CN116333384B - 一种耐磨耐热高弹橡胶大底 - Google Patents
一种耐磨耐热高弹橡胶大底 Download PDFInfo
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
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Abstract
本发明提出了一种耐磨耐热高弹橡胶大底,包括下述重量份组成:丁腈橡胶40~60份;EVA再生料30~40份;天然橡胶30~40份;包覆红磷10~15份;阻燃增塑剂10份;改性甲阶酚醛树脂5~10份;聚碳酸亚丙酯二醇5~10份;相容剂5~10份;硫磺2~6份;增强剂1~3份;发泡剂1~2份;本发明目的在于提供一种耐磨耐热高弹橡胶大底,通过在橡胶中添加EVA再生料、包覆红磷、改性甲阶酚醛树脂、增强剂等,不仅有助于提升橡胶的力学性能,并且使其具有更优良的耐热、阻燃、耐油、防滑、耐磨、耐酸碱、高弹等性能。
Description
技术领域
本发明涉及鞋品制造技术领域,尤其涉及一种耐磨耐热高弹橡胶大底。
背景技术
EVA(乙烯-醋酸乙烯共聚物)发泡材料具有比重轻,穿着舒适等特点,多用于运动鞋、皮鞋、凉鞋等底材中。EVA易制得超轻发泡材料,但其发泡材料拉伸、撕裂、回弹性以及耐磨性能较差,存在发泡后的热稳定性变化较大,容易变形,防滑性能较差,手感不好等缺陷。普通的EVA发泡鞋底使用的是硅酮耐磨剂,而硅酮耐磨剂虽然可以提高发泡鞋底的耐磨性,但是硅酮的润滑性导致鞋底的止滑性能下降,止滑和耐磨原理上是背道而驰,所以采用普通EVA发泡材料制成的鞋底难以兼顾止滑和耐磨;丁腈橡胶的耐油性极好,耐磨性较高,耐热性较好,粘结力强,缺点是弹性稍低。橡胶阻燃剂多为卤系阻燃剂,在塑料或者橡胶制品中,卤系中的溴系阻燃剂的使用在有机阻燃剂中占绝对优势,虽然此类阻燃剂在环保上存在着二次污染的问题,但一直以来难有其他阻燃剂体系取代。
发明内容
基于上述问题,本发明目的在于提供一种耐磨耐热高弹橡胶大底,通过在橡胶中添加EVA再生料、包覆红磷、改性甲阶酚醛树脂、增强剂等,不仅有助于提升橡胶的力学性能,并且使其具有更优良的耐热、阻燃、耐油、防滑、耐磨、耐酸碱、高弹等性能。
针对以上问题,提供了如下技术方案:一种耐磨耐热高弹橡胶大底,其特征在于:
包括下述重量份组成:
丁腈橡胶40~60份;
EVA再生料30~40份;
天然橡胶30~40份;
包覆红磷10~15份;
阻燃增塑剂10份;
改性甲阶酚醛树脂5~10份;
聚碳酸亚丙酯二醇5~10份;
相容剂5~10份;
硫磺2~6份;
白炭黑1~3份;
发泡剂1~2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯
的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
其制备方法为:
步骤一:将丁腈橡胶、EVA再生料、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将包覆红磷、阻燃增塑剂、改性甲阶酚醛树脂、聚碳酸亚丙酯二醇混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
本发明进一步设置为,所述改性甲阶酚醛树脂由下述重量份物质反应而成:
苯酚:25~35份;
氨基苯酚:10~15份;
甲醛:20~30份;
氯甲基三氧基硅烷:5~10份;
氢氧化钠或氢氧化钾:0.3~0.5份;
所述改性甲阶酚醛树脂的制备方法为:
步骤一:将苯酚、氨基苯酚、甲醛溶于水中,之后加入氢氧化钠或氢氧化钾;
步骤二:将溶液升温至70℃,反应时间为3~4小时;
步骤三:冷却至室温,加入盐酸调节pH值至7;
步骤四:加入氯甲基三氧基硅烷,升温至110℃~130℃,反应5~8小时;
步骤五:冷却至室温,通过蒸馏水进行水洗,在真空度为0.05~0.06MPa条件下,减压蒸馏脱除水分,得到改性甲阶酚醛树脂。
本发明的有益效果:
本发明以丁腈橡胶、EVA再生料、天然橡胶混合为主体,同时添加其他添加剂制备而成,具有较好的弹性和优良相容性,很好的改善了丁腈橡胶和EVA 的缺陷和不足,使得制备得到的鞋底具有良好的耐油和发孔性能,提高发泡效果,从而大大降低了大底的密度,更加轻质;天然橡胶的加入,一方面能够使加工更加容易;另一方面是能够大大提高大底的弹性,使得本发明制得的大底达到国家标准;
甲阶酚醛树脂是苯酚或取代苯酚同甲醛的反应产物,其特点是能够通过加入发泡剂能够发泡的一种树脂,并且与丁腈橡胶的相容性好,通过加入改性甲阶酚醛树脂增强,将硅烷引入到整个丁腈橡胶中,使得丁腈橡胶具有更好的力学性能和耐磨性;硫磺、白炭黑、相容剂的加入,一方面各种物质在橡胶中的分散能力,分散更加均匀,使得各种物质都能够充分发挥其作用;另一方面也有助于提高橡胶的耐油、耐酸碱腐蚀能力;
采用包覆红磷为阻燃剂,并配有环保阻燃增塑剂,使得橡胶材料具有较好的阻燃性能;添加的聚碳酸亚丙酯二醇使橡胶鞋底具有优良的耐磨性、耐水解性、高强度、高韧性、高耐磨性、耐弯折型等优点,可被广泛用于高档皮鞋、旅游鞋、运动鞋;发泡剂采用OBSH和歧化松香的混合物,能很好的进行发泡作用,从而大大降低了大底的密度,更加轻质,便于人们运动;
5,橡胶和EVA再生料相互混合,不仅具有极佳的柔韧性、优异的止滑性能及良好的耐磨性,能够解决现有EVA发泡鞋底止滑和耐磨难以兼顾的问题,满足EVA中底大面积外露使用和直接触地使用,同时极佳的柔韧性不仅赋予消费者极舒适的脚感,而且使鞋底具有优良的缓震性能,大大降低了消费者运动过程中受到的反冲击力的损害。
实施方式
下面结合实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例
改性甲阶酚醛树脂由下述重量份物质反应而成:
苯酚:35份;
氨基苯酚:15份;
甲醛:30份;
氯甲基三氧基硅烷:10份;
氢氧化钠或氢氧化钾:0.5份;
上述改性甲阶酚醛树脂的制备方法为:
步骤一:将苯酚、氨基苯酚、甲醛溶于水中,之后加入氢氧化钠或氢氧化钾;
步骤二:将溶液升温至70℃,反应时间为3~4小时;
步骤三:冷却至室温,加入盐酸调节pH值至7;
步骤四:加入氯甲基三氧基硅烷,升温至110℃~130℃,反应5~8小时;
步骤五:冷却至室温,通过蒸馏水进行水洗,在真空度为0.05~0.06MPa条件下,减压蒸馏脱除水分,得到改性甲阶酚醛树脂。
实施例
一种耐磨耐热高弹橡胶大底,包括下述重量份组成:
丁腈橡胶60份;
EVA再生料40份;
天然橡胶40份;
包覆红磷15份;
阻燃增塑剂10份;
改性甲阶酚醛树脂10份;
聚碳酸亚丙酯二醇10份;
相容剂5份;
硫磺2份;
白炭黑3份;
发泡剂2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
上述耐磨耐热高弹橡胶大底的制备方法为:
步骤一:将丁腈橡胶、EVA再生料、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将包覆红磷、阻燃增塑剂、改性甲阶酚醛树脂、聚碳酸亚丙酯二醇混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
对比例一:
一种耐磨耐热高弹橡胶大底,包括下述重量份组成:
丁腈橡胶60份;
EVA再生料40份;
天然橡胶40份;
改性甲阶酚醛树脂10份;
聚碳酸亚丙酯二醇10份;
相容剂5份;
硫磺2份;
白炭黑3份;
发泡剂2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
上述耐磨耐热高弹橡胶大底的制备方法为:
步骤一:将丁腈橡胶、EVA再生料、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将改性甲阶酚醛树脂、聚碳酸亚丙酯二醇混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
对比例二:
一种耐磨耐热高弹橡胶大底,包括下述重量份组成:
丁腈橡胶60份;
EVA再生料40份;
天然橡胶40份;
包覆红磷15份;
阻燃增塑剂10份;
聚碳酸亚丙酯二醇10份;
相容剂5份;
硫磺2份;
白炭黑3份;
发泡剂2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
上述耐磨耐热高弹橡胶大底的制备方法为:
步骤一:将丁腈橡胶、EVA再生料、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将包覆红磷、阻燃增塑剂、聚碳酸亚丙酯二醇混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
对比例三:
一种耐磨耐热高弹橡胶大底,包括下述重量份组成:
丁腈橡胶60份;
天然橡胶40份;
包覆红磷15份;
阻燃增塑剂10份;
改性甲阶酚醛树脂10份;
相容剂5份;
硫磺2份;
白炭黑3份;
发泡剂2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
上述耐磨耐热高弹橡胶大底的制备方法为:
步骤一:将丁腈橡胶、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将包覆红磷、阻燃增塑剂、改性甲阶酚醛树脂混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
将实施例二和对比例一、对比例二、对比例三得到的材料进行如下检测
拉伸强度测试:GB/T 528-92
断裂伸长率测试:GB/T 528-92
硬度:GB/T 2411-2008
磨耗体积V :GB/T 25262-2010
导热率测试:GB/T 11205-2009
通过上述检测结果可以看出,对比例一作为空白组,实施例二相对于对比例一,由于添加了包覆红磷和阻燃增塑剂,导热率明显降低,因此其制作出的橡胶大底在阻燃、隔热方面的性能明显增强;对比例二作为空白组,实施例二相对于对比例二,由于添加改性甲阶酚醛树脂,拉伸强度、断裂伸长率明显变高,磨耗体积明显变低,因此其制作出的橡胶大底明显看到力学性能和耐磨性能有了大幅度的提升;对比例三作为空白组,实施例二相对于对比例三,由于添加EVA再生料和聚碳酸亚丙酯二醇,硬度变弱,拉伸强度、断裂伸长率明显变高,因此其制作出的橡胶大底明显看到弹性和韧性得到大幅度的提升。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,上述假设的这些改进和变型也应视为本发明的保护范围。
Claims (2)
1.一种耐磨耐热高弹橡胶大底,其特征在于:
包括下述重量份组成:
丁腈橡胶40~60份;
EVA再生料30~40份;
天然橡胶30~40份;
包覆红磷10~15份;
阻燃增塑剂10份;
改性甲阶酚醛树脂5~10份;
聚碳酸亚丙酯二醇5~10份;
相容剂5~10份;
硫磺2~6份;
白炭黑1~3份;
发泡剂1~2份;
所述相容剂是马来酸酐、甲基乙烯基二氯硅烷和异丙基三(十二烷基苯磺酰基)钛酸酯
的混合物,其质量比为2:1:1;
所述发泡剂为发泡剂OBSH和歧化松香的混合物,其质量比为4:1;
其制备方法为:
步骤一:将丁腈橡胶、EVA再生料、天然橡胶在密炼机100℃下,加压翻炼30S;
步骤二:将包覆红磷、阻燃增塑剂、改性甲阶酚醛树脂、聚碳酸亚丙酯二醇混合投入密炼室中翻炼30S;
步骤三:将相容剂、硫磺、增强剂、发泡剂加入密炼室中加压翻炼90S;
步骤四:提栓扫灰,加压翻炼至120℃,升栓排胶;
步骤五:将胶料置入开炼机中,加入促进剂硫化剂均匀混炼、出片冷却;
步骤六:在平板硫化机上,将加硫好的胶料放在大底专用的模具上硫化成型。
2.根据权利要求1所述的一种耐磨耐热高弹橡胶大底,其特征在于:所述改性甲阶酚醛树脂由下述重量份物质反应而成:
苯酚:25~35份;
氨基苯酚:10~15份;
甲醛:20~30份;
氯甲基三氧基硅烷:5~10份;
氢氧化钠或氢氧化钾:0.3~0.5份;
所述改性甲阶酚醛树脂的制备方法为:
步骤一:将苯酚、氨基苯酚、甲醛溶于水中,之后加入氢氧化钠或氢氧化钾;
步骤二:将溶液升温至70℃,反应时间为3~4小时;
步骤三:冷却至室温,加入盐酸调节pH值至7;
步骤四:加入氯甲基三氧基硅烷,升温至110℃~130℃,反应5~8小时;
步骤五:冷却至室温,通过蒸馏水进行水洗,在真空度为0.05~0.06MPa条件下,减压蒸馏脱除水分,得到改性甲阶酚醛树脂。
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CN112175257A (zh) * | 2020-07-27 | 2021-01-05 | 浙江中瑞橡胶高分子材料股份有限公司 | 一种发泡耐磨型橡胶 |
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