CN115403815A - 一种具有取向泡孔的微孔泡沫材料的制备方法 - Google Patents
一种具有取向泡孔的微孔泡沫材料的制备方法 Download PDFInfo
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Abstract
本发明涉及发泡新材料技术领域,具体涉及一种具有取向泡孔的微孔泡沫材料的制备方法,包括以下步骤:(1)将制备聚合物复合材料的原料熔融共混后进行热拉伸,得到聚合物复合纤维;所述原料包括聚合物基体、成纤相物质和加工助剂;(2)将步骤(1)制得的聚合物复合纤维按同一方向排列后进行热压,得到具有取向纤维的聚合物复合板材;(3)将步骤(2)制得的聚合物复合板材进行超临界流体发泡,得到具有取向泡孔的微孔泡沫材料。采用本发明制备方法能够制备得到泡孔取向一致、泡孔大小均匀的聚合物泡沫材料。
Description
技术领域
本发明涉及新材料技术领域,具体涉及一种具有取向泡孔的微孔泡沫材料的制备方法。
背景技术
时至今日,聚合物发泡方法已相当之多。常规聚合物微孔发泡材料性能受到泡孔的大小及其分布、泡孔结构等因素的影响。由于聚合物和气体两相的热力学性质差异很大,导致在传统意义上制备的聚合物发泡材料存在泡孔分布大小不均、泡孔呈无序随机分布和泡孔结构不可调等缺点,这些结构上的缺陷降低了聚合物发泡材料的力学、隔热、吸声等性能,制约了其用途。
发明内容
针对现有技术中存在的问题和不足,本发明的目的旨在提供一种具有取向泡孔的微孔泡沫材料的制备方法。
为实现发明目的,本发明采用的技术方案如下:
本发明第一方面提供了一种具有取向泡孔的微孔泡沫材料的制备方法,包括以下步骤:
(1)将制备聚合物复合材料的原料熔融共混后进行热拉伸,得到聚合物复合纤维;所述原料包括聚合物基体、成纤相物质和加工助剂;
(2)将步骤(1)制得的聚合物复合纤维按同一方向排列后进行热压,得到具有取向纤维的聚合物复合板材;
(3)将步骤(2)制得的聚合物复合板材进行超临界流体发泡,得到具有取向泡孔的微孔泡沫材料。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述原料中聚合物基体的含量为80wt%~99wt%,成纤相物质的含量为1wt%~20wt%。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述加工助剂的用量为聚合物基体和成纤相物质总重的0.1wt%~10wt%。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,步骤(3)中超临界流体发泡的温度为130~165℃,超临界流体压力为17.90~21.69Mpa,超临界流体保压处理时间为0.5~5h。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,步骤(1)中熔融共混的温度为160~255℃;热拉伸处理的温度为255~230℃。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,步骤(2)中所述热压的温度为180~200℃。更加优选地,所述热压处理是采用真空压膜机中进行热压,真空压膜机的压力为3000-5000kg。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述聚合物复合纤维的直径为160~240μm。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,聚合物基体为聚丙烯;更加优选地,所述聚丙烯的MFR为25g/10min。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述成纤相物质为聚对苯二甲酸乙二醇酯或聚酰胺;更加优选地,所述聚酰胺为尼龙6(PA6)。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述加工助剂为苯氧基聚磷腈或聚氧化乙烯(POE)。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述原料还包括抗氧剂,所述抗氧剂的用量为聚合物基体和成纤相物质总重的0.1wt%~1wt%。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述抗氧剂为巴斯夫抗氧剂1010、巴斯夫抗氧剂168中的至少一种。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述聚合物复合板材的厚度为1-5mm。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,超临界流体发泡的具体操作为:将聚合物复合板材置于密闭反应容器中,在130~155℃下向密闭反应容器中充入超临界流体至密闭反应容器中压力达到17.90~21.69Mpa,保压处理0.5~5h,然后将反应容器泄压降温。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,所述超临界流体为二氧化碳或氮气。
根据上述的具有取向泡孔的微孔泡沫材料的制备方法,优选地,步骤(1)中采用双螺杆挤出机进行熔融共混,双螺杆挤出机的螺杆转速为75rad/min,双螺杆挤出机下料斗转速为3-8rad/min;所述热拉伸是采用高速滚筒进行热拉伸,高速滚筒的转速为950rad/min。
本发明第二方面提供了一种利用上述第一方面所述制备方法制备的具有取向泡孔的微孔泡沫材料产品。
根据上述的具有取向泡孔的微孔泡沫材料产品,优选地,所述泡孔直径为3.0~7.3μm。
本发明第二方面提供了上述第二方面所述的具有取向泡孔的微孔泡沫材料产品在吸油泡沫中的应用。
与现有技术相比,本发明取得的积极有益效果为:
(1)本发明以聚合物基体、成纤相物质和加工助剂为原料,通过熔融共混挤出、热拉伸来制备聚合物复合纤维,在熔融挤出热拉伸的过程中,成纤相物质被原位拉伸,会在聚合物复合纤维内部形成长径比较大的微纤维,因此,本发明制备的聚合物纤维主要是由聚合物基体和成纤相物质原位成纤的微纤维组成;聚合物复合纤维中成纤相物质原位成纤的微纤维与聚合物基体之间热力学不相容,在两者之间的接触界面上,泡孔极易成核,因此,在对具有取向纤维的聚合物复合板材超临界流体发泡时,微纤维能够作为泡孔的成核点,使泡孔沿微纤维的方向定向生长,形成取向泡孔,最终制备得到了泡孔取向一致、泡孔大小均匀的聚合物泡沫材料。
(2)本发明在对聚合物复合纤维进行热压处理时,控制热压温度为180~200℃,在该温度下聚合物复合纤维中的聚合物基体会熔融,但聚合物复合纤维中的微纤维不会熔融,确保形成的聚合物复合板材中微纤维不会被破坏变形,且微纤维的取向不会发生改变,有利于超临界流体发泡过程中取向泡孔的形成。
(3)本发明超临界流体发泡控制在较低的温度(130~155℃)下进行,该温度下聚合物复合板材中的微纤维不会熔融破坏,因此,超临界流体发泡过程中聚合物板材中微纤维的取向不会发生改变,能够诱导泡孔沿微纤维的方向定向生长,形成取向泡孔。
(4)本发明具有取向泡孔的微孔泡沫材料制备方法简单,易于操作,成本低,可重复性高。
(5)本发明制备的具有取向泡孔的微孔泡沫材料,泡孔有序排布且方向一致,泡孔尺寸小,大小均匀, 具有良好的力学性能和应用前景,可以在吸油泡沫中使用。
附图说明
图1为本发明实施例1制备的具有取向泡孔的微孔泡沫材料的横截面示意图;
图2为本发明实施例9制备的具有取向泡孔的微孔泡沫材料沿纤维取向方向的截面示意图;
图3为对比例1制备的微孔泡沫材料的横截面示意图。
具体实施方式
以下通过具体的实施例对本发明作进一步详细说明,但并不限制本发明的范围。
实施例1:
一种具有取向泡孔的微孔泡沫材料的制备方法,包括以下步骤:
(1)将制备聚合物复合材料的原料干燥后混合均匀,通过双螺杆挤出机进行熔融共混,然后采用高速滚筒热拉伸,冷却后得到聚合物复合纤维,聚合物复合纤维的直径为160~240μm。所述双螺杆挤出机的温度设置为160-250℃,螺杆转速为75rad/min,下料斗转速为6rad/min;热拉伸时高速滚筒的转速为950rad/min。
所述原料由聚合物基体、成纤相物质、加工助剂和抗氧剂组成,所述聚合物基体为聚丙烯,所述成纤相物质为聚对苯二甲酸乙二醇酯(PET),所述加工助剂为苯氧基聚磷腈,所述抗氧剂为巴斯夫抗氧剂1010,原料中聚丙烯的含量为93wt%,PET的含量为7wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的3wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的1%。
(2)将步骤(1)制得的聚合物复合纤维按同一方向排列后放入压膜机进行热压,热压温度为190℃,热压后得到内部具有取向纤维的聚合物复合板材。
(3)将步骤(2)制得的聚合物复合板材置于密闭反应容器中,向密闭反应容器中充入超临界流体(二氧化碳)至密闭反应容器中压力达到21.69Mpa,在155℃下保压处理1h,然后将反应容器迅速泄压降温,得到具有取向泡孔的微孔泡沫材料。
实施例2:
实施例2的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为99wt%,PET的含量为1wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的10wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的0.1%。
步骤(2)中:热压温度为200℃,热压后得到内部具有取向纤维的聚合物复合板材。
步骤(3)中:超临界流体发泡过程中密闭反应容器中的压力为17.9Mpa,在165℃下保压处理2h。
实施例3:
实施例3的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为80wt%,PET的含量为20wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的0.1wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的0.5%。
步骤(2)中:热压温度为180℃,热压后得到内部具有取向纤维的聚合物复合板材。
步骤(3)中:超临界流体发泡过程中密闭反应容器中的压力为20.0Mpa,在130℃下保压处理5h。
实施例4:
实施例4的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为90wt%,PET的含量为10wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的5wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的0.8%。
步骤(2)中:热压温度为190℃,热压后得到内部具有取向纤维的聚合物复合板材。
步骤(3)中:超临界流体发泡过程中密闭反应容器中的压力为19.8Mpa,在145℃下保压处理2h。
实施例5:
实施例5的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为85wt%,PET的含量为15wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的3wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的0.5%。
步骤(2)中:热压温度为200℃,热压后得到内部具有取向纤维的聚合物复合板材。
步骤(3)中:超临界流体发泡过程中密闭反应容器中的压力为21.69Mpa,在150℃下保压处理2h。
实施例6:
实施例6的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为89wt%,PET的含量为11wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的2wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的1%。
实施例7:
实施例7的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为95wt%,PET的含量为5wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的6wt%,巴斯夫抗氧剂1010的用量为聚丙烯和PET总重的0.8%。
实施例8:
实施例8的内容与实施例1基本相同,其不同之处在于:
步骤(1)中:原料中聚丙烯的含量为93wt%,PET的含量为7wt%,苯氧基聚磷腈的用量为聚丙烯和PET总重的3wt%。
实施例9:
实施例9与实施例1基本相同,其不同之处在于:
步骤(1)中:成纤相物质为尼龙6(PA6),所述加工助剂为聚氧化乙烯。
步骤(3)中:保压处理温度为160℃。
步骤(3)的具体实施步骤为:将步骤(2)制得的具有定向微纤的聚合物复合板材置于密闭反应容器中,向密闭反应容器中充入超临界流体(二氧化碳)至密闭反应容器中压力达到21.69Mpa,在160℃下保压处理1h,然后将反应容器迅速泄压降温,得到具有取向泡孔的微孔泡沫材料。
对比例1:
对比例1与实施例1基本相同,其不同之处在于:步骤(2)中不对聚合物复合纤维进行定向排列,聚合物复合纤维随机散乱地放置后放入压膜机中进行热压,得到聚合物复合板材。
步骤(2)的具体操作为:将步骤(1)制得的聚合物复合纤维随机散乱地放置后放入压膜机中进行热压,热压温度为155℃,热压后得到聚合物复合板材。
对实施例1、实施例9和对比例1制备的聚合物复合板材进行扫描电镜检测,其检测结果如图1、图2、图3所示。
由图1可知,具有取向聚合物复合纤维的聚合物复合板材经流体发泡后得到的微孔泡沫材料泡孔取向一致、泡孔大小均匀。这是由于纤维取向诱导效应,微纤维能够作为泡孔的成核点,使泡孔沿微纤维的方向定向生长,形成取向泡孔。
由图2可知,采用尼龙6作为成纤相物质,在发泡之后也可形成泡孔取向一致、泡孔大小均匀的微孔泡沫材料,不过由于发泡温度(160℃)更高,所以泡孔尺寸较大。
由图3可知,对比1制备的微孔泡沫材料中泡孔随机分布,并无固定取向。这是因为绝毫无板材中聚合物复合纤维发生缠结形成纤维网络分散在 PP 基体中,在发泡的过程中会产生更多的异质成核点。
上述实施例的作用在于说明本发明的实质性内容,但并不以此限定本发明的保护范围。本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和保护范围。
Claims (10)
1.一种具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,包括以下步骤:
(1)将制备聚合物复合材料的原料熔融共混后进行热拉伸,得到聚合物复合纤维;所述原料包括聚合物基体、成纤相物质和加工助剂;
(2)将步骤(1)制得的聚合物复合纤维按同一方向排列后进行热压,得到具有取向纤维的聚合物复合板材;
(3)将步骤(2)制得的聚合物复合板材进行超临界流体发泡,得到具有取向泡孔的微孔泡沫材料。
2.根据权利要求1所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,所述原料中聚合物基体的含量为80wt%~99wt%,成纤相物质的含量为1wt%~20wt%;所述加工助剂的用量为聚合物基体和成纤相物质总重的0.1wt%~10wt%。
3.根据权利要求1或2所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,步骤(3)中超临界流体发泡的温度为130~165℃,超临界流体压力为17.90~21.69Mpa,超临界流体保压处理时间为0.5~5h。
4.根据权利要求3所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,步骤(1)中熔融共混的温度为160~255℃,步骤(2)中所述热压的温度为180~200℃。
5.根据权利要求4所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,所述聚合物复合纤维的直径为160~240μm。
6.根据权利要求5所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,聚合物基体为聚丙烯;所述成纤相物质为聚对苯二甲酸乙二醇酯或聚酰胺;所述加工助剂为苯氧基聚磷腈或聚氧化乙烯。
7.根据权利要求7所述具有取向泡孔的微孔泡沫材料的制备方法,其特征在于,所述原料还包括抗氧剂,所述抗氧剂的用量为聚合物基体和成纤相物质总重的0.1wt%~1wt%。
8.权利要求1-7任一所述制备方法制备的具有取向泡孔的微孔泡沫材料产品。
9.根据权利要求8所述的具有取向泡孔的微孔泡沫材料产品,其特征在于,所述泡孔直径为3.0~7.3μm。
10.权利要求9或10所述的具有取向泡孔的微孔泡沫材料产品在吸油泡沫中的应用。
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