CN105367891B - 一种低阻尼发泡材料及其制备方法 - Google Patents

一种低阻尼发泡材料及其制备方法 Download PDF

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CN105367891B
CN105367891B CN201510951747.XA CN201510951747A CN105367891B CN 105367891 B CN105367891 B CN 105367891B CN 201510951747 A CN201510951747 A CN 201510951747A CN 105367891 B CN105367891 B CN 105367891B
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卢鑫
罗显发
丁思博
廖毅彬
王育玲
郭彩莲
林臭知
金校红
郑荣大
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Maotai Fujian New Material Technology Co ltd
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Abstract

本发明涉及有机高分子化合物技术领域，提供一种低阻尼发泡材料及其制备方法，该低阻尼发泡材料随着运动频率的增大，阻尼因子先减小后增大，并在0.1‑10Hz区间保持较小的阻尼因子，最小达到0.07，能最大化地提供反弹力；该低阻尼发泡材料由原料EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸经过密炼、开炼、造粒制得低阻尼发泡料米，再经一次射出成型得到，所述低阻尼发泡材料具有宽频率的低阻尼、低压缩变形、尺寸稳定性好等特点，特别适合生产高档环保的低阻尼材料，尤其是需要低阻尼的短跑鞋中底。

Description

一种低阻尼发泡材料及其制备方法
技术领域
本发明属于有机高分子化合物技术领域，特别涉及一种低阻尼发泡材料及其制备方法。
背景技术
阻尼材料是将固体机械振动能转变为热能而耗散的材料，评价阻尼大小的标准是阻尼因子。高分子材料阻尼性能可以用测回弹的方法直观的展现出来，如鞋材的回弹率，但是这种方法太过粗略只能简单的定性，而比较常用的一种方法就是动态力学实验法，采用动态热机械分析仪(简称DMA)测试，通过对材料的测试可以同时获得阻尼因子Tanδ随温度变化、频率变化的数据，能够直观的体现出该材料的阻尼性能，阻尼因子的大小代表了动态变形下能量损耗的大小。材料要与制品的使用温度和频率相匹配，才更具有实用性。现有技术都是研究如何拓宽橡胶阻尼温度范围、如何提高材料阻尼因子，极少研究报道发泡材料的低阻尼性能。
运动休闲发泡鞋材，通常使用温度在0-50摄氏度之间，运动频率通常在0.1-10Hz之间，如何改善发泡鞋材的阻尼性能应引起研究人员的重视。塑料发泡制品具有挺性好、收缩率小、定型后易保持形状等优点，广泛应用于发泡鞋材，回弹率是鞋材的一个重要性能指标，弹性好，能量损耗小，鞋底会因形变的恢复而将能量归还给穿着者，给穿着者以跑或跳的动力。一般地，高分子材料的大分子中侧基越大越多，内摩擦越强；分子的极性越强，其分子间作用力越大，内摩擦越强，内摩擦越强则内耗越大，阻尼性大，吸收冲击能量较大，体现为回弹性较差，相反则回弹性更好。
发明内容
本发明的目的就是针对现有技术存在的不足而提供一种低阻尼发泡材料及其制备方法，所述低阻尼发泡材料随着运动频率的增大，阻尼因子先减小后增大，并在0.1-10Hz区间保持较小的阻尼因子，最小达到0.07，尽可能地减少能量损耗、最大化地提供反弹力，具有宽频率的低阻尼、低压缩变形、尺寸稳定性好等特点，特别适合生产高档环保的低阻尼材料，尤其是需要低阻尼的短跑鞋中底。
为实现上述目的，本发明采取的解决方案为：一种低阻尼发泡材料，由以下原料组成制得：EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸。
进一步的是，各原料的重量份如下：
进一步优选的，各组分按下列重量份配置：
进一步的是：所述EVA是VA含量大于25％的EVA。
进一步的是：所述PP弹性体为DSC熔点在65-80度之间。
进一步的是：所述PP弹性体至少包括埃克森美孚3020、埃克森美孚3000中的一种。
进一步的是：所述乙烯辛烯共聚物为陶氏EngageTM系列共聚物。
进一步的是：所述陶氏EngageTM系列共聚物至少包括8150、8100中的一种。
进一步的是：所述成核剂是聚烯烃成核剂。
进一步的是：所述发泡剂是AC发泡剂。
进一步的是：所述交联剂是BIBP。
一种制备所述低阻尼发泡材料的制备方法，包括步骤：
步骤1：制备低阻尼发泡料米，先将原料EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸混合进行密炼，调整密炼温度为92-95℃，保持4-6min，然后翻料2次，继续密炼升温，出料温度为100-103℃，密炼结束后进行开炼、造粒，得到低阻尼发泡料米；
步骤2：将低阻尼发泡料米倒入一次EVA注射机台的吸料桶，经一次射出成型得到低阻尼发泡材料。
通过采取前述技术方案，本发明具有如下有益效果：
1，现有技术的高弹发泡材料均使用回弹率表示材料的回弹性能，却忽略了聚合物材料本身阻尼性能差异产生的能量吸收问题，本发明使用动态机械分析仪测试材料平台区的阻尼随运动频率的变化趋势，测试发现本发明低阻尼发泡材料随着运动频率的增大，阻尼因子先减小后增大，并在0.1-10Hz区间保持较小的阻尼因子，最小达到0.07，使得鞋底材料的载荷周期与裸足时的步态周期相接近，使鞋足系统高度整合，实现真正的回归自然，有效地减少能量损耗、最大化地提供反弹力，应用在短跑鞋上，可以更快地提供更多弹跳力，帮助运动员减少触地时间、扩大布幅宽度，有效提高运动速度。
2，研究发现，填料增加、单位面积内微孔数量增多、泡孔壁变薄都会增加发泡材料的阻尼因子，本发明使用少量聚烯烃成核剂完全替代无机填充剂，有效控制泡孔尺寸，降低了材料的密度，得到的低阻尼发泡材料定型速度快、结晶均匀，有效提高了材料的透光性，适合生产半透明、透明发泡材料。
3，本发明低阻尼发泡材料所用材料具有聚乙烯和聚丙烯的主链，饱和度高，内聚能低，分子链在较宽的温度范围内保持柔顺性，具有较好的力学性能和工艺性能。制得的低阻尼发泡材料具有低密度、宽频率的低阻尼、低压缩变形、尺寸稳定性好、力学性能优异等特点，可以广泛应用于轮胎、运动器材、鞋材等低阻尼材料领域，尤其是需要低阻尼的短跑鞋中底，具有很好的市场前景。
附图说明
图1是本发明实施例1-4中制备得到的发泡材料的动态机械分析仪测试数据。
测试说明：美国TA公司的动态机械分析仪RSA G2，使用8mm平行板，压缩模式，测试温度30度，扫描频率0.05-500rad/s，应变0.5％，静态力1000g，测试样品为直径12mm、高10mm的圆柱体。
具体实施方式
现结合具体实施例对本发明进一步说明。
实施例1：
本实施例中，所述低阻尼发泡材料由以下组分按重量份组成：
所述低阻尼发泡材料的制备方法，包括步骤：
步骤1：制备低阻尼发泡料米，先将原料EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸混合进行密炼，调整密炼温度为94℃，保持6min，然后翻料2次，继续密炼升温，出料温度为101℃，密炼结束后进行开炼、造粒，得到低阻尼发泡料米；
步骤2：将低阻尼发泡料米倒入一次EVA注射机台的吸料桶，经一次射出成型得到低阻尼发泡材料。
上述制备得到的低阻尼发泡材料，密度0.196g/cm3，硬度46，尺寸收缩0.2％，回弹率67％，压缩变形率18％，撕裂强度12.2N/mm，拉伸强度2.7MPa，1.4Hz的阻尼因子0.070。
实施例2：
本实施例中，一种低阻尼发泡材料的制备方法与实施例1中的制备方法相同，所不同的是原料配比中：
EVA 7470M 20份、EVA 40W 5份、乙烯辛烯共聚物8100 25份、乙烯辛烯共聚物815040份、PP弹性体3020 10份。
上述制备得到的低阻尼发泡材料，密度0.214g/cm3，硬度48，尺寸收缩0.1％，回弹率66％，压缩变形率21％，撕裂强度11.7N/mm，拉伸强度2.4MPa，1.4Hz的阻尼因子0.075。
实施例3：
本实施例中，一种低阻尼发泡材料的制备方法与实施例1中的制备方法相同，所不同的是原料配比中：
EVA 265 30份、乙烯辛烯共聚物8100 32份、乙烯辛烯共聚物8150 23份、PP弹性体3980 10份、成核剂0.4份、硬脂酸锌1.2份、硬脂酸1.8份。
上述制备得到的低阻尼发泡材料，密度0.223g/cm3，硬度51，尺寸收缩0.4％，回弹率61％，压缩变形率21％，撕裂强度13.4N/mm，拉伸强度2.6MPa，1.4Hz的阻尼因子0.091。
实施例4：
本实施例中，一种低阻尼发泡材料的制备方法与实施例1中的制备方法相同，所不同的是原料配比中：
EVA 7470M 20份、EVA 40W 15份、乙烯辛烯共聚物8450 30份、乙烯辛烯共聚物8150 30份、PP弹性体5份。
上述制备得到的低阻尼发泡材料，密度0.182g/cm3，硬度47，尺寸收缩2.8％，回弹率59％，压缩变形率36％，撕裂强度7.5N/mm，拉伸强度2.9MPa，1.4Hz的阻尼因子0.107。
将上述实施例1～4的数据整理后，得到如下表1(注：硬度采用GS-701N硬度计测试，尺寸收缩率按照60度1小时测试，回弹率测试采用GT-7042-RE型冲击弹性试验机，压缩变形率按照50度6小时测试，撕裂强度按照GB/T 529-2008测试直角撕裂，拉伸强度按照GB/T 528-2009测试)：
实施例 1 2 3 4
密度(g/cm3) 0.196 0.214 0.223 0.182
硬度 46 48 51 47
尺寸收缩率(％) 0.2 0.1 0.4 2.7
回弹性(％) 67 66 61 59
压缩变形率(％) 18 21 21 36
撕裂强度(N/mm) 12.2 11.7 13.4 7.5
拉伸强度(MPa) 2.7 2.4 2.6 2.9
Tanδ(1.4Hz) 0.070 0.075 0.091 0.107
表1、实施例1-4的性能参数对照表
综上所述，按照本发明的低阻尼发泡材料的制备方法，制得的低阻尼发泡材料随着运动频率的增大，阻尼因子先减小后增大，并在0.1-10Hz区间保持较小的阻尼因子，最小达到0.07，尽可能地减少能量损耗、最大化地提供反弹力，具有宽频率的低阻尼、低压缩变形、尺寸稳定性好等特点，特别适合生产高档环保的低阻尼材料，尤其是需要低阻尼的短跑鞋中底。
以上所记载，仅为利用本创作技术内容的实施例，任何熟悉本项技艺者运用本创作所做的修饰、变化，皆属本创作主张的专利范围，而不限于实施例所揭示者。

Claims (8)

1.一种低阻尼发泡材料，其特征在于，该发泡材料随着运动频率的增大，阻尼因子先减小后增大，在0.1-10Hz区间保持较小的阻尼因子,最小达到0.07；所述低阻尼发泡材料，由以下原料组成制得：EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸；所述低阻尼发泡材料的各原料的重量份如下：
EVA 25 - 35 份
乙烯辛烯共聚物 55 - 65 份
PP弹性体 5 - 10 份
成核剂 0.3 - 0.5 份
发泡剂 2.3 - 2.6 份
交联剂 1.2 - 1.4 份
硬脂酸锌 1.2 - 1.5 份
硬脂酸 1.8 - 2.0 份。
2.根据权利要求1所述的低阻尼发泡材料，其特征在于，由以下组分按下列重量份原料制备而成:
EVA 30 份
乙烯辛烯共聚物 62 份
PP弹性体 8 份
成核剂 0.5 份
发泡剂 2.5 份
交联剂 1.3 份
硬脂酸锌 1.4 份
硬脂酸 2.0 份。
3.根据权利要求1所述低阻尼发泡材料，其特征在于：所述EVA为VA含量在25%-42%之间；所述PP弹性体为DSC熔点在65-80度之间。
4.根据权利要求1所述低阻尼发泡材料，其特征在于：所述PP弹性体至少包括埃克森美孚3020、埃克森美孚3000中的一种。
5.根据权利要求1所述低阻尼发泡材料，其特征在于：所述乙烯辛烯共聚物为陶氏EngageTM系列共聚物。
6.根据权利要求5所述低阻尼发泡材料，其特征在于：所述陶氏EngageTM系列共聚物至少包括8150、8100中的一种。
7.根据权利要求1所述低阻尼发泡材料，其特征在于：所述成核剂是聚烯烃成核剂HPN-20E。
8.一种制备权利要求1-7任一所述低阻尼发泡材料的制备方法，其特征在于，包括步骤：
步骤1：制备低阻尼发泡料米，先将原料EVA、乙烯辛烯共聚物、PP弹性体、成核剂、发泡剂、交联剂、硬脂酸锌、硬脂酸混合进行密炼，调整密炼温度为92-95℃，保持4-6min，然后翻料2次，继续密炼升温，出料温度为100-103℃，密炼结束后进行开炼、造粒，得到低阻尼发泡料米；
步骤2：将低阻尼发泡料米倒入一次EVA注射机台的吸料桶，经一次射出成型得到低阻尼发泡材料。
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