CN114539595A - 一种基于eva改性爆米花中底鞋材的制备方法 - Google Patents
一种基于eva改性爆米花中底鞋材的制备方法 Download PDFInfo
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Abstract
本发明涉及鞋材发泡技术领域,提供一种基于EVA改性爆米花中底鞋材的制备方法,解决现有技术的鞋材制备方法有毒不环保、低熔点的非交联爆米花无法加工成型的问题,包括基于EVA改性的爆米花发泡珠粒的制备及基于EVA改性爆米花中底鞋材的成型步骤。
Description
技术领域
本发明涉及鞋材发泡技术领域,尤其涉及一种基于EVA改性爆米花中底鞋材的制备方法。
背景技术
近年来,我国的制鞋业发展迅猛已成为世界上最大的鞋类生产和出口国。目前在制鞋业,EVA发泡鞋材因其质轻、易着色、易加工成型和穿着舒适等优异的性能,在制鞋业被大量使用。但市场上EVA鞋材的制备,普遍通过添加过氧化物交联剂及偶氮二甲酰胺发泡剂在高温下硫化发泡,难免产生有毒物质的残留。随着人们生活品质的提高,在健康环保等方面的意识也逐渐增强,因而,急需开发一种较为环保的制鞋方法。
专利CN107200911A公开了一种超轻高弹环保鞋底及其制备方法,将添加了过氧化物交联剂的混合均匀的粒料通过注塑机预硫化,后采用降压法得到超临界微孔发泡鞋底。此方法虽采用了超临界物理发泡的工艺,但因在原料中添加了过氧化物交联剂,仍不能从根本上解决污染及有毒物质残留等的问题。
专利CN107501703A公开了一种环保EVA发泡珠粒及鞋中底的制作方法,以EVA颗粒、或EVA和POE共混物颗粒、或EVA和SEBS共混物颗粒、或者EVA、POE、SEBS三者的共混物颗粒为原料,采用辐照交联技术与间歇式超临界氮气发泡技术,制备得到高弹发泡珠粒,之后通过蒸汽热压成型,制得发泡中底。但是与目前市面上的爆米花中底鞋材制品相同,均是采用水蒸气热压成型,大大限制了爆米花发泡珠粒的成型温度,即对于低熔点的爆米花没有办法加工成型。
中国专利申请号201911208564.3公开了一种高回弹改性EVA材料、高回弹性EVA鞋底及其制作方法,包括按照质量百分比计的如下原料:EVA 65%-70%、橡塑弹性体18%-21%、滑石粉3%-4.8%、耐磨剂2%-3%、硬脂酸0.5%-0.7%、氧化锌1.5%-1.6%、架桥剂1.4%-2.0%、发泡剂1%-2%,该EVA材料制得的鞋底具有较高的回弹性和较佳的耐磨性。但是其发泡成型温度高达160-180℃,不适合低熔点材料的加工成型。
发明内容
因此,针对上述的问题,本发明提供一种基于EVA改性爆米花中底鞋材的制备方法,解决现有技术的鞋材制备方法有毒不环保、低熔点的非交联爆米花无法加工成型的问题。
为实现上述目的,本发明采用了以下技术方案:一种基于EVA改性爆米花中底鞋材的制备方法,包括如下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取一定质量份的EVA与热塑性弹性体,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将上述共混物颗粒与传导介质按一定比例投入高压反应釜中;
(3)调节高压反应釜的温度,并向高压反应釜内注入物理发泡剂,直至达到相应压力后,恒温恒压保持一定的渗透时间,使发泡剂均匀渗透到聚合物中;
(4)将釜内快速泄压至常压,取出颗粒,送入烘箱或烘道中进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将上述制得的基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用具有一定温度T的环保无毒液体自模具的喷眼中通入模腔内部,使爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
进一步的改进是:所述的EVA中醋酸乙烯的含量为18%-30%。
进一步的改进是:所述的热塑性弹性体为苯乙烯类弹性体、烯烃类弹性体或热塑性聚氨酯类弹性体;优选的,所述苯乙烯类弹性体为SBS、SEBS、SIS或SEPS;烯烃类弹性为POE、OBC、TPV或TPO;热塑性聚氨酯类弹性体为TPU。
进一步的改进是:所述的EVA与热塑性弹性体的质量份分别为:EVA30-95份,热塑性弹性体5-70份。
进一步的改进是:所述的双螺杆挤出机的工艺条件为:螺杆转速30-400r/min。
进一步的改进是:所述的传导介质包含空气、H2O。
进一步的改进是:所述的物理发泡剂为超临界状态的CO2、N2或两者以任意比混合的共混物。
进一步的改进是:所述的发泡方式为间歇式釜压发泡。
进一步的改进是:所述高压反应釜的温度为40-120℃,压力为7-30MPa,渗透时间为10min-10h。
进一步的改进是:所述烘箱或烘道的温度为30-140℃,二次发泡时间为5-30min。
进一步的改进是:所述基于EVA改性的爆米花发泡珠粒的密度为0.05-0.8g/cm3。
进一步的改进是:所述T为60-100℃。
进一步的改进是:所述环保无毒液体为水。
进一步的改进是:所述共混物颗粒经辐射交联后再放入高压反应釜中进行物理发泡。
通过采用前述技术方案,本发明的有益效果为:
1、本发明以EVA和热塑性弹性体共混物颗粒为原料,采用物理发泡剂,通过釜压发泡的方式,制备得到爆米花发泡珠粒,再通过热压成型,制得爆米花中底鞋材,与传统的发泡中底鞋材相比,具备发泡材料纯净,工艺清洁、绿色环保无有毒残留物的优势,且泡孔结构完整精细,性能稳定优异;可作为休闲鞋、旅游鞋、运动鞋等的中底鞋底,具有广泛的应用前景,可以被广泛推广。
2、与传统的制备方式不同,本发明以环保无毒液体(优选水)为导热介质,采用热压成型的工艺,弥补了传统水蒸汽热压成型的不足,使得低熔点的非交联爆米花发泡珠粒也能进行成型加工。传统的水蒸气热压成型只能适合熔点高于100℃的物质。而本发明采用的这种成型方式,对于熔点低于100℃的物质也能较好的成型,且获得的物质性能较为稳定。
3、本发明公开的基于EVA改性爆米花中底鞋材的制备方法,采用简单的釜压发泡,制备工艺简单,成本低廉。
附图说明
图1是EVA的核磁谱图;
图2是SEBS的核磁谱图;
图3是实施例2中基于EVA改性的爆米花发泡珠粒的扫描电镜图;
图4是实施例2中基于EVA改性的爆米花发泡珠粒的光学图片。
具体实施方式
下面以具体对比例和实施例来对本发明做进一步说明,但本发明的保护范围不限于此。
原料说明:
参考图1,EVA中醋酸乙烯含量为18%;
参考图2,SEBS是通过苯乙烯-丁二烯-苯乙烯(SBS)不饱和双键加氢制得。
对比例1
一种EVA爆米花中底鞋材,原料按质量份计算包含以下组分:
原料 | 配比 |
EVA | 100份 |
SEBS | 0份 |
一种EVA爆米花中底鞋材的制备,包括以下步骤:
S1、EVA爆米花发泡珠粒的制备
(1)将300gEVA颗粒与1L的H2O投入高压反应釜中;
(2)调节高压反应釜的温度至70℃,并向高压反应釜内注入物理发泡剂CO2,直至压力达到12MPa后,恒温恒压保持3h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为80℃的烘箱中5min进行二次发泡,制得所述的EVA爆米花发泡珠粒;
S2、EVA爆米花中底鞋材的成型
(1)将EVA爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为90℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例1
一种基于EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
原料 | 配比 |
EVA | 90份 |
SEBS | 10份 |
上述一种基于EVA改性爆米花中底鞋材的制备方法,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与SEBS,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒与1L的H2O投入高压反应釜中;
(3)调节高压反应釜的温度至60℃,并向高压反应釜内注入物理发泡剂CO2,直至压力达到12MPa后,恒温恒压保持3h的渗透时间,使发泡剂均匀渗透到聚合物中;
(4)将釜内快速泄压至常压,取出颗粒,送入温度为80℃的烘箱中5min进行二次发泡,制得所述的基于EVA改性爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为90℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例2
参考图3和图4,一种EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
原料 | 配比 |
EVA | 80份 |
SEBS | 20份 |
一种基于EVA改性爆米花中底鞋材的制备,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与SEBS,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒与1L的H2O投入高压反应釜中;
调节高压反应釜的温度至60℃,并向高压反应釜内注入物理发泡剂CO2,直至压力达到12MPa后,恒温恒压保持3h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为80℃的烘箱中5min进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为90℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例3
一种EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
一种基于EVA改性爆米花中底鞋材的制备,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与POE,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒与1L的H2O投入高压反应釜中;
调节高压反应釜的温度至60℃,并向高压反应釜内注入物理发泡剂CO2,直至压力达到12MPa后,恒温恒压保持3h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为80℃的烘道中5min进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为80℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例4
一种EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
一种基于EVA改性爆米花中底鞋材的制备,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与TPU,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒与1L的H2O投入高压反应釜中;
调节高压反应釜的温度至120℃,并向高压反应釜内注入物理发泡剂N2,直至压力达到12MPa后,恒温恒压保持10h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为30℃的烘道中30min进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为100℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例5
一种EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
原料 | 配比 |
EVA | 50份 |
SEPS | 50份 |
一种基于EVA改性爆米花中底鞋材的制备,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与SEPS,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒与1L的H2O投入高压反应釜中;
调节高压反应釜的温度至90℃,并向高压反应釜内注入物理发泡剂N2,直至压力达到16MPa后,恒温恒压保持2h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为70℃的烘道中20min进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为60℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
实施例6
一种EVA改性爆米花中底鞋材,原料按质量份计算包含以下组分:
原料 | 配比 |
EVA | 60份 |
SIS | 40份 |
一种基于EVA改性爆米花中底鞋材的制备,包括以下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取相应质量份的EVA与SIS,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将300g上述共混物颗粒经辐射交联后再与1L的H2O投入高压反应釜中;
调节高压反应釜的温度至90℃,并向高压反应釜内注入物理发泡剂N2,直至压力达到15MPa后,恒温恒压保持2h的渗透时间,使发泡剂均匀渗透到聚合物中;
(3)将釜内快速泄压至常压,取出颗粒,送入温度为70℃的烘道中20min进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用温度为60℃的水自模具的喷眼中通入模腔内部,使EVA爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
对上述实施例1-6及对比例的性能进行检测,检测结果如下表:
综合测试结果可以发现:实施例的爆米花发泡鞋中底,硬度与回弹性能明显优于对比例,说明本发明提供的基于EVA改性爆米花中底鞋材具有优异性能,可作为休闲鞋、旅游鞋、运动鞋等的中底。
尽管结合优选实施方案具体展示和介绍了本发明,但所属领域的技术人员应该明白,在不脱离所附权利要求书所限定的本发明的精神和范围内,在形式上和细节上可以对本发明做出各种变化,均为本发明的保护范围。
Claims (14)
1.一种基于EVA改性爆米花中底鞋材的制备方法,其特征在于,包括如下步骤:
S1、基于EVA改性的爆米花发泡珠粒的制备
(1)分别称取一定质量份的EVA与热塑性弹性体,均匀混合后喂入双螺杆挤出机进行塑化、混炼、挤出、牵引、冷却、造粒,制得共混物颗粒;
(2)将上述共混物颗粒与传导介质按一定比例投入高压反应釜中;
(3)调节高压反应釜的温度,并向高压反应釜内注入物理发泡剂,直至达到相应压力后,恒温恒压保持一定的渗透时间,使发泡剂均匀渗透到聚合物中;
(4)将釜内快速泄压至常压,取出颗粒,送入烘箱或烘道中进行二次发泡,制得所述的基于EVA改性的爆米花发泡珠粒;
S2、基于EVA改性爆米花中底鞋材的成型
(1)将上述制得的基于EVA改性的爆米花发泡珠粒放入模具的模腔中;
(2)采用具有一定温度T的环保无毒液体自模具的喷眼中通入模腔内部,使爆米花发泡珠粒膨胀并产生熔结,然后移模至模具完全闭合,使得已经产生熔结的膨胀珠粒表面受到挤压;
(3)冷却模具并脱模,得到爆米花中底鞋材。
2.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的EVA中醋酸乙烯的含量为18%-30%。
3.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的热塑性弹性体为苯乙烯类弹性体、烯烃类弹性体或热塑性聚氨酯类弹性体;优选的,所述苯乙烯类弹性体为SBS、SEBS、SIS或SEPS;烯烃类弹性为POE、OBC、TPV或TPO;热塑性聚氨酯类弹性体为TPU。
4.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的EVA与热塑性弹性体的质量份分别为:EVA30-95份,热塑性弹性体5-70份。
5.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的双螺杆挤出机的工艺条件为:螺杆转速30-400r/min。
6.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的传导介质包含空气、H2O。
7.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的物理发泡剂为超临界状态的CO2、N2或两者以任意比混合的共混物。
8.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述的发泡方式为间歇式釜压发泡。
9.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述高压反应釜的温度为40-120℃,压力为7-30MPa,渗透时间为10min-10h。
10.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述烘箱或烘道的温度为30-140℃,二次发泡时间为5-30min。
11.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述基于EVA改性的爆米花发泡珠粒的密度为0.05-0.8g/cm3。
12.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述T为60-100℃。
13.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述环保无毒液体为水。
14.根据权利要求1所述的基于EVA改性爆米花中底鞋材的制备方法,其特征在于:所述共混物颗粒经辐射交联后再放入高压反应釜中进行物理发泡。
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