CN106977871B - 微波处理竹炭改性聚烯烃复合材料及其制备方法 - Google Patents
微波处理竹炭改性聚烯烃复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种微波处理竹炭改性聚烯烃复合材料及其制备方法。复合材料包括以下质量份数的组份：活化竹炭5～40份，改性聚烯烃55～90份，润滑剂1～5份，光稳定剂0.1～1.0份，抗氧剂0.1～1.0份。活化竹炭采用竹炭经过碱液浸渍、微波活化、酸洗后制得，改性聚烯烃采用热塑性塑料和复合改性单体在引发剂作用下聚合制得。本发明制得的复合材料比竹炭拥有更优异的导电性能和吸附性能，其力学性能以及热加工性能均比竹炭、聚烯烃塑料更为优良。因此，利用活性炭与改性聚烯烃复合材料制备新型环保材料能够兼具质优和价廉的特点。
Description
技术领域
本发明属于复合材料领域，特别涉及一种微波处理竹炭改性聚烯烃复合材料及其制备方法。
背景技术
竹炭是竹材热解炭化后的产物由于竹炭的特殊孔径结构和具有特殊的内含物，而活性炭(activated carbon,简称AC)是利用竹炭、木炭等为原料，经炭化活化(物理活化或化学活化以及两者相结合)而得到的产品。活化的目的是利用蒸汽或化学物质来清除炭化过程中，积蓄在孔隙结构中的焦油物质及裂解产物及与炭原子氧化，扩大炭化料孔隙及创造微孔以提高孔洞体积或比表面积，产生高吸附量的活性炭。
竹炭活化后即活性炭与竹炭相比有以下优点：(1)经活化处理后竹炭材料的孔变大、变深,孔的通透性增强；(2)经活化后竹炭表面结构有了较大的修饰,增加了较多的表面化学官能团，而提高了竹炭的比表面积和吸附性能；(3)经活化处理后竹炭拥有更加优越的导电性能。
因此活性炭具有良好的物理化学性能和机械加工性能。在材料工业中，可作为新型的炭吸附材料和环境保护材料，活性竹炭的来源广泛，且价格便宜，以竹代木，依靠科技创新拓展竹材应用领域，是缓解森林木材资源贫乏、改善生态环境的有效措施。并且开发活性竹炭产品可以充分利用老龄竹和竹材板的加工剩余物，提高竹材的利用率，增加竹材的附加值，提高竹产业的经济效益。经过特殊工艺生产的竹炭具有导电特性，利用这一特性能够开发出以竹炭为原料的功能型复合新材料。因而拓展活性炭利用途径以及开发以竹炭为原料的新产品已刻不容缓。
已有众多学者研究了竹炭的优良性能，在竹炭复合材料方面也有学者进行了相关研究，但是作为如此优越性能的活性炭的应用领域却很狭窄，极少有针对用途广泛且价格便宜之热塑性塑料与活性炭的复合材料的研究。
因此，用活性炭与改性聚烯烃制备新型复合材料的研究顺应了21世纪材料发展与环境相协调的趋势。不仅提升了拓展传统的竹材的应用领域，还提升了产业附加值，对促进相关行业发展具有积极的意义。
发明内容
本发明要解决的技术问题是采用新型材料活性竹炭与改性聚烯烃制备复合材料，提供一种具有良好吸附性能且在一定条件下具有导电性能的新型环保复合材料，并提供上述复合材料的制备方法。
为了实现上述问题，本发明采用以下技术方案：一种微波活化竹炭改性聚烯烃复合材料，包括以下质量份数的组份：活化竹炭5～40份，改性聚烯烃55～90份，润滑剂1～5份，光稳定剂0.1～1.0份，抗氧剂0.1～1.0份。
进一步的，活化竹炭采用竹炭经过碱液浸渍、微波活化、酸洗后制得。
进一步的，改性聚烯烃采用热塑性塑料和复合改性单体在引发剂作用下聚合制得。
进一步的，润滑剂为硬脂酸、乙撑双硬脂酰胺、硬脂酸甲酯、硬脂酸丁酯、硬脂酸钙、硬脂酸锌、月桂酸铅、液体石蜡、固体石蜡、聚乙烯蜡或氧化聚乙烯蜡中的至少一种。
进一步的，光稳定剂为光稳定剂UV-531、光稳定剂UV-1084或光稳定剂UV-774中的至少一种。
进一步的，抗氧剂为抗氧剂BHT、抗氧剂1010、抗氧剂DLTP、抗氧剂330、抗氧剂SP或抗氧剂1084中的至少一种。
一种微波活化竹炭改性聚烯烃复合材料的制备方法，包括以下步骤：
(1)竹炭的微波活化：竹炭经过筛后再碱液浸渍1～36h，然后微波活化1～30min后，取出酸洗至中性，再用水洗，烘干，制得微波活化的活性竹炭；
(2)改性聚烯烃的制备：取100质量份热塑性塑料，将1～5质量份的复合改性单体和0.1～0.5质量份的引发剂加入至热塑性塑料中，混匀，将混合料加入挤出机于170～190℃下挤出造粒，得到改性塑料；
(3)复合材料的制备：将活化竹炭在80℃下烘干2h，将活性炭、改性聚烯烃以及润滑剂、光稳定剂、抗氧剂加入高速混合机混合均匀制得混合料；将混合料加入转矩流变仪混合塑炼均匀，制得预混料；将该预混料置入低噪音塑料粉碎机进行破碎，最后加入注塑成型机进行加工成型。
进一步的，碱液为氢氧化钠、氢氧化钾、氢氧化钙或氢氧化钡中的至少一种，质量浓度为5％～50％。
进一步的，热塑性塑料为聚乙烯、聚丙烯、ABS或聚苯乙烯中的至少一种；所述复合改性单体为马来酸酐或马来酸酐与苯乙烯、丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、丙烯腈中至少一种的混合。
进一步的，引发剂为过氧化异丙苯、过氧化苯甲酰、二叔丁基过氧化氢或叔丁基过氧化氢中的至少一种。
本发明制得的复合材料比竹炭拥有更优异的导电性能和吸附性能，其力学性能以及热加工性能均比竹炭、聚烯烃塑料更为优良。因此，利用活性炭与改性聚烯烃复合材料制备新型环保材料能够兼具质优和价廉(充分利用废旧塑料)的特点。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1
首先，按配方和步骤制备微波活化竹性炭。其中，工艺如下：
KOH质量分数：15％
浸渍时间：24h
活化时间：6min
其中配制15％氢氧化钾水溶液，将竹炭浸渍24h，微波活化6min后，取出用稀盐酸溶液洗至中性，再用水洗，烘干，制得微波活化的活性竹炭。
接下来，改性聚烯烃塑料制备配方如下(按质量份)：
改性聚烯烃的制备过程如下：
将PE加入拌料机搅拌，在搅拌时慢慢加入马来酸酐、DCP和苯乙烯搅匀得到混合料。将混合料加入同向平行双螺杆挤出机进行反应性挤出，接枝反应温度为175～185℃，制得接枝改性PE(即改性塑料)。
最后，活性炭改性聚烯烃复合材料的制备
微波活化竹炭改性聚烯烃复合材料原料制备得到：
具体制备过程如下：
将活化竹炭在80℃下烘干2h，按配方量称取适量的活性炭、改性聚乙烯以及其它加工助剂，加入高速混合机混合均匀(800～1000r/min，5～10min)，制得混合料；将混合料加入转矩流变仪混合塑炼均匀约7min，制得预混料；将该预混料置入低噪音塑料粉碎机进行破碎。最后加入注塑成型机进行加工成型。其中，流变仪三区温度为：150～160℃，塑料注塑成型机料筒温度设定分别为：150℃、155℃、150℃。
将本发明制得的复合材料成品测定拉伸强度、弯曲强度、无缺口简支梁冲击强度以及维卡软化点温度，测定结果见表1。
表1：复合材料性能测定结果
| 测定的项目名称 | 本发明复合材料 | 竹炭复合材料 | 纯PE树脂 |
| 拉伸强度/MPa | 27.5 | 21.5 | 19.7 |
| 弯曲强度/MPa | 26.3 | 25.1 | 19 |
| 维卡软化点温度/℃ | 135.2 | 133.1 | 128.5 |
同时，若能测定如上制得的复合材料成品的导电性能和吸附有害气体的性能为佳。
实施例2～5
实施例2～5的制备过程与实施例1相同，所不同的是配方。实施例2～5的配方见表2至表4。
表2：微波活化竹炭制备工艺
| 实施例 | 碱性水溶液/％ | 浸渍时间/h | 活化时间/min |
| 2 | KOH：15 | 12 | 4 |
| 3 | KOH：25 | 24 | 8 |
| 4 | NaOH：15 | 8 | 4 |
| 5 | NaOH：20 | 12 | 8 |
表3：改性聚烯烃的配方
| 实施例 | 热塑性塑料重/份 | 马来酸酐/份 | 苯乙烯/份 | DCP/份 |
| 2 | PE：100 | 2 | 1 | 0.3 |
| 3 | 回收PE：100 | 2 | 0 | 0.2 |
| 4 | PE：85/PP：15 | 3 | 1.5 | 0.3 |
| 5 | ABS：100 | 2 | 1 | 0.25 |
表4：微波活化竹炭改性聚烯烃复合材料制备配方
以上所述，仅是本发明的较佳实施例而已，并非对本发明做任何形式的限制。凡是依据本发明的技术和方法实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明的技术和方法方案的范围内。
Claims (5)
1.一种微波活化竹炭改性聚烯烃复合材料，其特征在于：包括以下质量份数的组份：活化竹炭5~40份，改性聚烯烃55~90份，润滑剂1~5份，光稳定剂0.1~1.0份，抗氧剂0.1~1.0份；
所述活化竹炭采用竹炭经过碱液浸渍、微波活化、酸洗后制得；
所述改性聚烯烃采用热塑性塑料和复合改性单体在引发剂作用下聚合制得；
所述润滑剂为硬脂酸、乙撑双硬脂酰胺、硬脂酸甲酯、硬脂酸丁酯、硬脂酸钙、硬脂酸锌、月桂酸铅、液体石蜡、固体石蜡、聚乙烯蜡或氧化聚乙烯蜡中的至少一种；
所述光稳定剂为光稳定剂UV-531、光稳定剂UV-1084或光稳定剂UV-774中的至少一种；
所述抗氧剂为抗氧剂BHT、抗氧剂1010、抗氧剂DLTP、抗氧剂330、抗氧剂SP或抗氧剂1084中的至少一种；
所述微波活化竹炭改性聚烯烃复合材料采用以下步骤制备而成：
（1）竹炭的微波活化：竹炭经过筛后再碱液浸渍1~36h，然后微波活化1~30min后，取出酸洗至中性，再用水洗，烘干，制得微波活化的活性竹炭；
（2）改性聚烯烃的制备：取100质量份热塑性塑料，将1~5质量份的复合改性单体和0.1~0.5质量份的引发剂加入至热塑性塑料中，混匀，将混合料加入挤出机于170~190℃下挤出造粒，得到改性聚烯烃；
（3）复合材料的制备：将活化竹炭在80℃下烘干2h，将活性炭、改性聚烯烃以及润滑剂、光稳定剂、抗氧剂加入高速混合机混合均匀制得混合料；将混合料加入转矩流变仪混合塑炼均匀，制得预混料；将该预混料置入低噪音塑料粉碎机进行破碎，最后加入注塑成型机进行加工成型。
2.一种微波活化竹炭改性聚烯烃复合材料的制备方法，其特征在于包括以下步骤：
（1）竹炭的微波活化：竹炭经过筛后再碱液浸渍1~36h，然后微波活化1~30min后，取出酸洗至中性，再用水洗，烘干，制得微波活化的活性竹炭；
（2）改性聚烯烃的制备：取100质量份热塑性塑料，将1~5质量份的复合改性单体和0.1~0.5质量份的引发剂加入至热塑性塑料中，混匀，将混合料加入挤出机于170~190℃下挤出造粒，得到改性聚烯烃；
（3）复合材料的制备：将活化竹炭在80℃下烘干2h，将活性炭、改性聚烯烃以及润滑剂、光稳定剂、抗氧剂加入高速混合机混合均匀制得混合料；将混合料加入转矩流变仪混合塑炼均匀，制得预混料；将该预混料置入低噪音塑料粉碎机进行破碎，最后加入注塑成型机进行加工成型。
3.根据权利要2所述的制备方法，其特征在于：所述碱液为氢氧化钠、氢氧化钾、氢氧化钙或氢氧化钡中的至少一种，质量浓度为5%~50%。
4.根据权利要求2所述的制备方法，其特征在于：所述热塑性塑料为聚乙烯、聚丙烯中的至少一种；所述复合改性单体为马来酸酐与苯乙烯、丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、丙烯腈中至少两种的混合。
5.根据权利要求2所述的制备方法，其特征在于：所述引发剂为过氧化异丙苯、过氧化苯甲酰、二叔丁基过氧化氢或叔丁基过氧化氢中的至少一种。
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