CN111171585B - 一种微孔的高膨胀胶带及其制备方法 - Google Patents

一种微孔的高膨胀胶带及其制备方法 Download PDF

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CN111171585B
CN111171585B CN202010047384.8A CN202010047384A CN111171585B CN 111171585 B CN111171585 B CN 111171585B CN 202010047384 A CN202010047384 A CN 202010047384A CN 111171585 B CN111171585 B CN 111171585B
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刘成
秦成博
聂志华
张晓光
王梓人
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Abstract

本发明公开了一种微孔的高膨胀胶带及其制备方法,该胶带由以下原料组成:生胶50~100重量份、增塑剂40~60重量份、复合发泡剂10~15重量份、填充料30~50份、硫化剂0.8~1.6重量份、硫化促进剂2~8重量份和硫化活化剂6~12份。本发明的高膨胀胶带具有发泡倍数高的同时孔径小的优点;另外,可根据吸音系数要求随机调整孔径大小、密封性能优异,是一种极有应用价值的2D型汽车空腔阻断材料。

Description

一种微孔的高膨胀胶带及其制备方法
技术领域
本发明涉及汽车用胶带领域,尤其涉及用于汽车的空腔阻断,以优化其NVH性能的一种微孔的高膨胀胶带及其制备方法。
背景技术
在评价汽车性能时,有一项内容非常重要,即良好的NVH性能。作为NVH性能的重要组成部分,车身A、B、C立柱上下边梁以及翼子板下部等位置,通常借助2D型发泡胶带以及3D型空腔阻隔件的高温膨胀进行阻隔,以提高密封性以及吸音性能。
2D型发泡胶带主要用于A柱或空腔较小的部位,3D型空腔阻隔件则主要用于截面较大的部位。
由三元乙丙胶与热塑性丁苯橡胶制得的2D发泡胶带已广泛应用于汽车的车身立柱、车桥等位置,在电泳烘烤过程,发泡材料膨胀、体积增大、充满空腔,可以起到降低声噪(吸音或隔音)、阻隔灰尘的作用。
在评价汽车空腔阻断材料的吸音性能时,噪音扫频范围通常在0-5000Hz范围内,大孔径的发泡材料在高频段(≥4000Hz)吸音性能优良,而小孔径的材料在低频(<4000Hz)吸音性能优良。
但现有的发泡材料往往存在孔径小的膨胀倍数不高、膨胀倍数高的孔径较大的矛盾,这给汽车制造时选用优化NVH性能的材料带来了困难。
发明内容
基于现有技术所存在的问题,本发明的目的是提供一种微孔的高膨胀胶带及其制备方法,能解决现有汽车用胶带的发泡材料存在孔径小的膨胀倍数不高、膨胀倍数高的孔径较大的矛盾,不利于优化汽车NVH性能。
本发明的目的是通过以下技术方案实现的:
本发明实施方式提供一种微孔的高膨胀胶带,该胶带由以下原料组成:生胶50~100重量份、增塑剂40~60重量份、复合发泡剂10~15重量份、填充料30~50重量份、硫化剂0.8~1.6重量份、硫化促进剂2~8重量份和硫化活化剂6~12重量份。
本发明实施方式还提供一种微孔的高膨胀胶带的制备方法,用于制备上述的高膨胀胶带,按上述的高膨胀胶带配方取各原料,采用密炼机、开炼机和单螺杆挤出机组成的设备,包括以下步骤:
步骤1)将生胶、增塑剂和填料在密炼机中进行塑炼得到塑炼胶;
步骤2)将所述步骤1得到的塑炼胶与复合发泡剂、硫化剂和硫化促进剂、硫化活化剂在密炼机及开炼机中进行混炼得到混料;
步骤3)将所述步骤2混炼后得到的混料经过所述单螺杆挤出机恒温模口挤出成型,即得到该微孔的高膨胀胶带。
由上述本发明提供的技术方案可以看出,本发明实施例提供的微孔的高膨胀胶带及其制备方法,其有益效果为:
由于采用了复合发泡剂、特定组成的生胶,特定用量的增塑剂、填充料、硫化剂、促进剂和硫化活化剂配合,使得该胶带的发泡高度达到500%以上,体积倍率可达到900%以上,在保持较高的膨胀倍率(体积与高度)的情况下,气孔较小,同时,该膨胀后的胶带具有质量轻和密度小的特点,实现了汽车轻质化,可以满足汽车在NVH改进中在不同音频段的吸音要求。另外,该高膨胀胶带的制备方式简单,生产效率高,有很好的市场应用前景。
具体实施方式
下面结合本发明的具体内容,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。本发明实施例中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
本发明实施例提供一种微孔的高膨胀胶带,该胶带由以下原料组成:生胶50~100重量份、增塑剂40~60重量份、复合发泡剂10~15重量份、填充料30~50重量份、硫化剂0.8~1.6重量份、硫化促进剂2~8重量份和硫化活化剂6~12重量份。
上述高膨胀胶带中,复合发泡剂由偶氮二甲酰胺(AC)和4,4'-氧代双苯磺酰肼(OBSH)按重量比为2.5~10:1组成。这种由偶氮二甲酰胺与4,4'-氧代双苯磺酰肼组成的复合发泡体系中,①偶氮二甲酰胺发泡剂发气量大,但是分解温度高、容易形成大孔结构,且需要另外加入发泡助剂;②4,4'-氧代双苯磺酰肼发泡气量小,但是分解温度较低,同时可以形成小孔结构;③由偶氮二甲酰胺与4,4'-氧代双苯磺酰肼复合加入,可以降低发泡温度,无需发泡助剂,同时可以根据吸音频率段的要求,通过调整发泡混合料中二者比例实现发泡材料孔径大小的选择。
上述高膨胀胶带中,生胶采用三元乙丙胶、丁苯橡胶和热塑性弹性体中的任一种或几种。其中,热塑性弹性体优选采用热塑性丁苯橡胶(SBS)和聚烯烃类热塑性弹性体(TPO)的复合物,两者按重量比为4.0~8.0:1组合,聚烯烃类热塑性弹性体具有节能环保的特性,且由于TPO主要成分为三元乙丙胶与PE的共聚物,可以增加与三元乙丙胶的共混效果,保证胶带的均匀发泡,从而保证微孔特性。
上述高膨胀胶带中,硫化剂采用硫磺、过氧化二异丙苯和过氧化苯甲酰中的任一种或几种。
上述高膨胀胶带中,填充料采用碳酸钙、滑石粉中的任一种或两种。
上述高膨胀胶带中,硫化活化剂采用氧化锌、硬脂酸中的任一种或几种。
上述高膨胀胶带中,硫化促进剂采用二甲基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌、二硫化四甲基秋兰姆、2-硫醇基苯丙噻唑和N-环己基-2-苯丙噻唑次磺酰胺任一种或几种。
上述高膨胀胶带中,增塑剂采用环烷烃油、石蜡油和芳烃油中的任一种或几种。
本发明实施例还提供一种微孔的高膨胀胶带的制备方法,用于制备上述的高膨胀胶带,按上述的高膨胀胶带配方取各原料,采用密炼机、开炼机和单螺杆挤出机组成的设备,包括以下步骤:
步骤1)将生胶、增塑剂和填料在密炼机中在110~120℃下混炼10~15min进行塑炼,塑炼后降至室温得到塑炼胶;
步骤2)将所述步骤1得到的塑炼胶与发泡剂、硫化剂、硫化促进剂和硫化活化剂在开炼机中在小于等于60℃环境下混炼10~15min得到均匀混炼胶;
步骤3)将所述步骤2混炼后得到的混炼胶在所述单螺杆挤出机的机头温度为35~45℃条件下挤出成型,即得到该微孔的高膨胀胶带。
上述方法制得的高膨胀胶带的发泡温度为150~170℃。
本发明的微孔的高膨胀胶带,由于采用了由偶氮二甲酰胺和4,4'-氧代双苯磺酰肼组成的特定复合发泡剂,热塑性丁苯橡胶和聚烯烃类热塑性弹性体复合的热塑性弹性体作为生胶,与特定用量的增塑剂、填充料、硫化剂、硫化促进剂与硫化活化剂配合,使得该胶带的发泡高度可达到500%以上,体积倍率可达到900%以上,在保持较高的膨胀倍率(体积与高度)的情况下,气孔较小,可以满足汽车在NVH改进中在不同音频段的吸音要求。由于发泡材料具有质量轻,密度小的优点,能实现汽车的轻质化;另外,该产品的制备过程简单,生产效率高,有很好的市场应用前景。该高膨胀胶带作为可实现高、低膨胀率下均为微孔的空腔阻断材料,主要用于汽车的A、B、C立柱内以及汽车轮罩空腔的填充,充分阻断风噪通过空腔的传递,提高行驶中车内的NVH环境。
下面结合具体实施例对本发明具体作进一步地详细说明。
本发明使用的设备包括密炼机、开炼机及单螺杆挤出机,均为市场通用橡塑加工设备。
实施例1
本实施例提供一种微孔的高膨胀胶带,其制备方法包括以下步骤:
步骤1)塑炼:按重量份数计,首先将三元乙丙胶40份、热塑性丁苯橡胶40份、聚烯烃类热塑性弹性体10份和石蜡油60份加入到密炼机中,在120℃下混炼10min,目测橡塑共混成均一相,再加入30份碳酸钙,在120℃下混炼5min,出胶,多次过两辊开炼机以加速降温,静置,制得塑炼胶;
步骤2)混炼:将上述步骤1制得的塑炼胶、1.2份硫磺、0.5份2-硫醇基苯丙噻唑、2份二丁基二硫代氨基甲酸锌、2份二硫化四甲基秋兰姆、10份偶氮二甲酰胺以及3份4,4'-氧代双苯磺酰肼、5份氧化锌和4份硬脂酸依次加入密炼机,在小于等于60℃条件下混炼10min,开炼机薄通三次,排胶,静置,制得胶棒;
步骤3)挤出成型:将上述步骤2制得的胶棒加入到单螺杆挤出机,在35~45℃下挤出,得到3.5×10×298mm的高膨胀胶带;
步骤4)将步骤3制得的胶带,放入170℃烘箱,烘烤20min,即得到微孔的高膨胀胶带,经测试体积膨胀率为920%,高度膨胀率为500%,孔径大小为2.1mm,经吸音率测试,20mm的膨胀样品,500和1000Hz的频率下,吸音率分别为0.21和0.28。
实施例2
本实施例提供一种微孔的高膨胀胶带,其制备方法包括以下步骤:
步骤1)塑炼:按重量份数计,首先把三元乙丙胶40份、丁苯橡胶10份、热塑性丁苯橡胶40份、聚烯烃类热塑性弹性体10份和环烷油60份加入到密炼机中,在120℃下混炼10min,目测橡塑共混成均一相,再加入30份碳酸钙,在120℃下混炼5min,出胶,多次过两辊开炼机以加速降温,静置,制得塑炼胶;
步骤2)混炼:将上述步骤1制得的塑炼胶、1.2份硫磺、0.8份2-硫醇基苯丙噻唑、2.2份二丁基二硫代氨基甲酸锌、2份二硫化四甲基秋兰姆、10份偶氮二甲酰胺以及5份4,4'-氧代双苯磺酰肼、5份氧化锌以及4份硬脂酸依次加入密炼机,在小于等于60℃条件下混炼10min,开炼机薄通三次,排胶、静置,制得胶棒;
步骤3)挤出成型:将上述步骤2制得的胶棒加入到单螺杆挤出机,在35~45℃下挤出,得到3.5×10×298mm的高膨胀胶带;
步骤4)将步骤3制得的胶带,放入170℃烘箱,烘烤20min,即得到微孔高膨胀的空腔阻断材料,经测试体积膨胀率为930%,高度膨胀率为503%,孔径大小为1.7mm,经吸音率测试,20mm的膨胀样品,500和1000Hz的频率下,吸音率分别为0.29和0.41。
对实施例1~2中不同配方得到的高膨胀胶带性能进行对比,如表1所示(吸音系数参照的试验方法为JIS A 1405)。
表1
Figure BDA0002369915530000051
本发明通过上述实施例可以看出:实施例2较实施例1而言,在满足高的膨胀率(体积与高度)的情况下,由于发泡材料孔径较小,可以对低频音段产生更好的吸收效果。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。

Claims (6)

1.一种微孔的高膨胀胶带,其特征在于,该胶带由以下原料组成:生胶50~100重量份、增塑剂40~60重量份、复合发泡剂10~15重量份、填充料30~50重量份、硫化剂0.8~1.6重量份、硫化促进剂2~8重量份和硫化活化剂6~12重量份;
所述复合发泡剂由偶氮二甲酰胺和4,4'-氧代双苯磺酰肼按重量比2.5~10:1组成;
所述生胶由三元乙丙胶、丁苯橡胶中任一种或几种,和热塑性弹性体组成;所述热塑性弹性体由热塑性丁苯橡胶和聚烯烃类热塑性弹性体按重量比4.0~8.0:1组成。
2.根据权利要求1所述的微孔的高膨胀胶带,其特征在于,所述硫化剂采用硫磺、过氧化二异丙苯和过氧化苯甲酰中的任一种或几种。
3.根据权利要求1所述的微孔的高膨胀胶带,其特征在于,所述填充料采用碳酸钙、滑石粉中的任一种或两种;
所述硫化活化剂采用氧化锌、硬脂酸中的任一种或几种。
4.根据权利要求1所述的微孔的高膨胀胶带,其特征在于, 所述硫化促进剂采用二甲基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌、二硫化四甲基秋兰姆、2-硫醇基苯丙噻唑和N-环己基-2-苯丙噻唑次磺酰胺任一种或几种。
5.根据权利要求1所述的微孔的高膨胀胶带,其特征在于,所述增塑剂采用环烷烃油、石蜡油和芳烃油中的任一种或几种。
6.一种用于制备权利要求1至5任一项所述的微孔的高膨胀胶带的制备方法,其特征在于,采用密炼机、开炼机和单螺杆挤出机组成的设备,包括以下步骤:
按配方取各原料;
步骤1)将生胶、增塑剂和填料在密炼机中在110~120℃下混炼10~15min进行塑炼,塑炼后降至室温得到塑炼胶;
步骤2)将所述步骤1得到的塑炼胶与发泡剂、硫化剂、硫化促进剂和硫化活化剂在开炼机中在小于等于60℃环境下混炼10~15min得到均匀混炼胶;
步骤3)将所述步骤2混炼后得到的混炼胶在所述单螺杆挤出机的机头温度为35~45℃下挤出成型,即得到发泡温度为150~170℃的该微孔的高膨胀胶带。
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