CN109487569A - 一种碳纤维/氧化石墨烯改性酚醛树脂发热膜及其制备方法 - Google Patents
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜及其制备方法 Download PDFInfo
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Abstract
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜,其特征在于所述发热膜由碳纤维布料层、绝缘层、2层氧化石墨烯改性酚醛树脂涂覆层和2层保护层组成;所述绝缘层厚度为0.1~0.3mm,均匀包覆于碳纤维布料中的碳纤维束表面;所述氧化石墨烯改性酚醛树脂涂覆层每层厚度0.5~1.5mm;所述保护层每层厚度1~2mm;所述氧化石墨烯改性酚醛树脂涂覆层由氧化石墨烯改性酚醛树脂浆料均匀涂覆于绝缘层包覆的碳纤维布料两侧形成。本发明所具有的有益效果是:柔韧性好,使用方便,
Description
技术领域
本发明涉及一种发热膜及其制备方法,特别是涉及一种碳纤维/氧化石墨烯改性酚醛树脂发热膜及其制备方法。
背景技术
碳纤维是一种含碳量在95%以上的高强度、高模量纤维的新型纤维材料。它是由片状石墨微晶等有机纤维沿纤维轴向方向堆砌而成,经碳化及石墨化处理而得到的微晶石墨材料。
石墨烯(Graphene)自2004年被英国曼彻斯特大学的教授Geim等报道以其奇特的性能引起了科学家的广泛关注和极大的兴趣被预测很有可能在很多领域引起革命性变化。单层石墨烯以二维晶体结构存在厚度只01334nm它是构筑其它维度炭质材料的基本单元它可以包裹起来形成零维的富勒烯卷起来形成一维的碳纳米管层层堆积形成三维的石墨。石墨烯是一种没有能隙的半导体具有比硅高100倍的载流子迁移率(2×10cm/v)在室温下具有微米级自由程和大的相干长度因此石墨烯是纳米电路的理想材料。石墨烯具有良好的导热性[3000W/(m·K)]、高强度(110GPa)和超大的比表面积(2630m/g)。这些优异的性能使得石墨烯在纳米电子器件、气体传感器、能量存储及复合材料等领域有光明的应用前景。
电热膜供暖是世界上新兴的供暖方式之一,它是一种以电能为源,通过红外辐射进行传热的新型供暖方式。因其具有耐高压、耐潮湿、承受温度范围广、高韧度和低收缩率等优良性能,进而得到了越来越广泛的应用。相比于传统的散热金属材料,采用石墨烯和碳纤维制备的高导热C/C复合材料因具有优异的低密度、高导热、低热胀系数和独有的高温高强度等性能而成为目前最佳的高导热候选材料。
公布号为CN 103338538 A的中国专利,提出了一种石墨烯辐射发热膜及其制备方法和应用。在纤维面料相间设置石墨烯辐射发热膜区和纳米金属远红外发热区,将纳米金属远红外发热区与包括导线、开关和电源的电路构成工作回路,石墨烯辐射发热膜区边缘与纳米金属远红外发热区及导线边缘存在2-3mm的间隙;以纳米金属远红外发热区为主要热源,以石墨烯辐射发热膜为辅助热源辐射发热,纤维面料上的石墨烯辐射发热膜区、纳米金属远红外发热区和导线正反表面均附着有柔性绝缘保护层。这样的设计比传统发热方式节能约60%,提高了电能的利用率;并且发热迅速,安全节能,且发热均匀,还能确保产品的安全性。
公布号为CN 108117716 A的中国专利,提出了一种石墨烯/酚醛树脂高导电纳米复合材料及其制备方法。采用特定以苯酚、甲酚、二甲酚、间苯二酚其中一种为主成分所制备成具有优良力学性能的酚醛树酯,配合拥有超低电阻率的石墨烯或氧化石墨烯、硅烷偶合剂、固化剂等原料。利用短时程、高效能且步骤明确的高速分散混炼技术制得具有高稳定批次均匀性与优异导电性能的酚醛树脂复合材料。本发明生产工艺简单明确、制程简短稳定和成本效益高等优点;其制备之产品拥有物性维持率高、加工性能优良且具备稳定的高效导电率等多项优异性质。
公布号为CN 108012349 A的中国专利,提出了一种石墨烯碳纤维高效节能地暖发热线及其制造工艺。在绝缘层和保护层之间设有石墨烯层,使得生产出的石墨烯碳纤维地暖发热线具有极佳的导热性能,地暖发热线由绝缘保温层上传的热量损耗节约5-8%,综合传热效率提高了45%,另外还公开了地暖发热线的具体制造工艺,制备工艺简单,有利于规模化生产。
目前在地暖系统中,石墨烯发热材料的添加都是以机械共混的方式将石墨烯混入浆料中,由于石墨烯具有较大的比表面积再范德华力作用下石墨烯容易形成团聚,而石墨烯材料的导电性能在很大程度上受到石墨烯填料分散性的,这极大的限制了石墨烯复合电热材料的应用和推广。此外,目前的柔性发热元件多为碳晶板或者镀银材料,碳晶板柔性效果较差,而镀银材料成本较高,银又具有毒性,因此不利于其推广和使用。
发明内容
本发明的目的旨在克服现有技术的不足,提供一种柔性碳纤维/氧化石墨烯改性酚醛树脂发热膜及其制备方法。通过反应过程中形成的尿素甲醛树脂和三聚氰胺甲醛树脂与氧化石墨烯改性酚醛树脂形成三元共混增韧改性,极大的提高了发热膜的柔性。此外,酚醛树脂大分子在氧化石墨烯反应活性位点上原位生长形成穿插增韧,并对氧化石墨烯形成部分还原,不仅有利于还原氧化石墨烯增强相的均匀分散增韧改性,结合还原氧化石墨烯具有优异的比表面积,在保证发热膜材料的柔性的同时还极大的提升了发热膜的电热性能,提高电热转化效率。本方案制备的柔性发热膜柔韧性极佳,可以在不同异形安装环境和机械操作条件下进行运输、铺设和安装,使用方便。
为实现本发明的目的采用的技术方案是:一种碳纤维/氧化石墨烯改性酚醛树脂发热膜,其特征在于所述发热膜由碳纤维布料层、绝缘层、2层氧化石墨烯改性酚醛树脂涂覆层和2层保护层组成;所述绝缘层包覆于碳纤维布料中的碳纤维束表面,所述氧化石墨烯改性酚醛树脂涂覆层由氧化石墨烯改性酚醛树脂浆料均匀涂覆于绝缘层包覆的碳纤维布料两侧形成,所述氧化石墨烯改性酚醛树脂浆料由下列组分按照重量份混合后形成:
氧化石墨烯改性酚醛树脂,4~8份
远红外发射剂,0.5~1份
其中,所述氧化石墨烯改性酚醛树脂包括由重量组分为8~12份的酚醛树脂,4~8份脲醛树脂,2~3份三聚氰胺甲醛树脂和10~20份的氧化石墨烯组成,所述酚醛树脂原位聚合生长于氧化石墨烯活性位点上,并将氧化石墨烯部分还原。
所述的氧化石墨烯改性酚醛树脂的制备方法包括下述顺序的步骤:
(1)取氧化石墨烯加去离子水配制浓度10~20wt%水溶液,超声0.5~1h获得氧化石墨烯溶液备用;
(2)取4~6.5份苯酚、4~7.5份甲醛、0.2~0.7份NaOH和50~100份步骤(1)所述的氧化石墨烯溶液,混合均匀,升温至60~70℃,恒温条件下反应1~2h,然后升温至80~90℃,恒温条件下反应1.5~2.5h,制得氧化石墨烯改性酚醛树脂溶液,其中氧化石墨烯被部分还原;
(3)向步骤(2)获得的溶液中按质量比例加入1~3份三聚氰胺和2~9份尿素,在45~60℃条件下恒温反应1~2h,然后快速冷却至室温,获得尿素和三聚氰胺增强增韧氧化石墨烯改性酚醛树脂溶液;
(4)将步骤(3)获得的溶液真空条件下旋蒸,获得氧化石墨烯改性酚醛树脂。
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜制备方法,其特征在于包括下述顺序的步骤:
(1)将准备好的碳纤维束通过注塑机,在130~160℃的高温度环境中,将绝缘层包裹于碳纤维束外围,在室温下冷却固化;
(2)将外围包裹有绝缘层的碳纤维束编织成绝缘层包覆的碳纤维布料;
(3)将氧化石墨烯改性酚醛树脂涂覆于步骤(2)制得的绝缘层包覆的碳纤维布料两侧,烘干形成氧化石墨烯改性酚醛树脂涂覆层;
(4)将步骤(3)中制作得到的产品的两侧包裹上保护层。
本发明所具有的有益效果是:柔韧性好,使用方便。通过反应过程中形成的尿素甲醛树脂和三聚氰胺甲醛树脂与氧化石墨烯改性酚醛树脂形成三元共混增韧改性,和酚醛树脂大分子在氧化石墨烯反应活性位点上原位生长形成穿插增韧,使得氧化石墨烯改性酚醛树脂涂覆层柔韧性极佳,可以在不同异形安装环境和机械操作条件下进行运输、铺设和安装,使用方便。电热效率高。酚醛树脂大分子在氧化石墨烯反应活性位点上原位生长形成穿插增韧,并对氧化石墨烯形成部分还原,提高氧化石墨烯均匀分散性和还原程度,少量氧化石墨烯的添加量就可以实现氧化石墨烯改性酚醛树脂涂覆层导电性能增加,有利于电热转化和热的均匀分散,提高电热效率。
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
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜,其特征在于所述发热膜由碳纤维布料层、绝缘层、2层氧化石墨烯改性酚醛树脂涂覆层和2层保护层组成;所述绝缘层包覆于碳纤维布料中的碳纤维束表面,所述氧化石墨烯改性酚醛树脂涂覆层由氧化石墨烯改性酚醛树脂浆料均匀涂覆于绝缘层包覆的碳纤维布料两侧形成,所述氧化石墨烯改性酚醛树脂浆料由下列组分按照重量份混合后形成:
氧化石墨烯改性酚醛树脂,4份
远红外发射剂,0.5份
其中,所述氧化石墨烯改性酚醛树脂包括由重量组分为8份的酚醛树脂,4份脲醛树脂,2份三聚氰胺甲醛树脂和10份的氧化石墨烯组成,所述酚醛树脂原位聚合生长于氧化石墨烯活性位点上,并将氧化石墨烯部分还原。
所述的氧化石墨烯改性酚醛树脂的制备方法包括下述顺序的步骤:
(1)取氧化石墨烯加去离子水配制浓度10wt%水溶液,超声0.5h获得氧化石墨烯溶液备用;
(2)取4份苯酚、4份甲醛、0.2份NaOH和50份步骤(1)所述的氧化石墨烯溶液,混合均匀,升温至60℃,恒温条件下反应1h,然后升温至80℃,恒温条件下反应2.5h,制得氧化石墨烯改性酚醛树脂溶液,其中氧化石墨烯被部分还原;
(3)向步骤(2)获得的溶液中按质量比例加入1份三聚氰胺和2份尿素,在45℃条件下恒温反应2h,然后快速冷却至室温,获得尿素和三聚氰胺增强增韧氧化石墨烯改性酚醛树脂溶液;
(4)将步骤(3)获得的溶液真空条件下旋蒸,获得氧化石墨烯改性酚醛树脂。
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜制备方法,其特征在于包括下述顺序的步骤:
(1)将准备好的碳纤维束通过注塑机,在130℃的高温度环境中,将绝缘层包裹于碳纤维束外围,在室温下冷却固化;
(2)将外围包裹有绝缘层的碳纤维束编织成绝缘层包覆的碳纤维布料;
(3)将氧化石墨烯改性酚醛树脂涂覆于步骤(2)制得的绝缘层包覆的碳纤维布料两侧,烘干形成氧化石墨烯改性酚醛树脂涂覆层;
(4)将步骤(3)中制作得到的产品的两侧包裹上保护层。
实施例2
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜,其特征在于所述发热膜由碳纤维布料层、绝缘层、2层氧化石墨烯改性酚醛树脂涂覆层和2层保护层组成;所述绝缘层包覆于碳纤维布料中的碳纤维束表面,所述氧化石墨烯改性酚醛树脂涂覆层由氧化石墨烯改性酚醛树脂浆料均匀涂覆于绝缘层包覆的碳纤维布料两侧形成,所述氧化石墨烯改性酚醛树脂浆料由下列组分按照重量份混合后形成:
氧化石墨烯改性酚醛树脂,8份
远红外发射剂,1份
其中,所述氧化石墨烯改性酚醛树脂包括由重量组分为12份的酚醛树脂,8份脲醛树脂,3份三聚氰胺甲醛树脂和20份的氧化石墨烯组成,所述酚醛树脂原位聚合生长于氧化石墨烯活性位点上,并将氧化石墨烯部分还原。
所述的氧化石墨烯改性酚醛树脂的制备方法包括下述顺序的步骤:
(1)取氧化石墨烯加去离子水配制浓度20wt%水溶液,超声1h获得氧化石墨烯溶液备用;
(2)取6.5份苯酚、7.5份甲醛、0.7份NaOH和100份步骤(1)所述的氧化石墨烯溶液,混合均匀,升温至70℃,恒温条件下反应1h,然后升温至90℃,恒温条件下反应2.5h,制得氧化石墨烯改性酚醛树脂溶液,其中氧化石墨烯被部分还原;
(3)向步骤(2)获得的溶液中按质量比例加入3份三聚氰胺和9份尿素,在60℃条件下恒温反应2h,然后快速冷却至室温,获得尿素和三聚氰胺增强增韧氧化石墨烯改性酚醛树脂溶液;
(4)将步骤(3)获得的溶液真空条件下旋蒸,获得氧化石墨烯改性酚醛树脂。
一种碳纤维/氧化石墨烯改性酚醛树脂发热膜制备方法,其特征在于包括下述顺序的步骤:
(1)将准备好的碳纤维束通过注塑机,在160℃的高温度环境中,将绝缘层包裹于碳纤维束外围,在室温下冷却固化;
(2)将外围包裹有绝缘层的碳纤维束编织成绝缘层包覆的碳纤维布料;
(3)将氧化石墨烯改性酚醛树脂涂覆于步骤(2)制得的绝缘层包覆的碳纤维布料两侧,烘干形成氧化石墨烯改性酚醛树脂涂覆层;
(4)将步骤(3)中制作得到的产品的两侧包裹上保护层。
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 (3)
1.一种碳纤维/氧化石墨烯改性酚醛树脂发热膜,其特征在于所述发热膜由碳纤维布料层、绝缘层、2层氧化石墨烯改性酚醛树脂涂覆层和2层保护层组成;所述绝缘层包覆于碳纤维布料中的碳纤维束表面,所述氧化石墨烯改性酚醛树脂涂覆层由氧化石墨烯改性酚醛树脂浆料均匀涂覆于绝缘层包覆的碳纤维布料两侧形成,所述氧化石墨烯改性酚醛树脂浆料由下列组分按照重量份混合后形成:
氧化石墨烯改性酚醛树脂,4~8份
远红外发射剂,0.5~1份
其中,所述氧化石墨烯改性酚醛树脂包括由重量组分为8~12份的酚醛树脂,4~8份脲醛树脂,2~3份三聚氰胺甲醛树脂和10~20份的氧化石墨烯组成,所述酚醛树脂原位聚合生长于氧化石墨烯活性位点上,并将氧化石墨烯部分还原。
2.根据权利要求1所述的发热膜,其特征在于所述的氧化石墨烯改性酚醛树脂的制备方法包括下述顺序的步骤:
(1)取氧化石墨烯加去离子水配制浓度10~20wt%水溶液,超声0.5~1h获得氧化石墨烯溶液备用;
(2)取4~6.5份苯酚、4~7.5份甲醛、0.2~0.7份NaOH和50~100份步骤(1)所述的氧化石墨烯溶液,混合均匀,升温至60~70℃,恒温条件下反应1~2h,然后升温至80~90℃,恒温条件下反应1.5~2.5h,制得氧化石墨烯改性酚醛树脂溶液,其中氧化石墨烯被部分还原;
(3)向步骤(2)获得的溶液中按质量比例加入1~3份三聚氰胺和2~9份尿素,在45~60℃条件下恒温反应1~2h,然后快速冷却至室温,获得尿素和三聚氰胺增强增韧氧化石墨烯改性酚醛树脂溶液;
(4)将步骤(3)获得的溶液真空条件下旋蒸,获得氧化石墨烯改性酚醛树脂。
3.一种碳纤维/氧化石墨烯改性酚醛树脂发热膜制备方法,其特征在于包括下述顺序的步骤:
(1)将准备好的碳纤维束通过注塑机,在130~160℃的高温度环境中,将绝缘层包裹于碳纤维束外围,在室温下冷却固化;
(2)将外围包裹有绝缘层的碳纤维束编织成绝缘层包覆的碳纤维布料;
(3)将氧化石墨烯改性酚醛树脂涂覆于步骤(2)制得的绝缘层包覆的碳纤维布料两侧,烘干形成氧化石墨烯改性酚醛树脂涂覆层;
(4)将步骤(3)中制作得到的产品的两侧包裹上保护层。
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