CN108864557A - 一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料及其制备方法 - Google Patents
一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种运动运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料及其制备方法,所述聚合物材料组分由以下质量份制备而成:乙烯‑丙烯酸共聚物5‑20份、聚醚嵌段酰胺5‑25份、乙烯‑乙酸乙烯酯共聚物55‑85份、偶氮二甲酰胺2‑5份、有机过氧化物0.6‑1.5份、氧化锌0.5‑5份、硬脂酸锌0.5‑2份、硬脂酸0.5‑1份、滑石粉3‑15份。本发明的聚合物材料采用注射一次交联发泡成型,发泡聚合物材料的硬度为47‑55 Shore C,拉伸强度不小于3.0 M Pa,断裂延伸率不小于300%,裤形撕裂强度不小于4.0 N/mm,回弹率不小于45%,压缩永久变形不大于40%。
Description
技术领域:
本发明涉及高分子材料技术领域,具体涉及一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料及其制备方法。
技术背景:
轻量化的运动鞋可以给人们带来轻便、快速、少付出能量和轻便运动的体验。而一双鞋子的核心技术在于鞋底,运动鞋底的发展趋向于超轻化。
运动鞋底材轻量化归功于采用了交联发泡的聚合物材料。乙烯-乙酸乙烯酯共聚物(EVA) 及其共混改性聚合物材料,易于交联、发泡、轻便、弹性好等诸多优点,但其发泡倍率受到一定的限制,致使以EVA为基体的交联发泡材料,当它的硬度在47-55Shore C时,其密度不小于0.2g/cm3,密度大,鞋底较重。
发明内容:
本发明目的在于提供一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料及其制备方法,在降低发泡鞋底材料密度的同时,保持运动鞋底材料的性能要求。
为了实现上述目的,本发明采用以下技术方案:
一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其由以下质量份的组分制备而成:
进一步,所述乙烯-丙烯酸共聚物为乙烯与丙烯酸的无规共聚物,是热塑性弹性体,例如 Dupont公司的514D。所述聚醚嵌段酰胺为热塑性弹性体,例如法国Arkema公司的2533。
进一步,所述乙烯-乙酸乙烯酯共聚物(EVA)为乙烯与乙酸乙烯酯的无规共聚物,是热塑性弹性体,其乙酸乙烯酯(VA)质量分数为18%-26%,例如中国台湾塑胶工业股份有限公司牌号为7350M的EVA,其VA含量18%,或者牌号7470M的EVA,其VA含量26%。
所述有机过氧化物为过氧化二异丙苯(DCP)、双叔丁基二异丙基苯(BIBP)、二叔丁基氧化物(DTPB)、叔丁基过氧化异丙苯(TBCP)、叔丁基过氧化氢(DBHP)中的一种,或者,它们的任意比例混合物。
上述运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料的制备方法,包括以下步骤:
1)将乙烯-丙烯酸共聚物、聚醚嵌段酰胺、乙烯-乙酸乙烯酯共聚物、氧化锌、硬脂酸锌、硬脂酸和滑石粉投入密炼机混炼,温度升高至100-105℃之后,每隔2-3℃翻料一次,在10min 内升高温度至105-115℃,然后加入有机过氧化物和偶氮二甲酰胺,继续混炼2-5min,温度每升高2℃翻料一次,当温度升高至115-125℃,出料;
2)上述出料后的物料转移至80-95℃的辊轮开炼机,辊距10-15mm,物料以三角包的形式混炼1-2次,物料再经过1mm辊距混炼1次后转入造粒机,控制模头温度为80-115℃,造粒,得到长径为2-4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为80±5℃,85±5℃,90±5℃, 95±5℃,射枪的注射压力为5-12M Pa,将粒料注射入模压为8-12M Pa,温度为160-195℃的模腔厚度为2-15mm的模具内,加热200-450s,得到离子/共价交联闭孔式发泡聚合物材料。
本发明综合无机、有机的化学反应进行以EVA为基体的聚合物材料的交联和闭孔式发泡,可以更大程度地提升聚合物及其共混物交联闭孔式发泡材料的交联优势,并可以增大发泡倍率,降低其密度。其中乙烯-丙烯酸共聚物(牌号:514D)分子里含有羧基,而聚醚嵌段酰胺(牌号:2533)分子含有酰胺键、氨基或羧基。这些基团,可以与金属氧化物,如氧化锌(ZnO)发生反应,以离子键形式产生羧酸锌,或与ZnO形成配位键。而氨基、羧基、酰胺键之间也可发生反应,或还可以形成氢键。如此这般,共混物体系里有离子键的生成而产生交联,又有过氧化物产生自由基引发产生共价键的交联,使材料产生新性能,然后再发泡成新交联发泡材料,可以获得更大的发泡倍率,从而具有较低的密度,成为超轻材料。
本发明的聚合物材料采用注射一次交联闭孔式发泡成型,得到密度不大于0.10g/cm3的超轻含离子键和共价键的超轻交联闭孔式发泡聚合物材料,具有以下有益效果:保证发泡鞋底材料的硬度为47-55Shore C,拉伸强度不小于3.0M Pa,断裂延伸率不小于220%,裤形撕裂强度不小于4.0N/mm,弹性不小于45%,压缩永久变形不大于40%。
具体实施方式:
下面结合具体实例对本发明进行进一步的说明。
以下实施例所用材料及其来源如下:
聚醚嵌段酰胺(2533),法国Arkema公司。
乙烯-乙酸乙烯酯共聚物(EVA),牌号7350M的EVA,其VA含量18%,或者牌号7470M的EVA,其VA含量26%,中国台湾塑胶工业股份有限公司。
乙烯-丙烯酸共聚物(514D),Dupont公司。
偶氮二甲酰胺(AC),杭州海虹精细化工有限公司。
适用的有机过氧化物:过氧化二异丙苯(DCP),二叔丁基氧化物(DTPB),叔丁基过氧化异丙苯(TBCP),或者,叔丁基过氧化氢(DBHP),它们的纯度均大于97%,上海高桥石化有限公司;双叔丁基二异丙基苯(BIBP),纯度大于99%,法国Arkema公司。
硬脂酸(St),硬脂酸锌(ZnSt),工业纯,杭州油脂化工有限公司。
氧化锌(ZnO),工业纯,上海京华化工有限公司。
滑石粉(TA),工业纯,泉州市旭丰粉体原料有限公司。
实施例1-10
表1实施例1-10原材料配方
按照表1的配方称取各原料,制备成运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,具体步骤如下:
1)将 514D、 2533、EVA、ZnO、ZnSt、St和TA投入密炼机混炼,温度升高至105℃之后,每隔3℃翻料一次,在10min内升高温度至108-112℃,然后加入有机过氧化物(BIBP或DCP)和AC,继续混炼2min,温度每升高2℃翻料一次,当温度升高至120℃,出料;
2)上述出料后的物料转移至90℃的辊轮开炼机,辊距10-15mm,物料以三角包的形式混炼2次,物料再经过1mm辊距混炼1次后转入造粒机,控制模头温度为105℃,造粒成长径均为2-4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为80±5℃,85±5℃,90±5℃, 95±5℃,射枪的注射压力为5-12M Pa,将粒料注射入模压为8-12M Pa,温度为160-195℃的模腔厚度为2-15mm的模具内,加热200-450s,得到离子/共价交联闭孔式发泡聚合物材料。
实施例1-10制得材料的性能测试结果如表2所示,其性能测定标准和方法均按照国家标准检测和该技术领域标准检测要求来检测的。
表2实施例1-10注射交联闭孔式发泡材料的性能
从表2可以看出,对鞋底材料的性能检测效果为:密度:0.095~0.10g/cm3,硬度48-53 Shore C,拉伸强度不小于3.0M Pa,断裂延伸率不小于300%,裤形撕裂强度不小于4.0N/mm,回弹率不小于45%,压缩永久变形不大于40%。材料的性能达到发泡鞋底材料的要求。本发明 514D和 2533的加入,可以提高发泡率,同时ZnO、 514D和 2533三者之间可以形成一定的离子键,在交联剂引发产生共价键交联以后,构成了一定的空间网络结构,从而增强了发泡后的材料的力学性能。
实施例11
运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其原料包括以下质量份的组分:
制备方法如下:
1)将 514D、 2533、EVA、ZnO、ZnSt、St和TA投入密炼机混炼,温度升高至100℃之后,每隔2℃翻料一次,在10min内升高温度至115℃,然后加入有机过氧化物(BIBP)和AC,继续混炼5min,温度每升高2℃翻料一次,当温度升高至125℃,出料;
2)上述出料后的物料转移至80℃的辊轮开炼机,辊距10mm,物料以三角包的形式混炼二次,物料再经过1mm辊距后转入造粒机,控制模头温度为80℃,造粒成长径均为3-4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为75℃,80℃,85℃,90℃,射枪的注射压力为12M Pa,将粒料注射入压力为12M Pa,温度为195℃的模腔厚度为2mm 的模具内,加热200s,得到离子/共价交联闭孔式发泡聚合物材料。
实施例12
运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其原料包括以下质量份的组分:
制备方法如下:
1)将 514D、 2533、EVA、ZnO、ZnSt、St和TA投入密炼机混炼,温度升高至105℃之后,每隔3℃翻料一次,在10min内升高温度至118℃,然后加入有机过氧化物(DCP)和AC,继续混炼3min,温度每升高2℃翻料一次,当温度升高至124℃,出料;
2)上述出料后的物料转移至80-95℃的辊轮开炼机,辊距15mm,物料以三角包的形式混炼2次,物料再经过1mm辊距混炼1次后转入造粒机,控制模头温度为115℃,造粒成长径均为3-4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为85℃,90℃,90℃,95℃,射枪的注射压力为12M Pa,将粒料注射入压力为12M Pa,温度为175℃的模腔厚度为15mm的模具内,加热450s,得到离子/共价交联闭孔式发泡聚合物材料。
实施例13
运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其原料包括以下质量份的组分:
制备方法如下:
1)将 514D、 2533、EVA、ZnO、ZnSt、St和TA投入密炼机混炼,温度升高至103℃之后,每隔2℃翻料一次,在10min内升高温度至108℃,然后加入有机过氧化物(BIBP)和AC,继续混炼5min,温度每升高2℃翻料一次,当温度升高至120℃出粒;
2)上述出料后的物料转移至85℃的辊轮开炼机,辊距15mm,物料以三角包的形式混炼二次,物料再经过1mm辊距后转入造粒机,控制模头温度为95℃,造粒成长径均为4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为80℃,85℃,90℃,95℃,射枪的注射压力为1.2M Pa,将粒料注射入压力为12M Pa,温度为190℃的模腔厚度为8mm的模具内,加热450s,得到离子/共价交联闭孔式发泡聚合物材料。
实施例14
运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其原料包括以下质量份的组分:
制备方法如下:
1)将 514D、 2533、EVA、ZnO、ZnSt、St和TA投入密炼机混炼,温度升高至103℃之后,每隔2℃翻料一次,在10min内升高温度至108℃,然后加入有机过氧化物(BIBP、DCP、TBCP、DBHP)和AC,继续混炼5min,温度每升高2℃翻料一次,当温度升高至120℃出粒;
2)上述出料后的物料转移至85℃的辊轮开炼机,辊距10mm,物料以三角包的形式混炼二次,物料再经过1mm辊距后转入造粒机,控制模头温度为95℃,造粒成长径均为4mm的粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为80℃,85℃,90℃,95℃,射枪的注射压力为5M Pa,将粒料注射入压力为8M Pa,温度为160℃的模腔厚度为6mm的模具内,加热420s,得到离子/共价交联闭孔式发泡聚合物材料。
本发明具体应用途径很多,以上所述仅是本发明的优选实施方式。以上实施例仅用于说明本发明,而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。
Claims (7)
1.一种运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其特征在于:其由以下质量份的组分制备而成:
乙烯-丙烯酸共聚物 5-20份;
聚醚嵌段酰胺 5-25份;
乙烯-乙酸乙烯酯共聚物 55-85份;
偶氮二甲酰胺 2-5份;
有机过氧化物 0.6-1.5份;
氧化锌 0.5-5份;
硬脂酸锌 0.5-2份;
硬脂酸 0.5-1份;
滑石粉 3-15份。
2.根据权利要求1所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其特征在于:所述有机过氧化物为过氧化二异丙苯、双叔丁基二异丙基苯、二叔丁基氧化物、叔丁基过氧化异丙苯、或叔丁基过氧化氢中的一种,或者,它们的任意比例混合物。
3.根据权利要求1所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其特征在于:所述乙烯-丙烯酸共聚物为Dupont 公司的Fusabond®514D。
4.根据权利要求1所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其特征在于:所述聚醚嵌段酰胺为法国Arkema公司的Pebax®2533。
5.根据权利要求1所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料,其特征在于:所述乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯的质量分数为18%-26%。
6.如权利要求1所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料的制备方法,其特征在于:其包括以下步骤:
1)将乙烯-丙烯酸共聚物、聚醚嵌段酰胺、乙烯-乙酸乙烯酯共聚物、氧化锌、硬脂酸锌、硬脂酸和滑石粉投入密炼机混炼,温度升高至100-105℃之后,每隔2-3℃翻料一次,在10min内升高温度至105-115℃,然后加入有机过氧化物和偶氮二甲酰胺,继续混炼2-5 min,温度每升高2℃翻料一次,当温度升高至115-125℃,出料;
2)上述出料后的物料转移至 80-95℃的辊轮开炼机 ,辊距 10-15 mm,物料以三角包的形式混炼1-2次,物料再经过 1 mm辊距混炼1次后转入造粒机 ,控制模头温度为80-115℃, 造粒,得到粒料;
3)将上述粒料投入到注射机内,射枪四段温度分别设置为80±5℃,85±5℃,90±5℃,95±5℃,射枪的注射压力为5-12 MPa,将粒料注射入模压为8-12 MPa,温度为160-195℃的模腔厚度为2-15 mm的模具内,加热200-450 s,得到离子/共价交联闭孔式发泡聚合物材料。
7.根据权利要求6所述的运动鞋底用超轻注射离子/共价交联闭孔式发泡聚合物材料的制备方法,其特征在于:步骤2)中,造粒得到的粒料长径为 2-4 mm。
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