CN110872413A - 一种高耐磨高环刚度芯层微发泡管材及其制备方法 - Google Patents
一种高耐磨高环刚度芯层微发泡管材及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种高耐磨高环刚度芯层微发泡管材及其制备方法。本发明的材料括以下重量份数的组分:第一组分聚合物70‑90份,第二组分聚合物10‑25份,填充物5‑15份,相容剂1‑5份,耐磨助剂1‑5份,润滑剂0.5‑3份,成核剂0.5‑5份,超细改性发泡剂1‑5份,其他助剂1‑3份。本发明通过科学配方、工艺设计,获得了具有环刚度超过8KN/m2的高环刚度芯层微发泡管材,甚至在管材环向弯折超过40%时仍不断裂,满足管材使用要求。
Description
技术领域
本发明涉及一种高耐磨高环刚度芯层微发泡管材及其制备方法,属于材料技术领域。
背景技术
微发泡技术因其特有的芯层发泡、表层结皮类三明治结构,赋予了产品轻量化、低成本、高尺寸稳定等多重优势,正在受到越来越多关注。然而,由于其泡孔存在,容易造成缺陷,导致产品力学性能下降。例如,在管材领域,为了保证塑料埋地排水管在外压负载下安全工作,环刚度的选择是设计中的关键之一。如果管材的环刚度太小,管材可能发生过大变形或出现压屈失稳破坏。目前,当微发泡技术运用到管材领域,因现用材料、工艺等原因,泡孔孔径控制不均、分布不良,极易造成管材环刚度变差,甚至发脆,渗漏等,无法正常应用。
发明内容
为解决上述技术问题,本发明通过科学合理的配方、工艺设计,不但提高了微发泡聚乙烯管环刚度,降低表面摩擦力,系统性解决了微发泡聚乙烯管道环刚度差、 耐久性差问题,可实现长期稳定耐磨效果,满足预埋聚乙烯波纹管道使用要求,还实现了管材减重超过25%,有效符合了产品降本增效。
为实现上述目的,本发明采用如下技术方案:
一种高耐磨高环刚度芯层微发泡管材,包括以下重量份数的组分:
第一组分聚合物70-90份,
第二组分聚合物10-25份,
填充物5-15份,
相容剂1-5份,
耐磨助剂1-5份,
润滑剂0.5-3份,
成核剂0.5-5份,
超细改性发泡剂1-5份,
其他助剂 1-3份。
进一步的技术方案,所述第一组分聚合物为高密度聚乙烯、双峰聚乙烯中的一种或两种混合物,所述聚乙烯熔融指数小于等于2g/10min,在190℃,21.6kg载荷条件下,优选熔融指数为1g/10min的高密度聚乙烯与双峰聚乙烯的混合物。
进一步的技术方案,所述第二组分聚合物为支化聚丙烯、超高分子量聚乙烯、高分子量乙烯-丙烯酸共聚物中的一种或两种混合物,其中,支化聚丙烯熔体强度超过20cN,超高分子量聚乙烯分子量大于等于400万,乙烯-丙烯酸共聚物分子量大于等于100万;优选熔体强度为28cN的支化聚丙烯。
进一步的技术方案,所述相容剂为丙烯酸接枝聚乙烯、丙烯酸接枝SEBS、丙烯酸接枝乙烯-醋酸乙烯共聚物中的一种,且丙烯酸单体残留量小于等于0.5%;优选丙烯酸接枝聚乙烯。丙烯酸单体残留量过高,与管内运输物质发生萃取,容易引起管材渗漏风险,故严格控制丙烯酸单体残留量。
进一步的技术方案,所述耐磨助剂为玻璃微珠、纳米氧化铝、氨基硅酮、纳米碳化硅中的一种,优选纳米碳化硅;
所述成核剂为超细碳酸钙、磷酸二异辛酯、聚甲基丙烯酸盐盐、三环二萜类化合物中的一种;优选超细碳酸钙。
进一步的技术方案,所述填充剂为玻璃纤维、玻璃棉、石英砂中的一种;优选石英砂。
进一步的技术方案,所述润滑剂为乙烯合成蜡、硬脂酸、丙烯蜡、硬脂酸酰胺中的一种;优选丙烯蜡;所述其他助剂包括抗氧剂、光老化剂;所述抗氧剂为抗氧剂1010、168、1076、1098中的一种;优选抗氧剂1010;所述光老化剂为氰特3808。
一种高耐磨高环刚度芯层微发泡管材的制备方法,包括以下步骤:
(1)将改性剂在40-60℃条件下溶入介质中,然后将其加入到盛有超细发泡剂的高速混合机中,温度设置60-80℃,混合10-50min,待介质挥发完成,得到改性超细发泡剂,其中转速为大于等于1000r/min。所述超细发泡剂为碳酸氢钠、碳酸氢钙、柠檬酸、戊烷微球、己烷微球中的一种,粒径大于等于2500目;其中,改性剂为亚油酸、羟基丁二酸、酒石酸、邻羟基苯甲酸、十八碳酸中的一种,优选亚油酸;介质为无水乙醇、乙二醇、丙醇中的一种,优选无水乙醇。
(2)将第一组分聚合物70-90份,第二组分聚合物10-25份,相容剂1-5份,耐磨助剂1-5份,润滑剂0.5-3份,成核剂0.5-5份,超细改性发泡剂1-5份,其他助剂 1-3份按照重量份数加入到混合机中混合1-3min,再将混合物料加入到锥形双螺杆挤出机中;同时将填充物5-15份通过侧喂料口按照重量份数进入挤出机,经过塑化、剪切分散、挤出成管。其中,挤出机温度设置120-200℃,机头建压大于等于10MPa,真空-0.6-1MPa,螺杆转速20-200r/min。
有益效果
与现有技术相比,本发明具有如下显著优点:
1、本发明通过科学配方、工艺设计,获得了具有环刚度超过8KN/m2的高环刚度芯层微发泡管材,甚至在管材环向弯折超过40%时仍不断裂,满足管材使用要求;辅以填充剂、成核剂、耐磨改性剂协同配合,实现了芯层微发泡管的表面高硬度和低摩擦系数,有效降低磨损过程的破坏强度使得产品具有优良的耐摩擦磨损性和耐久性;选用丙烯酸单体残留单体量超低相容剂,有效改善体系内各组分界面相容性的同时,有效消除其在失效过程中的粗糙、粉化、渗漏等风险问题。
2、本发明选用的聚乙烯、乙烯-丙烯酸共聚物均为高分子量的,高分子量是为了保证微发泡材料在遭环向破环时,仍保持较好的强度及延伸率,进而实现微发泡产品高环刚度及强度要求。
3、本发明选用的第一组分聚合物保证了原始强度及稳定的加工性,第二组分聚合物可在体系中形成类似网状结构,调控气泡孔径,改善发泡均匀性,提高闭孔率,同时,可以进一步提高产品抗弯性能及延伸率。
4、本发明采用超细发泡剂,有利于获得均匀泡孔结构,有利于产品力学强度的保留,同时通过对超细发泡剂改性,有效提升了发泡剂在聚合物材料中的均匀分散,亦避免了发泡剂提前分解,为获得高质量芯层发泡管材有力支撑。
5、本发明所选配方组分,安全、环保、无毒,可满足无毒无害物质要求管件产品的使用。
6、本发明提供的材料制备方法工艺简单易行,生产效率高、成品率高、易于实现工业化特点。
具体实施方式
下面结合实施例对本发明作进一步详细的说明。
实施例
一种高耐磨高环刚度芯层微发泡管材的制备方法,包括以下步骤:
(1)将改性剂在40-60℃条件下溶入介质中,然后将其加入到盛有超细发泡剂的高速混合机中,温度设置60-80℃,混合10-50min,待介质挥发完成,得到改性超细发泡剂,其中转速为大于等于1000r/min。所述超细发泡剂为碳酸氢钠、碳酸氢钙、柠檬酸、戊烷微球、己烷微球中的一种,粒径大于等于2500目;其中,改性剂为亚油酸、羟基丁二酸、酒石酸、邻羟基苯甲酸、十八碳酸中的一种,优选亚油酸;介质为无水乙醇、乙二醇、丙醇中的一种,优选无水乙醇。
(2)将第一组分聚合物70-90份,第二组分聚合物10-25份,相容剂1-5份,耐磨助剂1-5份,润滑剂0.5-3份,成核剂0.5-5份,超细改性发泡剂1-5份,其他助剂 1-3份按照重量份数加入到混合机中混合1-3min,再将混合物料加入到锥形双螺杆挤出机中;同时将填充物5-15份通过侧喂料口按照重量份数进入挤出机,经过塑化、剪切分散、挤出成管。其中,挤出机温度设置120-200℃,机头建压大于等于10MPa,真空-0.6-1MPa,螺杆转速20-200r/min。
所述第一组分聚合物为高密度聚乙烯、双峰聚乙烯中的一种或两种混合物,所述聚乙烯熔融指数小于等于2g/10min,190℃,21.6kg载荷条件下;优选熔融指数为1g/10min的高密度聚乙烯与双峰聚乙烯的混合物。
所述第二组分聚合物为支化聚丙烯、超高分子量聚乙烯、高分子量乙烯-丙烯酸共聚物中的一种或两种混合物,其中,支化聚丙烯熔体强度超过20cN,超高分子量聚乙烯分子量大于等于400万,乙烯-丙烯酸共聚物分子量大于等于100万;优选熔体强度为28cN的支化聚丙烯。
所述相容剂为丙烯酸接枝聚乙烯、丙烯酸接枝SEBS、丙烯酸接枝乙烯-醋酸乙烯共聚物中的一种,且丙烯酸单体残留量小于等于0.5%;优选丙烯酸接枝聚乙烯。丙烯酸单体残留量过高,与管内运输物质发生萃取,容易引起管材渗漏风险,故严格控制丙烯酸单体残留量。
所述耐磨助剂为玻璃微珠、纳米氧化铝、氨基硅酮、纳米碳化硅中的一种,优选纳米碳化硅;
所述成核剂为超细碳酸钙、磷酸二异辛酯、聚甲基丙烯酸盐盐、三环二萜类化合物中的一种;优选超细碳酸钙。
所述填充剂为玻璃纤维、玻璃棉、石英砂中的一种;优选石英砂。
所述润滑剂为乙烯合成蜡、硬脂酸、丙烯蜡、硬脂酸酰胺中的一种;优选丙烯蜡;所述其他助剂包括抗氧剂、光老化剂;所述抗氧剂为抗氧剂1010、168、1076、1098中的一种;优选抗氧剂1010;所述光老化剂为氰特3808。
按照上述方法,通过调整具体组分和份数,制备3种高耐磨高环刚度芯层微发泡管材以及对比例,具体配方如下表1所示。
表1 对比例与实施例配方
组分 | 对比例1 | 实施例1 | 实施例2 | 实施例3 |
高密度聚乙烯 | 100 | 70 | 70 | 40 |
双峰聚乙烯 | 20 | 40 | ||
支化聚丙烯 | 10 | |||
超高分子量聚乙烯 | 20 | 20 | ||
乙烯-丙烯酸共聚物 | 5 | |||
丙烯酸接枝聚乙烯 | 1 | 3 | ||
丙烯酸接枝SEBS | 5 | |||
纳米氧化铝 | 3 | |||
氨基硅酮 | 5 | |||
纳米碳化硅 | 1 | |||
超细碳酸钙 | 3 | |||
聚甲基丙烯酸钠 | 0.5 | |||
磷酸二异辛酯 | 5 | |||
石英砂 | 5 | 15 | ||
玻璃纤维 | 10 | |||
碳酸氢钠 | 5 | |||
碳酸氢钙 | 3 | |||
戊烷微球 | 1 | |||
乙烯合成蜡 | 3 | |||
硬脂酸 | 1 | |||
丙烯蜡 | 0.5 | |||
其他助剂 | 1 | 2 | 3 |
本项目实施例性能
检测方法 | 对比例1 | 实施例1 | 实施例2 | 实施例3 | |
拉伸强度/MPa | ISO 527 | 25 | 26 | 28 | 27 |
弯曲模量/MPa | ISO 178 | 1000 | 2300 | 3200 | 3300 |
缺口冲击强度/kj/m2 | ISO 180 | 38 | 45 | 50 | 48 |
环刚度/ | GB/T 9647 | 6.5 | 7.6 | 8.6 | 7.9 |
磨损/mg | GB/T 3960 | 5.7 | 0.2 | 0.5 | 0.3 |
以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本领域的技术人员根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种高耐磨高环刚度芯层微发泡管材,其特征在于,包括以下重量份数的组分:
第一组分聚合物70-90份,
第二组分聚合物10-25份,
填充物5-15份,
相容剂1-5份,
耐磨助剂1-5份,
润滑剂0.5-3份,
成核剂0.5-5份,
超细改性发泡剂1-5份,
其他助剂1-3份。
2.根据权利要求1所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述第一组分聚合物为高密度聚乙烯、双峰聚乙烯中的一种或两种混合物,所述聚乙烯熔融指数小于等于2g/10min,190℃,21.6kg载荷条件下。
所述第二组分聚合物为支化聚丙烯、超高分子量聚乙烯、高分子量乙烯-丙烯酸共聚物中的一种或两种混合物;其中,支化聚丙烯熔体强度超过20cN,超高分子量聚乙烯分子量大于等于400万,乙烯-丙烯酸共聚物分子量大于等于100万。
3.根据权利要求2所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述第一组分聚合物为熔融指数为1g/10min的高密度聚乙烯与双峰聚乙烯的混合物;
所述第二组分聚合物为熔体强度为28cN的支化聚丙烯。
4.根据权利要求1所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述相容剂为丙烯酸接枝聚乙烯、丙烯酸接枝SEBS、丙烯酸接枝乙烯-醋酸乙烯共聚物中的一种,且丙烯酸单体残留量小于等于0.5%;
所述耐磨助剂为玻璃微珠、纳米氧化铝、氨基硅酮、纳米碳化硅中的一种;
所述成核剂为超细碳酸钙、磷酸二异辛酯、聚甲基丙烯酸盐盐、三环二萜类化合物中的一种;
所述填充剂为玻璃纤维、玻璃棉、石英砂中的一种。
5.根据权利要求1所述高耐磨高环刚度芯层微发泡管材,其特征在于:述相容剂为丙烯酸接枝聚乙烯;
所述耐磨助剂为纳米碳化硅;
所述成核剂为超细碳酸钙;
所述填充剂为石英砂。
6.根据权利要求1所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述超细改性发泡剂的制备方法:将改性剂在40-60℃条件下溶入介质中,然后将其加入到盛有超细发泡剂的高速混合机中,温度设置60-80℃,混合10-50min,待介质挥发完成后,得到改性超细发泡剂;其中,转速为大于等于1000r/min。
7.根据权利要求6所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述超细发泡剂为碳酸氢钠、碳酸氢钙、柠檬酸、戊烷微球、己烷微球中的一种,粒径大于等于2500目;
改性剂为亚油酸、羟基丁二酸、酒石酸、邻羟基苯甲酸、十八碳酸中的一种,介质为无水乙醇、乙二醇、丙醇中的一种。
8.根据权利要求6或7所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述改性剂为亚油酸;所述介质为无水乙醇。
9.根据权利要求1所述高耐磨高环刚度芯层微发泡管材,其特征在于:所述润滑剂为乙烯合成蜡、硬脂酸、丙烯蜡、硬脂酸酰胺中的一种;
所述其他助剂包括抗氧剂、光老化剂;所述光老化剂为氰特3808;所述抗氧剂为抗氧剂1010、168、1076、1098中的一种。
10.权利要求1-9任一项所述高耐磨高环刚度芯层微发泡管材的制备方法,其特征在于:包括以下步骤:
(1)将改性剂在40-60℃条件下溶入介质中,然后将其加入到盛有超细发泡剂的高速混合机中,温度设置60-80℃,混合10-50min,待介质挥发完成,得到改性超细发泡剂,其中转速为大于等于1000r/min;
(2)将第一组分聚合物70-90份,第二组分聚合物10-25份,相容剂1-5份,耐磨助剂1-5份,润滑剂0.5-3份,成核剂0.5-5份,超细改性发泡剂1-5份,其他助剂1-3份按照重量份数加入到混合机中混合1-3min,再将混合物料加入到锥形双螺杆挤出机中;同时将填充物5-15份通过侧喂料口按照重量份数进入挤出机,经过塑化、剪切分散、挤出成管;其中,挤出机温度设置120-200℃,机头建压大于等于10MPa,真空-0.6-1MPa,螺杆转速20-200r/min。
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