CN107200911B - 一种超轻高弹环保鞋底及其制备方法 - Google Patents

一种超轻高弹环保鞋底及其制备方法 Download PDF

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CN107200911B
CN107200911B CN201610150971.3A CN201610150971A CN107200911B CN 107200911 B CN107200911 B CN 107200911B CN 201610150971 A CN201610150971 A CN 201610150971A CN 107200911 B CN107200911 B CN 107200911B
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张振秀
张昕
李一楠
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Fujian Xingxun New Material Technology Co., Ltd
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Abstract

本发明公开了一种超轻高弹环保鞋底及其制备方法，超轻高弹鞋底配方为：乙烯与醋酸乙烯共聚物(EVA)0‑100份，聚烯烃嵌段共聚物(OBC)20‑80份，聚氨酯橡胶10‑50份，沙林树脂5‑20份，硬脂酸0.5‑2份、钛白粉5‑20份、抗氧剂1010 0.1‑0.5份，交联剂0.2‑1份。并以上述配方提供制备方法：将密炼机温度控制在90‑110℃之间，将所需原料依次加入密炼机中，最后加入交联剂，混合均匀后出料、下片、造粒。之后将所的混合料注入鞋模，得到预硫化鞋底，将此鞋底放入发泡装置中，采用降压法得到微孔发泡材料，此发泡材料用于鞋底的中底。

Description

一种超轻高弹环保鞋底及其制备方法
技术领域
本发明涉及高分子材料微孔发泡技术领域，具体涉及一种超轻高弹环保鞋底及其制备方法。
背景技术
近年来，随着制鞋业的迅速发展，鞋底材料的品种日益多样化。传统制鞋业中占主体地位的聚氯乙烯和橡胶实心鞋底已逐渐被新兴的橡塑并用发泡鞋所取代。发泡鞋底的主体材料一般有聚氯乙烯(PVC)、聚乙烯(PE)、苯乙烯—丁二烯—苯乙烯共聚物(SBS)、聚氨酯(PU)、乙烯—醋酸乙烯酯共聚物(EVA)等。
PVC类发泡鞋底的特点具有耐磨、耐化学腐蚀、价格低廉、着色鲜艳等特点，但其低温挠曲性、防滑性和穿着舒适性欠佳。PE类发泡鞋底材料强韧、耐挠曲、耐磨耗，具有优异的耐化学性和和隔热性，大量用于制作旅游鞋和沙滩拖鞋。不过，聚乙烯鞋底也存在着弹性差、防滑性能差、长时间穿着后易变形等缺点。SBS类发泡鞋底，SBS 可配合其它高聚物改性，添加软化油、填料、加工助剂等，经加工制得TPR(热塑性弹性体)鞋底材料。TPR鞋底材料具有防滑、耐低温、弯曲性强、透气性好、密度小、粘接强度高、废料可回收等优点。PU类发泡鞋底的特点：与普通塑料、橡胶鞋底料比较，聚氨酯鞋底具有密度小、耐磨耗、弹性好、强度高、耐挠曲性好、穿着舒适等优点。此外，根据需要调整配方，可使其具有防酸碱、耐油、防老化、抗水解、防静电、绝缘等性能。可满足便鞋、运动鞋、劳保鞋、军用鞋、时装鞋及童靴鞋等不同需要。但聚氨酯发泡工艺条件苛刻，不易控制，目前国内制鞋业生产聚氨酯发泡鞋底的原料和设备几乎都要依靠进口。鞋底用聚氨酯原液分聚醚型和聚酯型两类。EVA是一类具有橡胶弹性的热塑性塑料，在EVA分子中由于有醋酸乙烯(VA)的存在，使分子链有较大的柔顺性，宏观上表现为很高的弹性。因其隔热、防震，回弹性优良，压缩变形小，耐候性好而大量用于制鞋业。但EVA发泡材料的机械强度、抗撕裂性及抗剥离性不够好，目前EVA发泡鞋底材料因其质轻、穿着舒适受到人们的广泛喜爱。EVA具有很好的可塑性，极好的弹性，所以，EVA在运动鞋中底中的应用极为普遍。
目前市场上发泡鞋底基本都采用化学发泡方法制备，交联剂通常选用过氧化二异丙苯(DCP)，加入发泡剂偶氮二甲酰胺(AC)，在高温下硫化发泡的到成品。如果使用交联剂过氧化二异丙苯，则会在发泡产品中产生丙酮、丁醇、苯乙酮、2-苯基2-丙醇等，其中苯乙酮占分解产物的30.9％，不易挥发，且有臭味，此物对人的危害主要是对眼和皮肤的刺激作用，可引起皮肤局部灼伤和角膜损害；2-苯基2-丙醇也有异味，对人体和环境存在潜在危害，被欧盟禁止使用。同时，发泡剂偶氮二甲酰胺分解后可产生氮气、一氧化碳、二氧化碳、少量氨气、异氰酸、氨基脲等，其中氨气具有刺激性气味，会使呼吸道产生不适；另一种分解产物氨基脲是一种致癌物；同时还有未完全分解的甲酰胺，据了解，甲酰胺已经被欧盟化学品管理局分类为具有生殖毒性的物质，目前被欧盟相关法规列为高关注物质候选清单中。为了减少甲酰胺对儿童健康的影响，目前中国 台湾地区对于拼接塑料地垫中甲酰胺含量限定在2毫克/千克以内，法国限定甲酰胺含量在200毫克/千克以内。鉴于，目前对鞋材舒适度、功能性、轻便度越来越高的要求，以及对人体健康、环境保护方面越来越严格的标准，新一代高性能无毒环保的鞋材急需面向市场，尤其针对婴幼儿、青少年的环保鞋材的需求更为迫切。
发明内容
本发明的目的在于提供一种质量轻、弹性好、无毒环保的发泡鞋底，及其制备工艺。本发明在传统EVA材质的基础上加入聚氨酯橡胶提高鞋底的弹性和韧性；加入沙林树脂以及一种新型烯烃嵌段共聚物(OBC)，不仅改善了其加工性能，而且可以提高发泡鞋底的回弹性，具有较好的耐温性，减小发泡鞋底的压缩形变。而且本品一改通常制造发泡鞋底的化学发泡法，采用物理发泡技术，做到无异味、零二甲酰胺残留；在精简了配方的同时，采用无味高效交联剂，制备真正意义上的环保鞋材，尤其适用于高标准的婴幼儿、青少年鞋底材料。
为实现上述目的，本发明一种超轻高弹环保鞋底及其制备方法。
其中，所述一种超轻高弹环保鞋底及其制备方法，配方如下：乙烯与醋酸乙烯共聚物(EVA)0-100份，聚烯烃嵌段共聚物(OBC)20-100份，聚氨酯橡胶10-50份，沙林树脂5-20份，硬脂酸0.5-2份、钛白粉5-20份、抗氧剂1010 0.1-0.5份，交联剂0.2-1 份。
在一种超轻高弹环保鞋底及其制备方法的配方中，所述交联剂为双叔丁基过氧化二异丙基苯(BIPB)、1,1-双(叔丁基过氧)-3,3,5-三甲基环已烷或4,4-二(叔丁基过氧化)戊酸正丁酯的任一种。
所述一种超轻高弹环保鞋底及其制备方法，其制备步骤如下：
1)将密炼机温度设置为90-110℃，转速为40-60rpm，按重量分别称取所需原料，先将沙林树脂投入密炼机中，待其熔融后依次加入OBC、EVA、聚氨酯橡胶、硬脂酸、钛白粉、抗氧剂、交联剂。混炼均匀后排料、压片、造粒，冷却停放12h。
2)将混炼均匀的粒料投入注塑机中，注入鞋模。开模得到预硫化鞋底。
3)预硫化鞋底放入高压反应釜中，向釜中通入物理发泡剂并升温、加压，饱和后，快速泄压，得到微孔发泡鞋底。
4)发泡鞋底二次定型，冷却，得到成品。
步骤2)中，所述注塑机温度为165-180℃，模具温度设为165-180℃，保压时间300s-1200s，之后冷却拿出。
步骤3)中，所述物理发泡剂为二氧化碳，氮气或两种气体混合气体。
步骤3)中，所述微孔发泡釜中温度为70-150℃，压力为8-60Mpa，饱和时间为 0.5-10h，泄压时间为2-30s。
步骤4)中所述二次定型时，模具温度为140℃-170℃，时间为8-25min，冷却后得到成品。
所述的一种超轻高弹环保鞋底及其制备方法，所得到的发泡鞋底用于鞋材的中底或大底。
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2的扫描电镜图；
图3本发明制备方法中，实施例3的扫描电镜图。
具体实施方式：
下面结合实施例对本发明做进一步说明：
实施例1
乙烯-醋酸乙烯共聚物(EVA)80份，聚烯烃嵌段共聚物(OBC)20份，硬脂酸0.5 份、钛白粉20份、抗氧剂1010 0.2份，双叔丁基过氧化二异丙基苯0.6份。
将密炼机温度设置为90℃，转速为60rpm，按重量分别称取所需原料，依次加入EVA、OBC、硬脂酸、钛白粉、抗氧剂1010、交联剂BIPB。混炼均匀后排料、压片、造粒，冷却停放12h。之后将粒料投入注塑机中，注入鞋模，注塑机机头温度为170℃，模具温度为170℃。保压1200s后，冷却，开模得到预硫化鞋底。将预硫化鞋底放入高压反应釜中，向釜中通入氮气并升温至80℃、加压至16Mpa，饱和后4h后，快速泄压，得到微孔发泡鞋底。最后将发泡鞋底放入在140℃模具中二次定型，20min，然后冷却，得到成品。
实施例2
乙烯-醋酸乙烯共聚物(EVA)60份，聚烯烃嵌段共聚物(OBC)15份，聚氨酯橡胶20份，沙林树脂5份，硬脂酸0.5-2份、钛白粉13份、抗氧剂1010 0.5份，双叔丁基过氧化二异丙基苯0.8份。
将密炼机温度设置为110℃，转速为60rpm，按重量分别称取所需原料，先加入沙林树脂，待其熔融后，依次加入EVA、OBC、硬脂酸、钛白粉、抗氧剂1010、交联剂 BIPB。混炼均匀后排料、压片、造粒，冷却停放12h。之后将粒料投入注塑机中，注入鞋模，注塑机机头温度为170℃，模具温度为165℃。保压1800s后，冷却，开模得到预硫化鞋底。将预硫化鞋底放入高压反应釜中，向釜中通入氮气并升温至100℃、加压至20Mpa，饱和后1h后，快速泄压，得到微孔发泡鞋底。最后将发泡鞋底放入在160℃模具中二次定型，8min，然后冷却，得到成品。
实施例3
乙烯-醋酸乙烯共聚物(EVA)50份，聚氨酯橡胶40份，沙林树脂10份，硬脂酸 1份、钛白粉17份、抗氧剂1010 0.5份，1,1-双(叔丁基过氧)-3,3,5-三甲基环已烷1 份。
将密炼机温度设置为100℃，转速为50rpm，按重量分别称取所需原料，先加入沙林树脂，待其熔融后，依次加入EVA、OBC、硬脂酸、钛白粉、抗氧剂1010、交联剂 BIPB。混炼均匀后排料、压片、造粒，冷却停放12h。之后将粒料投入注塑机中，注入鞋模，注塑机机头温度为160℃，模具温度为155℃。保压2000s后，冷却，开模得到预硫化鞋底。将预硫化鞋底放入高压反应釜中，向釜中通入氮气并升温至70℃、加压至18Mpa，饱和后6h后，快速泄压，得到微孔发泡鞋底。最后将发泡鞋底放入在150℃模具中二次定型，10min，然后冷却，得到成品。
将上述实施例1至实施例3制得样品，并对其进行物性进行检测，其检测结果见表1。
以上所述仅为本发明的实施例，并不限制本发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。

Claims (4)

1.一种超轻高弹环保鞋底的制备方法，其特征在于：
其配方如下：乙烯与醋酸乙烯共聚物0-100份，聚烯烃嵌段共聚物20-100份，聚氨酯橡胶10-50份，沙林树脂5-20份，硬脂酸0.5-2份、钛白粉5-20份、抗氧剂1010 0.1-0.5份，交联剂0.2-1份；其制备步骤如下：
1)将密炼机温度设置为90-110℃，转速为40-60rpm，按重量分别称取所需原料，先将沙林树脂投入密炼机中，待其熔融后依次加入聚烯烃嵌段共聚物、乙烯与醋酸乙烯共聚物、聚氨酯橡胶、硬脂酸、钛白粉、抗氧剂、交联剂，混炼均匀后排料、压片、造粒，冷却停放12h；
2)将混炼均匀的粒料投入注塑机中，注入鞋模，注塑机温度为165-180℃，模具温度设为165-180℃，时间300s-1200s，开模得到预硫化鞋底；
3)预硫化鞋底放入高压反应釜中，向釜中通入物理发泡剂并升温、加压，饱和后，快速泄压，反应釜中温度为70-150℃，压力为8-60Mpa，饱和时间为0.5-10h，泄压时间为2-30s，得到微孔发泡鞋底；
4)微孔发泡得到的发泡鞋底要放入140℃-170℃模具中二次定型，时间为8-25min，冷却，得到成品。
2.根据权利要求1所述的一种超轻高弹环保鞋底的制备方法，其特征在于，所述交联剂为双叔丁基过氧化二异丙基苯、1,1-双(叔丁基过氧)-3,3,5-三甲基环已烷或4,4-二(叔丁基过氧化)戊酸正丁酯。
3.根据权利要求1所述的一种超轻高弹环保鞋底的制备方法，其特征在于，所述物理发泡剂为二氧化碳，氮气或两种气体混合。
4.根据权利要求1-3中的任意一项所述的一种超轻高弹环保鞋底的制备方法，其特征在于，所述发泡鞋底用于鞋材的中底或大底。
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