CN107351470A - 一种阻燃麻纤维/热塑性聚合物复合板及其制备方法 - Google Patents

一种阻燃麻纤维/热塑性聚合物复合板及其制备方法 Download PDF

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CN107351470A
CN107351470A CN201710608102.5A CN201710608102A CN107351470A CN 107351470 A CN107351470 A CN 107351470A CN 201710608102 A CN201710608102 A CN 201710608102A CN 107351470 A CN107351470 A CN 107351470A
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thermoplastic polymer
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盛旭敏
吴承操
谭伟文
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Chongqing University of Technology
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Abstract

本发明公开了一种阻燃麻纤维/热塑性聚合物复合板，为夹芯结构，由上、下表层和中间芯层热压构成；所述上、下表层为回收碳纤维/热塑性聚合物复合材料片料，中间芯层为麻纤维/热塑性聚合物复合材料的片料。本发明明显减小复合材料燃烧时火焰的蔓延距离，较之未添加碳纤维的复合材料阻燃性提高了34.6%。且冲击强度、拉伸强度优于未添加碳纤维的复合材料的复合材料板。通过在表层加入氢氧化铝，能进一步的提高阻燃性。该复合材料兼顾阻燃性能及力学性能，环保，可修复，降低成本，提高了经济效益。在汽车行业中有广阔的应用前景。

Description

一种阻燃麻纤维/热塑性聚合物复合板及其制备方法
技术领域
本发明涉及阻燃板材，具体涉及一种阻燃麻纤维/热塑性聚合物复合板，属于复合材料技术领域。
背景技术
为满足汽车零部件轻量化、环保化的需求，植物纤维/热塑性聚合物复合材料在汽车领域的应用比例逐年增加。以麻纤维、木纤维为代表的植物纤维具有密度小、可生物分解等优点，能够加速复合材料废弃物的降解；热塑性聚合物的可回收性也明显优于热固性聚合物基复合材料，因此植物纤维/热塑性聚合物复合材料具有质轻、环保的优势。车用聚合物基复合材料往往需要具有一定的阻燃性，而植物纤维及热塑性聚合物均属于易燃物质，植物纤维/热塑性聚合物复合材料需要经过阻燃改性才能适用于上述领域。对材料进行阻燃改性的常用方法是添加阻燃剂。传统的卤系阻燃剂虽然具有添加量低、阻燃效果明显、价格适中等优点，但在燃烧时会放出大量腐蚀性气体和有毒烟雾，不符合环保要求。而氢氧化铝、氢氧化镁、硼酸锌、聚磷酸铵等无卤阻燃剂虽然符合环保要求，但其添加量大，对复合材料的力学性能有较大的负面影响。
碳纤维(长纤)增强热固性聚合物基复合材料由于具有耐腐蚀、抗疲劳、高比强度和比模量、可设计性好等优异性能，广泛应用于航空航天、汽车等领域。但采用这类复合材料制备的零部件不能修复只能替代，因此容易产生大量废弃物。热固性碳纤维(长纤)复合材料废弃物经机械碾压法、化学法处理后可以分离出长短不一的碳纤维(短纤)。与碳纤维(长纤)相比，这些回收碳纤维(短纤)的增强作用大幅削弱，目前主要用于改善热塑性聚合物的模量，应用范围狭窄。
发明内容
针对现有技术存在的上述不足，本发明的目的在于提供一种阻燃麻纤维/热塑性聚合物复合板，解决目前阻燃板材环保要求和力学性能差等问题。
本发明还提供所述阻燃麻纤维/热塑性聚合物复合板的制备方法，进一步提高回收碳纤维的应用价值。
为实现上述目的，本发明采用如下技术方案：一种阻燃麻纤维/热塑性聚合物复合板，为夹芯结构，由上、下表层和中间芯层热压构成；所述上、下表层为回收碳纤维/热塑性聚合物复合材料片料，中间芯层为麻纤维/热塑性聚合物复合材料的片料。
所述回收碳纤维/热塑性聚合物复合材料片料由碳纤维和热塑性聚合物按重量比为 5-7.5：50配料在双辊开炼机中混炼而成；所述麻纤维/热塑性聚合物复合材料的片料由麻纤维和热塑性聚合物按重量比为10-15：50配料混炼而成。所述热塑性聚合物为低密度聚乙烯。
进一步，所述回收碳纤维/热塑性聚合物复合材料片料由碳纤维、热塑性聚合物和氢氧化铝按重量比为5：50：20配料在双辊开炼机中混炼而成；所述麻纤维/热塑性聚合物复合材料的片料由麻纤维、热塑性聚合物按重量比为10：50配料混炼而成。
本发明还提供一种阻燃麻纤维/热塑性聚合物复合板的制备方法，包括如下步骤：
1)将麻纤维用质量浓度2％的氢氧化钠水溶液浸泡24h后洗净干燥备用；
2)将麻纤维和热塑性聚合物在双辊开炼机中混炼成复合材料片料得片料I，其组份麻纤维和热塑性聚合物按重量比为10-15：50；
3)将碳纤维和热塑性聚合物在双辊开炼机中混炼成复合材料片料得片料II，其组份碳纤维和热塑性聚合物按重量比为5-7.5：50；
4)将片料I、片料II按模具尺寸裁剪，将片料II放在两片料I之间，使其叠合成“片料II-片料I-片料II”的复合结构，然后将其放入压制模，置于平板硫化机中热压成型，热压温度为135-140℃，热压时间为8-10min。
进一步，所述步骤2)和3)中混炼的前辊温度为115-120℃，后辊温度为110-115℃，混炼时间为10-15min。
相比现有技术，本发明具有如下有益效果：
1、兼顾阻燃性能及力学性能：本发明以回收碳纤维/热塑性聚合物片料作为复合材料的上、下表层，以麻纤维/热塑性聚合物片料为中间芯层，可以明显减小复合材料燃烧时火焰的蔓延距离，较之未添加碳纤维的复合材料阻燃性提高了34.6％。且冲击强度、拉伸强度优于未添加碳纤维的复合材料的复合材料板。其中冲击强度高达16.48KJ/㎡，拉伸强度 9.15MPa。通过在表层加入氢氧化铝，能进一步的提高该复合材料的阻燃性约28.3％，所以本发明制备的复合材料兼顾力学性能、阻燃性、环保和修复等特点，在汽车行业中有广阔的应用前景。
2、工艺简便、效果显著：本发明将回收碳纤维与二分之一用量的热塑性聚合物混合成片后作为表层材料，与麻纤维/热塑性聚合物片料进行叠合压制。这样不仅使回收碳纤维的阻燃作用得到最大程度的发挥，也解决了热塑性聚合物、麻纤维、阻燃剂混料困难的问题，具有工艺过程简化，操作简单的特点。
3、拓宽回收碳纤维应用范围：本发明将回收碳纤维用于麻纤维/热塑性聚合物复合材料阻燃改性，为回收碳纤维的应用提供了新的途径，扩大了其应用范围，降低成本，提高经济效益。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明。
一、本发明阻燃麻纤维/热塑性聚合物复合板
一种阻燃麻纤维/热塑性聚合物复合板为夹芯结构，由上、下表层和中间芯层热压构成；所述上、下表层为回收碳纤维/热塑性聚合物复合材料片料，中间芯层为麻纤维/热塑性聚合物复合材料的片料。所述回收碳纤维/热塑性聚合物复合材料片料由碳纤维和热塑性聚合物按重量比为5-7.5：50配料在双辊开炼机中混炼而成；所述麻纤维/热塑性聚合物复合材料的片料由麻纤维和热塑性聚合物按重量比为10-15：50配料混炼而成。其重量配比在上述范围内均可实现，并且效果相当。
所述碳纤维为热固性碳纤维(长纤)复合材料的废弃物经机械碾压法、化学法处理后分离的碳纤维(短纤)；所述的麻纤维为苎麻纤维、红麻纤维、亚麻纤维、剑麻纤维和洋麻纤维中的一种。
二、本发明阻燃麻纤维/热塑性聚合物复合板的制备方法
制备方法中工艺参数在权利要求范围内均可实现，并且效果相当，不受实施例的限制。
实施例1
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
实施例2
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料II 放在2个片料I之间，使其叠合成“片料I-片料II-片料I”的复合结构，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
实施例3
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维、5g回收碳纤维、100g低密度聚乙烯在双辊开炼机中混炼成复合材料片料，其中双辊开炼机前辊为115℃，后辊温度为110℃。将复合材料片料按模具尺寸裁剪后，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
实施例4
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 15g上述的苎麻纤维、100g低密度聚乙烯在双辊开炼机中混炼成复合材料片料，其中双辊开炼机前辊为115℃，后辊温度为110℃。将复合材料片料按模具尺寸裁剪后，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
将实施例1-4制得的三种不同的复合材料的阻燃性及力学性能进行对比，如表1所示。
表1
从表1可以看出，将碳纤维直接与麻纤维、热塑性聚合物直接混炼后，复合材料的阻燃性较之未添加碳纤维的复合材料提高了12.6％；而以回收碳纤维/热塑性聚合物片料作为表层，麻纤维/热塑性聚合物片料作为芯层的复合结构最有利于提高复合材料的阻燃性，具有这种结构的复合材料的阻燃性较之未添加碳纤维的复合材料提高了34.6％，且冲击强度、拉伸强度也优于未添加碳纤维的复合材料的复合材料板。
实施例5
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维、50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维、20g氢氧化铝(无卤阻燃剂)和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II 按模具尺寸裁剪后，再将片料I放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
实施例6
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维、20g氢氧化铝(无卤阻燃剂)和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维、50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料 II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成板(热压温度为140℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
实施例7
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维、10g氢氧化铝(无卤阻燃剂)和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维、10g氢氧化铝(无卤阻燃剂)和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为 110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成板(热压温度为140 ℃，热压时间为10min)并制成样条，测试其力学性能并记录样条点燃离火后1min内火焰蔓延的距离。
将实施例5-7制得的三种不同的复合材料的阻燃性及力学性能进行对比，如表2所示。
表2
从表2可以看出，回收碳纤维与一定量的氢氧化铝(无卤阻燃剂)配合使用，可以使复合材料的阻燃性进一步下降，不同的氢氧化铝添加方式对应不同的下降幅度。其中将氢氧化铝全部加入由回收碳纤维及热塑性聚合物构成的表层，最有助于发挥氢氧化铝的阻燃作用。采用将氢氧化铝全部加入由回收碳纤维及热塑性聚合物构成的表层添加方式后，复合材料的阻燃性进一步提高了28.3％，但其冲击强度、拉伸强度均低于未添加氢氧化铝的复合材料。
实施例8
将苎麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成型(热压温度为140℃，热压时间为10min)。
实施例9
将红麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成型(热压温度为140℃，热压时间为10min)。
实施例10
将亚麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成型(热压温度为140℃，热压时间为10min)。
实施例11
将剑麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成型(热压温度为140℃，热压时间为10min)。
实施例12
将洋麻纤维用浓度为2％的氢氧化钠水溶液浸泡24h，再用去离子水洗净、干燥。称取 10g上述的苎麻纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料I，其中双辊开炼机前辊为115℃，后辊温度为110℃；称取5g回收碳纤维和50g低密度聚乙烯，再放入双辊开炼机中混炼成复合材料片料即片料II。其中双辊开炼机的前辊温度为115℃，后辊温度为110℃；将片料I、片料II按模具尺寸裁剪后，再将片料I 放在2个片料II之间，使其叠合成“片料II-片料I-片料II”的复合结构，置于平板硫化机中热压成型(热压温度为140℃，热压时间为10min)。
实施例8-12说明本发明涉及的麻纤维包括但不限于苎麻、红麻、亚麻、纤维、剑麻和洋麻等植物纤维，用于制备的复合材料板在冲击强度、拉伸强度和断裂伸长率等力学性能相当。
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (7)

1.一种阻燃麻纤维/热塑性聚合物复合板，其特征在于，为夹芯结构，由上、下表层和中间芯层热压构成；所述上、下表层为回收碳纤维/热塑性聚合物复合材料片料，中间芯层为麻纤维/热塑性聚合物复合材料的片料。
2.根据权利要求1所述阻燃麻纤维/热塑性聚合物复合板，其特征在于，所述回收碳纤维/热塑性聚合物复合材料片料由碳纤维和热塑性聚合物按重量比为5-7.5：50配料在双辊开炼机中混炼而成；所述麻纤维/热塑性聚合物复合材料的片料由麻纤维和热塑性聚合物按重量比为10-15：50配料混炼而成。
3.根据权利要求1所述阻燃麻纤维/热塑性聚合物复合板，其特征在于，所述碳纤维为热固性碳纤维（长纤）复合材料的废弃物经机械碾压法、化学法处理后分离的短纤碳纤维；所述的麻纤维为苎麻纤维、红麻纤维、亚麻纤维、剑麻纤维和洋麻纤维中的一种。
4.根据权利要求1所述阻燃麻纤维/热塑性聚合物复合板，其特征在于，所述热塑性聚合物为低密度聚乙烯。
5.根据权利要求2所述阻燃麻纤维/热塑性聚合物复合板，其特征在于，所述回收碳纤维/热塑性聚合物复合材料片料由碳纤维、热塑性聚合物和氢氧化铝按重量比为5：50：20配料在双辊开炼机中混炼而成；所述麻纤维/热塑性聚合物复合材料的片料由麻纤维、热塑性聚合物按重量比为10：50配料混炼而成。
6.一种阻燃麻纤维/热塑性聚合物复合板的制备方法，其特征在于，包括如下步骤：
1）将麻纤维用质量浓度2%的氢氧化钠水溶液浸泡24h后洗净干燥备用；
2）将麻纤维和热塑性聚合物在双辊开炼机中混炼成复合材料片料得片料I，其组份麻纤维和热塑性聚合物按重量比为10-15：50；
3）将碳纤维和热塑性聚合物在双辊开炼机中混炼成复合材料片料得片料II， 其组份碳纤维和热塑性聚合物按重量比为5-7.5：50；
4）将片料I、片料II按模具尺寸裁剪，将片料II放在两片料I之间，使其叠合成“片料II-片料I-片料II”的复合结构，然后将其放入压制模，置于平板硫化机中热压成型，热压温度为135-140°C，热压时间为8-10min。
7.根据权利要求6所述阻燃麻纤维/热塑性聚合物复合板的制备方法，其特征在于，步骤2）和3）中所述的混炼的前辊温度为115-120°C，后辊温度为110-115°C，混炼时间为10-15min。
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