CN115384130A - 一种三明治结构的热塑性复合材料及其应用 - Google Patents

一种三明治结构的热塑性复合材料及其应用 Download PDF

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CN115384130A
CN115384130A CN202210841255.5A CN202210841255A CN115384130A CN 115384130 A CN115384130 A CN 115384130A CN 202210841255 A CN202210841255 A CN 202210841255A CN 115384130 A CN115384130 A CN 115384130A
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resin
thermoplastic
layers
composite material
thermoplastic composite
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杨铁军
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Suzhou Lingyu Electronic Technology Co Ltd
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Abstract

本发明公开一种三明治结构的热塑性复合材料及其应用，结构包括n层，其中n≥3，且n为奇数，奇数层为热塑性树脂基的纤维预浸带叠层，偶数层为热塑性树脂制备的硬泡沫，均以热塑性聚碳酸酯树脂为基材，通过添加纤维起到增强作用，三明治结构的材料的结合稳定性好，将三层或者更多层材料以熔融或者胶黏的方式即可结合得到，制备工艺简单，所得热塑性复合材料具有重量轻、密度小、硬度高、弯曲强度及弯曲模量低的特性，且其还表现出优异的耐水性、防腐蚀性、阻燃性、抗老化性，所用的聚碳酸酯树脂为可回收再利用的热塑性材料，经济环保，实用方便，可广泛用于建材领域，如墙板、墙体衬板、以及建筑板材、移动电子设备、家用电器、汽车、飞行器行业等领域。

Description

一种三明治结构的热塑性复合材料及其应用
技术领域
本发明涉及热塑性复合材料的制备领域，B29C70/34，尤其涉及一种三明治结构的热塑性复合材料及其应用。
背景技术
板材，是根据需求设计为标准尺寸的建筑材料板，主要用于建筑行业，用作墙壁、天花板、地板的构件，目前，对于有强度需要的复合板材通常采用热固性树脂合成。热固性树脂的分子量可以通过化学反应发生交联，进而形成刚性的三维网络结构，具有高强度、耐热性、耐老化性、尺寸稳定性，可以很好地满足建筑板材的需求，但是热固性树脂材料难以回收，若硬泡沫材料的基料同样为热固性树脂还存在无法再次热成型的弊端。若利用热塑性树脂材料代替热固性树脂时，通常会需要添加纤维来进行增强作用，其中连续纤维的增强效果较为显著，但是所得连续纤维的复合材料价格昂贵，限制了其应用。
专利CN201810749883.4公开了一种高强热塑性轻质复合板材及其制备方法，该复合板材包括芯材、布设于芯材两侧的中间层、布设于中间层两侧的外层，芯材为发泡芯材，外层为阻燃高分子材料层，中间层为纤维增强的高强度阻燃高分子材料层，发泡芯材为阻燃发泡高分子材料，可以改善产品的强度、抗冲击性和耐久性，而且质量轻，但是其需要通过及粘结层实现多层结构的粘结，且粘结稳定性较差。专利CN201910956707.2提供了一种碳纤维增强热塑性树脂板材及其制造方法，通过将碳纤维和热塑性树脂共混形成预浸料，然后铺层后在模压温度下成型即得，不需要进行预热，节约了制造工序和成本，但板材是通过从上下两面对开纤后的碳纤维进行夹持，所以其强度、抗冲击性和耐久性等力学性能较差。
发明内容
本发明的第一个方面提供了一种三明治结构的热塑性复合材料，其结构包含n层，其中n≥3，且n为奇数。
在一些优选的实施方式中，所述奇数层为热塑性树脂基的纤维预浸带叠层。
在一些优选的实施方式中，所述偶数层为热塑性树脂制备的硬泡沫。
在一些优选的实施方式中，所述热塑性树脂基的纤维预浸带叠层由单向纤维预浸带交错叠放至少2层，在一定温度、压力下加工处理得到；优选地，交错角度为90°；优选地，所述在一定温度、压力下加工处理具体为依次经过热压，冷压处理，制备得到热塑性树脂基的纤维预浸带叠层。
在一些优选的实施方式中，所述单向纤维预浸带由纤维和热塑性树脂制备得到。
在一些优选的实施方式中，所述纤维选自碳纤维、克维拉纤维、玻璃纤维、芳纶纤维、碳化硅纤维、陶瓷纤维中的一种或多种；优选地，所述纤维为碳纤维；进一步优选地，所述碳纤维为连续碳纤维。
在一些优选的实施方式中，所述单向纤维预浸带采用本领域常规技术手段制备得到，对制备工艺不做特别限定；也可通过市售产品购买获得，例如科思创的CF-GP-1003T型号产品。
在一些优选的实施方式中，所述纤维预浸带的厚度为0.1～0.3nn，纤维预浸带叠层的厚度为0.2～1mm，纤维预浸带叠层的密度为1～2g/cm3；优选地，所述热塑性树脂基的纤维预浸带叠层的厚度为0.7mm，密度为1.4g/cm3。
优选地，所述热压的温度为220～250℃，压力为2～4MPa，处理时间为2～10min。
优选地，所述冷压的温度为常温，压力为6～8MPa，处理时间为1～6min。
在一些优选的实施方式中，所述奇数层、偶数层中的热塑性树脂均为同一种热塑性树脂。
在一些优选的实施方式中，所述热塑性树脂选自PP树脂(聚丙烯)、PEEK树脂(聚醚醚酮)、PLA树脂(聚乳酸)、聚碳酸酯树脂(聚碳酸酯)、PA树脂(聚酰胺)、PPS树脂(聚苯硫醚)中的一种或多种。
在一些优选的实施方式中，所述偶数层中热塑性树脂制备的硬泡沫的制备方法包括：将热塑性树脂研磨成粉末，与耐高温型热膨胀微胶囊颗粒混合均匀，置于模具中施加一定温度，静置发泡，即得热塑性树脂制备的硬泡沫；优选地，所述热塑性树脂为聚碳酸酯(Polycarbonate)树脂。
在一些优选的实施方式中，所述聚碳酸酯树脂300℃/1.2kg的熔融指数为10～35g/10min，23℃时拉伸模量为2000～3000MPa；优选地，所述聚碳酸酯树脂300℃/1.2kg的熔融指数为20g/10min，23℃时拉伸模量为2400MPa。
在一些优选的实施方式中，所述耐高温型热膨胀微胶囊颗粒的材质为乙烯基酸酯树脂和乙烯基腈类树脂的混合物；所述耐高温型热膨胀微胶囊颗粒可为市售，例如上海华谊(集团)公司的SKEM230D型号产品。
聚碳酸酯树脂，是分子链中含有碳酸酯基的高分子聚合物，无色透明，耐热、抗冲击性能、加工性能、耐热老化性能好。本申请选择聚碳酸酯树脂基的纤维预浸带叠层，其熔融状态下与热塑性树脂制备的硬泡沫具有极佳的相容性，能够稳固结合。本申请人发现，在该体系中，选择300℃/1.2kg的熔融指数为10～35g/10min，23℃时拉伸模量为2000～3000MPa的聚碳酸酯树脂包覆耐高温型热膨胀微胶囊制备硬泡沫，聚碳酸酯树脂在特定温度下呈现较高的表面张力，既保护耐高温型热膨胀微胶囊膨胀发泡的过程中不受损伤，又促使偶数层与奇数层紧密结合形成夹心三明治结构，减少了孔隙的形成，增强了所得预浸带叠层的力学强度。进一步的，耐高温型热膨胀微胶囊颗粒与特定的热塑性树脂协同增效，在高温熔融状态下触发碰撞，形成微米级的气孔，所得硬泡沫的硬度高，既有效降低了板材的密度，又提高了板材的尺寸稳定性，所得板材的弯曲强度和弯曲模量显著提升。该方法赋予板材优异的高强轻量化，且易于加工设计，制得的板材可全部回收利用，实际应用价值高。
在一些优选的实施方式中，所述偶数层热塑性树脂制备的硬泡沫的泡孔尺寸为10～100μm；优选地，所述偶数层热塑性树脂制备的硬泡沫的泡孔尺寸为20～70μm。
在一些优选的实施方式中，所述偶数层热塑性树脂制备的硬泡沫的厚度为0.5～3mm，密度为0.2～0.8g/cm3；优选地，所述偶数层热塑性树脂制备的硬泡沫的厚度为0.7mm，密度为0.6g/cm3；
在一些优选的实施方式中，所述三明治结构的热塑性复合材料的制备方法为将奇数层和偶数层按顺序结合在一起即可；优选地，所述三明治结构的热塑性复合材料的制备方法为将奇数层和偶数层按顺序通过热熔或者粘胶的方式结合在一起即可；进一步优选地，所述三明治结构的热塑性复合材料的制备方法为将奇数层和偶数层按顺序通过热熔的方式结合在一起即可。
在一些优选的实施方式中，所述三明治结构的热塑性复合材料的综合密度为0.7～1.2g/cm3；优选地，所述三明治结构的热塑性复合材料的综合密度为1.13g/cm3。
本发明第二方面提供了一种三明治结构的热塑性复合材料的应用，其用于建筑板材、移动电子设备、家用电器、汽车、飞行器行业。
有益效果：
(1)本申请中的三明治结构的热塑性复合材料均以热塑性聚碳酸酯树脂为基材，通过热塑性树脂基的纤维预浸带叠层与热塑性树脂制备的硬泡沫协同增强，三明治结构的材料的结合稳定性好，将三层或者更多层材料以熔融或者胶黏的方式即可结合得到，制备工艺简单，易于加工设计，所得热塑性复合材料具有重量轻、密度小、硬度高、弯曲强度及弯曲模量低的特性，且其还表现出优异的耐水性、防腐蚀性、阻燃性、抗老化性。
(2)偶数层的硬泡沫具有均匀孔径的蜂窝结构，重量可以减轻10％至70％，其与奇数层的预浸带叠层具有相同的基材，软化点和熔融点相近，三明治结构的设计有助于形成高强轻质的材料，还可以通过复合后再次热熔成型，而且所用的聚碳酸酯树脂为可回收再利用的热塑性材料，板材所用原料可全部回收利用，经济环保，实用方便，可广泛用于建材领域，移动电子设备、家用电器、汽车、飞行器行业等多种领域。
附图说明
图1三明治结构的热塑性复合材料的结构图
具体实施方式
实施例1.
1、一种三明治结构的热塑性复合材料，其结构包括n层，其中n＝3。
所述三层均为热塑性树脂基的纤维预浸带叠层。
所述热塑性树脂基的纤维预浸带叠层由单向纤维预浸带90°交错叠放2层，依次经过热压，冷压处理，制备纤维预浸带叠层。
所述热压的温度为232.5±2.5℃，压力为3±1MPa，处理时间为5min；所述
所述冷压的温度为26±2℃，压力为7±1MPa，处理时间为3min。
所述单向纤维预浸带购自科思创，型号为CF-GP-1003T。
所述单向纤维预浸带由纤维和热塑性树脂制备得到，其中的热塑性树脂为聚碳酸酯(Polycarbonate)树脂；其中的纤维为碳纤维，具体为单向连续碳纤维。
所述三明治结构的热塑性复合材料的制备方法为将奇数层和偶数层通过热熔的方式结合在一起即可。
所述三明治结构的热塑性复合材料的厚度为2.1mm，密度为1.4g/cm3。
2、一种两层结构的热塑性复合材料的应用，用于建筑板材、移动电子设备、家用电器、汽车、飞行器行业。
实施例2：
1、一种三明治结构的热塑性复合材料，其结构包括包含n层，其中n＝3；
所述奇数层(第一层、第三层)为热塑性树脂基的纤维预浸带叠层。
所述偶数层(第二层)为热塑性树脂制备的硬泡沫。
所述奇数层、偶数层中的热塑性树脂均为同一种热塑性树脂，具体为聚碳酸酯树脂。
所述热塑性树脂基的纤维预浸带叠层由单向纤维预浸带90°交错叠放2层，依次经过热压，冷压处理，制备纤维预浸带叠层。
所述热压的温度为232.5±2.5℃，压力为3±1MPa，处理时间为5min；所述
所述冷压的温度为26±2℃，压力为7±1MPa，处理时间为3min。
所述单向纤维预浸带购自科思创，型号为CF-GP-1003T。
所述单向纤维预浸带由纤维和热塑性树脂制备得到，其中的热塑性树脂为聚碳酸酯(Polycarbonate)树脂；其中的纤维为碳纤维，具体为单向连续碳纤维。
所述奇数层热塑性树脂基的纤维预浸带叠层的厚度为0.7mm，密度为1.4g/cm3。
所述偶数层中热塑性树脂制备的硬泡沫的制备方法包括：
将热塑性树脂(聚碳酸酯树脂)研磨成粉末，与耐高温型热膨胀微胶囊颗粒混合均匀，置于模具中施加一定温度(120℃)，静置发泡，即得热塑性树脂制备的硬泡沫。
所述耐高温型热膨胀微胶囊购自上海华谊(集团)公司，型号为SKEM230D。
所述聚碳酸酯树脂购自科思创，型号为
Figure BDA0003750471210000051
其300℃/1.2kg的熔融指数为20g/10min，23℃时拉伸模量为2400MPa。
所述偶数层热塑性树脂制备的硬泡沫的厚度为0.7mm，密度为0.6g/cm3；
所述三明治结构的热塑性复合材料的制备方法为将奇数层、偶数层按顺序通过热熔的方式结合在一起即可；
所述三明治结构的热塑性复合材料的综合密度为1.13g/cm3；
2、一种三明治结构的热塑性复合材料的应用，用于建筑板材、移动电子设备、家用电器、汽车、飞行器行业。
性能测试：
1、弯曲强度：根据标准ISO14125-1998《纤维增强塑料复合材料弯曲性能的测定》对实施例所得材料进行测定；
2、弯曲模量：根据标准ISO14125-1998《纤维增强塑料复合材料弯曲性能的测定》对实施例所得材料进行测定；
表1实施例性能测试结果
Figure BDA0003750471210000061

Claims (10)

1.一种三明治结构的热塑性复合材料，其特征在于，其结构包括包含n层，其中n≥3，且n为奇数；
所述奇数层为热塑性树脂基的纤维预浸带叠层；
所述偶数层为热塑性树脂制备的硬泡沫。
2.根据权利要求1所述的一种三明治结构的热塑性复合材料，其特征在于，所述热塑性树脂基的纤维预浸带叠层由单向纤维预浸带交错叠放至少2层，在一定温度、压力下加工处理得到。
3.根据权利要求2所述的一种三明治结构的热塑性复合材料，其特征在于，所述单向预浸带由纤维和热塑性树脂制备得到。
4.根据权利要求3所述的一种三明治结构的热塑性复合材料，其特征在于，所述奇数层、偶数层中的热塑性树脂均为同一种热塑性树脂。
5.根据权利要求4所述的一种三明治结构的热塑性复合材料，其特征在于，所述热塑性树脂选自PP树脂、PEEK树脂、PLA树脂、聚碳酸酯树脂、PA树脂、PPS树脂中的一种或多种。
6.根据权利要求5所述的一种三明治结构的热塑性复合材料，其特征在于，所述热塑性树脂为聚碳酸酯树脂。
7.根据权利要求3或4所述的一种三明治结构的热塑性复合材料，其特征在于，所述纤维选自碳纤维、克维拉纤维、玻璃纤维、芳纶纤维、碳化硅纤维、陶瓷纤维中的一种或多种。
8.根据权利要求所述的一种三明治结构的热塑性复合材料，其特征在于，所述偶数层中热塑性树脂制备的硬泡沫的制备方法包括：将热塑性树脂研磨成粉末，与耐高温型热膨胀微胶囊颗粒混合均匀，置于模具中施加一定温度，静置发泡，即得热塑性树脂制备的硬泡沫。
9.根据权利要求8所述的一种三明治结构的热塑性复合材料，其特征在于，所述耐高温型热膨胀微胶囊的材质为乙烯基酸酯树脂和乙烯基腈类树脂的混合物。
10.一种根据权利要求1-9任一项所述的三明治结构的热塑性复合材料的应用，其特征在于，其用于建筑板材、移动电子设备、家用电器、汽车、飞行器行业。
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