CN102504398B - 改性eva发泡体及其制备方法与应用 - Google Patents

改性eva发泡体及其制备方法与应用 Download PDF

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CN102504398B
CN102504398B CN2011103064393A CN201110306439A CN102504398B CN 102504398 B CN102504398 B CN 102504398B CN 2011103064393 A CN2011103064393 A CN 2011103064393A CN 201110306439 A CN201110306439 A CN 201110306439A CN 102504398 B CN102504398 B CN 102504398B
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vinyl acetic
acetic monomer
foam
core
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CN102504398A (zh
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郝新敏
甘舸
张建春
赵鹏程
黄杰
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Quartermaster Research Institute of General Logistics Department of CPLA
Li Ning China Sports Goods Co Ltd
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Li Ning China Sports Goods Co Ltd
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Abstract

本发明公开了一种改性EVA发泡体及其制备方法与应用。该改性EVA发泡体，包括乙烯醋酸乙酯共聚物、聚烯烃弹性体、木质纤维素粉体、发泡剂、架桥剂、活性剂和氧化锌。所述乙烯醋酸乙酯共聚物、所述聚烯烃弹性体、所述木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为70∶30∶20-80∶3.0-5.0∶0.4-1.0∶1.0-3.0∶0.5-2.5。该改性EVA发泡体的比重在0.2以下，质量轻，耐压缩歪在50％以下，能经受长时间的穿着，以该改性发泡体制备的鞋中底轻质、耐久性能佳，适用于各种竞技类和休闲类的鞋中底与鞋垫，具有重要的应用价值。

Description

改性EVA发泡体及其制备方法与应用
技术领域
本发明涉及一种改性EVA发泡体及其制备方法与应用。
背景技术
射出乙烯醋酸乙酯共聚物(简称EVA)是将EVA原材料塑炼造粒高温熔融后，通过管道射出到模具，继而在模外发泡得到的产品。一般运动鞋的鞋底是由发泡中底和耐磨橡胶大底组成，由于乙烯与醋酸乙烯共聚物(EVA)具有很好的可塑性、弹性、可加工性，发泡后材料密度小、力学性能好、易着色等优点。目前绝大多数运动鞋的中底或鞋垫采用EVA发泡材料。
一般射出EVA产品存在收缩和压缩变形严重等缺点，对后续的生产和使用有很大的障碍和局限，因此，需要一种新的改性EVA发泡体。
发明内容
本发明的目的是提供一种改性EVA发泡体及其制备方法与应用。
本发明提供的改性EVA发泡体，包括乙烯醋酸乙酯共聚物、聚烯烃弹性体(简称POE)、木质纤维素粉体、发泡剂、架桥剂、活性剂和氧化锌。
上述改性EVA发泡体也可只由上述组分组成。
其中，所述乙烯醋酸乙酯共聚物的数均分子量为400-4000，优选800-2000，所述乙烯醋酸乙酯共聚物中醋酸乙酯(VA)的质量百分含量为10-21％，优选16-19％；
所述聚烯烃弹性体的数均分子量为400-4000，优选600-2000；
所述木质纤维素粉体选自针叶材植物秆芯粉体、阔叶材植物秆芯粉体和禾本科植物秆芯粉体中的至少一种，优选大麻杆芯、汉麻秆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子中的至少一种，所述木质纤维素粉体的粒径为200目-1000目，优选400-800目，更优选500目；
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种，优选偶氮二甲酰胺；
所述架桥剂选自过氧化二异丙苯(DCP)、硫磺和二叔丁基过氧化物中的至少一种，优选过氧化二异丙苯；
所述活性剂选自硬脂酸、碳酸镁和氧化钙中的至少一种，优选硬脂酸。
所述乙烯醋酸乙酯共聚物、所述聚烯烃弹性体、所述木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为70∶30∶20-80∶3.0-5.0∶0.4-1.0∶1.0-3.0∶0.5-2.5，优选70∶30∶40-70∶3.5-4.5∶0.6-0.8∶2-2.5∶1-1.5，更优选70∶30∶50∶4∶0.6∶2∶1。
本发明提供的制备所述发泡体的方法，包括如下步骤：将前述各组分混合后进行硫化成型，得到所述发泡体。
该方法所述硫化步骤中，温度为165-175℃，优选168-175℃，更优选175℃，时间为5～15分钟，优选6-10分钟，更优选6分钟。
另外，为了使各组分混合得更加均匀，所述制备发泡体的方法，还包括如下步骤：在所述硫化步骤之前，所述混合步骤中混合的方式可为混炼，可包括如下步骤：将EVA、乙烯醋酸乙酯共聚物、POE和木质纤维素粉体进行混炼(该步骤中，温度不超过70度，混炼温度为80-100℃，混炼时间可为0.2小时)，同时将发泡剂、架桥剂、活性剂和氧化锌于另一密炼机中进行混炼(该步骤中，温度不超过70℃，混炼温度为100-110℃，混炼时间为0.1小时)。
上述本发明提供的发泡体在制备鞋底中的应用，及以所述发泡体为底的鞋底，也属于本发明的保护范围。其中，所述鞋底为鞋中底或鞋大底。
本发明改性发泡体EVA不仅具有较轻重量的性能，而且还具有较佳的耐久性能，由其制成的鞋中底重量轻、耐久性好，可适用于用作耐久性能要求较高的鞋大底。
本发明采用乙烯醋酸乙酯共聚物(EVA)、聚烯烃弹性体(POE)和木质纤维素粉体为主体胶料，经混炼、造粒和射出硫化制成。该改性EVA发泡体的比重在0.2以下，质量轻，耐压缩歪在50％以下，能经受长时间的穿着，以该改性发泡体制备的鞋中底轻质、耐久性能佳，适用于各种竞技类和休闲类的鞋中底，具有重要的应用价值。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述材料如无特别说明均能从公开商业途径而得。
实施例1、制备改性EVA发泡体
将70重量份的商品名为EVA7350、数均分子量为800-2000的乙烯醋酸乙酯共聚物(其中醋酸乙酯(VA)的质量百分含量为18％)、30重量份的商品名为POE8003、数均分子量为600-2000的聚烯烃弹性体和50重量份的粒径为500目的汉麻杆芯粉体投入密炼机中混炼，混炼过程中，开炼机温度不超过70度，混炼温度为80-100℃，混炼时间为0.2小时；
同时将4重量份的商品名为AC3000的发泡剂偶氮二甲酰胺、0.6重量份的架桥剂过氧化二异丙苯(DCP)、2重量份的活性剂硬脂酸和1重量份的氧化锌投入另一密炼机中混炼，混炼过程中，开炼机温度不超过70℃，混炼温度为100-110℃，混炼时间为0.1小时；
混炼完毕后将所有原料于110℃进行排料，排料后在开炼机台继续薄通，然后造粒干燥后，通过射出机注入模具后硫化，硫化温度为175℃，时间为6分钟，硫化后于定型烘箱中成型后，得到本发明的改性EVA发泡体。
按照与上完全相同的步骤，仅将各组分按照表1所列重量份数进行替换，得到实施例2-7制备所得的改性EVA发泡体。
表1、实施例1-7制备改性EVA发泡体中各原料的重量份数列表
Figure BDA0000097791160000031
经测定，实施例1～7制备所得改性EVA发泡体的物性如表2所示。
表2、实施例1～7制备所得改性EVA发泡体的物性列表
  实施例   S.G(比重)   硬度   拉力强度(kg/cm2)   延伸率(％)   撕裂(kg/cm)   压缩率(％)
  测试方法   GB/T533-91   GB/T531-99   GB/T528-92   GB/T528-92   GB/T529-99   ASTM D395
  1   0.19   55   26   272   19.5   48
  2   0.19   56   26   275   18   44
  3   0.18   53   25   280   18.5   45
  4   0.19   55   25   271   16   41
  5   0.19   55   26   277   19   46
  6   0.19   56   25   252   18.5   44
  7   0.19   56   26   260   16.2   43
另改性EVA发泡体的物性标准如表3所示。
表3、改性EVA发泡体的物性标准
由表2和表3可知，本发明提供的改性发泡体EVA不仅具有较轻重量的性能，而且还具有较佳的耐久性能，由其制成的鞋中底重量轻、耐久性好，可适用于用作耐久性能要求较高的鞋中底。

Claims (9)

1.一种改性EVA发泡体，由乙烯醋酸乙酯共聚物、聚烯烃弹性体、木质纤维素粉体、发泡剂、架桥剂、活性剂和氧化锌组成；
所述乙烯醋酸乙酯共聚物的数均分子量为400-4000，所述乙烯醋酸乙酯共聚物中醋酸乙酯的质量百分含量为10-21%；
所述聚烯烃弹性体的数均分子量为400-4000；
所述木质纤维素粉体选自大麻杆芯、汉麻秆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子中的至少一种，所述木质纤维素粉体的粒径为400-800目；
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种；
所述架桥剂选自过氧化二异丙苯、硫磺和二叔丁基过氧化物中的至少一种；
所述活性剂选自硬脂酸、碳酸镁和氧化钙中的至少一种；
所述乙烯醋酸乙酯共聚物、所述聚烯烃弹性体、所述木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为70：30：20-80：3.0-5.0：0.4-1.0：1.0-3.0：0.5-2.5。
2.根据权利要求1所述的发泡体，其特征在于：所述乙烯醋酸乙酯共聚物的数均分子量为800-2000，所述乙烯醋酸乙酯共聚物中醋酸乙酯的质量百分含量为16-19%；
所述聚烯烃弹性体的数均分子量为600-2000；
所述发泡剂为偶氮二甲酰胺；
所述架桥剂为过氧化二异丙苯；
所述活性剂为硬脂酸。
3.根据权利要求1或2所述的发泡体，其特征在于：所述乙烯醋酸乙酯共聚物、所述聚烯烃弹性体、所述木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为70：30：40-70：3.5-4.5：0.6-0.8：2-2.5：1-1.5。
4.一种制备权利要求1-3任一所述发泡体的方法，包括如下步骤：将权利要求1-3任一所述组分混合后进行硫化成型，得到所述发泡体。
5.根据权利要求4所述的方法，其特征在于：所述硫化步骤中，温度为165-175℃，时间为5～15分钟。
6.根据权利要求5所述的方法，其特征在于：所述硫化步骤中，温度为168-175℃，时间为6-10分钟。
7.权利要求1-3任一所述发泡体在制备鞋底或鞋垫中的应用。
8.以权利要求1-3任一所述发泡体为底的鞋底。
9.根据权利要求7所述的应用或权利要求8所述的鞋底，其特征在于：所述鞋底为鞋中底或鞋大底。
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