CN110564139B - 一种用于尼龙微发泡材料的高光母粒及其制备方法 - Google Patents

一种用于尼龙微发泡材料的高光母粒及其制备方法 Download PDF

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CN110564139B
CN110564139B CN201910661610.9A CN201910661610A CN110564139B CN 110564139 B CN110564139 B CN 110564139B CN 201910661610 A CN201910661610 A CN 201910661610A CN 110564139 B CN110564139 B CN 110564139B
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王滨
刘曙阳
蒋顶军
王笃金
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NANJING JULONG TECHNOLOGY CO LTD
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Abstract

本发明涉及一种用于尼龙微发泡材料的高光母粒及其制备方法。本发明包括以下重量份数的组分：聚酰胺100份，高光泽组分10‑35份，纳米高光填料5‑25份，耐磨助剂1‑5份，熔体补强剂5‑20份，其他助剂0.5‑2份。本发明可为尼龙微发泡材料提供高光泽、表面硬度高、耐划伤、耐磨、耐水解等特性，满足尼龙微发泡材料在汽车部件、卫浴、建筑等领域应用要求。

Description

一种用于尼龙微发泡材料的高光母粒及其制备方法
技术领域
本发明涉及一种用于尼龙微发泡材料的高光母粒及其制备方法，属于材料技术领域。
背景技术
尼龙微发泡材料因其芯层发泡表层结皮的特殊“三明治”结构赋予制品轻量化的同时，提供良好机械强度，满足使用要求。广泛应用在汽车内外饰、结构件等领域。然而，因其发泡导致的产品密度降低，加之，产品不同部位泡孔均匀性差异，导致产品表面光泽普遍差，无法实现高光泽性。同时，微发泡后，产品面临变脆、韧性差等问题，因此，目前微发泡尼龙微发泡材料还无法用于要求光泽度高、韧性好的产品制件。另一方面，随着人们对长期保持表面性能的要求越来越高，微发泡材料的耐刮性和耐摩擦性也常常无法满足需要。
发明内容
为解决上述技术问题，本发明提供一种用于尼龙微发泡材料的高光母粒及其制备方法，高光母粒一方面补强尼龙熔体强度，保证了材料微发泡过程中的均匀性，减少产品表面光泽性差异；另一方面，通过非结晶高光组分与细度极高的高光填料协同作用，可实现尼龙微发泡材料表面的高光泽度，用于对光泽度要求高的部件。
为实现上述目的，本发明采用如下技术方案：
一种用于尼龙微发泡材料的高光母粒，原料由以下重量份的组分组成：
聚酰胺100份
高光泽组分10-35份
纳米高光填料5-25份
耐磨助剂1-5份
熔体补强剂5-20份
其他助剂0.5-2份
进一步方案，所述聚酰胺为共聚聚酰胺，聚合单体为丙内酰胺、丁内酰胺、己内酰胺、戊二酸、己二酸、己二胺、辛二酸、二氨基庚二酸、辛二胺、癸二酸、癸二胺、丙氨酸、苯丙氨酸中的两种或几种的组合物；优选己内酰胺、己二酸、己二胺、癸二酸、癸二胺为单体合成的共聚聚酰胺。
进一步方案，所述高光泽组分为苯乙烯-丙烯酰胺共聚物、丙烯腈-苯乙烯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丁二烯-丙烯酸酯共聚物、乙烯-丙烯-丙烯腈共聚物、醋酸乙烯-丙烯酸共聚物、丙烯酸-丙烯酸羟丙酯共聚物、甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸甲酯共聚物、苯乙烯-甲基丙烯酸甲酯共聚物中的一种或几种组合物，优选丙烯腈-苯乙烯-丙烯酸共聚物。
进一步方案，所述纳米高光填料为表面活性剂处理的纳米硫酸钡、纳米玻璃微珠、纳米陶瓷粉、纳米石英砂中的一种或两种组合物，优选纳米硫酸钡。
进一步方案，所述耐磨助剂为聚四氟乙烯、二硫化钼、纳米碳化硅、石墨烯、石墨中的一种；优选石墨烯。
进一步方案，所述熔体补强剂为乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物、马来酸酐接枝乙丙三元橡胶、氯丁橡胶中的一种，优选乙烯-乙烯醇共聚物。
进一步方案，所述其他助剂为润滑剂和抗氧剂，润滑剂为硅酮粉、硬脂酸盐、乙撑双硬脂酰胺、氧化聚乙烯蜡、改性乙撑双脂肪酰胺（TAF）中的一种或两种组合物，优选氧化聚乙烯蜡与改性乙撑双脂肪酰胺（TAF）组合物。降低各组分间的界面张力、使得复合混合更加均匀、有利于实现各组分最优性能组合，实现加工过程更优化；所述抗氧剂为1098、168、624、138中的一种，优选抗氧剂1098。
一种用于尼龙微发泡材料的高光母粒的制备方法，包括以下步骤：
（1）将聚酰胺100份，高光泽组分10-35份，耐磨助剂1-5份，熔体补强剂5-20份，其他助剂0.5-2份，加入到混料机中，预混1-4min，得到混合物。
（2）将以上步骤（1）得到的混合物通过料斗加入双螺杆挤出机中，将纳米高光填料5-25份通过失重称准确称量并通过侧喂料机引入挤出机中，经啮合塑化、混合、挤出、拉条、风干、造粒，得到可用于尼龙微发泡材料的高光母粒；其中，挤出机温度设置一区至机头：210-280℃。
有益效果
相比现有技术，本发明具有如下优势：
1、本发明充分利用非结晶组分聚合物的高光泽性，与共聚尼龙作为载体，一方面可以实现高光母粒与尼龙微发泡材料的良好相容，共聚尼龙优良的韧性可以在基本不损失尼龙微发泡材料强度的前提下，弥补尼龙微发泡后材料韧性不足；另一方面，高光组分聚合物与高光填料、熔体补强剂的协同作用，可实现尼龙微发泡材料表面高光泽度，同时，非晶聚合物还可以改善尼龙微发泡材料熔体强度，有利于实现材料在微发泡过程中发泡均匀性，实现了微发泡产品的均匀、质轻特性。本发明特别适合需要表面高光泽度、耐刮耐磨要求高的微发泡汽车内外饰部件。本发明还具有优良的耐水解性。
2、本发明采用耐磨助剂与润滑剂协同作用，一方面降低各组分间的界面张力、使得复合混合更加均匀、有利于实现各组分最优性能组合，实现加工过程更优化；另一方面增加材料体系的均一性，改善发泡过程中的熔体破裂，有利于实现微发泡制件各部位泡孔均匀性。同时，本发明采用耐磨助剂和高光无机填料协同作用，有效增强了材料表面硬度和耐磨性，可以满足人们对产品表面耐磨和耐刮性要求。
3、本发明材料制备方法工艺经济、操作易行、生产效率高、易于实现工业化。
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
一种用于尼龙微发泡材料的高光母粒的制备方法，包括以下步骤：
（1）将聚酰胺100份，高光泽组分10-35份，耐磨助剂1-5份，熔体补强剂5-20份，其他助剂0.5-2份，加入到混料机中，预混1-4min，得到混合物。
（2）将以上步骤（1）得到的混合物通过料斗加入双螺杆挤出机中，将纳米高光填料5-25份通过失重称准确称量并通过侧喂料机引入挤出机中，经啮合塑化、混合、挤出、拉条、风干、造粒，得到可用于尼龙微发泡材料的高光母粒；其中，挤出机温度设置一区至机头：210-280℃。
所述聚酰胺为共聚聚酰胺，聚合单体为丙内酰胺、丁内酰胺、己内酰胺、戊二酸、己二酸、己二胺、辛二酸、二氨基庚二酸、辛二胺、癸二酸、癸二胺、丙氨酸、苯丙氨酸中的两种或几种的组合物；优选己内酰胺、己二酸、己二胺、癸二酸、癸二胺为单体的共聚聚酰胺。
所述高光泽组分为苯乙烯-丙烯酰胺共聚物、丙烯腈-苯乙烯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丁二烯-丙烯酸酯共聚物、乙烯-丙烯-丙烯腈共聚物、醋酸乙烯-丙烯酸共聚物、丙烯酸-丙烯酸羟丙酯共聚物、甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸甲酯共聚物、苯乙烯-甲基丙烯酸甲酯共聚物中的一种或几种组合物，优选丙烯腈-苯乙烯-丙烯酸共聚物。
所述纳米高光填料为表面活性剂处理的纳米硫酸钡、纳米玻璃微珠、纳米陶瓷粉、纳米石英砂中的一种或两种组合物，优选纳米硫酸钡。
所述耐磨助剂为聚四氟乙烯、二硫化钼、纳米碳化硅、石墨烯、石墨中的一种；优选石墨烯。
所述熔体补强剂为乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物、马来酸酐接枝乙丙三元橡胶、氯丁橡胶中的一种，优选乙烯-乙烯醇共聚物。
所述其他助剂为润滑剂和抗氧剂，润滑剂为硅酮粉、硬脂酸盐、乙撑双硬脂酰胺、氧化聚乙烯蜡、改性乙撑双脂肪酰胺（TAF）中的一种或两种组合物，优选氧化聚乙烯蜡与改性乙撑双脂肪酰胺（TAF）组合物。降低各组分间的界面张力、使得复合混合更加均匀、有利于实现各组分最优性能组合，实现加工过程更优化；所述抗氧剂为1098、168、624、138中的一种，优选抗氧剂1098。
按照上述方法，通过调整具体组分和份数，制备3种低高光母粒，具体配方如下表所示。
实施例配方如下：
组成 实施例1 实施例2 实施例3
共聚尼龙 100 100 100
苯乙烯-丙烯酰胺共聚物 30
丙烯腈-苯乙烯-丙烯酸共聚物 10
甲基丙烯酸甲酯-丙烯腈共聚物 25
纳米硫酸钡 10
纳米玻璃微珠 5
纳米石英砂 25
石墨 5
纳米碳化硅 3
石墨烯 1
乙烯-醋酸乙烯酯共聚物 20
乙烯-乙烯醇共聚物 10
氯丁橡胶 5
硬脂酸钠 0.3
氧化聚乙烯蜡 1 0.5
TAF 0.5
硅酮粉 0.3
抗氧剂1098 0.5 0.5
抗氧剂168 0.2
上述实施例中的共聚尼龙配方如下：
单体 实施例1 实施例2 实施例3
己内酰胺 20 30
己二酸 30 50
己二胺 10
癸二胺 20 20
癸二酸 20
丙内酰胺、 10
丁内酰胺、 25 30
二氨基庚二酸 35
本发明的高光母粒应用于尼龙微发泡材料的实施例如下表所示
Figure DEST_PATH_IMAGE002
本发明产品实施例性能表
检测项目 标准 对比例1 实施例1A 实施例2A 实施例3A
拉伸强度/MPa ISO 527 165 170 168 167
弯曲模量/MPa ISO 178 7600 8000 7750 7820
悬臂梁缺口冲击强度/kJ/m<sup>2</sup>（23℃） ISO 179 12 17 15 18
光泽度 GB 8807-1988 34 98 88 89
耐磨实验 自测 褪色 无变化 无变化 无变化
以上表格数据表明：与对比例相比，本发明实施例添加如尼龙微发泡材料后，在基本不影响材料强度同时，提高了材料韧性，同时，显著提高了尼龙微发泡材料的光泽度，达到高光泽性能要求。
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)

1.一种用于尼龙微发泡材料的高光母粒，其特征在于，包括以下重量份数的组分：
聚酰胺100份
高光泽组分10-35份
纳米高光填料5-25份
耐磨助剂1-5份
熔体补强剂5-20份
其他助剂0 .5-2份；
所述高光泽组分为苯乙烯-丙烯酰胺共聚物、丙烯腈-苯乙烯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丁二烯-丙烯酸酯共聚物、乙烯-丙烯-丙烯腈共聚物、醋酸乙烯-丙烯酸共聚物、丙烯酸-丙烯酸羟丙酯共聚物、甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸甲酯共聚物、苯乙烯-甲基丙烯酸甲酯共聚物中的一种或几种组合物；
所述熔体补强剂为乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物、马来酸酐接枝乙丙三元橡胶、氯丁橡胶中的一种。
2.根据权利要求1所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述聚酰胺为共聚聚酰胺，其聚合单体为丙内酰胺、丁内酰胺、己内酰胺、戊二酸、己二酸、己二胺、辛二酸、二氨基庚二酸、辛二胺、癸二酸、癸二胺、丙氨酸、苯丙氨酸中至少两种的组合物。
3.根据权利要求2所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述聚酰胺采用己内酰胺、己二酸、己二胺、癸二酸、癸二胺为单体合成。
4.根据权利要求1所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述高光泽组分为丙烯腈-苯乙烯-丙烯酸共聚物。
5.根据权利要求1所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述纳米高光填料为表面活性剂处理的纳米硫酸钡、纳米玻璃微珠、纳米陶瓷粉、纳米石英砂中的一种。
6.根据权利要求5所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述纳米高光填料为纳米硫酸钡。
7.根据权利要求1所述一种用于尼龙微发泡材料的高光母粒，其特征在于：
所述熔体补强剂为乙烯-乙烯醇共聚物。
8.根据权利要求1所述一种用于尼龙微发泡材料的高光母粒，其特征在于：所述耐磨助剂为聚四氟乙烯、二硫化钼、纳米碳化硅、石墨烯、石墨中的一种；
所述其他助剂为润滑剂和抗氧剂，所述润滑剂为硅酮粉、硬脂酸盐、乙撑双硬脂酰胺、氧化聚乙烯蜡、改性乙撑双脂肪酰胺中的一种或两种组合物；所述抗氧剂为1098、168、624、138中的一种。
9.根据权利要求8所述一种用于尼龙微发泡材料的高光母粒，其特征在于：
所述润滑剂为氧化聚乙烯蜡与改性乙撑双脂肪酰胺组合物
所述抗氧剂为抗氧剂1098。
10.权利要求1-9任一项所述的用于尼龙微发泡材料的高光母粒的制备方法，其特征在于，包括以下步骤：
(1)将聚酰胺100份，高光泽组分10-35份，耐磨助剂1-5份，熔体补强剂5-20份，其他助剂0 .5-2份，加入到混料机中，预混1-4min，得到混合物；
(2)将以上步骤(1)得到的混合物通过料斗加入双螺杆挤出机中，将纳米高光填料5-25份准确称量并通过侧喂料机引入挤出机中，经啮合塑化、混合、挤出、拉条、风干、造粒，得到可用于尼龙微发泡材料的高光母粒；其中，挤出机温度设置一区至机头：210-280℃。
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