CN107987444A - 一种石墨烯/pmma导热复合材料、制备方法及其应用 - Google Patents

一种石墨烯/pmma导热复合材料、制备方法及其应用 Download PDF

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CN107987444A
CN107987444A CN201711319464.9A CN201711319464A CN107987444A CN 107987444 A CN107987444 A CN 107987444A CN 201711319464 A CN201711319464 A CN 201711319464A CN 107987444 A CN107987444 A CN 107987444A
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pmma
graphene
preparation
composite materials
temperature
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周慧
刘文斌
时杰
刘日鑫
唐惠东
肖雪军
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Changzhou Vocational Institute of Engineering
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Abstract

本发明公开了一种石墨烯/PMMA、制备方法及其应用，属于有机材料领域，其组分和含量构成为：石墨烯0～2份；聚甲基丙烯酸甲酯100份；表面活性剂0～0.2份；溶剂500份～1000份。在制备方法中，采用的石墨烯的含量较低，石墨烯在PMMA中实现了均匀分散，导热性增加的同时，透光率下降很少。本发明还提供上述石墨烯/PMMA复合材料的应用，具有较好的分散性、导热性、硬度高，耐磨，能够应用于LED透镜材料等照明领域。

Description

一种石墨烯/PMMA导热复合材料、制备方法及其应用
技术领域
本发明属于有机材料领域，具体涉及一种石墨烯/PMMA、制备方法及其应用。
背景技术
LED与传统的白炽灯、荧光灯等光源相比，工作电流非常小，消耗的电能仅是传统光源的1/10，不使用严重污染环境的汞，具有节能、发光效率高、环保、体积小、轻便、寿命长等优点，被誉为21世纪新光源。目前LED已在广告媒体视频屏幕、汽车车灯、背光电源、标识与指示性照明、景观照明、室内照明(白色LED)得到了广泛应用。
而LED透镜是与LED紧密联系在一起有助于提升LED的出光效率、改变LED的光场分布的光学***。高透明光扩散树脂是制作LED透镜的主要材料，主要有PMMA(聚甲基丙烯酸甲酯)、PC(聚碳酸酯)、有机硅、PS(聚苯乙烯)等高透光率的树脂。PMMA透光率92％、加工性能良好、抗紫外老化，但其吸湿强、韧性差、易燃；PC透光率89％、力学性能良好、吸湿小、阻燃性好，但紫外线或辐射线照射易发黄；有机硅柔韧，耐老化，耐热老化，耐紫外线老化，常用于直接封装LED器件。随着LED需求的提升，LED透镜的市场也逐渐扩大，应用前景广阔，对其透镜材料的导热性能和折射率的要求进一步提升。
通过高导热无机物对聚合物进行填充，制备无机物/聚合物导热复合材料。由于良好导热性能高聚物价格昂贵，填充制备导热聚合物是目前广泛采用的方法。
石墨烯是具有碳碳sp2杂化而成的六边形晶格结构的碳单质，形成大共轭键，石墨烯的晶格结构决定了其成键极其稳定，因此其在不发生化学反应的情形下热稳定性很高。石墨烯的声子的平均自由程远远大于通常意义上的高导热石墨材料及其他材料的声子自由程，其声子自由程大约775nm，石墨烯的面内热传导系数高达5000W/(m·K)左右，可以用作良好的散热材料。
发明内容
本发明的目的在于克服现有技术存在的不足，利用石墨烯突出的力学、导热和透光性，提供一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料，可应用在LED透镜材料领域。
为达到以上目的，本发明采用的技术方案是提供一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料，其组分和含量构成如下：
本发明技术方案提供一种如上所述的石墨烯/PMMA复合材料的制备方法，采用溶液混合法，包括以下步骤：
(1)将聚甲基丙烯酸甲酯(PMMA)与适量溶剂在磁力搅拌作用下磁力搅拌2～8h，得到PMMA聚合物溶液；PMMA与溶剂的质量比为1∶5～20；
(2)在PMMA聚合物溶液中加入表面活性剂，称取PMMA质量0～2％的石墨烯，继续磁力搅拌15～30min，超声分散0.5～1h，高速均质分散机分散5～20min；
(3)步骤(2)所得混合溶液升温至50～100℃，脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；
(4)将石墨烯/PMMA母料，与PMMA经高速混合机中混合5～10min，得到混合料，石墨烯/PMMA母料与PMMA的质量比为1∶1～100；
(5)将混合料于双螺杆挤出机上挤出造粒，温度为150～230℃，螺杆转速为20～30r/min；
(6)将上述粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。
上述制备方案中，石墨烯为导热型石墨烯，粉末状，其片层薄，易分散，导热性能优异，其O的质量分数＜1％，比表面积450～500m2/g；
上述制备方案中，聚甲基丙烯酸甲酯为光学级，粉末状；
上述制备方案中，表面活性剂为OP-10、吐温-80、吐温-20、司班-60等中的一种，利于石墨烯的分散；
上述制备方案中，溶剂为丙酮、丁酮、二甲基甲酰胺、四氢呋喃、三氯甲烷等中的一种或几种复配。
本发明还提供上述石墨烯/PMMA复合材料的应用，具有较好的分散性、导热性、硬度高，耐磨，能够应用于LED透镜材料等照明领域。
最佳实施条件：聚甲基丙烯酸甲酯与溶剂四氢呋喃的质量比为1：10，35℃磁力搅拌4h；加石墨烯后继续磁力搅拌15min，超声分散40min以及高速均质分散5min；50℃脱除溶剂、烘干。破碎后与光学级PMMA经高速混合机中混合10min；挤出成型工艺参数：温度210～250℃，螺杆转速20～30r/min；粒料用精密注塑机注塑成型，注塑温度180～240℃，注塑压力80～130MPa，模温60℃。
有益效果：
(1)本发明提供了一种石墨烯/PMMA导热复合材料的制备方法，在制备方法中，采用的石墨烯的含量较低，石墨烯在PMMA中实现了均匀分散，导热性增加的同时，透光率下降很少。
(2)本发明制备的石墨烯/PMMA导热复合材料原料来源丰富，制备工艺简单，易于操作，且对设备的要求低，在传统透镜材料PMMA的制备工艺基础上只是增加了分散装置。
(3)本发明制备的石墨烯/PMMA导热复合材料具有良好的导热性、热稳定性、硬度高、耐磨、使用寿命延长。
说明书附图
图1是按本发明实施例1技术方案制备的材料样品的导热系数结果；
图2是按本发明实施例1技术方案制备的材料样品的DSC分析结果。
具体实施方式
下面结合附图和实施例对本发明技术方案作进一步描述。
比较例：
PMMA的制备
量取10ml甲基丙烯酸甲酯单体，加入0.01g过氧化苯甲酰搅拌均匀后，于85～90℃条件下预聚合30～40min；所得预聚体浇铸到模具中，并于45℃条件下低温聚合8h，100℃条件下高温聚合2h，自然冷却脱模后，即得到PMMA。
实施例1：
称取10g PMMA置于100ml四氢呋喃中，35℃磁力搅拌4h，得到PMMA聚合物溶液；称取0.05g的石墨烯，继续磁力搅拌15min，再超声分散30min，最后高速均质分散机上分散5min；所得混合溶液升温至50℃脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；将石墨烯/PMMA母料，与100g经85℃干燥3h的光学级PMMA粉料经高速混合机中混合10min，得到混合料；将混合料于双螺杆挤出机挤出造粒，温度为210～250℃，螺杆转速为20～30r/min；粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。其导热系数、热重分析结果、透光率、分散性与实施例1相似。
实施例1：
称取10g PMMA置于100ml四氢呋喃中，35℃磁力搅拌4h，得到PMMA聚合物溶液；称取0.044g的石墨烯，继续磁力搅拌15min，再超声分散30min，最后高速均质分散机上分散5min；所得混合溶液升温至50℃脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；将石墨烯/PMMA母料，与100g经85℃干燥3h的光学级PMMA粉料经高速混合机中混合10min，得到混合料；将混合料于双螺杆挤出机挤出造粒，温度为210～250℃，螺杆转速为20～30r/min；粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。其导热系数、热重分析结果、透光率、分散性与实施例1相似。
实施例2：
称取10g PMMA置于100ml四氢呋喃中，35℃磁力搅拌4h，得到PMMA聚合物溶液；称取0.11g的石墨烯，继续磁力搅拌15min，再超声分散30min，最后高速均质分散机上分散5min；所得混合溶液升温至50℃脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；将石墨烯/PMMA母料，与100g经85℃干燥3h的光学级PMMA粉料经高速混合机中混合10min，得到混合料；将混合料于双螺杆挤出机挤出造粒，温度为210～250℃，螺杆转速为20～30r/min；粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。其导热系数、热重分析结果、透光率、分散性与实施例1相似。
实施例3：
称取10g PMMA置于100ml四氢呋喃中，35℃磁力搅拌4h，得到PMMA聚合物溶液；称取0.22g的石墨烯，继续磁力搅拌15min，再超声分散30min，最后高速均质分散机上分散5min；所得混合溶液升温至50℃脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；将石墨烯/PMMA母料，与100g经85℃干燥3h的光学级PMMA粉料经高速混合机中混合10min，得到混合料；将混合料于双螺杆挤出机挤出造粒，温度为210～250℃，螺杆转速为20～30r/min；粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。其导热系数、热重分析结果、透光率、分散性与实施例1相似。
实施例4
称取10g PMMA置于100ml二甲基甲酰胺中，35℃磁力搅拌4h，得到PMMA聚合物溶液；称取0.044g的石墨烯，继续磁力搅拌15min，再超声分散30min，最后高速均质分散机上分散5min；所得混合溶液升温至50℃脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；将石墨烯/PMMA母料，与100g经85℃干燥3h的光学级PMMA粉料经高速混合机中混合10min，得到混合料；将混合料于双螺杆挤出机挤出造粒，温度为210～250℃，螺杆转速为20～30r/min；粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到一种具有良好导热性、分散均匀的石墨烯/PMMA复合材料。其导热系数、热重分析结果、透光率、分散性与实施例1相似。
各实施实例的性能如表1所示。
表1石墨烯/PMMA复合材料的性能

Claims (9)

1.一种石墨烯/PMMA复合材料，其特征在于：其组分和质量比含量如下：
所述的表面活性剂为OP-10、吐温-80、吐温-20、司班-60中的一种；所述溶剂为丙酮、丁酮、二甲基甲酰胺、四氢呋喃、三氯甲烷等中的一种或几种。
2.一种石墨烯/PMMA复合材料的制备方法，其特征在于：采用溶液混合法，包括以下步骤：
(1)将3～12％的光学级聚甲基丙烯酸甲酯(PMMA)与溶剂在磁力搅拌作用下磁力搅拌2～8h，得到PMMA聚合物溶液；PMMA与溶剂的质量比为1∶5～20；
(2)在PMMA聚合物溶液中加入表面活性剂，称取PMMA质量0～2％的石墨烯，继续磁力搅拌15～30min，超声分散0.5～1h，高速均质分散机分散5～20min；
(3)步骤(2)所得混合溶液升温至50～100℃，脱除溶剂并烘干，破碎后即得石墨烯/PMMA母料；
(4)将石墨烯/PMMA母料，与不同比例的光学级PMMA经高速混合机中混合5～10min，得到混合料；石墨烯/PMMA母料与PMMA的质量比为1∶1～100；
(5)将混合料于双螺杆挤出机上挤出造粒，温度为150～230℃，螺杆转速为20～30r/min；
(6)将上述粒料用精密注塑机注塑成型，注塑温度为180～240℃，注塑压力为80～130MPa，模温为40～80℃，即得到石墨烯/PMMA复合材料。
3.根据权利要求2所述的制备方法，其特征在于，所述表面活性剂为OP-10、吐温-80、吐温-20、司班-60中的一种；所述溶剂为丙酮、丁酮、二甲基甲酰胺、四氢呋喃、三氯甲烷等中的一种或几种。
4.根据权利要求2或3所述的制备方法，其特征在于，所述步骤(2)中，称取PMMA质量0～2％的石墨烯。
5.根据权利要求4所述的制备方法，其特征在于，所述步骤(2)中，称取PMMA质量0～2％的石墨烯。
6.根据权利要求2或3或5所述的制备方法，其特征在于，所述步骤(2)超声分散的时间为20～40min。
7.根据权利要求4所述的制备方法，其特征在于，所述步骤(2)超声分散的时间为20～40min。
8.根据权利要求2所述的制备方法，其特征在于：聚甲基丙烯酸甲酯与溶剂四氢呋喃的质量比为1：10，35℃磁力搅拌4h；加石墨烯后磁力搅拌15min，超声分散40min以及高速均质分散5min；50℃脱除溶剂、烘干；破碎后与光学级PMMA经高速混合机中混合10min；挤出成型工艺参数：温度210～250℃，螺杆转速20～30r/min；粒料用精密注塑机注塑成型，注塑温度180～240℃，注塑压力80～130MPa，模温60℃，即得到石墨烯/PMMA复合材料。
9.一种如权利要求1-8任意一项所述的石墨烯/PMMA复合材料的应用，其特征在于：应用于LED透镜材料照明领域。
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