CN107501703A - 一种环保eva鞋中底 - Google Patents
一种环保eva鞋中底 Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 40
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 38
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 38
- 230000005855 radiation Effects 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 6
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- 238000010894 electron beam technology Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 230000002421 anti-septic effect Effects 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 206010070834 Sensitisation Diseases 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 11
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229920001684 low density polyethylene Polymers 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000007731 hot pressing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
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- C08L23/04—Homopolymers or copolymers of ethene
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Abstract
本发明提供一种环保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,与现有传统的化学发泡鞋底相比,超临界氮气发泡的交联弹性体发泡材料泡孔结构更完整,饱满,弹性更佳且无有害残留物。
Description
技术领域
本发明涉及一种环保EVA发泡珠粒及鞋中底的制作方法。
背景技术
近年来,随着人们对身体健康的关注,越来越多的人们开始热衷于各种体育运动,高性能的运动鞋也就成为紧俏产品。目前市场上的EVA发泡鞋底基本都采用化学发泡法,通过加入过氧化物交联剂和发泡剂偶氮二甲酰胺(AC),在高温下硫化发泡得到成品。着此种鞋底中,交联剂和化学发泡剂在制备过程中都会有部分有毒物质的残留,人们对残留物、气味的关注度也逐渐提高,因此新型环保的鞋材需求非常迫切。
现在市场上阿迪达斯的BOOST鞋非常火爆,不仅是因为TPU所带来的高性能,而且它采用的是超临界发泡工艺制备的,但是相对于EVA,TPU的价格昂贵,而降低成本,在达到环保的同时保证鞋材的性能就显得尤为关键。对于含有EVA的超临界发泡材料也有相关的专利。在专利2016101509713中EVA的共混物是以过氧化物为交联剂,之后再采用间歇式降压法发泡工艺,得到超临界的EVA发泡材料,在专利201510014608.4中仅公开了一种环保发泡材料的成型方法,虽然提及超临界发泡EVA材料,但是并没有公开其超临界发泡材料的具体制备步骤和工艺参数。王波等人研究了γ射线辐照改性对于LDPE/EVA共混物结构和性能的影响,但其共混物中LDPE占主要份数,且使用的是超临界二氧化碳为物理发泡剂。
发明内容
本发明的目的在于提供一种完全环保的高性能的发泡中底,采用辐射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,与现有传统的化学发泡鞋底相比,超临界氮气发泡的交联弹性体发泡材料泡孔结构更完整,饱满,弹性更佳且无有害残留物。
为实现上述目的,一种EVA发泡珠粒及鞋中底的制作方法,其中,主要原料包括乙烯-醋酸乙烯酯(EVA)、或EVA与聚烯烃弹性体POE的共混物、或EVA与聚苯乙烯—丁二烯—苯乙烯三嵌段共聚物(SEBS)的共混物、或EVA、POE、SEBS三者的共混物,敏化剂0-2份,碳酸钙0.1-20份,抗氧剂1010 0.5-2份,抗菌剂ZnO 0.1-2份,钛白粉0.1-10份,染料0.1-2份,其特征在于,制备步骤如下:
(1)将原料依次放入密炼机中于110-140℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;
(2)将上述颗粒放入电子束辐射器中对其进行辐照交联,辐照量为30-90kGy;
(3)将辐照交联的颗粒放入反应釜中,通入氮气,密封饱和2-12h,之后泄压,将颗粒卸出,放入烘箱/烘道中进行发泡,得到EVA发泡珠粒;
(4)将发泡珠粒放入模具中进行蒸汽热压成型,得到发泡鞋中底。
其中,EVA和POE的共混物中EVA含量为60%-95%,POE含量为5%-40%;EVA和SEBS的共混物中EVA含量为60%-95%,SEBS含量为5%-40%;EVA、POE和SEBS的共混物中,EVA含量为60%-90%,SEBS含量为5%-20%,POE含量为5%-20%。
其中,所述敏化剂为TAIC或TMPTMA中的任一种。
其中,制备步骤(3)中反应釜的温度为30-90℃,通入氮气后釜内压力为15-60Mpa,烘箱/烘道发泡时温度为70-140℃。
其中,发泡珠粒在蒸汽压成型过程中,蒸汽压力为0.5-4Mpa,时间为20-100s。
本发明的有益效果为:通过辐射交联-超临界氮气发泡技术可以制备得到真正意义上的环保鞋底材料,采用间歇式超临界升温法可以大大提高其产率,且密度低于目前市面上的发泡鞋底,具有良好的回弹性及较低的压缩永久变形。
附图说明
图1本发明制备方法中,实施例1的扫描电镜图;
图2本发明制备方法中,实施例1的照片。
具体实施方式:
下面结合实施例对本发明做进一步说明:
对比例1
配方:乙烯-醋酸乙烯酯(EVA)60份,苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)40份,DCP 0.7份,AC3000H 2.8份,ZnO 0.8份,
制备步骤:调整开炼机的辊轮温度为90℃,辊距0.5mm,加入主要树脂原料打料,包辊后放大辊距再依次加入填料、AC(发泡剂)、ZnO,打散后在加入DCP(交联剂),打均匀,在将料束薄3次,出片并按模具形状进行裁片,装模热压发泡170℃,800s,冷却定型,在室温下放置24h,裁样,进行性能测试。
基本性能:密度为0.23g/cm3,回弹为48,压缩永久变形为率为32%。
实施例1
配方:EVA 100份、碳酸钙3份,抗氧剂1010 0.5份,抗菌剂ZnO 1份,钛白粉6份。
制备步骤:将原料依次放入密炼机中于120℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;将上述颗粒放入电子束辐射器中对其进行辐照交联,辐照量为80kGy;将辐照交联的颗粒放入反应釜中釜中温度为55℃,通入氮气后使釜内压力达到30Mpa,密封饱和16h,之后泄压,将颗粒卸出,放入110℃烘箱中发泡10min,得到发泡珠粒;之后将发泡珠粒放入模具中进行蒸汽热压成型,蒸汽压力为1.2MPa,得到发泡鞋中底。
基本性能:密度为0.16g/cm3,回弹为55,硬度48,压缩永久变形率为45%,拉伸强度为1.6MPa,扯断伸长率为270%,耐黄变级别4级。
实施例2
配方:EVA70份、POE 30份,TMPTMA 1份,碳酸钙5份,抗氧剂1010 1份,抗菌剂ZnO 1份。
制备步骤:将原料依次放入密炼机中于115℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;将上述颗粒放入电子束辐射器中对其进行辐照交联,辐照量为50kGy;将辐照交联的颗粒放入反应釜中釜中温度为30℃,通入氮气后使釜内压力达到35Mpa,密封饱和8h,之后泄压,将颗粒卸出,放入120℃烘箱中发泡12min,得到发泡珠粒;之后将发泡珠粒放入模具中进行蒸汽热压成型,蒸汽压力为1.2MPa,得到发泡鞋中底。
基本性能:密度为0.18g/cm3,回弹为58,硬度45,压缩永久变形率为40%,拉伸强度为1.3MPa,扯断伸长率为201%,耐黄变级别4级。
实施例3
EVA85份,SEBS 15份,TMPTMA 0.2份,碳酸钙5份,抗氧剂1010 1份,抗菌剂ZnO1份。
制备步骤:将原料依次放入密炼机中于115℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;将上述颗粒放入电子束辐射中对其进行辐照交联,辐照量为60kGy;将辐照交联的颗粒放入反应釜中釜中温度为70℃,通入氮气后使釜内压力达到30Mpa,密封饱和8h,之后泄压,将颗粒卸出,放入120℃烘箱中发泡,得到发泡珠粒;之后将发泡珠粒放入模具中进行蒸汽热压成型,蒸汽压力为1.2MPa,得到发泡鞋中底。
基本性能:密度为0.165g/cm3,回弹为62,硬度42,压缩永久变形率为39%,拉伸强度为1.2MPa,扯断伸长率为175%,耐黄变级别4级。
实施例3
EVA60份,POE30份,SEBS 10份,TMPTMA 0.1份,碳酸钙3份,抗氧剂1010 1份。制备步骤:将原料依次放入密炼机中于115℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;将上述颗粒放入电子束辐射中对其进行辐照交联,辐照量为65kGy;将辐照交联的颗粒放入反应釜中釜中温度为70℃,通入氮气后使釜内压力达到30Mpa,密封饱和8h,之后泄压,将颗粒卸出,放入120℃烘箱中发泡,得到发泡珠粒;之后将发泡珠粒放入模具中进行蒸汽热压成型,蒸汽压力为1.2MPa,得到发泡鞋中底。
基本性能:密度为0.17g/cm3,回弹为65,硬度41,压缩永久变形率为40%,拉伸强度为1.0MPa,扯断伸长率为215%,耐黄变级别4级。
Claims (5)
1.一种环保EVA发泡珠粒及鞋中底的制作方法,其主要原料包括乙烯-醋酸乙烯酯(EVA)、或EVA与聚烯烃弹性体POE的共混物、或EVA与聚苯乙烯—丁二烯—苯乙烯三嵌段共聚物(SEBS)的共混物、或EVA、POE、SEBS三者的共混物,敏化剂0-2份,碳酸钙0.1-20份,抗氧剂1010 0.5-2份,抗菌剂ZnO 0.1-2份,钛白粉0.1-10份,染料0.1-2份。其特征在于,制备步骤如下:
(1)将原料依次放入密炼机中于110-140℃下混炼,待混炼均匀后,排出,将胶片加入挤出机中,挤出造粒,烘干;
(2)将上述颗粒放入电子束辐射器中对其进行辐照交联,辐照量为30-90kGy;
(3)将辐照交联的颗粒放入反应釜中,通入氮气,密封饱和2-12h,之后泄压,将颗粒卸出,放入烘箱或烘道中进行发泡,得到EVA发泡珠粒;
(4)将EVA发泡珠粒放入模具中进行蒸汽热压成型,得到发泡鞋中底。
2.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法,其特征在于EVA和POE的共混物中EVA含量为60%-95%,POE含量为5%-40%;EVA和SEBS的共混物中EVA含量为60%-95%,SEBS含量为5%-40%;EVA、POE和SEBS的共混物中,EVA含量为60%-90%,SEBS含量为5%-20%,POE含量为5%-20%。
3.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法,其特征在于敏化剂为三烯丙基异氰脲酸酯(TAIC)或三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)中的任一种。
4.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法,其特征在于制备步骤(3)中反应釜的温度为30-90℃,通入氮气后釜内压力为15~60Mpa,烘箱/烘道发泡时温度为70~140℃,发泡时间为2-20min。
5.根据权利要求1所述的一种环保EVA发泡珠粒及鞋中底的制作方法,其特征在于发泡珠粒在蒸汽压成型过程中,蒸汽压力为0.5-4Mpa,时间为20-100s。
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