CN113337029A - Eva发泡复合材料及eva制品 - Google Patents
Eva发泡复合材料及eva制品 Download PDFInfo
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- CN113337029A CN113337029A CN202010100554.4A CN202010100554A CN113337029A CN 113337029 A CN113337029 A CN 113337029A CN 202010100554 A CN202010100554 A CN 202010100554A CN 113337029 A CN113337029 A CN 113337029A
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Abstract
本发明提供一种EVA发泡复合材料及EVA制品,该EVA发泡复合材料,包括主料,主料包括EVA和含甲壳素的有机钙。有机钙在加工生产的过程中会产生抗生素衍生物(甲壳素),甲壳素具有无毒,低致敏性,生物兼容性和生物降解性的特点。EVA发泡复合材料制得的EVA制品在降解的过程中,有机钙分解会有二个过程,小碎片化及全分解化,有机钙融入塑胶制品经过太阳紫外线照射,会破碎成小碎片,而甲壳素溶入塑胶制品,可触发大量细菌啃食塑胶,加速生物降解,减少塑化原料的使用量。利用该EVA发泡复合材料制得的EVA制品,具有减少塑料量、经焚化后气体及残留物无毒及对环境无害、废弃后可生物降解及远红外线功能的特点。
Description
技术领域
本发明涉及EVA制品技术领域,尤其涉及一种EVA发泡复合材料及EVA制品。
背景技术
塑胶,凭借着它良好的物性、多用途的应用、以及较低的成本,快速取代了传统上金属、木头、玻璃、纸等材料在我们生活中的地位。然而,在带给人类无穷便利的同时,塑胶也造成地球环境前所未有的生态破坏,因此如何减塑、可燃无毒或可降解的生质塑胶已成长为一个重要的课题,生质塑胶的发展还只能算是起步。然而随着各国政策的支持,让这诞生不过二十余年的产业正快速地渗透着各行各业。总的来说,生质塑胶可视为以下三种塑胶类型:
1.生物可分解塑胶(Biodegradable plastics),
2.生物基塑胶(Biobased plastics),
3.含生物基的生物可分解塑胶(Biobased biodegradable plastics)。
其中,生物可分解塑胶的优点是快速分解,虽然初始的物理性能与传统塑料相近,但毕竟制品会随着时间而较快衰退,因此应用上偏向取代一次性、抛弃性的塑胶制品,例如:塑料袋、商品包材、吸管、食饮容器、抛弃式餐具、农业资材等。生物可分解塑胶(Biodegradable plastics)既然强调快速分解,如果把它应用在去做需要耐久性的鞋材,非但无法彰显材料的优势,反而让它变成商品的致命缺点。倘若利用生物可分解塑胶生产环保鞋,但是一段时间没穿,鞋底就会碎裂崩解。因此,其不适合EVA耐久产品。
生物基塑胶的成分中部分或全部成分源自于可再生的生物基质(biomass),例如淀粉、蔗糖、纤维、碳酸钙等。这类塑胶所强调的是生物基质含量高,以及生物基质是属于天然、永续性原料所带来的环境友善优点。但此类塑胶并不具备生物可分解特性,着重在原料的可再生性,不强调可分解性。目前产业上的发展与应用主要是针对有耐久需求的传统塑胶制品来做取代,例如:3C产品机壳、塑胶零件,汽车零组件、饮料瓶等。有的技术采用以聚乙烯(PE)塑胶为主,掺混有机或无机物,如在PE中加入淀粉、纤维或碳酸钙等,这类制品唯一的优点是降低塑化资源的使用,但由于PE本身是不分解的,它并不能透过添加这些有机或无机物就达到可分解、可堆肥的条件,也是不可分解的。也有人在塑胶制品中采用裂解剂(OXO)来实现分解,OXO是一种塑胶添加剂,OXO可以把完整的塑胶给崩解、粉末化,但这反而会引发难以控制的塑胶微粒之祸,造成的污染远甚于随意抛弃。欧盟在2018年初已正式做出结论,呼吁各会员国针对OXO添加剂进行管制或禁用,同时美国也有超过150个企业与团体正在推动禁用。
含生物基的生物可分解塑胶(Biobased biodegradable plastics),既具有可分解特性、又含生物基质,对环境友善,是目前产品所要追求的目标。
EVA主要是乙烯-醋酸乙烯共聚物(也称乙烯-乙酸乙烯共聚物),是有乙烯(E)和乙酸乙烯(VA)共聚而制得,英文名称为:EthyleneVinylAcetate,简称EVA。EVA发泡材料具有优良的化学性能,EVA产品因质地轻盈及价格低廉功能性佳等特点,被广泛应用于制造鞋材、箱包内衬、玩具用材、体育用品材料、建材、以及各类新兴应用例如电子配件和汽车内饰等。由于EVA制品大量在消费市场使用,加上其材料特性,其废弃的塑料,在自然条件下很难降解,进而造成环境污染日益严重的问题。
对此,有必要开发一种EVA发泡复合材料及EVA制品来解决上述技术问题。
发明内容
本发明的目的是提供一种EVA发泡复合材料及EVA制品,利用该EVA发泡复合材料制得的EVA制品,具有减少塑料量、经焚化后气体及残留物无毒及对环境无害、废弃后可生物降解及远红外线功能的特点。
为实现上述目的,本发明提供了一种EVA发泡复合材料,包括主料,所述主料包括EVA和含甲壳素的有机钙。
本发明还提供了一种借助EVA发泡复合材料制得的EVA制品。
与现有技术相比,本发明的EVA发泡复合材料中,因主料包括含甲壳素的有机钙,有机钙在加工生产的过程中会产生抗生素衍生物(甲壳素),甲壳素具有无毒,低致敏性,生物兼容性和生物降解性的特点。EVA发泡复合材料制得的EVA制品在降解的过程中,有机钙分解会有二个过程,小碎片化及全分解化,有机钙融入塑胶制品经过太阳紫外线照射,会破碎成小碎片,而甲壳素溶入塑胶制品,可触发大量细菌啃食塑胶,加速生物降解,减少塑化原料的使用量。同时,有机钙在煅烧后,拥有较高的pH值,具有抑菌、杀菌效果。此外,通过本发明的EVA发泡复合材料制得的EVA制品具远红外线功能,能促进血液循环、蓄热保温。
附图说明
图1为本申请实施例1的EVA发泡复合材料制得的EVA制品的室外3个月分解记录图。
图2为本申请实施例1的EVA发泡复合材料制得的EVA制品与对比例1的EVA制品燃烧后的图。
具体实施方式
本发明提供了一种EVA发泡复合材料,包括主料,所述主料包括EVA和含甲壳素的有机钙。
较佳地,所述EVA中醋酸乙烯的含量为5-40%。
较佳地,所述有机钙选自有机碳酸钙或有机氧化钙中的一种或两种。进一步,含所述甲壳素的所述有机钙由海洋生物的壳或近海养殖业所产生的废弃物制得。优选地,采用含甲壳素的有机碳酸钙。由于本申请的含甲壳素的有机碳酸钙,经过煅烧后,它转化为pH值超过12的氧化钙,是一种非常强的碱性物质,有机碳酸钙粉的恒定值比氢氧化钠的高,杀死细菌更强,而且粉末越细,抗生素强度越强。例如,2×10-4k的氢氧化钠抗生素的恒定值远远低于煅烧后的有机碳酸钙粉为4×10-3k,可见煅烧后的有机碳酸钙粉不仅具有强碱性,还具有抑菌作用。
一实施例中,利用浸泡法去除近海养殖业所产生的废弃物体上的有机物,然后采用压碎机压碎,再过筛,经105℃烘干24小时,制得所述有机氧化钙,外观呈乳黄色的片状。也就是说,通过该方法制备的有机氧化钙是已包含甲壳素的有机氧化钙,有机碳酸钙亦是如此。进一步,过筛控制有机氧化钙的粒径为9.5mm。
具体地,所述海洋生物的壳选自贝壳、蟹壳、虾壳或牡蛎壳中的至少一种。较佳地,所述主料还包括PE、POE(聚烯烃弹性体)或EPDM(三元乙丙橡胶)中的至少一种。PE可为但不限于LDPE、LLDPE、HDPE。优选地,主料的制备方法包括:将PE与含甲壳素的有机钙先煅烧成复合材料,然后与EVA、POE共混,可提高EVA制品的延伸性和撕裂度。
较佳地,所述EVA发泡复合材料还包括副料,所述副料选自填充剂、发泡剂、架桥剂、发泡促进剂、润滑剂和色粒中的至少一种。具体地,填充剂选为但不限于滑石粉、轻质碳酸钙、重质碳酸钙;发泡剂选为但不限于偶氮二甲酰胺(AC-6000);架桥剂选为但不限于1,4-双叔丁基过氧异丙基苯、三烯丙基异氰脲酸酯;发泡促进剂选为但不限于氧化锌、硬脂酸;润滑剂选为但不限于硬脂酸锌;色粒根据具体情况加入。
较佳地,按重量百分数计,EVA发泡复合材料,包括80-120份主料和10-30份副料,所述主料包括40-80份EVA、10-40份含甲壳素的有机钙、1-10份PE、2-15份POE;所述副料选自10-30份填充剂、1-5份发泡剂、0.1-2份架桥剂、0.1-5份发泡促进剂、0.1-2份润滑剂和0-10份色粒中的至少一种。例如,EVA的用量可为但不限于40份、45份、50份、55份、60份、65份、70份、75份、80份;含甲壳素的有机钙的用量可为但不限于10份、15份、20份、25份、30份、35份、40份;PE的用量可为但不限于1份、2份、4份、6份、8份、10份;POE的用量可为但不限于2份、4份、6份、8份、10份、12份、15份;填充剂的用量可为但不限于10份、15份、20份、25份、30份;发泡剂的用量可为但不限于1份、2份、3份、4份、5份;架桥剂的用量可为但不限于0.1份、0.4份、0.8份、1.2份、1.6份、2份;发泡促进剂的用量可为但不限于0.1份、0.2份、0.3份、0.4份、0.5份;润滑剂的用量可为但不限于0.1份、0.5份、1份、1.5份、2份;色粒的用量可为但不限于0份、1份、5份、8份、10份。
本发明还提供一种由上述的EVA发泡复合材料制得的EVA制品。具体地,所述EVA制品为鞋材。
下面通过具体实施方式来进一步说明本发明的技术方案,但不构成对本发明的任何限制。
实施例1
本实施例的EVA发泡复合材料,按重量份数计,包括:
其中,EVA制品的制备方法如下:
(1)将配方量的EVA、POE、LDPE、有机氧化钙、滑石粉、硬脂酸、硬脂酸锌、氧化锌倒入混合槽,放下加压盖及防尘盖,加冷却水开始密炼,利拿机倒料,前料缸温度为80±5℃,当材料温度升至95±5℃时,加入AC-6000和1,4-双叔丁基过氧异丙基苯继续混炼,蜜炼温度为100-120℃,密炼时间为10~12分钟,得到混合物;
(2)将得到的混合物采用滚轮机打薄,然后采用造粒机进行造粒得到EVA粒子,采用EVA粒子进行发泡,得到EVA制品。
其中,利用浸泡法去除近海养殖业所产生的废弃物体上的有机物,然后采用压碎机压碎,再过筛得到粒径为9.5mm,经105℃烘干24小时,制得含甲壳素的有机氧化钙,外观呈乳黄色的片状。
1.1对实施例1制得的EVA粒子进行物性检测,物性检测结果如表1:
表1EVA粒子物性检测表
检测项目 | 单位 | 检测方法 | 结果 |
MI(190oC@2.16kg) | g/10min | ASTM D1238 | 2.07 |
密度 | g/cm<sup>3</sup> | ASTM D792 | 1.56 |
硬度 | Shore A | ASTM D2240 | 80±2 |
抗拉强度 | kg/cm<sup>2</sup> | ASTM D412 | 38 |
延伸率 | % | ASTM D412 | 820 |
撕裂强度 | kg/cm | ASTM D624 | 23 |
软化点 | ℃ | ASTM D1525 | 95-100 |
1.2对实施例1制备的EVA制品制作样品进行燃烧后的燃烧毒性气体检测(燃烧测试是燃烧4分钟产生的毒性气体含量),制备样品1-3,检测后取平均值,气体检测结果如表2:
表2燃烧毒性气体检测结果
1.3生物降解性能测试
由于本申请的EVA制品中含有有机碳酸钙或有机氧化钙。将实施例1的EVA制品制备出薄膜样品进行生物降解性能测试,其中,室外自然降解检测结果如图1所示。其中,图1中NO.1是对照组,NO.2-NO.4分别指1-3个月的分解图。从图1可知,该薄膜样品,在室外可在3~6个月内完全分解。利用ISO 14855-1:5005测试标准进行降解测试,检测结果如表3所示。从表3的ISO 14855-1检验数据可知,薄膜样品在45天的降解率为35.9%,而在127天的降解率可高达80.6%。
表3生物降解程度测试结果
1.4远红外线功能测试
将实施例1制备的EVA制品做成样品,采用远红外线频仪进行放射率测试,放射率越高越好(最佳值为100%),平均放射率在80%以上可称为高效率,测试结果如表4所示。由表4可知,实施例1制备的EVA制品远红外线放射率高达91%。
表4远红外线放射率测试结果
测试项目 | 测试条件 | 测试结果 |
远红外放射率 | 60℃ | 91.0% |
实施例2
本实施例的EVA发泡复合材料,按重量份数计,包括:
本实施例的EVA制品的制备方法包括:
(1)制备主料,将配方量的LDPE与含甲壳素的有机氧化钙先煅烧成复合材料,然后与EVA、POE共混,制得主料,将配方量的主料、滑石粉、硬脂酸、硬脂酸锌、氧化锌倒入混合槽,放下加压盖及防尘盖,加冷却水开始密炼,利拿机倒料前料缸温度为80±5℃,当材料温度升至95±5℃时,加入AC-6000和1,4-双叔丁基过氧异丙基苯继续混炼,蜜炼温度为100-120℃,密炼时间为10~12分钟,得到混合物;
(2)将得到的混合物采用滚轮机打薄,然后采用造粒机进行造粒得到EVA粒子,采用EVA粒子进行发泡,得到EVA制品。
实施例3
本实施例的EVA发泡复合材料,按重量份数计,包括:
本实施例的EVA制品的制备方法与实施例1相同,在此不详细阐述。
对比例1
本对比例的EVA发泡复合材料与实施例1基本相同,不同在于:实施例1中,主料采用有机氧化钙,而对比例1采用普通的市售氧化钙,其余均相同。
对实施例1和对比例1制得的EVA制品进行燃烧,对燃烧后的灰烬观察外观,两制品燃烧后的情况如图2所示。由图2可知,实施例1制得的EVA制品(图中B所示)燃烧后,呈现白色乳化,对比例1制得的EVA制品(图中A所示)燃烧后,仍有焦油残留。
由此可见,利用该EVA发泡复合材料制得的EVA制品,具有减少塑料量、经焚化后气体及残留物无毒及对环境无害、废弃后可生物降解及远红外线功能的特点。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明做了详细的说明,但本发明并不局限于以上揭示的实施例,而应当涵盖各种根据本发明的本质进行的修改、等效组合。
Claims (10)
1.一种EVA发泡复合材料,包括主料,所述主料包括EVA,其特征在于,所述主料还包括含甲壳素的有机钙。
2.如权利要求1所述的EVA发泡复合材料,其特征在于,所述EVA中醋酸乙烯的含量为5-40%。
3.如权利要求1所述的EVA发泡复合材料,其特征在于,所述有机钙选自有机碳酸钙或有机氧化钙中的一种或两种。
4.如权利要求1所述的EVA发泡复合材料,其特征在于,含甲壳素的所述有机钙由海洋生物的壳或近海养殖业所产生的废弃物制得。
5.如权利要求1所述的EVA发泡复合材料,其特征在于,所述海洋生物的壳选自贝壳、蟹壳、虾壳或牡蛎壳中的至少一种。
6.如权利要求3所述的EVA发泡复合材料,其特征在于,利用浸泡法去除近海养殖业所产生的废弃物体上的有机物,然后采用压碎机压碎,再过筛,经105℃烘干24小时,制得所述有机氧化钙。
7.如权利要求1所述的EVA发泡复合材料,其特征在于,所述主料还包括PE和POE,所述主料的制备方法包括:将所述PE与含甲壳素的所述有机钙先煅烧成复合材料,然后与所述EVA和所述POE共混。
8.如权利要求1所述的EVA发泡复合材料,其特征在于,所述EVA发泡复合材料还包括副料,所述副料选自填充剂、发泡剂、架桥剂、发泡促进剂、润滑剂和色粒中的至少一种。
9.一种EVA制品,其特征在于,由权利要求1-8任一项所述的EVA发泡复合材料制得。
10.如权利要求9所述的EVA制品,其特征在于,所述EVA制品为鞋材。
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