CN105504472B - 一种汽车用空腔膨胀胶及其制备方法 - Google Patents

一种汽车用空腔膨胀胶及其制备方法 Download PDF

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CN105504472B
CN105504472B CN201511007613.9A CN201511007613A CN105504472B CN 105504472 B CN105504472 B CN 105504472B CN 201511007613 A CN201511007613 A CN 201511007613A CN 105504472 B CN105504472 B CN 105504472B
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王威
张立伟
谢宇
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Haicheng New Materials Wuhu Co ltd
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Abstract

本发明公开了一种汽车用空腔膨胀剂及其制备方法，所述汽车用空腔膨胀剂包含以下原料及重量份：乙烯‑辛烯共聚物50‑100份；乙烯‑丙烯酸共聚物0‑50份；发泡剂2‑20份；交联剂0.1‑2份；发泡助剂0.3‑6份；交联助剂0‑1份；抗老化助剂0.1‑1份。将配方量的原料经混合、造粒、注塑成型即可得到汽车用空腔膨胀剂，其制备方法简单，并通过对材料组分的选择和用量配比的调节降低了材料的散发性，特别是降低了VOC类散发性物质的含量，使有机挥发物含量TVOC＜50μg C/g，使产品更加的环保，对于人们的身体危害更低。

Description

一种汽车用空腔膨胀胶及其制备方法
技术领域
本发明属于汽车用降噪材料领域，具体涉及一种汽车用空腔膨胀胶及其制备方法。
背景技术
近年来，随着国民生活水平的不断提高，汽车保有量也在不断增长，汽车已经成为人们日常生活中的必备品，人们在关注汽车安全性和美观性的同时，消费者越来越多的关注汽车的舒适性和汽车内部环境。
有机物的挥发量成为衡量汽车内部环境的指标，低VOC(挥发性有机物)代表着更少的挥发物和析出物，因此，低气味，低散发性的空间环境更有利于乘车人的身体健康；对于汽车生产的主机厂而言，低VOC材料的使用不仅可以吸引更多的消费者，还可以改善员工的工作环境。
现有技术中，汽车用空腔膨胀胶的制备方法通常为在乙烯-醋酸乙烯酯共聚物(EVA)内添加发泡剂、交联剂及其他功能助剂，如增粘剂、发泡促进剂和交联促进剂等，将其造粒后注塑在尼龙卡扣上，尼龙卡扣用于固定材料位置。在汽车车身制造过程中，高温烘烤使材料发泡膨胀封堵空腔，达到密封减振降噪的作用。
但是，EVA由于含有醋酸乙烯基团而使材料散发出特有的酸味，特别是为了提高材料的弹性和粘结性，现有技术中往往选择醋酸乙烯基团含量高的EVA和增粘树脂，如松香树脂，萜烯树脂，碳氢树脂，古马隆树脂等。但是醋酸乙烯含量越高，材料散发出的酸味越重，此外，EVA在交联过程中会发生降解断链，生成醛酮类物质，进一步提高了材料的VOC；增粘树脂在高温下易挥发，从而进一步增加了材料中有机物的散发性。
发明内容
针对以上不足，本发明提供了一种汽车用空腔膨胀胶及其制备方法，通过对材料组分的选择和用量配比的调节降低了材料的散发性，特别是降低了VOC类散发性物质的含量，使产品更加的环保，对于人们的身体危害更低。
本发明提供的技术方案为：一种汽车用空腔膨胀剂，包含以下原料及重量份：
优选为：
所述乙烯-辛烯共聚物至少一种熔融指数范围在0.5-30g/10min(190℃，2.16kg)内。
所述乙烯-丙烯酸共聚物至少一种熔融指数范围在50-200g/10min(190℃，2.16kg)内。
所述发泡剂包括偶氮类化合物、亚硝酸基盐衍生物、苯磺酰肼类中的一种或几种。
所述交联剂包括过氧化二异丙苯、过氧化二苯甲酰、双叔丁基过氧化二异丙基苯中的一种或几种
所述发泡助剂包括氧化锌、硬脂酸、硬脂酸锌的共混物，氧化锌与硬脂酸和硬脂酸锌配合使用可以降低汽车用空腔膨胀剂在发泡过程中的分解温度。
所述交联助剂包括三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三烯丙基异三聚氰酸酯、三烯丙基氰脲酸酯中的一种或几种。
本发明还提供了上述汽车用空腔膨胀剂的制备方法，将上述配方量的原料混合、造粒、注塑成型即可得到汽车用空腔膨胀剂。
所述制备方法具体包括：将上述配方量的原料经高速搅拌机混合并由双螺杆挤出机造粒后，最终由注塑机注塑成型。
所述造粒的温度为45-105℃。
本发明使用乙烯-辛烯共聚物替代乙烯-醋酸乙烯酯共聚物作为材料的主体树脂，来改善材料的主体树脂造成的气味问题以及交联所产生的醛酮类物质，降低材料的VOC。使用乙烯-丙烯酸共聚物树脂替代增粘树脂，在保持粘结力的同时，降低材料的散发性。
本发明通过对材料组分的选择和用量配比的调节降低了材料的散发性，特别是降低了VOC类散发性物质的含量，使有机挥发物含量TVOC＜50μg C/g，使产品更加的环保，对于人们的身体危害更低。
具体实施方式
本发明所使用的各种原料均可从市场上的销售厂家直接购买得到。
一种汽车用空腔膨胀剂，所用原料及重量份如表1所示：
表1：汽车用空腔膨胀剂，所用原料及重量份
实施例1
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例1所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在95℃造粒后，最终由注塑机注塑成型。
实施例2
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例2所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在105℃造粒后，最终由注塑机注塑成型。
实施例3
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例3所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在85℃造粒后，最终由注塑机注塑成型。
实施例4
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例4所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在75℃造粒后，最终由注塑机注塑成型。
实施例5
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例5所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在60℃造粒后，最终由注塑机注塑成型。
实施例6
一种汽车用空腔膨胀剂，所用原料及重量份如表1实施例6所示。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在45℃造粒后，最终由注塑机注塑成型。
比较例1
一种汽车用空腔膨胀剂，所用原料及重量份如下：60份EVA SV1055；30份EVAV5110J；10份增粘树脂；15份4，4-氧代双苯磺酰肼；1.0份过氧化二苯甲酰；1.5份氧化锌，0.5份硬脂酸锌，0.5份硬脂酸；0.2份三烯丙基异三聚氰酸酯；0.3份抗老化助剂。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在95℃造粒后，最终由注塑机注塑成型。
比较例2
一种汽车用空腔膨胀剂，所用原料及重量份如下：80份EVA SV1055；20份EVAV5110J；5份增粘树脂；10份偶氮二甲酰胺；5份4，4-氧代双苯磺酰肼；1.0份双叔丁基过氧化二异丙基苯；1.5份氧化锌，0.5份硬脂酸锌，0.5份硬脂酸；0.5份三烯丙基氰脲酸酯；0.4份抗老化助剂。
上述汽车用空腔膨胀剂的制备方法为：将配方量的原料经高速搅拌机混合，并由双螺杆挤出机在60℃造粒后，最终由注塑机注塑成型。
实验测试过程：
将实施例1-6、比较例1-2注塑好的片材在180℃下发泡30分钟，待样品完全冷却后，将样品裁剪为大于10mg并小于25mg的块状样品，任意选取裁剪后的样品至重量为1.000g±0.001g放入10ml的顶空瓶中，保持(120±1)℃恒温5h±5min。采用顶空进样法，以氦气为载气，丙酮溶液作标定曲线，利用带有分流-不分流-进样口和火焰电离化检测器(FID)的气相色谱仪对材料的有机挥发物进行分析，得到有机挥发物的色谱图。最后对色谱图进行分析，通过计算公式计算出各有机物的挥发值。
碳的总散发值(TVOC)的计算公式如下：
EG＝[(总峰值面积-峰值面积空白值)/k(G)]×2×0.6204；
式中，“EG”表示碳的总散发值(TVOC)，单位为μg C/g；“k(G)”表示丙酮标定曲线的斜率；“0.6204”表示丙酮中碳的含量。
单个有机物的散发值计算公式如下：Ei＝[材料的峰值面积/k(i)]×2；式中，“Ei”表示单个材料的碳散发值，单位为μg C/g；“k(i)”表示单个物质丙酮标定曲线的斜率。
上述各实施例和比较例的测试结果如表2所示：
表2：汽车用空腔膨胀剂中挥发性有机物分析
注：表中各数值的单位均为μg C/g；“N.D.”表示未检出
从表2中的数据可以看出，本发明所公开的汽车用空腔膨胀剂，其挥发性有机物含量较低，有机物挥发的总碳量小于50μg C/g。
上述各实施例和比较例的其它性能测试结果如表3所示：
表3
试验项目 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 比较例1 比较例2 限值
吸水率/％ 2 4 3 4 6 5 7 9 <10％
气味 3.5 4 4 4 4 3.5 4.5 5 ≤4
发泡倍率/％ 750 1025 802 960 1015 950 762 1100 >700％
上述参照实施例对汽车用空腔膨胀胶及其制备方法进行的详细描述，是说明性的而不是限定性的，可按照所限定范围列举出若干个实施例，因此在不脱离本发明总体构思下的变化和修改，应属本发明的保护范围之内。

Claims (8)

1.一种汽车用空腔膨胀剂，其特征在于，所述汽车用空腔膨胀剂包含以下原料及重量份：
乙烯-辛烯共聚物 50-100份；
乙烯-丙烯酸共聚物 0-50份；
发泡剂 2-20份；
交联剂 0.1-2份；
发泡助剂 0.3-6份；
交联助剂 0-1份；
抗老化助剂 0.1-1份；
所述汽车用空腔膨胀剂的制备方法为：将配方量的原料混合、45-105℃造粒、注塑成型即可得到汽车用空腔膨胀剂。
2.根据权利要求1所述的汽车用空腔膨胀剂，其特征在于，所述汽车用空腔膨胀剂包含以下原料及重量份：
乙烯-辛烯共聚物 50-90份；
乙烯-丙烯酸共聚物 10-40份；
发泡剂 5-15份；
交联剂 0.5-1.5份；
发泡助剂 1.4-6份；
交联助剂 0.4-0.8份；
抗老化助剂 0.3-0.6份。
3.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述乙烯-辛烯共聚物熔融指数范围在0.5-30g/10min内，测试条件为190℃，2.16kg。
4.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述乙烯-丙烯酸共聚物熔融指数范围在50-200g/10min内，测试条件为190℃，2.16kg。
5.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述发泡剂包括偶氮类化合物、亚硝酸基盐衍生物、苯磺酰肼类中的一种或几种。
6.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述交联剂包括过氧化二异丙苯、过氧化二苯甲酰、 双叔丁基过氧化二异丙基苯中的一种或几种。
7.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述发泡助剂包括氧化锌、硬脂酸、硬脂酸锌的共混物。
8.根据权利要求1或2所述的汽车用空腔膨胀剂，其特征在于，所述交联助剂包括三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三烯丙基异三聚氰酸酯、三烯丙基氰脲酸酯中的一种或几种。
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