CN107820338B - 一种基于聚吡咯的抗氧化复合碳晶粉 - Google Patents
一种基于聚吡咯的抗氧化复合碳晶粉 Download PDFInfo
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Abstract
本发明涉及一种基于聚吡咯的抗氧化复合碳晶粉,以质量计的组成为:44份石墨、18份抗氧化聚吡咯树脂粉、20份黑磷、8份氮化硼、7份4‑氟苯基硼酸、非离子型高分子水性分散剂1.0份、脂肪酸甘油酯0.10份。本发明的优点为:(1)首次将具有较高导电性的黑磷用于碳晶粉材料;(2)合成出抗氧化聚吡咯树脂粉,同时加入有机硼抗氧化剂,提高了所述碳晶粉的抗氧化性与持久稳定性。
Description
技术领域
本发明涉及一种基于聚吡咯的抗氧化复合碳晶粉,属于供暖材料技术领域。
技术背景
相对于传统的取暖系统,碳晶发热材料具有安装简单、环保节能、使用灵活等优点,但是目前国内的碳晶发热材料普遍存在着用寿命短、发热温度通常很低,而且经常发现有脱落的情况,在遇到高温条件下作业很不耐热,通常局部容易出现烧焦的点,易出现老化分解的现象,所制得的填料容易被空气氧化,导致电热材料在使用过程中存在变质、稳定性差的问题。
中国专利CN201410389857.7提供一种高稳定碳晶粉及其制备方法,其特征在于所述高稳定碳晶粉包含功0.5~2%石墨烯和碳纳米管、2~9%助剂和89~97.5%的炭材料。其中助剂包括分散剂、光引发剂、增稠剂、热引发剂、流平剂、稳定剂、消泡剂、紫外吸收剂;碳材料包括石墨、炭黑、煅烧石油焦、石墨纤维、炭纤维;石墨、炭黑、煅烧石油焦的粒径大于300nm,小于50μm,石墨纤维、炭纤维直径大于300nm,小于60μm,长度不大于600μm,该发明制备的碳晶电热材料发热均匀、使用寿命也得到了极大的提高。但是由于该发明仅添加稳定性能更优的碳纤维等,提高稳定性,其稳定持久性相对差。
目前国内对于碳晶发热材料性能的改进多是通过简单的尝试不同碳材料的混合配比而得到复合型碳晶粉,虽然这种方法在一定程度上可以改善碳晶材料的热电性能,但是碳晶发热材料的高温使用性能、快速升温性能以及稳定性却依然无法解决。
发明内容
为克服现有碳晶粉存在的导电导热持久性差的缺点,本发明合成出具有导电特性的抗氧化聚吡咯树脂粉,辅以有机硼抗氧化剂,提高碳晶粉的抗氧化能力,本发明的目的旨在提供一种基于聚吡咯的抗氧化复合碳晶粉。
一种基于聚吡咯的抗氧化复合碳晶粉,以质量计的组成为:40~50份基体炭材料、15~20份抗氧化聚吡咯树脂粉、15~25份黑磷、5~10份氮化硼、4~8份有机硼抗氧化剂、分散剂0.1~1.5份、消泡剂0.02~0.2份。
所述的抗氧化聚吡咯树脂粉,以质量计的制备方法为:通氮气条件下,将150份浓度为0.5mol/L~1mol/L吡咯的水溶液加入到反应器中,然后在搅拌条件下向反应器快速加入120~240份6mol/L~10mol/L的盐酸,室温反应1~3h,然后加入1~3份抗氧化改性剂,继续反应8~12h,过滤分离出聚合物,用大量去离子水冲洗至中性,然后经真空干燥造粒后,得抗氧化聚吡咯树脂粉;所述的抗氧化改性剂为3-叔丁基-4-羟基-苯胺、2,4,6-三叔丁基苯胺、2,6-二叔丁基-4-羟基-苯胺中的至少一种。
所述的基体炭材料、抗氧化聚吡咯树脂粉、氮化硼、有机硼抗氧化剂的粒度为400目~1000目,所述的黑磷的粒度为1000目~2000目。
所述的基体碳材料为炭黑、石墨、石墨烯、碳纤维、碳纳米管、富勒烯中的至少一种。
所述的有机硼抗氧化剂为4-氯苯硼酸、正丙基硼酸、苯乙基硼酸、3-氟苯基硼酸、仲丁基硼酸、对乙基苯硼酸、2-氟吡啶-3-硼酸、4-溴苯硼酸、苯基硼酸4-氟苯基硼酸、3-甲氧基苯基硼酸、正丁基硼酸、2-甲氧基苯基硼酸中的至少一种。
所述的分散剂选用聚羧酸型阴离子分散剂、非离子型高分子水性分散剂中的至少一种。
所述的消泡剂选用有机硅消泡剂、脂肪酸甘油酯、磷酸酯类、聚醚类非离子表面活性剂中的至少一种。
一种基于聚吡咯的抗氧化复合碳晶粉的制备方法,包括以下步骤:
按各组分的重量配比称取基体炭材料、氮化硼、黑磷、有机硼抗氧化剂混合研磨,加水调整粘度,超声波处理10~20min;向上述处理过的材料中按质量比例加入抗氧化聚吡咯树脂粉、分散剂、消泡剂,并用三辊机充分分散均匀,制成粘稠状悬浮液体,在100~160℃条件下烘干6~24h得到高导电、高热辐射碳晶粉。
相对于现有技术,本发明的优点为:(1)首次将具有较高导电性的黑磷用于碳晶粉材料,所述的碳晶粉制成的碳晶取暖材料发热效率更高;(2)合成出抗氧化聚吡咯树脂粉,同时加入有机硼抗氧化剂,提高了所述碳晶粉的抗氧化性与持久稳定性。
具体实施方式
实施例1
一种基于聚吡咯的抗氧化复合碳晶粉,以质量计的组成为:44份石墨、18份抗氧化聚吡咯树脂粉、20份黑磷、8份氮化硼、7份4-氟苯基硼酸、非离子型高分子水性分散剂1.0份、脂肪酸甘油酯0.10份。
本实施例的抗氧化聚吡咯树脂粉,以质量计的制备方法为:通氮气条件下,将150份浓度为0.65mol/L吡咯的水溶液加入到反应器中,然后在搅拌条件下向反应器快速加入130份9mol/L的盐酸,室温反应9h,然后加入2份2,6-二叔丁基-4-羟基-苯胺,继续反应10h,过滤分离出聚合物,用大量去离子水冲洗至中性,然后经真空干燥造粒后,得抗氧化聚吡咯树脂粉。
本实施例的基于聚吡咯的抗氧化复合碳晶粉的制备方法,包括以下步骤:
按各组分的重量配比称取石墨、氮化硼、黑磷、4-氟苯基硼酸混合研磨,加水调整粘度,超声波处理20min;向上述处理过的材料中按质量比例加入抗氧化聚吡咯树脂粉、非离子型高分子水性分散剂、脂肪酸甘油酯,并用三辊机充分分散均匀,制成粘稠状悬浮液体,在100℃条件下烘干24h得到高导电、高热辐射碳晶粉。
实施例2
一种基于聚吡咯的抗氧化复合碳晶粉,以质量计的组成为:35份炭黑、15份石墨、15份抗氧化聚吡咯树脂粉、25份黑磷、5份氮化硼、8份正丙基硼酸、聚羧酸型阴离子分散剂0.1份、有机硅消泡剂0.2份。
本实施例的抗氧化聚吡咯树脂粉,以质量计的制备方法为:通氮气条件下,将150份浓度为0.5mol/L吡咯的水溶液加入到反应器中,然后在搅拌条件下向反应器快速加入240份6mol/L的盐酸,室温反应3h,然后加入1份2,4,6-三叔丁基苯胺,继续反应12h,过滤分离出聚合物,用大量去离子水冲洗至中性,然后经真空干燥造粒后,得抗氧化聚吡咯树脂粉。
本实施例的基于聚吡咯的抗氧化复合碳晶粉的制备方法,包括以下步骤:
按各组分的重量配比称取炭黑、石墨、氮化硼、黑磷、正丙基硼酸混合研磨,加水调整粘度,超声波处理10min;向上述处理过的材料中按质量比例加入抗氧化聚吡咯树脂粉、聚羧酸型阴离子分散剂、有机硅消泡剂,并用三辊机充分分散均匀,制成粘稠状悬浮液体,在160℃条件下烘干6h得到高导电、高热辐射碳晶粉。
实施例3
一种基于聚吡咯的抗氧化复合碳晶粉,以质量计的组成为:30份炭黑、10份碳纤维、20份抗氧化聚吡咯树脂粉、15份黑磷、10份氮化硼、4份2-氟吡啶-3-硼酸、聚羧酸型阴离子分散剂1.5份、聚醚类非离子表面活性剂消泡剂0.02份。
本实施例的抗氧化聚吡咯树脂粉,以质量计的制备方法为:通氮气条件下,将150份浓度为1mol/L吡咯的水溶液加入到反应器中,然后在搅拌条件下向反应器快速加入120份10mol/L的盐酸,室温反应1h,然后加入3份2,6-二叔丁基-4-羟基-苯胺,继续反应8h,过滤分离出聚合物,用大量去离子水冲洗至中性,然后经真空干燥造粒后,得抗氧化聚吡咯树脂粉。
本实施例的基于聚吡咯的抗氧化复合碳晶粉的制备方法,包括以下步骤:
按各组分的重量配比称取炭黑、碳纤维、氮化硼、黑磷、2-氟吡啶-3-硼酸混合研磨,加水调整粘度,超声波处理16min;向上述处理过的材料中按比例加入抗氧化聚吡咯树脂粉、聚羧酸型阴离子分散剂、聚醚类非离子表面活性剂消泡剂,并用三辊机充分分散均匀,制成粘稠状悬浮液体,在130℃条件下烘干14h得到高导电、高热辐射碳晶粉。
性能检测:实施例1-3中基于聚吡咯的抗氧化复合碳晶粉,采用等离子辅助化学气相沉积的方法,将实施例1-3中基于聚吡咯的抗氧化复合碳晶粉在硬质塑料板的表面沉积约300±50nm厚,然后在板的的两表面涂覆耐高温绝缘层,即制得碳晶发热板。按照上述方法制得3.0m2碳晶发热板安装于墙面,并与市售碳晶板(对比例)在220v交流电压与其它条件相同时的检测数据如下表:
平均功率/w | 升温时间 | 表面温度/℃ | |
实施例1 | 392 | 3min45s | 93.4 |
实施例2 | 385 | 3min45s | 89.2 |
实施例3 | 384 | 3min45s | 86.8 |
对比例 | 401 | 3min45s | 75.0 |
Claims (7)
1.一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于:以质量计的组成为:40~50份基体炭材料、15~20份抗氧化聚吡咯树脂粉、15~25份黑磷、5~10份氮化硼、4~8份有机硼抗氧化剂、分散剂0.1~1.5份、消泡剂0.02~0.2份;
其中,所述的抗氧化聚吡咯树脂粉,以质量计的制备方法为:通氮气条件下,将150份浓度为0.5mol/L~1mol/L吡咯的水溶液加入到反应器中,然后在搅拌条件下向反应器快速加入120~240份6mol/L~10mol/L的盐酸,室温反应1~3h,然后加入1~3份抗氧化改性剂,继续反应8~12h,过滤分离出聚合物,用大量去离子水冲洗至中性,然后经真空干燥造粒后,得抗氧化聚吡咯树脂粉;所述的抗氧化改性剂为3-叔丁基-4-羟基-苯胺、2,4,6-三叔丁基苯胺、2,6-二叔丁基-4-羟基-苯胺中的至少一种。
2.根据如权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于,所述的基体炭材料、抗氧化聚吡咯树脂粉、氮化硼、有机硼抗氧化剂的粒度为400目~1000目,所述的黑磷的粒度为1000目~2000目。
3.根据权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于:所述的基体碳材料为炭黑、石墨、石墨烯、碳纤维、碳纳米管、富勒烯中的至少一种。
4.根据权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于:所述的有机硼抗氧化剂为4-氯苯硼酸、正丙基硼酸、苯乙基硼酸、3-氟苯基硼酸、仲丁基硼酸、对乙基苯硼酸、2-氟吡啶-3-硼酸、4-溴苯硼酸、苯基硼酸4-氟苯基硼酸、3-甲氧基苯基硼酸、正丁基硼酸、2-甲氧基苯基硼酸中的至少一种。
5.根据权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于:所述的分散剂选用聚羧酸型阴离子分散剂、非离子型高分子水性分散剂中的至少一种。
6.根据权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于:所述的消泡剂选用有机硅消泡剂、脂肪酸甘油酯、磷酸酯类、聚醚类非离子表面活性剂中的至少一种。
7.根据权利要求1所述的一种基于聚吡咯的抗氧化复合碳晶粉,其特征在于,其制备方法,包括以下步骤:
按各组分的重量配比称取基体炭材料、氮化硼、黑磷、有机硼抗氧化剂混合研磨,加水调整粘度,超声波处理10~20min;向上述处理过的材料中按质量比例加入抗氧化聚吡咯树脂粉、分散剂、消泡剂,并用三辊机充分分散均匀,制成粘稠状悬浮液体,在100~160℃条件下烘干6~24h得到高导电、高热辐射碳晶粉。
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