CN106117766B - 一种高回弹耐老化eva发泡材料及其制备方法 - Google Patents
一种高回弹耐老化eva发泡材料及其制备方法 Download PDFInfo
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Abstract
一种高回弹耐老化EVA发泡材料及其制备方法。该方法包括如下步骤：1)利用硅烷偶联剂对木质纤维素粉体进行改性，得到改性木质纤维素粉体；2)将部分氢化苯乙烯丁二烯聚合物、乙烯‑醋酸乙烯共聚物和改性木质纤维素粉体加入密炼机中进行混炼；3)将发泡剂、架桥剂、活性剂和氧化锌加入密炼机中进行混炼；4)经步骤2)和步骤3)密炼后的物料进行造粒，然后进行射出发泡，经冷却成型即得高回弹耐老化EVA发泡材料。EVA加入麻杆粉发泡后可以使其压缩变形明显改善，加入麻杆粉发泡EVA的压缩变形比不加麻杆粉EVA的压缩变形高15％。以本发明改性发泡体制备的鞋中底轻质、耐久、避震、高弹、抗撕裂性能好，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。
Description
技术领域
本发明涉及一种高回弹耐老化EVA发泡材料及其制备方法。
背景技术
射出木质纤维素粉体是将木质纤维素粉体等原材料塑炼造粒高温熔融后，通过管道射出到模具，继而在模外发泡直接得到的产品。一般运动鞋的鞋底是由发泡中底和耐磨橡胶大底组成，由于木质纤维素粉体具有很好的可塑性、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，长时间穿着后容易变形，不易回复，并且产生臭味令人不悦。
一般射出EVA产品存在着回弹性差，耐老化不好，热收缩过大等缺点，对后续的生产和使用有很大的障碍和局限，因此，需要提供一种新的高回弹耐老化EVA发泡材料来解决上述一般射出EVA无法克服的缺点。
发明内容
本发明的目的是提供一种高回弹耐老化EVA发泡材料及其制备方法，本发明提供的高回弹耐老化EVA发泡材料不仅具有较轻重量的性能，而且还具有很好的弹性和回弹性，同时也具有耐老化性能和抗撕裂性能，可用于制备鞋底，特别是鞋中底。
本发明所提供的高回弹耐老化EVA发泡材料的制备方法，包括如下步骤：
1)利用硅烷偶联剂对木质纤维素粉体进行改性，得到改性木质纤维素粉体；
2)将部分氢化苯乙烯丁二烯聚合物、乙烯-醋酸乙烯共聚物和所述改性木质纤维素粉体混合后进行混炼；
3)将发泡剂、架桥剂、活性剂和氧化锌加入所述混炼的体系中进行混炼；
4)经步骤2)和步骤3)密炼后的物料进行造粒，然后进行射出发泡，经冷却成型即得所述高回弹耐老化EVA发泡材料。
上述的制备方法中，所述硅烷偶联剂可为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基-三甲氧基硅烷、γ-甲基丙烯酰氧基丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-甲基-三甲氧基硅烷、γ-氯丙基-三甲氧基硅烷、γ-巯丙基-三甲氧基硅烷和γ-氨丙基-三甲氧基硅烷中至少一种；
所述硅烷偶联剂的用量可为所述木质纤维素粉体质量的0.1～1.5％，如1％；
进行所述改性时，将所述硅烷偶联剂喷淋到所述木质纤维素粉体，实现对所述木质纤维素粉体的表面改性。
上述的制备方法中，所述木质纤维素粉体可为汉麻杆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子至少一种；
所述木质纤维素粉体的粒径可为200目～1000目。
上述的制备方法中，所述部分氢化苯乙烯丁二烯聚合物的数均分子量可为12000～50000；
所述乙烯-醋酸乙烯共聚物的数均分子量可为400～4000，所述乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量可为20～40％；
所述发泡剂可选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种；
所述架桥剂可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；
所述活性剂可选自硬脂酸、碳酸镁和氧化钙中的至少一种。
上述的制备方法中，所述乙烯-醋酸乙烯共聚物、所述部分氢化苯乙烯丁二烯聚合物、所述改性木质纤维素粉体、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可为50：50：20～80：3.0～5.0：0.4～1.0：1.0～3.0：0.5～2.5，具体可为50：50：40～70：3.5～4.5：0.6～0.8：2～2.5：1～1.5、50：50：50：4.0：0.6：2：1、50：50：50：4.5：0.6：2：1、50：50：50：4.0：0.8：2：1、50：50：50：4.0：0.6：2.5：1、50：50：50：4.0：0.6：2：1.5、50：50：50：3.5：0.6：2：1.5或50：50：50：4.5：0.6：2.5：1。
上述的制备方法中，步骤2)中，所述混炼的温度可为80～90℃，如90℃，每5℃进行除尘翻料；
所述混炼的时间可为7.5～12min，如12min；
步骤3)中，所述混炼的温度可为90℃～110℃，如100℃；
所述混炼的时间可为6～8min，如6min。
上述的制备方法中，步骤4)中，所述射出发泡的条件如下：模具的上模温度为177～183℃，模具的下模温度为177～183℃。
本发明提供的高回弹耐老化EVA发泡材料不仅具有较轻重量的性能，而且还具有很好的弹性和回弹性，同时也具有耐老化性能和抗撕裂性能，因此可用于制备鞋中底。
本发明采用乙烯-醋酸乙烯共聚物(EVA)、部分氢化聚苯乙烯-丁二烯-苯乙烯嵌段共聚物和改性木质纤维素粉体为主体胶料，经混炼、造粒和射出硫化制成。该改性木质纤维素粉体发泡体的比重为0.2以下，质量轻；回弹性为95％以上，能量回复达到60％以上，抗撕裂强度为2500N/m，耐冲击指数为10～12g；能给穿着者(尤其是竞技运动员)提供舒适的感觉并极大缓冲剧烈运动带来的冲击。EVA加入麻杆粉发泡后可以使其压缩变形明显改善，加入麻杆粉发泡EVA的压缩变形比不加麻杆粉EVA的压缩变形高15％。电镜像片揭示麻杆粉加入后在EVA内形成皱褶，类似弹簧机理，有利于EVA受压缩后恢复弹性。以本发明改性发泡体制备的鞋中底轻质、耐久、避震、高弹、抗撕裂性能好，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。
附图说明
图1为本发明实施例1中制备的加入改性麻杆粉的发泡体的电镜照片。
图2为未加入改性麻杆粉得到的EVA的电镜照片。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、制备改性木质纤维素粉体发泡体
将50重量份的粒径为500目的木质纤维素粉体用5重量份的硅烷偶联剂进行均匀的喷淋，储存、烘干制成均匀的改性木质纤维素粉体。
将50重量份的商品名为EVA7470、数均分子量为1800的乙烯-醋酸乙烯共聚物(其中醋酸乙烯(VA)的质量百分含量为26％)、50重量份的商品名为GT-01、数均分子量为20000的部分氢化苯乙烯丁二烯聚合物和50重量份的粒径为500目的改性木质纤维素粉体投入密炼机中混炼，混炼过程中，开炼机温度不超过70℃，混炼温度为90℃，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℃，混炼时间为0.1小时。
投入造粒机中间造粒：设定造粒机温度：第一段95℃，第二段95℃，第三段95℃，第四段90℃，主机转速35转，入料机转速30转，切刀转速15转，每批次的料进入搅拌桶搅拌均匀，时间20分钟。
输入至射出发泡成型机中进行射出发泡成型，模具温度：上模177～183℃；下模177～183℃。
经冷却成型得到发泡材料，恒温箱温度：85±5℃、75±5℃、65±5℃；恒温时间：30℃±5分钟；恒温机轮速：125±10转。
图1为本实施例制备的发泡体(加入改性麻杆粉)的电镜照片，与未加入改性麻杆粉的EVA的电镜照片(图2)相比，可以看出，麻杆粉加入后在EVA内形成皱褶，类似弹簧机理，有利于EVA受压缩后恢复弹性。
实施例2-7、制备改性木质纤维素粉体发泡体
按照与实施例1中相同的步骤，仅将各组分按照表1中所列重量份数进行替换，得到实施例2-7制备所得的改性木质纤维素粉体发泡体。
表1、实施例1-7制备的改性木质纤维素粉体发泡体中各原料的重量份数列表
实施例3、改性木质纤维素粉体发泡体的性能测试
经测定，实施例1～7制备的木质纤维素粉体发泡体的物性如表2中所示。
表2中，各指标的测试方法如下：
视密度：HG/T 2872-2009，测试片带皮；
拉伸强度：GB/T 10654-2001，测试片带皮，标线距离为50mm，取两个垂直方向测试结果的平均值；
拉断伸长率：GB/T 10654-2001，测试片带皮，标线距离为50mm，取两个垂直方向测试结果的平均值；
直角形撕裂强度：GB/T 10808-2006，测试片带皮，测试速度50mm/min；
回弹性：GB/T 10652-2001，测试片带皮；
加湿老化后鞋底周圈剥离强度：GB/T 3903.7-2005，附录E.5.1，70℃、120h、95％RH。
表2、实施例1～7制备的木质纤维素粉体发泡体的物性
由表2中的数据可得知，本发明提供的改性木质纤维素粉体发泡体具有轻质、耐久、避震、高弹和抗撕裂性能，适用于制备各种竞技类和休闲类的鞋中底，具有重要的应用价值。
Claims (10)
1.一种高回弹耐老化EVA发泡材料的制备方法，包括如下步骤：
1)利用硅烷偶联剂对木质纤维素粉体进行改性，得到改性木质纤维素粉体；
2)将部分氢化苯乙烯丁二烯聚合物、乙烯-醋酸乙烯共聚物和所述改性木质纤维素粉体混合后进行混炼；
3)将发泡剂、架桥剂、活性剂和氧化锌进行混炼；
4)经步骤2)和步骤3)混炼后的物料进行造粒，然后进行射出发泡，经冷却成型即得所述高回弹耐老化EVA发泡材料。
2.根据权利要求1所述的制备方法，其特征在于：所述硅烷偶联剂为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷和γ-氨丙基三甲氧基硅烷中至少一种；
所述硅烷偶联剂的用量为所述木质纤维素粉体质量的0.1～1.5％。
3.根据权利要求1或2所述的制备方法，其特征在于：所述木质纤维素粉体为汉麻杆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子至少一种；
所述木质纤维素粉体的粒径为200目～1000目。
4.根据权利要求1或2所述的制备方法，其特征在于：所述部分氢化苯乙烯丁二烯聚合物的数均分子量为12000～50000；
所述乙烯-醋酸乙烯共聚物的数均分子量为400～4000，所述乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量为20～40％；
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。
5.根据权利要求1或2所述的制备方法，其特征在于：所述乙烯-醋酸乙烯共聚物、所述部分氢化苯乙烯丁二烯聚合物、所述改性木质纤维素粉体、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50：50：20～80：3.0～5.0：0.4～1.0：1.0～3.0：0.5～2.5。
6.根据权利要求1或2所述的制备方法，其特征在于：步骤2)中，所述混炼的温度为90～115℃，每5℃进行除尘翻料；
所述混炼的时间为7.5～8.5min；
步骤3)中，所述混炼的温度为80℃～90℃。
7.根据权利要求1或2所述的制备方法，其特征在于：步骤4)中，所述射出发泡的条件如下：模具的上模温度为177～183℃，模具的下模温度为177～183℃。
8.权利要求1-7中任一项所述方法制备的高回弹耐老化EVA发泡材料。
9.权利要求8所述高回弹耐老化EVA发泡材料在制备鞋底中的应用。
10.根据权利要求9所述的应用，其特征在于：所述鞋底为鞋中底。
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