CN108943917A - 一种改性酚醛树脂基复合材料及其制备方法 - Google Patents

一种改性酚醛树脂基复合材料及其制备方法 Download PDF

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CN108943917A
CN108943917A CN201810946793.4A CN201810946793A CN108943917A CN 108943917 A CN108943917 A CN 108943917A CN 201810946793 A CN201810946793 A CN 201810946793A CN 108943917 A CN108943917 A CN 108943917A
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phenolic resin
composite material
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王飞
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Suzhou Superlong Aviation Heat Resistance Material Technology Co Ltd
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Abstract

本发明公开了一种改性酚醛树脂基复合材料及其制备方法，复合材料由改性酚醛树脂与玻璃纤维布组成，所述改性酚醛树脂由石墨烯、尿素和三聚氰胺改性得到，制备步骤包括：将石墨烯溶液与苯酚、甲醛溶液混合后在水浴锅中加热反应，冷却后加入硫酸溶液、尿素、三聚氰胺继续反应，再经过旋转蒸发后得到改性酚醛树脂溶液，将酚醛树脂溶液与玻璃纤维布层层逐步涂覆并经高温固化后得到改性酚醛树脂基复合材料。本发明通过石墨烯的改性作用，提高了复合材料的强度、韧性、耐摩擦性能和耐高温性能；采用层层涂覆的方式，可以提高相互之间的结合力，而且该方法操作简单，成本较低。

Description

一种改性酚醛树脂基复合材料及其制备方法
技术领域
本发明涉及一种复合材料的制备方法，尤其涉及一种改性酚醛树脂基复合材料及其制备方法。
背景技术
玻璃纤维增强树脂基复合材料以独特的轻量化效果成为汽车工业、风力发电、轨道交通、体育休闲、家电、建筑和航空航天等众多领域的主流技术趋势，其在国民经济中占有重要地位，是国家产业政策重点鼓励发展的行业，发展空间巨大。石墨烯是由单层原子紧密堆积而成的二维蜂窝状晶格结构纳米材料，不仅具有电学性能优异、导热性能好、比表面积大、弹性模量高等优点，还具有极低的摩擦系数和优秀的耐磨损性能。目前，已经有人将石墨烯改性的玻璃纤维或石墨烯改性的酚醛树脂应用于复合材料中，在提高复合材料力学性能、耐热性能、摩擦性能等方面取得了一定成果。
申请号为201410413574.1的中国发明专利公开了一种石墨烯涂覆玻璃纤维增强树脂基复合材料，其是通过如下方法制备得到的：先将经过硅烷偶联剂改性的石墨烯分散于水中形成分散均匀的水分散液；再将玻璃纤维浸渍于改性石墨烯的水分散液中，通过静电吸附作用，在玻璃纤维表面形成均匀且致密的石墨烯涂覆层；最后带有石墨烯涂覆层的玻璃纤维与树脂基体经复合成型形成复合材料。本发明在玻璃纤维表面构筑石墨烯涂覆层，不但能增大纤维与基体的相互作用面积及界面结合力，还能有效解决石墨烯的分散问题，使复合材料的力学性能更优异。
申请号为201610208113.X的中国发明专利公开了一种基于石墨烯改性的玻璃纤维增强复合材料的制备方法，具体步骤为：将石墨烯用浓酸预处理后，加入硅烷偶联剂进行改性；先将改性后的石墨烯与聚乙烯蜡混合，再加入到液态树脂中混合均匀，并真空导入到放置有玻璃纤维的模具中，固化得到石墨烯改性玻纤增强树脂基复合材料。本发明的方案同时促进了石墨烯材料和玻璃纤维在树脂基体中的分散。
申请号为201510108461.5的中国发明专利公开了一种含有石墨烯的酚醛树脂基复合材料及其制备方法，先超声分散石墨烯，再将分散的石墨烯与酚醛树脂超声共混，保持超声下除去大部分溶剂，以免石墨烯聚集，再将含有石墨烯的酚醛树脂与助剂共混，制备过程简单，操作方便，便于大规模生产。制备的复合材料力学性能、耐热性能及润滑性能优异。
以上专利都是采用石墨烯涂覆玻璃纤维或者将石墨烯与树脂直接共混的方式来制备复合材料，虽然制备方法简单且起到了一定的改性效果，但是由于石墨烯的分散性较差、在复合材料中的含量较低，因此未能从根本上有效改善复合材料的性能。因此有必要发明一种将石墨烯均匀分散在树脂基体中的方法并将其应用到复合材料中。
发明内容
本发明旨在克服现有技术的不足，提供一种改性酚醛树脂基复合材料及其制备方法。
为实现本发明目的采用的技术方案是：提供了一种改性酚醛树脂基复合材料，其特征在于所述改性酚醛树脂基复合材料由改性酚醛树脂与玻璃纤维布组成，所述改性酚醛树脂占复合材料质量的60%~90%，由石墨烯、尿素和三聚氰胺改性得到，所述玻璃纤维布占复合材料质量的10%~40%，在复合材料中呈层状平行排布，每两层玻璃纤维布之间由酚醛树脂相粘结，所述玻璃纤维布为方格布或网格布，是平纹、斜纹或缎纹中的一种，所述改性酚醛树脂基复合材料的制备方法包括下列步骤：
（1）将1~2份浓度为0.1~0.5mg/mL的石墨烯溶液、550~650份苯酚和2200~2300份甲醛溶液混合，放入水浴锅中，升温后不断搅拌，然后加入5~20份氢氧化钠，继续升温后恒温反应一段时间后停止加热；
（2）当反应体系降温后，依次加入120~150份浓度为30wt%的硫酸溶液、520~550份尿素和130~180份三聚氰胺，继续升温后恒温反应一段时间后停止加热，将反应体系冷却；
（3）将混合溶液放入旋转蒸发仪中，在恒温下旋转蒸发一段时间，直到溶液黏度达到3000~6000 mPa•s，得到改性酚醛树脂溶液；
（4）在模具表面均匀涂覆一层脱模剂，再涂覆一层改性酚醛树脂溶液，用压辊在模具表面滚动，直到酚醛树脂在模具表面均匀分布，在酚醛树脂表面铺上一层玻璃纤维布，在玻璃纤维布表面再涂覆一层改性酚醛树脂溶液，并使用压辊使得酚醛树脂均匀分布，所述压辊施加的压力为4000~8000Pa，速度为2~5cm/s；
（5）重复以上步骤5~20次，即在铺设5~20层玻璃纤维布后，将模具闭合并放入烘箱加热至酚醛树脂固化温度以上，保温一段时间使其充分固化后，取出并打开模具，得到改性酚醛树脂基复合材料。
应用效果：本发明与现有技术相比，具有以下优点：（1）通过将石墨烯与苯酚、甲醛溶液混合后制备酚醛树脂，提高了石墨烯在酚醛树脂中的分散性和结合力，充分发挥了石墨烯在复合材料中的改性作用，提高了复合材料的强度、韧性、耐摩擦性能和耐高温性能；（2）通过添加三聚氰胺和尿素可以有效减少酚醛树脂中游离甲醛的含量，减少复合材料的刺激性气味，同时提高了复合材料的阻燃性能；（3）将改性酚醛树脂与玻璃纤维布采用层层涂覆的方式，可以提高相互之间的结合力，而且该方法操作简单，成本较低，适合工业化大规模生产。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
实施例1
一种改性酚醛树脂基复合材料，由改性酚醛树脂与玻璃纤维布组成，改性酚醛树脂占复合材料质量的70%，由石墨烯、尿素和三聚氰胺改性得到，玻璃纤维布为网格布斜纹，占复合材料质量的30%，在复合材料中呈层状平行排布，每两层玻璃纤维布之间由酚醛树脂相粘结。
一种改性酚醛树脂基复合材料的制备方法，包括下列步骤：
（1）将1份浓度为0.2mg/mL的石墨烯溶液、600份苯酚和2250份甲醛溶液混合，放入水浴锅中，升温至45℃，并不断搅拌，然后加入10份氢氧化钠，升温至80℃，恒温反应3小时后停止加热；
（2）当反应体系降温至30℃时，依次加入130份浓度为30wt%的硫酸溶液、530份尿素和150份三聚氰胺，升温至55℃，恒温反应60min后停止加热，将反应体系冷却至35℃；
（3）将混合溶液放入旋转蒸发仪中，在75℃温度下蒸发1.5h，直到溶液黏度达到5000mPa•s，得到改性酚醛树脂溶液；
（4）在模具表面均匀涂覆一层脱模剂，再涂覆一层改性酚醛树脂溶液，用压辊在模具表面滚动，压辊施加的压力为5000Pa，速度为3cm/s，直到酚醛树脂在模具表面均匀分布，在酚醛树脂表面铺上一层玻璃纤维布，在玻璃纤维布表面再涂覆一层改性酚醛树脂溶液，并使用压辊使得酚醛树脂均匀分布；
（5）重复以上步骤10次，即在铺设10层玻璃纤维布后，将模具闭合并放入烘箱加热至180℃，保温30min，取出并打开模具，得到改性酚醛树脂基复合材料。
实施例2
一种改性酚醛树脂基复合材料，由改性酚醛树脂与玻璃纤维布组成，改性酚醛树脂占复合材料质量的75%，由石墨烯、尿素和三聚氰胺改性得到，玻璃纤维布为网格布平纹，占复合材料质量的25%，在复合材料中呈层状平行排布，每两层玻璃纤维布之间由酚醛树脂相粘结。
一种改性酚醛树脂基复合材料的制备方法，包括下列步骤：
（1）将1份浓度为0.3mg/mL的石墨烯溶液、620份苯酚和2280份甲醛溶液混合，放入水浴锅中，升温至50℃，并不断搅拌，然后加入15份氢氧化钠，升温至82℃，恒温反应2.5小时后停止加热；
（2）当反应体系降温至30℃时，依次加入140份浓度为30wt%的硫酸溶液、520份尿素和160份三聚氰胺，升温至52℃，恒温反应45min后停止加热，将反应体系冷却至35℃；
（3）将混合溶液放入旋转蒸发仪中，在77℃温度下蒸发1.5h，直到溶液黏度达到4000mPa•s，得到改性酚醛树脂溶液；
（4）在模具表面均匀涂覆一层脱模剂，再涂覆一层改性酚醛树脂溶液，用压辊在模具表面滚动，压辊施加的压力为6000Pa，速度为4cm/s，直到酚醛树脂在模具表面均匀分布，在酚醛树脂表面铺上一层玻璃纤维布，在玻璃纤维布表面再涂覆一层改性酚醛树脂溶液，并使用压辊使得酚醛树脂均匀分布；
（5）重复以上步骤12次，即在铺设12层玻璃纤维布后，将模具闭合并放入烘箱加热至190℃，保温28min，取出并打开模具，得到改性酚醛树脂基复合材料。
上述仅为本发明的两个具体实施方式，但本发明的设计构思并不局限于此，凡利用此构思对本发明进行非实质性的改动，均应属于侵犯本发明保护的范围的行为。但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何形式的简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (1)

1.一种改性酚醛树脂基复合材料，其特征在于所述改性酚醛树脂基复合材料由改性酚醛树脂与玻璃纤维布组成，所述改性酚醛树脂占复合材料质量的60%~90%，由石墨烯、尿素和三聚氰胺改性得到，所述玻璃纤维布占复合材料质量的10%~40%，在复合材料中呈层状平行排布，每两层玻璃纤维布之间由酚醛树脂相粘结，所述玻璃纤维布为方格布或网格布，是平纹、斜纹或缎纹中的一种，所述改性酚醛树脂基复合材料的制备方法包括下列步骤：
（1）将1~2份浓度为0.1~0.5mg/mL的石墨烯溶液、550~650份苯酚和2200~2300份甲醛溶液混合，放入水浴锅中，升温后不断搅拌，然后加入5~20份氢氧化钠，继续升温后恒温反应一段时间后停止加热；
（2）当反应体系降温后，依次加入120~150份浓度为30wt%的硫酸溶液、520~550份尿素和130~180份三聚氰胺，继续升温后恒温反应一段时间后停止加热，将反应体系冷却；
（3）将混合溶液放入旋转蒸发仪中，在恒温下旋转蒸发一段时间，直到溶液黏度达到3000~6000 mPa•s，得到改性酚醛树脂溶液；
（4）在模具表面均匀涂覆一层脱模剂，再涂覆一层改性酚醛树脂溶液，用压辊在模具表面滚动，直到酚醛树脂在模具表面均匀分布，在酚醛树脂表面铺上一层玻璃纤维布，在玻璃纤维布表面再涂覆一层改性酚醛树脂溶液，并使用压辊使得酚醛树脂均匀分布，所述压辊施加的压力为4000~8000Pa，速度为2~5cm/s；
（5）重复以上步骤5~20次，即在铺设5~20层玻璃纤维布后，将模具闭合并放入烘箱加热至酚醛树脂固化温度以上，保温一段时间使其充分固化后，取出并打开模具，得到改性酚醛树脂基复合材料。
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