CN102627849A - 一种耐黄变高温尼龙材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种耐黄变高温尼龙材料及其制备方法，该耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：高温尼龙44-94％，玻璃纤维5-50％，第一稳定剂0.1-2％，第二稳定剂0.1-2％，第三稳定剂0.1-2％。本发明制备的耐黄变高温尼龙材料，具有机械性能好、热变型温度高、初始白度佳，尤其是耐高温烘烤黄变性能优异，可弥补现在高温尼龙技术上的缺陷，广泛应用于高温电子元器件中，特别适用于LED支架，连接器，线圈骨架，高温灯座配件等。
Description
[技术领域]
本发明涉及高分子材料领域，尤其涉及一种耐黄变高温尼龙材料及其制备方法。
[背景技术]
上世纪末，因电子、电机零件、汽车配件的塑料化，对塑料的耐高温方面有进一步的要求，耐高温尼龙的出现，填补了通用工程塑料如尼龙66，聚酯和超耐高温工程塑料如LCP，PEEK之间的空白。近年来各种高温尼龙如PA46，PPA，PA6T，PA9T等不断开发走向市场并成熟化，以其优异的性价比在电子电气和汽车工业市场等得到广泛的认可和应用。
高温尼龙由于熔点高、结晶度高，在使用过程中表现出卓越的耐热黄变的优点。尽管如此，在实际应用中高温尼龙仍然有令人不太满意的黄变出现。如电子表面封装技术(SMT)制程中，塑胶原料长时间在高温锡炉中交替升温，导致高温尼龙材料黄变明显，造成一些高端产业，如LED支架产业，即使选择耐黄变最佳的PPA材料，仍然难以满足日益提高的客户应用需要。又如医用照明节能灯，内部工作温度长期处于200度高温，只能选择一些非常特殊白色的PPS材料，而普通的高温尼龙材料会在这样的工作环境中严重黄变，难以在高端节能灯市场上推广应用。传统的尼龙抗氧剂如1098/168复配体系，对高温尼龙的抗黄变作用不大，这是因为高温尼龙加工温度或工作温度太高，普通抗氧剂长期在如此环境中，要么分解，要么析出挥发，难以发挥正常的抗氧作用。因此，如何解决高温尼龙的黄变问题，对于扩展高温尼龙的应用范围，是一个迫切需要解决的问题。
[发明内容]
本发明提供了一种耐黄变高温尼龙材料及其制备方法，制备的耐黄变高温尼龙材料具有机械性能好、热变型温度高、初始白度佳，尤其是耐高温烘烤黄变性能优异。
本发明的技术方案是：
一种耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：
一种如上述所述的耐黄变高温尼龙材料的制备方法，包括步骤：
步骤一、按照上述所述的重量百分比含量分别称取各组分；
步骤二、将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌10-30min；
步骤三、将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度280-310℃，二区温度290-320℃，三区温度300-330℃，四区温度290-320℃，机头温度300-330℃，停留时间为1-2min，熔体压力10-20MPa。
本发明制备的耐黄变高温尼龙材料，具有机械性能好、热变型温度高、初始白度佳，尤其是耐高温烘烤黄变性能优异，可弥补现在高温尼龙技术上的缺陷，广泛应用于高温电子元器件中，特别适用于LED支架，连接器，线圈骨架，高温灯座配件等。
[具体实施方式]
为了使本发明的技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
其中，高温尼龙优选熔点高于280度的聚酰胺材料，如PPA，PA46，PA6T，PA9T，PA10T或类似的二元或多元共聚物等；优选耐黄变性能优异的PPA材料，分子量在20000-100000之间；
第一稳定剂优选耐高温非变色型受阻胺稳定剂，如二(2，2，6，6-四甲基-3-哌啶氨基)间苯二甲酰胺(商品牌号S-eed)，丁二酸与4羟基-2，2，6，6-四甲基-1-哌啶乙醇聚合物(商品牌号BW-10LD)，对，对’-二异丙苯基二苯胺(商品牌号N445)等，此类稳定剂兼备抗氧剂和热稳定剂的效果，耐温高，与高温尼龙相容性好，不析出；其中优选二(2，2，6，6-四甲基-3-哌啶氨基)间苯二甲酰胺(商品牌号S-eed)，该稳定剂与高温尼龙高度相容，并与与高温尼龙分子键反应结合在一起，使其对尼龙的稳定性超越传统光稳定剂的极限；
第二稳定剂优选苯基次磷酸钠，此助剂还原性强，热稳定性佳。在高温加工和烘烤过程中，苯基次膦酸钠通过持续的还原反应，将聚酰胺受氧化显色基团还原回初始状态。同时苯基次磷酸钠是高温尼龙高效的成核剂，能大大提高高温尼龙的结晶度和热变型温度，易被氧化黄变的非晶区大大减少，将有效减少聚酰胺的黄变。
第三稳定剂优选无水磷酸二氢钠，此助剂在200度加工条件下生成热稳定性极强的焦磷酸钠，能有效螯合聚酰胺中残留或加工过程带入的金属离子，尤其是最易催化塑料黄变的铁离子，避免高温尼龙催化黄变反应发生。
实施例1
该实施例中，本发明的耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：
PPA 79.4％，玻璃纤维20％，第一稳定剂0.2％，第二稳定剂0.3％，第三稳定剂0.1％。
其制备方法如下：
按上述重量百分比含量称取上述原料；将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌15min；将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度280℃，二区温度290℃，三区温度310℃，四区温度310℃，机头温度320℃，停留时间为1.5min，熔体压力12Mpa。
实施例2
该实施例中，本发明的耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：
PPA 69％，玻璃纤维30％，第一稳定剂0.3％，第二稳定剂0.5％，第三稳定剂0.2％。
其制备方法如下：
按上述重量百分比含量称取上述原料；将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌20min；将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度290℃，二区温度300℃，三区温度320℃，四区温度300℃，机头温度325℃，停留时间为1.2min，熔体压力14Mpa。
实施例3
该实施例中，本发明的耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：
PPA 58.5％，玻璃纤维40％，第一稳定剂0.4％，第二稳定剂0.8％，第三稳定剂0.3％。
其制备方法如下：
按上述重量百分比含量称取上述原料；将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌24min；将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度295℃，二区温度310℃，三区温度330℃，四区温度320℃，机头温度330℃，停留时间为1.7min，熔体压力16Mpa。
实施例4
该实施例中，本发明的耐黄变高温尼龙材料，按重量百分比含量，由以下组分组成：
PPA 48％，玻璃纤维50％，第一稳定剂0.5％，第二稳定剂1％，第三稳定剂0.5％。
其制备方法如下：
按上述重量百分比含量称取上述原料；将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌28min；将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度285℃，二区温度315℃，三区温度325℃，四区温度310℃，机头温度320℃，停留时间为2min，熔体压力18Mpa。
对比例1
该对比例中的材料配方如下：
PPA 69％，玻璃纤维30％，抗氧剂1098 0.5％，抗氧剂168 0.5％。
其制备方法是：
将上述组分中的PPA与抗氧剂1098、168在高混机中搅拌混合均匀25min；将上述混合物置于双螺杆挤出机中，玻璃纤维从侧喂料口加入，经熔融反应，挤出造粒；工艺条件为：一区温度285℃，二区温度315℃，三区温度325℃，四区温度310℃，机头温度320℃，停留时间为2min，熔体压力15MPa。
对比例2
该对比例中的材料配方如下：
PPA 48％，玻璃纤维50％，抗氧剂10981％，抗氧剂1681％。
其制备方法是：
将上述组分中的PPA与抗氧剂1098、168在高混机中搅拌混合均匀25min；将上述混合物置于双螺杆挤出机中，玻璃纤维从侧喂料口加入，经熔融反应，挤出造粒；工艺条件为：一区温度290℃，二区温度315℃，三区温度330℃，四区温度320℃，机头温度320℃，停留时间为2min，熔体压力18MPa。
性能测试及评价：
将上述实施例1-4及对比例1、2制备的粒子物料在鼓风干燥箱中120℃干燥4小时，然后再将干燥好的粒子材料在注射机上进行注射成型制样，注射成型模温控制在120℃。
其中，拉伸强度测试按ASTM D638标准进行，试样尺寸为180×12.7×3.2mm，拉伸速度为50mm/mi n；弯曲性能测试按ASTM D790标准进行，试样尺寸为128mm×13mm×3.2mm，弯曲速度为3mm/min，跨距为64mm；悬臂梁冲击强度按ASTMD256标准进行，试样尺寸为63.5mm×12.7mm×4.2mm，缺口尺寸为试样厚度的五分之一；热变型温度按ASTM D648标准进行测试负荷为1.82MPa，样条尺寸为128mm×13mm×6.4mm；初始白度按GB 2913-82标准进行测试，样条尺寸为100mm×100mm×3.2mm；黄变指数按JIS K 7103-1977标准进行测试，测试样条尺寸为50mm×50mm×3.2mm，材料分别在200度的烘箱中烘烤24h，72h和168h后测试。
实施例1-4及对比例1、2的组成配方和性能测试数据如下表1：
表1
从实施例与对比例的测试数据进行比较发现，添加相同分量复配稳定剂体系，比添加传统的抗氧剂1098/168稳定体系，机械强度，韧性，热变型温度和材料的白度都有所提高，尤其是200度高温热烘烤后，黄变指数YI变化更小。这充分说明了本发明的高温尼龙材料的耐热黄变效果十分优异，其中实施例4中的各组分配比所制备的高温尼龙材料的耐黄变效果最佳。
本发明所制备的高温尼龙复合材料，具有良好的物理机械性能及优异的耐热黄变性能，可弥补现在高温尼龙技术上的缺陷，广泛应用于高温电子元器件中，特别适用于如LED支架，连接器，线圈骨架，高温灯座配件等，以满足聚酰胺加工应用企业在电子电器，通讯照明设备，以及国防工业等领域的使用需求。且本发明的制备方法，操作简单、成本低廉，对设备要求低，非常适于工业化生产，具有广阔的应用前景。
以上对本发明实施例进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。
Claims (7)
1.一种耐黄变高温尼龙材料，其特征在于，按重量百分比含量，由以下组分组成：
2.根据权利要求1所述的耐黄变高温尼龙材料，其特征在于：所述高温尼龙为熔点高于280度的聚酰胺材料。
3.根据权利要求1所述的耐黄变高温尼龙材料，其特征在于：所述第一稳定剂为耐高温非变色型受阻胺抗氧剂。
4.根据权利要求1所述的耐黄变高温尼龙材料，其特征在于：所述第二稳定剂为苯基次膦酸钠。
5.根据权利要求1所述的耐黄变高温尼龙材料，其特征在于：所述第三稳定剂为无水磷酸二氢钠。
6.根据权利要求1所述的耐黄变高温尼龙材料，其特征在于：所述高温尼龙为熔点高于280度的聚酰胺材料；所述第一稳定剂为耐高温非变色型受阻胺抗氧剂；所述第二稳定剂为苯基次膦酸钠；所述第三稳定剂为无水磷酸二氢钠。
7.一种如权利要求1-6任一权利要求所述的耐黄变高温尼龙材料的制备方法，其特征在于，包括步骤：
步骤一、按照权利要求1所述的重量百分比含量分别称取各组分；
步骤二、将称取的高温尼龙与第一稳定剂、第二稳定剂、第三稳定剂混合搅拌10-30min；
步骤三、将混合后的混合物置于双螺杆挤出机中，玻纤纤维从侧喂料口加入，经熔融反应，挤出造粒；双螺杆挤出机的工艺条件为：一区温度280-310℃，二区温度290-320℃，三区温度300-330℃，四区温度290-320℃，机头温度300-330℃，停留时间为1-2min，熔体压力10-20MPa。
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| WO2013135193A1 (zh) * | 2012-03-16 | 2013-09-19 | 深圳市科聚新材料有限公司 | 一种耐黄变高温尼龙复合材料及其制备方法 |
| CN103556459A (zh) * | 2013-10-28 | 2014-02-05 | 四川大学 | 一种锦纶、氨纶及其混纺织物用复合抗热黄变整理剂 |
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| CN115895239A (zh) * | 2022-10-31 | 2023-04-04 | 广东泰塑新材料科技有限公司 | 一种耐温尼龙的制备工艺 |
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Denomination of invention: Yellowing high temperature-resistant nylon material and preparation method thereof Effective date of registration: 20170106 Granted publication date: 20140618 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Anhui science and Technology Co., Ltd.|Shenzhen branch poly new materials Co., Ltd.|Xu Dong Registration number: 2016990001133 |
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Date of cancellation: 20180904 Granted publication date: 20140618 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd.|Xu Dong Registration number: 2016990001133 |
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Denomination of invention: Yellowing high temperature-resistant nylon material and preparation method thereof Effective date of registration: 20181119 Granted publication date: 20140618 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Shenzhen Keju New Material Co., Ltd.|Polymer Science (Anhui) New Material Co., Ltd. Registration number: 2018440020071 |
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