CN111826104A - 用于终止胶带的阻燃胶粘剂、阻燃终止胶带及其制备方法 - Google Patents
用于终止胶带的阻燃胶粘剂、阻燃终止胶带及其制备方法 Download PDFInfo
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Abstract
本发明提供了用于终止胶带的阻燃胶粘剂、阻燃终止胶带及其制备方法,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶50~150份、DOPO5~30份、饱和石油树脂10~50份、防老剂1~10份、补强粉1~40份、偶联剂0~10份、阻燃粉0~40份、溶剂200~1000份。采用所述阻燃胶粘剂制备的所述阻燃终止胶带具有优秀的阻燃性能,耐电解液性能、耐高温性能,并且与传统的终止胶带相比,本发明中所述的阻燃终止胶带具有较长的保质期,因此能提高新能源汽车用动力电池的使用寿命及电池可靠性。
Description
技术领域
本发明属于新能源技术领域,具体涉及用于终止胶带的阻燃胶粘剂、阻燃终止胶带及其制备方法。
背景技术
目前,新能源汽车的主要发展方向是尽可能地提高续航里程,而要提高新能源汽车的续航能力其核心为提高电芯的能量密度,而高能量密度的电芯则给电池的带来了不小的挑战,因此在新能源汽车中电池的稳定不容忽视。
在电池生产过程中,其重要一环为采用终止胶带对电池中电芯、极耳以及终止部位进行固定、绝缘和保护;目前市场上的电池终止胶带都是采用丙烯酸胶黏剂作为胶层,少数国外厂家采用橡胶作为胶层,而这些都不具备阻燃性。
发明内容
为了克服上述技术缺陷,本发明提供用于终止胶带的阻燃胶粘剂,其具有优秀的阻燃性能。
为了实现上述技术目的,本发明采用下述技术方案。
用于终止胶带的阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶 50~150份、DOPO5~30份、饱和石油树脂10~50份、防老剂1~10份、补强粉 1~40份、偶联剂0~10份、阻燃粉0~40份、溶剂200~1000份。
与现有技术相比,本发明中所述阻燃胶粘剂具有以下有益效果:DOPO的化学名为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,DOPO及其衍生物由于分子结构中含有联苯环和菲环结构,特别是侧磷基团以环状O=P-O键的方式引入,比一般的、未成环的有机磷酸酯热稳定性和化学稳定性高,阻燃性能更好;因此本发明通过采用DOPO对丙烯酸橡胶进行改性,将DOPO分子结构中的侧磷基团接枝到丙烯酸橡胶分子中,这样就明显地提高了丙烯酸橡胶的阻燃特性;同时, DOPO也能将其改性成大分子结构,即保留了丙烯酸橡胶的高的粘结强度,并且也具有了更好的阻燃性能。
进一步地,所述丙烯酸橡胶为羟基型丙烯酸橡胶;羟基型丙烯酸橡胶具有优秀的耐候性、保色性、附着力及耐水性,因此采用羟基型丙烯酸橡胶来制备阻燃胶粘剂能提高其综合性能。
进一步地,所述防老剂为防老剂4010、防老剂4020中的一种或两种。
进一步地,所述补强粉为气相白炭黑,其平均粒径小于1μm。
气相白炭黑又称气相二氧化硅、烟化二氧化硅,是利用硅烷的卤化物,如四氯硅烷(SiCl4)、甲基三氯硅烷(CH3SiCl3)等,在氢氧燃烧火焰中高温水解制得的一种无定形二氧化硅;由于气相白炭黑分子表面缺陷大、非配对原子多,表面活性高,产生巨大的表面及界面效应,将其作为所述阻燃胶粘剂的补强剂,因此可以显著提高所述阻燃胶粘剂的机械强度;并且本发明中添加的气相白炭黑的平均粒径小于1μm,此时,气相白炭黑的比表面积、表面活性更大,发生物理结合和化学结合的可能性更大,从而使得界面承担了一定的载荷,能吸收更多的冲击能量;并且由于气相白炭黑分子平均粒径小于1μm,则会在所述阻燃胶粘剂中产生应力集中,从而在其中产生大量的细纹或小裂纹,这些细纹或小裂纹的发展需要消耗大量的能量,因此在所述阻燃胶粘剂的宏观力学性能上表现为具有强的增韧性能;气相白炭黑分子在所述阻燃胶粘剂中,可以形成一个二氧化硅聚集体网络,聚集体通过表面的硅醇基(Si-OH)与聚合物分子形成氢键,使体系的流动性受到限制,体系的粘度增加,从而起到增稠的作用,同时,在剪切力的作用下,氢键和二氧化硅网络受到破坏,导致体系粘度下降,即发生触变效应,因此便于操作,一旦剪切力消除,二氧化硅网络和氢键又重新形成,因此能有效防止产品储存期间的沉降和使用过程中的流挂。
进一步地,所述偶联剂为KH550、KH560中的一种或两种。
进一步地,所述阻燃粉为氢氧化镁、氢氧化铝中的一种或两种。
氢氧化镁作为阻燃剂具有良好的阻燃效果,同时还能具有消烟的作用;氢氧化镁还具有安全无毒,高温加工时热稳定性好等优点;氢氧化铝作为阻燃剂时,其燃烧速率慢,阻燃性好,并且能对早期材料的温度上升起作用。
进一步地,所述溶剂为乙酸乙酯、甲苯、二甲苯的混合液或者单一溶液。
本发明还提供了一种阻燃终止胶带,所述阻燃终止胶带的胶粘剂为上述所述的阻燃胶粘剂。本发明中所述阻燃终止胶带具有优秀的阻燃性能,耐电解液性能、耐高温性能,并且与传统的终止胶带相比,本发明中所述的阻燃终止胶带具有较长的保质期,因此能提高新能源汽车用动力电池的使用寿命及电池可靠性。
本发明还提供了一种阻燃终止胶带的制备方法,包括以下步骤:
对丙烯酸橡胶进行混炼:将丙烯酸橡胶及DOPO加入到捏合机中,然后对其进行加热,在80~150℃下混炼1~3h,冷却后,即完成丙烯酸橡胶的混炼;
将完成混炼的丙烯酸橡胶加入溶剂中,然后在向溶剂中加入饱和石油树脂,然后对其进行加热,在80~150℃下反应1~3h后,降温到50~90℃后,加入防老剂、补强粉、偶联剂、阻燃粉,然后继续在温度为50~90℃下搅拌20~40min,降温冷却后即制得所述阻燃胶粘剂;
向上述制得的阻燃胶粘剂中加入3%的固化剂,然后混合均匀后,将其涂布于阻燃聚酯基材上,然后在温度条件为50~90℃下烘烤1~10min,即制得所述阻燃终止胶带。
所述阻燃终止胶带的制备方法简单易操作,有利于大规模工业化生产。
进一步地,所用固化剂为改性三聚氰胺树脂固化剂。
采用改性三聚氰胺树脂作为固化剂,能与所述阻燃胶粘剂协同工作,起到阻燃效果,因此能进一步提高所述终止胶带的阻燃性能;并且采用改性三聚氰胺树脂作为固化剂能避免在阻燃时候,所述阻燃终止胶带失去粘性,从而进一步提高了新能源汽车用动力电池的安全性能。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
用于终止胶带的阻燃胶粘剂,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶100份、DOPO10份、饱和石油树脂20份、防老剂3份、补强粉5份、偶联剂2份、阻燃粉10份、溶剂300份。
其中,所述丙烯酸橡胶为羟基型丙烯酸橡胶,所述防老剂为:防老剂4010;所述补强粉为气相白炭黑,且平均粒径小于1μm;所述偶联剂为:KH550;所述阻燃粉为氢氧化铝;所述溶剂为乙酸乙酯。
采用上述所述的阻燃胶粘剂的阻燃终止胶带的制备方法为:
按上述所述阻燃胶粘剂进行成分配比;
对丙烯酸橡胶进行混炼:将丙烯酸橡胶及DOPO加入到捏合机中,然后对其进行加热,在110℃下混炼2h,冷却后,即完成丙烯酸橡胶的混炼;
将完成混炼的丙烯酸橡胶加入溶剂中,然后在向溶剂中加入饱和石油树脂,然后对其进行加热,在110℃下反应2h后,降温到80℃后,加入防老剂、补强粉、偶联剂、阻燃粉,然后继续在温度为80℃下搅拌30min,降温冷却后即制得所述阻燃胶粘剂;
向上述制得的阻燃胶粘剂中加入3%的固化剂,然后混合均匀后,将其涂布于厚度为25μm的阻燃聚酯基材上,然后在温度条件为80℃下烘烤2min,即制得所述阻燃终止胶带。
其中,所用到的固化剂为改性三聚氰胺树脂,其制备方法为:
将重量份数为100份的三聚氰胺树的温度加热至130℃,然后加入重量份数为20份的多聚甲醛,混合均匀后在温度为130℃下反应1h后,冷却至室温后,再加入乙酸乙酯混合均匀后,即得到改性三聚氰胺树脂。
实施例2
用于终止胶带的阻燃胶粘剂,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶100份、DOPO20份、饱和石油树脂20份、防老剂3份、补强粉5份、偶联剂2份、阻燃粉10份、溶剂400份。
其中,所述丙烯酸橡胶为羟基型丙烯酸橡胶,所述防老剂为:防老剂4020;所述补强粉为气相白炭黑,且平均粒径小于1μm;所述偶联剂为:KH560;所述阻燃粉为氢氧化铝;所述溶剂为乙酸乙酯。
采用上述所述的阻燃胶粘剂的阻燃终止胶带的制备方法与实施例1中所述阻燃终止胶带的制备方法相同。
实施例3
用于终止胶带的阻燃胶粘剂,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶100份、DOPO10份、饱和石油树脂30份、防老剂3份、补强粉5份、偶联剂2份、阻燃粉20份、溶剂400份。
其中,所述丙烯酸橡胶为羟基型丙烯酸橡胶,所述防老剂为:防老剂4020;所述补强粉为气相白炭黑,且平均粒径小于1μm;所述偶联剂为:KH560;所述阻燃粉为氢氧化镁;所述溶剂为乙酸乙酯。
采用上述所述的阻燃胶粘剂的阻燃终止胶带的制备方法与实施例1中所述阻燃终止胶带的制备方法相同。
实施例4
用于终止胶带的阻燃胶粘剂,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶100份、DOPO20份、饱和石油树脂30份、防老剂3份、补强粉5份、偶联剂2份、阻燃粉20份、溶剂400份。
其中,所述丙烯酸橡胶为羟基型丙烯酸橡胶,所述防老剂为:防老剂4020;所述补强粉为气相白炭黑,且平均粒径小于1μm;所述偶联剂为:KH560;所述阻燃粉为氢氧化镁;所述溶剂为乙酸乙酯。
采用上述所述的阻燃胶粘剂的阻燃终止胶带的制备方法与实施例1中所述阻燃终止胶带的制备方法相同。
对实施例1、实施例2、实施例3及实施例4中制得所述阻燃终止胶带进行耐电解液测试、耐温测试;并且购买市面上售卖的新能源汽车动力电池专用的终止胶带作为对比例。
其结果如表1所示。
表1实施例1~4及对比例测试数据
※此测试数据其测试环境室温为23±2℃;湿度65%±5%RH,请知悉。
剥离力测试标准:GB/T2792-2014
耐电解液测试方法:胶带贴在铝箔上1)常温24h浸泡电解液;2)85℃下4h浸泡电解液。观察胶带是否变色、脱色、脱胶、收缩及卷缩等现象;使用的电解液为东莞杉杉电解液。
耐温测试方法:胶带贴在钢板上在温度为150℃下,烘烤2h,然后冷剥看是否残胶,胶带是否变形,收缩,卷缩等现象。
从表1中可以看出实施例1~4中制得的阻燃终止胶带虽然初始剥离力比对比例中的要低,但是实施例1~4中制得的阻燃终止胶带经过耐电解液测试后其剥离力明显高于对比例中的终止胶带,并且实施例1~4中的阻燃终止胶经过耐电解液测试后,并没有出现变色、脱色、脱胶、收缩及卷缩现象,因此采用本发明中所述阻燃胶粘剂制得的阻燃终止胶带具有优秀的耐电解液性能,并且从表1可以看出,实施例1~4中的阻燃终止胶带在阻燃测试中能实现离火熄灭,而对比例中在阻燃测试中并不能实现离火熄灭,因此可以说明本发明中所述阻燃胶粘剂及阻燃终止胶带具有优秀的阻燃性能。
比现在市面所售的终止胶带的耐电解液性能,耐温性能及阻燃性能都好。
应当理解的是,以上仅为本发明的优选实施例,不能因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.用于终止胶带的阻燃胶粘剂,其特征在于,所述阻燃胶粘剂包括以下重量份数配比的原料:丙烯酸橡胶50~150份、DOPO5~30份、饱和石油树脂10~50份、防老剂1~10份、补强粉1~40份、偶联剂0~10份、阻燃粉0~40份、溶剂200~1000份。
2.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,所述丙烯酸橡胶为羟基型丙烯酸橡胶。
3.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,防老剂为防老剂4010、防老剂4020中的一种或两种。
4.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,所述补强粉为气相白炭黑,其平均粒径小于1μm。
5.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,所述偶联剂为KH550、KH560中的一种或两种。
6.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,所述阻燃粉为氢氧化镁、氢氧化铝中的一种或两种。
7.根据权利要求1所述的用于终止胶带的阻燃胶粘剂,其特征在于,所述溶剂为乙酸乙酯、甲苯、二甲苯的混合液或者单一溶液。
8.一种阻燃终止胶带,其特征在于,所述阻燃终止胶带的胶粘剂为权利要求1~7任意一所述的阻燃胶粘剂。
9.一种阻燃终止胶带的制备方法,其特征在于,包括以下步骤:
对丙烯酸橡胶进行混炼:将丙烯酸橡胶及DOPO加入到捏合机中,然后对其进行加热,在80~150℃下混炼1~3h,冷却后,即完成丙烯酸橡胶的混炼;
将完成混炼的丙烯酸橡胶加入溶剂中,然后在向溶剂中加入饱和石油树脂,然后对其进行加热,在80~150℃下反应1~3h后,降温到50~90℃后,加入防老剂、补强粉、偶联剂、阻燃粉,然后继续在温度为50~90℃下搅拌20~40min,降温冷却后即制得所述阻燃胶粘剂;
向上述制得的阻燃胶粘剂中加入3%的固化剂,然后混合均匀后,将其涂布于阻燃聚酯基材上,然后在温度条件为50~90℃下烘烤1~10min,即制得所述阻燃终止胶带。
10.根据权利要求9所述的阻燃终止胶带的制备方法,其特征在于,所用固化剂为改性三聚氰胺树脂固化剂。
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