CN113956530A - 一种节能的发泡聚丙烯珠粒及其模塑制件 - Google Patents
一种节能的发泡聚丙烯珠粒及其模塑制件 Download PDFInfo
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Abstract
本发明属于发泡聚丙烯技术领域,具体涉及一种节能的发泡聚丙烯珠粒及其模塑制件,发泡聚丙烯珠粒是通过复合微粒经过高温高压釜式发泡法制备而成,复合微粒包括芯层和皮层,芯层包括如下质量百分比的各组分:40‑60%的聚丙烯A、20‑40%的聚丙烯B、15‑30%的聚丙烯C、0.05‑2%的助膨胀剂、0.05‑0.5%的泡孔成核剂、0.5‑3%的马来酸酐改性聚丙烯;皮层包含如下质量百分比的各组分:90‑100%的聚烯烃D,0‑10%的其他助剂。本申请所用复合微粒有皮层包覆芯层的结构,皮层主体树脂的熔点低,易熔结,与芯层所用主基材树脂有很好的相容性;芯层树脂采用特殊选型的混合料,助膨胀剂进一步促进模塑膨胀性,利于EPP珠粒在1.4bar成型压力下更优异的模塑膨胀,牢固烧结的同时体现模塑制件优异的表观质量。
Description
技术领域
本发明属于发泡聚丙烯技术领域,具体涉及一种节能的发泡聚丙烯珠粒及其模塑制件。
背景技术
釜式法生产的发泡聚丙烯珠粒(EPP)及其模塑制品材料回弹性优异、耐高温性更好(理解为可在更高温度下使用)且生产过程清洁无污染,是PU泡沫、EPS和EPE的理想替代品,目前EPP已经广泛应用在保温隔热、缓冲包装和汽车轻量化领域。
EPP珠粒固有的熔融特性,导致了其水蒸气模塑时需要较高的蒸汽压力才能实现牢固的烧结,特别是对比EPS的模塑过程,EPP珠粒高的成型能耗是一个阻碍其进一步发展推广的因素。
中国发明专利CN101679662A使用熔点115-135℃的聚丙烯材料,得到了成型压力低于0.18MPa的发泡聚丙烯珠粒及其模塑制品;本发明人经过反复验证实验,发现该技术产品有抗压缩性能低(手感偏软)的风险缺陷。中国发明专利CN112457596A得到了低熔点聚烯烃包覆高熔点聚丙烯的节能型发泡珠粒,其成型压力低于2.2bar,但在EPS成型机模(成型压力低于1.6bar)塑存在烧结不良和制件表观质量差的风险。
鉴于此,有必要提供一种低成型能耗的发泡聚丙烯珠粒,降低模塑制件成型压力的同时,保证模塑制件表面质量和力学性能优异。
发明内容
为了解决上述问题,本申请公开了一种节能的发泡聚丙烯珠粒及其模塑制件,该发泡聚丙烯珠粒所用的是低熔点聚烯烃包覆芯层聚丙烯的复合微粒,利于发泡珠粒的低模塑成型压力和模塑制件优异的力学性能,芯层多组分聚丙烯配比及助膨胀剂有利于提升发泡珠粒的模塑膨胀性,促进低于1.4bar的模塑成型压力下,发泡芯层有足够的模塑膨胀能力,利于成型制件有优异的表面。
为了实现上述目的,本发明采用如下技术方案:
一种节能的发泡聚丙烯珠粒,所述发泡聚丙烯珠粒是通过复合微粒经过高温高压釜式发泡法制备而成,所述复合微粒包括芯层和皮层,所述芯层包括如下质量百分比的各组分:40-60%的聚丙烯A、20-40%的聚丙烯B、15-30%的聚丙烯C、0.05-2%的助膨胀剂、0.05-0.5%的泡孔成核剂、0.5-3%的马来酸酐改性聚丙烯;所述皮层包含如下质量百分比的各组分:90-100%的聚烯烃D,0-10%的其他助剂。
作为优选,上述聚丙烯A的熔点为120-130℃,熔融指数为5-10g/10min;所述聚丙烯B的熔点为130-140℃,熔融指数为5-12g/10min;所述聚丙烯C的熔点为140-152℃,熔融指数为5-30g/10min;所述聚烯烃D的熔点为104-122℃,熔融指数为4-15g/10min。
作为优选,上述聚丙烯A、聚丙烯B和聚丙烯C均为无规共聚聚丙烯,优选茂金属催化剂系列的产品;所述聚丙烯A的弯曲模量不低于700MPa,所述聚丙烯B的弯曲模量不低于900MPa,所述聚丙烯C的弯曲模量不低于1200MPa;所述聚烯烃D为LLDPE、LDPE、HDPE、三元无规共聚PP、POE、POP、OBC中的一种或几种。
作为优选,上述泡孔成核剂为聚四氟乙烯粉末、硼酸锌、滑石粉、硫酸钡、碳酸钙、硬脂酸钙、二氧化硅中的一种或几种,所述泡孔成核剂的粒径为10-15μm。
作为优选,上述助膨胀剂为亲水性物质。
作为优选,上述助膨胀剂为硫酸铝钾,平均粒径为1-15μm。
作为优选,上述皮层占复合微粒总质量的3-8%;所述复合微粒的长度为1.2-2.5mm,单重为0.5-1.8mg。
作为优选,上述发泡聚丙烯珠粒的制备方法为:
(1)聚丙烯A、聚丙烯B、聚丙烯C、助膨胀剂、泡孔成核剂、马来酸酐改性聚丙烯按一定比例混合后,双螺杆挤出造粒制得芯层母料;
(2)聚烯烃D与其他助剂按一定比例混合均匀后,双螺杆挤出造粒制得皮层母料;
(3)将芯层母料和皮层母料分别加入双单螺杆共挤出机组的芯层挤出机和皮层挤出机,塑化后同时经由共挤出口模出丝造粒,得到皮层包覆芯层的复合微粒;
(4)将复合微粒与分散剂和水一起加入到高压釜,密封后加入CO2,不停搅拌,升高反应釜的温度至发泡温度,调节釜内压力至发泡压力,在此温度和压力条件下保持5-30min,泄压将物料排放到常压的发泡管道中进行发泡,发泡管道内气氛温度为85-98℃,物料在发泡管道中经历的时间为4-15s,最终得到堆积密度15-120g/L的发泡珠粒,发泡珠粒第一次DSC熔融曲线中高于固有熔点的熔化峰吸热焓值8-15J/g(后面称高温熔化峰吸热焓值)。
一种节能的发泡聚丙烯珠粒的模塑制件,采用上述的发泡聚丙烯珠粒通过水蒸气烧结成型获得,具体步骤为:发泡珠粒经空气载压后,水蒸气模塑成型。
作为优选,上述模塑制件的成型压力低于1.4bar,可以在EPS模塑机上进行成型生产,所述模塑制件表面质量优异;所述模塑制件的密度为58-62g/L,50%应变时压缩应力不低于500KPa。
本发明具有如下的有益效果:
(1)本申请的发泡聚丙烯珠粒所用的复合微粒有皮层包覆芯层的结构,皮层主体树脂的熔点低,易熔结,与芯层所用主基材树脂有很好的相容性,皮层可以牢固包覆于芯层表面;芯层树脂采用特殊选型的混合料,EPP在低成型压力模塑过程膨胀性优异且保证优异的力学性能。助膨胀剂的添加进一步促进模塑膨胀性,利于EPP珠粒在低于1.4bar成型压力更优异的模塑膨胀,牢固烧结的同时体现模塑制件优异的表观质量。
(2)本申请的助膨胀剂硫酸铝钾,强吸湿性有助于釜压发泡的高膨胀性及优异的泡孔均匀性,利于珠粒模塑膨胀。
(3)本申请所用复合微粒发泡得到的发泡珠粒,其芯层是闭孔结构,皮层不起泡或极少微泡,复合微粒的皮层占比为3-8%,在保证稳定的促进珠粒表皮烧结的前提下,有助于发泡珠粒获得较好的回弹性和成型制件的优异的抗压缩性。
(4)在EPP逐步替代EPS应用的背景趋势下,本技术产品适合应用于EPS成型厂家向EPP模塑加工业务的转型(不用投入新成型设备费用,直接用现有EPS模塑机就能生产EPP制件),同时进一步促进EPP对EPS部分应用的替代。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明所制备的发泡聚丙烯珠粒的截面扫描电镜照片。
具体实施方式
现在结合实施例对本发明作进一步详细的说明。
主要实验物料性能见表1。
表1
复合微粒S1-S7和复合微粒D1-D4的配方及参数如表2所示。
表2
发泡聚丙烯珠粒的制备方法为:
(1)聚丙烯A、聚丙烯B、聚丙烯C、助膨胀剂、泡孔成核剂、马来酸酐改性聚丙烯按一定比例混合后,双螺杆挤出造粒制得芯层母料;
(2)聚烯烃D与其他助剂按一定比例混合均匀后,双螺杆挤出造粒制得皮层母料;
(3)将芯层母料和皮层母料分别加入双单螺杆共挤出机组的芯层挤出机和皮层挤出机,塑化后同时经由共挤出口模出丝造粒,得到皮层包覆芯层的复合微粒;
(4)将复合微粒与分散剂和水一起加入到高压釜,密封后加入CO2,不停搅拌,升高反应釜的温度至发泡温度,调节釜内压力至发泡压力,在此温度和压力条件下保持5-30min,泄压将物料排放到常压的发泡管道中进行发泡,发泡管道内气氛温度为85-98℃,物料在发泡管道中经历的时间为4-15s,最终得到堆积密度15-120g/L的发泡珠粒,发泡珠粒第一次DSC熔融曲线中高于固有熔点的熔化峰吸热焓值8-15J/g。
所制备的发泡珠粒经空气载压后,水蒸气模塑成型,获得模塑制件。
实施例1-7和对比例1-4制备过程中的各项参数及模塑件性能见表3。
表3
其中,最低成型压力:发泡珠粒模塑件折断面泡孔被破坏的粒子占比在95%以上所需要的最低蒸汽烧结压力。
制件表观质量:“ⅰ”表示制件表面较多的凹坑或缝隙;“ⅱ”表示制件表面少量的凹坑或缝隙;“ⅲ”表示制件表面没有或者极少或极小的凹坑或缝隙。
实施例1-4均在技术要求范围,体现出优异的低压模塑成型性和抗压缩能力,完全有潜质在EPS模塑成型机加工模塑制件。图1是实施例4的发泡珠粒截面的SEM图片,可以观察到均匀的闭孔结构,且珠粒内部中心部分与靠近表层部分的泡孔差异小,利于体现优异的模塑膨胀性。
对比例1-4分别使用带有极性亲水基团的液体状助膨胀剂,物料机械混合阶段均匀性差且在基体中容易析出流失,导致助膨胀效果相对弱,在采用与实施例4相近的发泡条件的情况下,虽然所获得的发泡珠粒堆积密度在58.5-59.5g/L,高温熔化峰吸热焓值为9.4-10J/g范围内,都接近于实施例4的相应参数59g/L,9.7J/g,但对比例1-4的最低模塑成型压力相对偏高。
对比例5缺少了高模量聚丙烯C的增强作用,抗压缩能力降低;对比例6缺少了高模量聚丙烯C的增强,且利于低成型压力模塑膨胀的聚丙烯A含量不足,抑制了模塑膨胀性,最低成型压力需要1.6bar,抗压缩能力降低;对比例7添加过多的高模量聚丙烯C,抑制模塑膨胀性,最低成型压力需要1.7bar;对比例8缺少助膨胀剂的发泡效果,抑制模塑膨胀性,最低成型压力需要1.6bar,且制件外观出现少量缺陷。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (10)
1.一种节能的发泡聚丙烯珠粒,其特征在于:所述发泡聚丙烯珠粒是通过复合微粒经过高温高压釜式发泡法制备而成,所述复合微粒包括芯层和皮层,所述芯层包括如下质量百分比的各组分:40-60%的聚丙烯A、20-40%的聚丙烯B、15-30%的聚丙烯C、0.05-2%的助膨胀剂、0.05-0.5%的泡孔成核剂、0.5-3%的马来酸酐改性聚丙烯;所述皮层包含如下质量百分比的各组分:90-100%的聚烯烃D,0-10%的其他助剂。
2.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述聚丙烯A的熔点为120-130℃,熔融指数为5-10g/10min;所述聚丙烯B的熔点为130-140℃,熔融指数为5-12g/10min;所述聚丙烯C的熔点为140-152℃,熔融指数为5-30g/10min;所述聚烯烃D的熔点为104-122℃,熔融指数为4-15g/10min。
3.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述聚丙烯A、聚丙烯B和聚丙烯C均为无规共聚聚丙烯,优选茂金属催化剂系列的产品;所述聚丙烯A的弯曲模量不低于700MPa,所述聚丙烯B的弯曲模量不低于900MPa,所述聚丙烯C的弯曲模量不低于1200MPa;所述聚烯烃D为LLDPE、LDPE、HDPE、三元无规共聚PP、POE、POP、OBC中的一种或几种。
4.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述泡孔成核剂为聚四氟乙烯粉末、硼酸锌、滑石粉、硫酸钡、碳酸钙、硬脂酸钙、二氧化硅中的一种或几种,所述泡孔成核剂的粒径为10-15μm。
5.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述助膨胀剂为亲水性物质。
6.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述助膨胀剂为硫酸铝钾,平均粒径为1-15μm。
7.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述皮层占复合微粒总质量的3-8%;所述复合微粒的长度为1.2-2.5mm,单重为0.5-1.8mg。
8.如权利要求1所述的节能的发泡聚丙烯珠粒,其特征在于:所述发泡聚丙烯珠粒的制备方法为:
(1)聚丙烯A、聚丙烯B、聚丙烯C、助膨胀剂、泡孔成核剂、马来酸酐改性聚丙烯按一定比例混合后,双螺杆挤出造粒制得芯层母料;
(2)聚烯烃D与其他助剂按一定比例混合均匀后,双螺杆挤出造粒制得皮层母料;
(3)将芯层母料和皮层母料分别加入双单螺杆共挤出机组的芯层挤出机和皮层挤出机,塑化后同时经由共挤出口模出丝造粒,得到皮层包覆芯层的复合微粒;
(4)将复合微粒与分散剂和水一起加入到高压釜,密封后加入CO2,不停搅拌,升高反应釜的温度至发泡温度,调节釜内压力至发泡压力,在此温度和压力条件下保持5-30min,泄压将物料排放到常压的发泡管道中进行发泡,发泡管道内气氛温度为85-98℃,物料在发泡管道中经历的时间为4-15s,最终得到堆积密度15-120g/L的发泡珠粒,发泡珠粒第一次DSC熔融曲线中高于固有熔点的熔化峰吸热焓值8-15J/g。
9.一种节能的发泡聚丙烯珠粒的模塑制件,其特征在于:采用如权利要求1-8任一项所述的发泡聚丙烯珠粒通过水蒸气烧结成型获得,具体步骤为:发泡珠粒经空气载压后,水蒸气模塑成型。
10.如权利要求9所述的节能的发泡聚丙烯珠粒的模塑制件,其特征在于:所述模塑制件的成型压力低于1.4bar,可以在EPS模塑机上进行成型生产,所述模塑制件表面质量优异;所述模塑制件的密度为58-62g/L,50%应变的压缩应力不低于500KPa。
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