的“界面陷阱”,提高电荷捕获的能力,改善静电强度与滤效。
所述超支化缔合聚合物的相对粘度过高,不利于加工成形,无法发挥防止黏连并丝的作用,粘度过低,则易在喷丝孔处累积,形成熔滴,影响制品外观。因此,优选的,所述超支化缔合聚合物的相对粘度为200-2000,更优选为500-1500。
更优选的,所述超支化缔合聚合物为端羧基超支化芳香族聚酯聚醚或超支化聚乙烯接枝甲基丙烯酸甲酯中的一种或两种的混合。
所述界面阻隔剂选自全氟丙烯酸酯、聚偏氟乙烯、全氟聚醚、四氟乙烯-六氟丙烯-偏二氟乙烯共聚物、聚二甲基硅氧烷中的一种或多种。
本发明选用的界面阻隔剂的表面能较低,在加工过程中倾向于分布在材料表面,促使纤维快速固化,可有效防止纤维黏连,减少并丝现象,改善手感和蓬松度,有利于提高熔喷布的柔性,此外,所选择的低表面能的界面阻隔剂具有良好的憎水/绝缘性能,有效防止熔喷布的电荷耗散,保证熔喷布的长效过滤效率。
本发明通过引入包含有超支化缔合聚合物和界面阻隔剂的成纤调节母粒,超支化缔合聚合物和界面阻隔剂具有协同增效作用,可从晶型结构、纤维形貌与“界面构筑”三方面综合改善产品的过滤效率。所述的界面阻隔剂的熔融指数过高,分子量低,迁移速率快,长效性受限,熔融指数过低,分子量高,难迁移,界面阻隔作用弱,因此,优选的,本发明所述的界面阻隔剂在测试条件为265℃/5kg时,熔融指数为4-20g/10min。更优选的,所述界面阻隔剂为聚偏氟乙烯或四氟乙烯-六氟丙烯-偏二氟乙烯共聚物中的一种或两种的混合。
所述自由基引发剂选自过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁基过氧)己烷、3,6,9-三乙基-3,6,9-三甲基-1,4,7-三过氧壬烷、双(过氧化叔丁基)二异丙苯中的一种或多种,自由基引发剂可以促进聚丙烯的降解,使分子量分布变窄,制备高流动熔喷聚丙烯。
抗氧剂选自抗氧剂1010、抗氧剂168、抗氧剂1790、抗氧剂412S中的一种或多种。
润滑剂选自芥酸酰胺、油酸酰胺、EBS酰胺类、PE蜡、硬脂酸盐中的一种或几种。
本发明还提供了上述熔喷聚丙烯组合物的制备方法,包括如下步骤:
(1)制备成纤调节母粒:按比例称量各组分并混合均匀,经双螺杆挤出机挤出拉条切粒得到成纤调节母粒;
(2)将所制备成纤调节母粒及其他各组分按比例混合均匀,经双螺杆挤出机挤出拉条切粒得到熔喷聚丙烯组合物。
本发明工艺先制备成纤调节母粒,再与聚丙烯树脂混合,有利于改善成纤调节组分在基体中的分散效果,提高熔喷料的综合性能。
本发明还提供了上述熔喷聚丙烯组合物在熔喷过滤领域中的应用。由本发明上述熔喷聚丙烯组合物制备的熔喷无纺布纤维具有均匀的直径,良好的手感和蓬松度,同时兼具良好的过滤效率,有效提高了口罩的安全性和舒适性。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
现对实施例及对比例所用的原材料做如下说明,但不限于这些材料:
聚丙烯PP1:均聚聚丙烯,PP 320粉,熔体流动速率为30g/10min(230°C/2.16kg);
聚丙烯PP2:均聚聚丙烯,PP 668V粉,熔体流动速率为150g/10min(230°C/2.16kg);
超支化缔合聚合物:
超支化含氟聚醚酰亚胺,相对粘度为800,市购;
端羧基超支化芳香族聚酯聚醚,相对粘度为650,市购;
超支化聚乙烯接枝甲基丙烯酸甲酯1,相对粘度为500,市购;
超支化聚乙烯接枝甲基丙烯酸甲酯2,相对粘度为2100,市购;
界面阻隔剂:
全氟聚醚,熔融指数为12g/10min(265℃/5kg),市购;
全氟丙烯酸酯,熔融指数为10g/10min(265℃/5kg),市购;
聚二甲基硅氧烷,熔融指数为8g/10min(265℃/5kg),市购;
四氟乙烯-六氟丙烯-偏二氟乙烯共聚物,熔融指数为16g/10min(265℃/5kg),市购;
自由基引发剂:2,5-二甲基-2,5-双(叔丁基过氧)己烷,市购;
抗氧剂:1010:Y-001;168:Y-002;市购;
润滑剂:EBS B50,市购。
实施例1-8与对比例1-4:
(1)按表1的配比,按比例称量各组分后,经双螺杆挤出机挤出拉条切粒得到成纤调节母粒;
(2)按表2配比,将所制备的成纤调节母粒及其他各组分按比例混合均匀,经双螺杆挤出机挤出拉条切粒得到熔喷聚丙烯组合物。
对比例5:
将聚丙烯100份、超支化含氟聚醚酰亚胺0.45份、全氟聚醚0.45份、2,5-二甲基-2,5-双(叔丁基过氧)己烷0.3份、抗氧剂1010 0.05份、抗氧剂168 0.05份、EBS0.1份按比例称量并混合均匀,经双螺杆挤出机挤出拉条切粒得到熔喷聚丙烯组合物。
性能测试结果如表3和表4所示。
表1 成纤调节母粒的具体配比(重量份)
Figure 881939DEST_PATH_IMAGE002
表2 实施例和对比例中各组分配比(重量份)
Figure 267921DEST_PATH_IMAGE004
表3各实施例试样的性能测试数据
Figure 250921DEST_PATH_IMAGE006
表4各对比例试样的性能测试数据
Figure 380551DEST_PATH_IMAGE007
从表3和表4结果可以看出:由实施例和对比例1对比可以看出,在熔喷聚丙烯组合物中引入成纤调节剂,可以有效改善材料的柔韧性、滤效和纤维的均匀性,减少黏连和并丝:1)纤维直径:实施例中所制备熔喷布的纤维直径较小,且分布较窄,介于1-6μm之间,且纤维微观形貌基本观察不到并丝现象,对比例1所制备熔喷布的纤维直径分布在2-10μm之间,存在并丝现象,工艺敏感性高;2)滤效:实施例的颗粒过滤效率介于97%-100%之间,并且,在70℃处理24h后,滤效降低幅度很小,甚至不降低,而对比例1的颗粒滤效仅92.9%,经过热处理后,滤效降低至89.91%;3)空气透气性&阻力:由于形成三维交错结构,实施例的空气透气性具有显著提升,介于870-980 I/m2/s之间,而对比例1的空气透气性仅710 I/m2/s,同时,阻力由对比例1中的30.5 Pa降低到12.5-17.5 Pa;4)熔喷布强力:熔喷布的横向断裂强力和纵向断裂强力均有显著提升,分别从7.6 N/scm与10.5 N/scm提高到11.5-15.4 N/scm和14.2-18.1 N/scm。由实施例6、7和对比例2、3对比可知,与单独添加超支化缔合聚合物(对比例2)或者界面阻隔剂(对比例3)的体系相比;同时在熔喷聚丙烯中引入超支化缔合聚合物与界面阻隔剂的体系,具有更高的滤效、空气透气性以及更低的阻力等。由实施例8和实施例5对比可知,优选的四氟乙烯-六氟丙烯-偏二氟乙烯共聚物具有更优异的综合性能,由对比例4和实施例6对比可知,超支化缔合聚合物的粘度过高,不利于成形,整体滤效和透气性有所降低。由实施例2和对比例5对比可知,先制备成纤调节母粒,再与聚丙烯共混改性,有利于改善超支化缔合聚合物与界面阻隔剂在基体中的分散效果,改善综合性能。

Claims (10)

1.一种熔喷聚丙烯组合物,其特征在于,按重量份计,包括以下组份:
聚丙烯树脂 90-99份;
成纤调节母粒 0.5-10份;
自由基引发剂 0.1-1份;
抗氧剂0-3份;
润滑剂0-1份;
其中,所述成纤调节母粒,按重量份计,包括组分:
聚丙烯树脂 30-90份;
超支化缔合聚合物 5-35份;
界面阻隔剂 5-35份;
抗氧剂0-1份;
润滑剂0-1份;
所述超支化缔合聚合物选自超支化含氟聚醚酰亚胺、端羧基超支化芳香族聚酯聚醚、超支化聚酯酰胺、超支化聚乙烯接枝甲基丙烯酸甲酯中的一种或多种;
所述超支化缔合聚合物的相对粘度为200-2000;
所述界面阻隔剂选自全氟丙烯酸酯、聚偏氟乙烯、全氟聚醚、四氟乙烯-六氟丙烯-偏二氟乙烯共聚物、聚二甲基硅氧烷中的一种或多种;
所述自由基引发剂选自过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁基过氧)己烷、3,6,9-三乙基-3,6,9-三甲基-1,4,7-三过氧壬烷、双(过氧化叔丁基)二异丙苯中的一种或多种。
2.根据权利要求1所述的熔喷聚丙烯组合物,其特征在于,所述成纤调节母粒,按重量份计,包括组分:
聚丙烯树脂60-80份;
超支化缔合聚合物10-20份;
界面阻隔剂10-20份;
抗氧剂0-1份;
润滑剂0-1份。
3.根据权利要求1或2所述的熔喷聚丙烯组合物,其特征在于,所述聚丙烯树脂为均聚聚丙烯,在测试条件为230℃/2.16kg时,其熔体流动速率为10-200g/10min。
4.根据权利要求1或2所述的熔喷聚丙烯组合物,其特征在于,所述超支化缔合聚合物的相对粘度为500-1500。
5.根据权利要求4所述的熔喷聚丙烯组合物,其特征在于,所述超支化缔合聚合物为端羧基超支化芳香族聚酯聚醚或超支化聚乙烯接枝甲基丙烯酸甲酯中的一种或两种的混合。
6.根据权利要求1或2所述的熔喷聚丙烯组合物,其特征在于,所述界面阻隔剂在测试条件为265℃/5kg时,熔融指数为4-20g/10min。
7.根据权利要求6所述的熔喷聚丙烯组合物,其特征在于,所述界面阻隔剂为聚偏氟乙烯或四氟乙烯-六氟丙烯-偏二氟乙烯共聚物中的一种或两种的混合。
8.根据权利要求1或2所述的熔喷聚丙烯组合物,其特征在于,所述抗氧剂选自抗氧剂1010、抗氧剂168、抗氧剂1790、抗氧剂412S中的一种或多种;所述润滑剂选自芥酸酰胺、油酸酰胺、EBS酰胺类、PE蜡、硬脂酸盐中的一种或几种。
9.根据权利要求1-8任一项所述的熔喷聚丙烯组合物的制备方法,其特征在于,包括如下步骤:
(1)制备成纤调节母粒:按比例称量各组分并混合均匀,经双螺杆挤出机挤出拉条切粒得到成纤调节母粒;
(2)将所制备成纤调节母粒及其他各组分按比例混合均匀,经双螺杆挤出机挤出拉条切粒得到熔喷聚丙烯组合物。
10.一种权利要求1所述的熔喷聚丙烯组合物在熔喷过滤领域中的应用。
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