CN104277318B - 一种质轻、减震橡塑发泡材料及其制备方法 - Google Patents

一种质轻、减震橡塑发泡材料及其制备方法 Download PDF

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CN104277318B
CN104277318B CN201410430484.3A CN201410430484A CN104277318B CN 104277318 B CN104277318 B CN 104277318B CN 201410430484 A CN201410430484 A CN 201410430484A CN 104277318 B CN104277318 B CN 104277318B
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罗显发
卢鑫
丁思博
王育玲
廖毅彬
林臭知
金校红
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Maotai Fujian New Material Technology Co ltd
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Abstract

本发明属于有机高分子化合物技术领域，特别涉及一种质轻、减震橡塑发泡材料及其制备方法，由原料EVA、丁基橡胶、乙烯‑辛烯共聚物、增容剂、发泡剂、交联剂、纳米氧化锌、硬脂酸锌、硬脂酸、快熟剂、无机填料经过密炼、开炼、造粒制得橡塑粒子，再经一次注射成型，得到质轻、减震橡塑发泡材料。所述质轻、减震橡塑发泡材料具有质轻、高减震、耐黄变性能好、尺寸稳定性高等特点，并且具有优良的抗拉强度和抗撕强度，可应用于汽车防震材料、各类减震片、鞋底材料等方面的应用，特别适合作为慢跑鞋的中底，可以吸收来自地面的反作用力，很好地保护足部免受伤害。

Description

一种质轻、减震橡塑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，特别涉及一种质轻、减震橡塑发泡材料及其制备方法。
背景技术
随着大众健身及运动产业的发展，对运动鞋的轻量化、富有弹性、减震等性能要求也逐渐提高，避震系统是运动鞋中非常重要的一部分。运动时，人体会不停地承受很大重力，脚落地时，还会产生相当大的冲击力，由此产生震荡波，在没有及时得到缓冲的情况下，就会对人体的不同部位造成不同程度的慢性疲劳性损伤、运动伤害。鞋底的减震功能是吸收或降低该震荡波的能力，可以通过良好的减震结构或有良好吸震能力的材料来实现，如李宁公司的“李宁弓”结构减震、耐克公司的空气垫减震、阿迪达斯的减震胶减震、鸿星尔克公司的GDS减震系统。鞋底在具有一定的减震性能情况下，人在运动过程中受到的冲击不会直接反作用于人体，而是将部分能量吸收，在运动进行到登伸阶段时，鞋底会因形变的恢复而将能量再度归还给穿着者，给穿着者以跑或跳的动力。
中国专利CN 102051003 A公布了减震橡塑复合材料，使用耐黄变性质较差的氢化苯乙烯- 丁二烯共聚物为主体材料，且未公布材料的密度、减震、拉伸强度等具体性能参数，不适合用于耐黄变要求高的鞋材。专利CN 102702642 B公布了一种具有很好减震性能的EVA发泡材料，但是使用大量热稳定性差、耐老化性能差的PVC原料，PVC加工过程中对热敏感，受热时会引起不同的降解，释放有害物质、腐蚀生产设备，高温下甚至会释放出一级致癌物二恶英。丁国芳报道了具有优异阻尼性能的硅橡胶／IIR泡沫合金材料(2010年全国高分子材料科学与工程研讨会论文集)，硅橡胶添加到鞋材中会直接导致鞋材的剥离强度下降，且材料的密度较大、拉伸强度小，不适合作为运动鞋材使用。
发明内容
为了克服现有专利技术的缺陷，本发明采用减震阻尼性能优异的丁基橡胶、力学性能较好的乙烯-辛烯共聚物，与具有柔韧性能好、较高玻璃化转变温度的EVA共混、再经一次注射成型，提供了一种具有质轻、高减震、耐黄变性能好、尺寸稳定性好等特点的环保型的质轻、减震橡塑发泡材料，可广泛应用于汽车防震材料、各类减震片、鞋底材料等方面，且提供了所述质轻、减震橡塑发泡材料的制备方法，工艺简单，适合工业化生产。
为实现上述目的，本发明采取的解决方案为：
一种质轻、减震橡塑发泡材料，由以下原料组成制得： EVA、丁基橡胶、乙烯-辛烯共聚物、增容剂、发泡剂、交联剂、纳米氧化锌、硬脂酸锌、硬脂酸、快熟剂、无机填料。
进一步的是，各原料的重量份如下：
EVA 30份
丁基橡胶 20 - 80份
乙烯-辛烯共聚物 5 - 15份
增容剂 4 - 8份
发泡剂 1.5 - 3.5份
交联剂 1.0 - 3份
纳米氧化锌 0.5 - 3份
硬脂酸锌 0.5 – 1.5份
硬脂酸 1.0 – 2.5份
快熟剂 2 - 6份
无机填料 5 - 15份。
进一步优选的，各组分按下列重量份配置:
EVA 30份
丁基橡胶 40 - 60份
乙烯-辛烯共聚物 8 - 10份
增容剂 4 - 5份
发泡剂 2.2 - 2.8份
交联剂 1.5 - 1.8份
纳米氧化锌 1.0 - 2.0份
硬脂酸锌 1.0 – 1.5份
硬脂酸 1.8 – 2.3份
快熟剂 2.5 - 3.5份
无机填料 9 - 12份。
进一步的是：丁基橡胶是不饱和度小于2%、拉伸强度大于18MPa的丁基橡胶。
进一步的是：乙烯-辛烯共聚物是熔融温度在80-105度、拉伸强度大于20MPa的乙烯-辛烯共聚物。
进一步的是：增容剂至少包括聚乙烯马来酸酐接枝共聚物、聚乙烯丙烯酸接枝共聚物、乙烯丙烯酸乙酯共聚物中的一种；发泡剂是AC发泡剂或者OBSH发泡剂；交联剂是DCP或者BIBP;快熟剂至少包括TAIC、TMPTMA或顺丁橡胶中的一种；无机填料至少包括白炭黑、碳酸钙或滑石粉中的一种。
一种制备前述质轻、减震橡塑发泡材料的制备方法，包括步骤：
步骤1：制备橡塑粒子，所述橡塑粒子由以下原料制得：EVA、丁基橡胶、乙烯-辛烯共聚物、增容剂、发泡剂、交联剂、纳米氧化锌、硬脂酸锌、硬脂酸、快熟剂、无机填料; 先将除了交联剂、快熟剂以及发泡剂之外的其他原料混合进行密炼，密炼温度控制为 90-100℃，保持 4-6min，然后加入交联剂、快熟剂以及发泡剂，继续密炼升温，出料温度为110-115℃，密炼结束后进行开炼、造粒，得到橡塑粒子。
步骤2：将橡塑粒子放入一次注射机台的料斗，经一次注射成型，控制温度在165-175度，得到质轻、减震橡塑发泡材料。
通过采用前述技术方案，本发明的有益效果是：所述质轻、减震橡塑发泡材料，采用丁基橡胶作为基体橡胶，其分子链上侧甲基十分密集，形成蠕虫链结构，因而具有较高的阻尼系数，又因为玻璃化转变温度附近存在着次级转变，内耗峰既高又宽，是一种较理想的减震阻尼材料，而且耐热性、耐臭氧性、耐候性能好,由于EVA分子链的交联在一定程度上阻碍了分子链上侧甲基的运动，增加了内耗，进而有效提高了丁基橡胶的损耗因子，同时拓宽丁基橡胶阻尼材料的使用范围。因此，相对于现有技术，本发明的质轻、减震橡塑发泡材料具有如下进步特点：
1. 本发明的橡塑发泡材料，保持突出减震性能的同时，具有质轻、耐黄变性能好、耐候性能好等特点。
2. 本发明的橡塑发泡材料，使用环保型材料，且具有很好的抗拉强度和抗撕强度。
3. 本发明的橡塑发泡材料，通过添加增容剂，改性聚乙烯材料，改善了丁基橡胶自粘性与互粘性能较差的问题。
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， 质轻、减震橡塑发泡材料由以下组分按重量份组成：
EVA 5110J 30份、丁基橡胶50份、乙烯-辛烯共聚物8540 10份、乙烯丙烯酸乙酯共聚物5份、AC发泡剂2.3份、交联剂BIBP 1.8份、纳米氧化锌1.6份、硬脂酸锌1.3份、硬脂酸2.0份、快熟剂TAIC 2.5份、碳酸钙10份;
先将除了交联剂、快熟剂以及发泡剂之外的其他原料混合进行密炼，密炼温度控制为 96℃，保持 5min，然后加入交联剂、快熟剂以及发泡剂，继续密炼升温，出料温度为110℃，密炼结束后进行开炼、造粒，得到橡塑粒子。
将橡塑粒子放入一次注射机台的料斗，经一次注射成型，控制温度在170度，得到质轻、减震橡塑发泡材料。
上述制备得到的质轻、减震橡塑发泡材料， 密度0.268 g/cm3、邵氏硬度39、回弹率15%、永久压缩歪度25%，尺寸收缩0.5%，撕裂强度7.2N/mm，延伸率259%，拉伸强度2.9MPa，耐黄变测试5级。
实施例2：
本实施例中，一种质轻、减震橡塑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：
实施例2：EVA E260F 30份、丁基橡胶20份、乙烯-辛烯共聚物8003 10份、聚乙烯马来酸酐接枝共聚物4份、AC发泡剂1.5份、交联剂DCP 1.0份、快熟剂TMPTMA 2份、成型温度控制在168度。
上述制备得到的质轻、减震橡塑发泡材料， 密度0.249 g/cm3、邵氏硬度47、回弹率39%、永久压缩歪度21%，尺寸收缩0.2%，撕裂强度9.5N/mm，延伸率268%，拉伸强度2.4MPa，耐黄变测试5级。
实施例3：
本实施例中，一种质轻、减震橡塑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：
实施例3：EVA 5110J 15份、EVA 7470M 15份、丁基橡胶80份、乙烯丙烯酸乙酯共聚物8份、AC发泡剂3.5份、交联剂BIBP 2.1份、快熟剂TAIC 3.8份、成型温度控制在174-175度。
上述制备得到的质轻、减震橡塑发泡材料， 密度0.225 g/cm3、邵氏硬度43回弹率10%、永久压缩歪度32%，尺寸收缩2.7%，撕裂强度8.3N/mm，延伸率294%，拉伸强度3.4MPa，耐黄变测试4-5级。
实施例4：
本实施例中，一种质轻、减震橡塑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：
实施例4：EVA 7470M 30份、乙烯-辛烯共聚物8445 15份、聚乙烯丙烯酸接枝共聚物4份、发泡剂OBSH 3.5份、交联剂DCP 1.0份、快熟剂TAIC 3.2份、滑石粉15份。
上述制备得到的质轻、减震橡塑发泡材料， 密度0.247 g/cm3、邵氏硬度41、回弹率20%、永久压缩歪度22%，尺寸收缩0.7%，撕裂强度7.6N/mm，延伸率273%，拉伸强度3.1MPa，耐黄变测试4-5级。
实施例5：
本实施例中，一种质轻、减震橡塑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：
实施例5：EVA E180F 30份、丁基橡胶60份、乙烯-辛烯共聚物8003 5份 、快熟剂顺丁橡胶 2份、白炭黑5份、成型温度控制在172-173度。
上述制备得到的质轻、减震橡塑发泡材料， 密度0.252 g/cm3、邵氏硬度37、回弹率16%、永久压缩歪度27%，尺寸收缩0.4%，撕裂强度6.4N/mm，延伸率223%，拉伸强度2.1MPa，耐黄变测试5级。
将上述实施例1 ～ 5 的数据整理后，得到如下表1（注：邵氏硬度按照HG/T2489-93测试，回弹率测试采用GT-7042-RE型冲击弹性试验机，永久压缩歪度按照HG/T 2876-2009测试，尺寸收缩按照ISO 20873：2001测试，撕裂强度按照GB/T 529-2008测试直形试片，延伸率和拉伸强度按照GB/T 528-2009测试，耐黄变测试按照HG/T 3689-2001测试）：
实施例 1 2 3 4 5
密度(g/cm3) 0.268 0.249 0.225 0.247 0.252
邵氏硬度 39 47 43 41 37
回弹率(%) 15 39 10 20 16
永久压缩歪度(%) 25 21 32 22 27
尺寸收缩(%) 0.5 0.2 2.7 0.7 0.4
撕裂强度(N/mm) 7.2 9.5 8.3 7.6 6.4
延伸率(%) 259 268 294 273 223
拉伸强度(MPa) 2.9 2.4 3.4 3.1 2.1
耐黄变测试(A法) 5级 5级 4-5级 4-5级 5级
耐黄变测试(B法) 5级 5级 4-5级 4-5级 5级
表1 ：实施例1～5制备的质轻、减震橡塑发泡材料的性能参数对照表。
综上所述，按照本发明的质轻、减震橡塑发泡材料的制备方法，能够制得质轻、高减震、耐黄变性能好、尺寸稳定性高、并且具有优良抗拉强度和抗撕强度的橡塑发泡材料，可应用于汽车防震材料、各类减震片、鞋底材料等方面的应用，特别适合作为慢跑鞋的中底，可以吸收来自地面的反作用力，很好地保护足部免受伤害，而且制备工艺简单，易实现，适合批量化生产。
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 (6)

1.一种质轻、减震橡塑发泡材料，其特征在于：由以下原料组成制得：
EVA 30份
丁基橡胶 20 - 80份
乙烯-辛烯共聚物 5 - 15份
增容剂 4 - 8份
发泡剂 1.5 - 3.5份
交联剂 1.0 - 3份
纳米氧化锌 0.5 - 3份
硬脂酸锌 0.5 – 1.5份
硬脂酸 1.0 – 2.5份
快熟剂 2 - 6份
无机填料 5 - 15份。
2.根据权利要求1所述一种质轻、减震橡塑发泡材料，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
丁基橡胶 40 - 60份
乙烯-辛烯共聚物 8 - 10份
增容剂 4 - 5份
发泡剂 2.2 - 2.8份
交联剂 1.5 - 1.8份
纳米氧化锌 1.0 - 2.0份
硬脂酸锌 1.0 – 1.5份
硬脂酸 1.8 – 2.3份
快熟剂 2.5 - 3.5份
无机填料 9 - 12份。
3.根据权利要求1所述一种质轻、减震橡塑发泡材料，其特征在于：丁基橡胶是不饱和度小于2%、拉伸强度大于18MPa的丁基橡胶。
4.根据权利要求1所述一种质轻、减震橡塑发泡材料，其特征在于：乙烯-辛烯共聚物是熔融温度在80-105度、拉伸强度大于20MPa的乙烯-辛烯共聚物。
5.根据权利要求1所述一种质轻、减震橡塑发泡材料，其特征在于：增容剂至少包括聚乙烯马来酸酐接枝共聚物、聚乙烯丙烯酸接枝共聚物、乙烯丙烯酸乙酯共聚物中的一种；发泡剂是AC发泡剂或者OBSH发泡剂；交联剂是DCP或者BIBP;快熟剂至少包括TAIC、TMPTMA或顺丁橡胶中的一种；无机填料至少包括白炭黑、碳酸钙或滑石粉中的一种。
6.一种权利要求1-5任一所述质轻、减震橡塑发泡材料的制备方法，其特征在于：包括如下步骤：
步骤1：制备橡塑粒子，所述橡塑粒子由以下原料制得：EVA、丁基橡胶、乙烯-辛烯共聚物、增容剂、发泡剂、交联剂、纳米氧化锌、硬脂酸锌、硬脂酸、快熟剂、无机填料; 先将除了交联剂、快熟剂以及发泡剂之外的其他原料混合进行密炼，密炼温度控制为 90-100℃，保持 4-6min，然后加入交联剂、快熟剂以及发泡剂，继续密炼升温，出料温度为110-115℃，密炼结束后进行开炼、造粒，得到橡塑粒子；
步骤2：将橡塑粒子放入一次注射机台的料斗，经一次注射成型，控制温度在165-175度，得到质轻、减震橡塑发泡材料。
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