CN114479235A - 一种无毒无害环保运动垫的制造方法 - Google Patents
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Abstract
本发明公开了一种无毒无害环保运动垫的制造方法。将热塑性聚合物颗粒在脆化温度下进行高速气流粉碎至微米级尺寸,然后在钴60射线装置或者电子束射线设备下进行射线交联,使用物理发泡剂将聚合物颗粒在高压釜内渗透并发泡,通过二次发泡增大发泡倍率。蒸汽加热至已发泡聚合物粒子到玻璃化温度以上,成型大块状聚合物泡沫材料,最后切片并覆膜成型为爬行垫或者瑜伽垫。该产品无化学发泡剂、交联剂分解的有毒有异味的残留物,并且发泡产品没有珠粒的融合缝,拉伸强度大,抗冲击性能好。
Description
技术领域
本发明属于聚合物成型领域,具体涉及一种无毒无害环保运动垫的制造方法。
背景技术
运动垫,包括爬行垫和瑜伽垫,爬行垫主要应用于婴幼儿的玩耍铺垫使用,瑜伽垫用于练习瑜伽等健身时铺在地面上,两者都属于发泡聚合物材料,都要求气泡饱满,手感柔软,且防滑、回弹能力强等性能。材质一般分为橡胶、XPE、 TPE发泡、PVC发泡、EVA、乳胶垫、NBR垫子等。目前市场上销售的爬行垫、瑜伽垫质量参差不齐,大多数存在异味。以市场接受广泛的XPE材质为例,异味原因是使用偶氮二甲酰胺发泡剂和过氧化二异丙苯(DCP)交联剂引起的。偶氮二甲酰胺分解产生氨气、甲酰胺等分解物。欧洲化学品管理局将甲酰胺归类于具有生殖毒性物质。DCP交联剂分解后也会产生苯乙酮等有异味的分解物。
公布号为CN110157083A的一种爬行垫发泡材料及应用其制得的爬行垫及制备工艺就是使用偶氮二甲酰胺发泡剂和过氧化二异丙苯作为原料。授权公告号CN105498148B的一种瑜伽垫及其制造方法使用PVC材质,偶氮二甲酰胺作为发泡剂。另外,偶氮二甲酰胺发泡剂和过氧化二异丙苯均属于危险化学品,生产、运输、使用过程中容易发生火灾和爆炸。
另外,爬行垫和瑜伽垫用于运动时对人体的缓冲,对回弹性、拉伸强度等等力学性能要求高。偶氮二甲酰胺本身具有一定范围的粒径分布,发泡的泡沫材料泡孔不均匀,容易产生大泡孔,导致力学性能、产品均一性能差。
综上所述,现有的爬行垫/瑜伽垫制造方法的不足之处:
1、化学发泡剂和过氧化学交联剂使用危险,并且含有甲酰胺、苯乙酮、氨气等有毒有异味的分解物;
2、现有爬行垫/瑜伽垫的泡孔不均匀,回弹性、拉伸强度等力学性能较差。
发明内容
本发明目的之一在于解决现有技术的不足,提供一种无毒无害环保运动垫的制造方法。
本发明解决上述问题所采用的技术方案是:
一种无毒无害环保运动垫的制造方法,包括以下步骤:
步骤一、微米级聚合物颗粒制备,将热塑性聚合物颗粒在脆化温度下进行气流粉碎,粉碎后中位粒径达到1~500微米;脆化温度的控制采用液氮冷却的方式来控制;
步骤二、射线交联,将粉碎后的聚合物颗粒在钴60射线装置或者电子束射线设备下进行物理射线交联,射线剂量为20~100kGy;
步骤三、预发泡,使用物理发泡剂将射线交联处理后的聚合物颗粒在高压釜内渗透1~48小时,压力1~85MPa,加热至聚合物玻璃化温度以上,高压釜内组分还包括去离子水和分散剂;渗透完成后泄压,泄压速率0.5~100MPa/s;
步骤四、二次发泡,将预发泡的聚合物颗粒在压缩空气条件下预压1~16 小时,压力0.2~2MPa,加热至聚合物玻璃化温度以上,预压完成后泄压,泄压速率0.5~20MPa/s;
步骤五、模塑成型,将预发泡或者二次发泡的聚合物颗粒加入模具内,通入蒸汽加热至聚合物玻璃化温度以上,卸模干燥后得到成型的大块状聚合物泡沫材料;
步骤六、切片并覆膜,根据需要的尺寸,将聚合物泡沫材料裁切成片材,并覆膜或者热压成型为运动垫。
进一步的,步骤一中的热塑性聚合物包括LDPE、HDPE、LLDPE、EVA、 PP、NBR、PVC、TPE、TPV、PS、PET、聚烯烃热塑性弹性体(TPO)、TPU 中的任意一种或几种的混合物,其MFR为0.5~12g/10min,所述MFR为190℃, 2.16kg负荷下测得。
进一步的,步骤一中气流粉碎使用的压缩空气压力为0.5~3MPa。
进一步的,步骤二中电子束射线设备产生的电子能量在0.5MeV~10MeV 之间。
进一步的,步骤二中去离子水的用量是聚合物颗粒总质量的5%~70%,分散剂的用量是聚合物颗粒总质量的0.1%~25%。
进一步的,步骤三中物理发泡剂包括二氧化碳、氮气、空气中的一种或其混合物。
进一步的,步骤三中分散剂为滑石粉、碳酸钙、白炭黑、硫酸钡、氢氧化铝、氢氧化镁和十二烷基磺酸钠中的一种或其混合物。
本发明的有益效果是:
1.使用二氧化碳、氮气、空气中的一种或其混合物作为发泡剂,解决爬行垫/瑜伽垫产品使用化学发泡剂导致的有毒有害分解物残留的问题,并且得到的产品的泡孔细腻、均一性好,从而提高其压缩回弹性;
2.将热塑性聚合物颗粒在脆化温度下进行高速气流粉碎后,使物理发泡剂渗透加快,提高生产效率。并且,微米级的聚合物颗粒减弱甚至消除模塑成型的泡沫材料中发泡颗粒的熔接缝,提高了聚合物的力学性能;
3.不使用过氧化物等化学交联剂,使用射线交联,射线交联均匀稳定,提高产品的拉伸、回弹性能,并且无异味。
附图说明
图1是一种无毒无害环保运动垫的制造方法流程示意图;
具体实施方式
以下对本发明的实施例进行详细说明,但是本发明可以由权利要求限定和覆盖的多种不同方式实施。
实施例1
参考图1所示,一种无毒无害环保运动垫的制造方法:
步骤一、使用中石化牌号2426H的LDPE塑胶粒子,MFR为2g/10min,中位粒径为2mm,脆化温度为-75℃,脆化温度按照国家标准GB/T5470-2008测定,使用液氮冷却到-110℃,使LDPE材料达到脆化温度以下,通过气流粉碎,压缩空气压力1.5MPa,粉碎后聚合物中位粒径达到23微米;
步骤二、射线交联,将粉碎后的聚合物颗粒在电子束射线设备下进行射线物理交联,电子束能量3.0MeV,射线剂量20kGy;
步骤三、预发泡;使用二氧化碳将聚合物颗粒在高压釜内渗透12小时,压力22MPa,蒸汽加热至118℃,高压釜内的组分去离子水占LDPE塑胶粒子总质量的20%,分散剂十二烷基磺酸钠占LDPE塑胶粒子总质量的1%,分散剂滑石粉占LDPE塑胶粒子总质量的1%;渗透完成后,快速泄压,聚合物颗粒预发泡至275g/cm3,泄压速率1.6MPa/s;
步骤四、二次发泡,将预发泡的聚合物颗粒在压缩空气条件下预压12小时,压力0.5MPa,蒸汽加热至118℃,预压完成后,快速泄压,泄压速率100MPa/s;
步骤五、模塑成型,将二次发泡的聚合物颗粒加入模具内,通入蒸汽加热至 118℃,卸模干燥后得到成型的长2m宽1.8m高0.8m的块状聚合物泡沫材料;
步骤六、切片并覆膜,将聚合物泡沫材料裁切成10mm厚度,长2m宽1.8m的薄片,并覆上彩色PE膜成型为爬行垫。
成型的爬行垫无异味,对其检测密度、力学性能,拉伸强度检测方法为ISO 1798,结果见表1。
对比例1-1
参照实施1,取消步骤一,由于颗粒大,成型的泡沫塑料有明显的珠粒之间的熔接痕,得到爬行垫的检测结果见表1,可见,本发明使用的聚合物的粒径的缩小,物理发泡剂渗透快,得到的产品密度小,并且,拉伸性能好。
对比例1-2
参照实施1,取消步骤二,得到爬行垫的检测结果见表1,可见,射线交联明显提高了产品的拉伸性能。
对比例1-3
检测一款市场销售的偶氮二甲酰胺化学发泡制备的XPE爬行垫,检测结果见表1,有明显的异味,是由于发泡剂和交联剂带来的,并且拉伸强度偏低。
实施例2~4
参照实施1,改变步骤一中的粉碎用压缩空气压力分别为0.5、0.8和3MPa,得到中位粒径分别为489、120、1.2微米的聚合物颗粒,得到爬行垫的检测结果见表1,可见,随着粒径的缩小,产品拉伸性能得到显著提高。
实施例5~7
参照实施1,改变步骤二中射线剂量分别为40、80、100kGy,得到爬行垫的检测结果见表1,可见,物理射线交联的增加,产品密度、拉伸性能增大。
实施例8
参考图1所示,一种无毒无害环保运动垫的制造方法:步骤一、陶氏9010 的TPE塑胶粒子,MFR为0.5g/10min。脆化温度为-95℃,脆化温度按照国家标准GB/T5470-2008测定。使用液氮冷却到-130℃,通过高速气流粉碎,压缩空气压力2.5MPa,粉碎后聚合物中位粒径达到362微米;
步骤二、射线交联,将粉碎后的聚合物颗粒在钴60射线设备下进行射线交联,电子束能量0.5MeV,射线剂量100kGy;
步骤三、预发泡;使用氮气将聚合物颗粒在高压釜内渗透24小时,压力 45MPa,蒸汽加热至65℃,高压釜内的组分去离子水占TPE塑胶粒子总质量的 5%,分散剂碳酸钙、硫酸钡、氢氧化铝各占TPE塑胶粒子总质量的0.1%;渗透完成后,快速泄压,聚合物颗粒预发泡至330g/cm3,泄压速率0.5MPa/s;
步骤四、模塑成型,将预发泡的聚合物颗粒加入模具内,通入蒸汽加热至 65℃,卸模干燥后得到成型的块状聚合物泡沫材料;
步骤五、切片并覆膜,将聚合物泡沫材料裁切成8mm厚度,长1.8m宽0.6m 的薄片,85℃辊热压成型为瑜伽垫。
成型的瑜伽垫无异味,检测力学性能按照实施例1的方法,如表1所示。
对比例8-1
检测一款市场销售的偶氮二甲酰胺化学发泡制备的TPE瑜伽垫,检测结果见表1,有明显的异味,是由于发泡剂和交联剂带来的,并且拉伸强度偏低。
实施例9~11
参照实施1,按照表2改变步骤三、四中的实验条件,得到爬行垫的检测结果见表1。
表1实施例产品检测结果
表2实验条件
实施例12~17
参照实施1,将聚合物材料换成如表3所示材料,其他不变,得到不同发泡密度的爬行垫,产品密度见表3。
表3实施例产品检测结果
以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种无毒无害环保运动垫的制造方法,其特征在于,包括以下步骤:
步骤一、微米级聚合物颗粒制备,将热塑性聚合物颗粒在脆化温度下进行气流粉碎,粉碎后中位粒径达到1~500微米;
步骤二、射线交联,将粉碎后的聚合物颗粒在钴60射线装置或者电子束射线设备下进行物理射线交联,射线剂量为20~100kGy;
步骤三、预发泡,使用物理发泡剂将聚合物颗粒在高压釜内渗透1~48小时,压力1~85MPa,加热至聚合物玻璃化温度以上,高压釜内组分还包括去离子水和分散剂;渗透完成后泄压,泄压速率0.5~100MPa/s;
步骤四、模塑成型,将预发泡的聚合物颗粒加入模具内,加热至聚合物玻璃化温度以上,卸模干燥后得到成型的大块状聚合物泡沫材料;
步骤五、切片并覆膜,根据需要的尺寸,将聚合物泡沫材料裁切成片材,并覆膜或者热压成型为运动垫。
2.根据权利要求1所述无毒无害环保运动垫的制造方法,其特征在于,模压成型前还包括二次发泡步骤,将预发泡的聚合物颗粒在压缩空气条件下预压1~16小时,压力0.2~2MPa,加热至聚合物玻璃化温度以上,预压完成后,快速泄压,泄压速率0.5~20MPa/s。
3.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤一中的热塑性聚合物包括LDPE、HDPE、LLDPE、EVA、PP、NBR、PVC、TPE、TPV、PS、PET、聚烯烃热塑性弹性体和TPU中的任意一种或几种的混合物,热塑性聚合物的MFR为0.5~12g/10min,所述MFR为190℃,2.16kg负荷下测得值。
4.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤一中气流粉碎使用的压缩空气压力为0.5~3MPa。
5.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤二中电子束射线设备产生的电子能量在0.5MeV~10MeV之间。
6.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤二中去离子水的用量是聚合物颗粒总质量的5%~70%,分散剂的用量是聚合物颗粒总质量的0.1%~25%。
7.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤三中物理发泡剂包括二氧化碳、氮气、空气中的一种或其混合物。
8.根据权利要求1或2所述无毒无害环保运动垫的制造方法,其特征在于,步骤三中分散剂为滑石粉、碳酸钙、白炭黑、硫酸钡、氢氧化铝、氢氧化镁、十二烷基磺酸钠中的一种或其混合物。
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