CN112552475A - 一种碳纳米管与磷系阻燃剂复配改性水性聚氨酯及制备方法 - Google Patents
一种碳纳米管与磷系阻燃剂复配改性水性聚氨酯及制备方法 Download PDFInfo
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Abstract
本发明涉及了一种碳纳米管与磷系阻燃剂复配改善聚氨酯及其制备方法。将酸化后的碳纳米管接入水性聚氨酯中,使用含磷三元醇三羟甲基氧化磷为扩链剂,进行反应合成出复配阻燃水性聚氨酯。酸化后的碳纳米管上具有一定数量的羟基和羧基,羧基可以参与聚氨酯的合成,提高了聚氨酯改性材料的交联密度,从而有效抑制了聚氨酯主链的分解。燃烧过程中,磷具有催化成炭的作用,形成的炭层覆盖在聚合物的表面,起到隔热隔气的作用,加入碳纳米管后,其残炭表面能够观察到由碳纳米管交织形成的网络结构,这些网络结构可以提高残炭层的力学强度,避免裂纹,使残炭表面连续,具有更好的致密性,更有效地阻隔热量和可燃物的传递。
Description
技术领域
本发明属于水性聚氨酯材料技术领域,涉及聚氨酯材料的阻燃性能研究,尤其是一种利用碳纳米管与磷系阻燃剂复配改性水性聚氨酯的制备方法。
背景技术
水性聚氨酯具有良好的综合性能,如耐低温,耐腐蚀,耐屈挠等,又具有不污染、运输安全、工作环境好等特点,除了可以满足环保要求的无VOC排放外,还可以得到与有机溶剂型相似的形态,在基本不改变有机溶剂型使用工艺前提下保持有机溶剂型的产品性能,因而水性聚氨酯越来越受到人们的重视。不过,水性聚氨酯涂膜的耐热性、机械性能等也存在着许多不足,因此,近些年来,对水性聚氨酯改性的研究较多,研发既能保持水性聚氨酯的优良性能,同时又提高其阻燃性的改性水性聚氨酯越来越重要。
纳米材料的涌现为研究开发高性能材料和对现有材料进行改性提供了一个新的途径。在众多的纳米材料中,碳纳米管(CNTs)是以碳原子形成的石墨片层卷成中空的管体,径向尺寸为纳米级,具有力学强度高、稳定性好等优点,成为理想的聚合物增强材料。碳纳米管/水性聚氨酯复合材料,既保留了聚氨酯材料的基本性能,又能使水性聚氨酯的阻燃性、热稳定性等性能得到明显提高。
发明内容
本发明的目的在于针对现有技术的不足,提供一种利用碳纳米管与磷系阻燃剂复配改性水性聚氨酯的制备方法。将酸化后的碳纳米管接入水性聚氨酯中,使用含磷三元醇三羟甲基氧化磷为扩链剂,进行反应合成出复配阻燃水性聚氨酯。酸化后的碳纳米管上具有一定数量的羟基和羧基,羧基可以参与聚氨酯的合成,提高了聚氨酯改性材料的交联密度,从而有效抑制了聚氨酯主链的分解。燃烧过程中,磷具有催化成炭的作用,形成的炭层覆盖在聚合物的表面,起到隔热隔气的作用,加入碳纳米管后,其残炭表面能够观察到由碳纳米管交织形成的网络结构,这些网络结构可以提高残炭层的力学强度,避免裂纹,使残炭表面连续,具有更好的致密性,更有效地阻隔热量和可燃物的传递。
本发明的技术方案为:
(1)将不同比例的酸化后的碳纳米管分散于10-20%聚丙二醇1000中,然后与10-20%异佛尔酮二异氰酸酯、0.1-0.3%二月桂酸二正丁基锡混合均匀,在200-500r/min转速下,在氮气保护下,70-100℃,反应至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,得到聚氨酯预聚体;
(2)降温至60-80℃,加入1-2%阴离子型扩链剂二羟甲基丙酸,继续搅拌反应,加入稀释剂丙酮,反应4h,降温至50-60℃,加入1.5-2.5%三乙胺溶液,中和30min;
(3)在1000-1500r/min转速下,向上述预聚体中缓慢加入55-75%去离子水,乳化后,把三羟甲基氧化磷与二元醇扩链剂按不同比例进行复配,加入反应体系,反应0.5h,减压蒸馏出溶剂,得到复配阻燃水性聚氨酯乳液。
其中,步骤(1)中的酸化后的碳纳米管在反应物中所占质量分数比为1-5%。步骤(3)中的三羟甲基氧化磷物质的量在二元醇扩链剂中的比例为20-100%。
本发明的技术优点如下:
(1)本发明中的碳纳米管/磷阻燃水性聚氨酯属于反应型阻燃水性聚氨酯,阻燃效果持久,不含卤素,安全环保,阻燃效果更好。
(2)本发明的制备方法简单易操作。
(3)本发明制备的碳纳米管/磷阻燃水性聚氨酯具有良好的力学性能和持久的阻燃性,能用作阻燃涂料或涂饰剂。
具体实施方式
实施例1
(1)聚丙二醇1000、二羟甲基丙酸在真空干燥箱中真空脱水2小时,放入干燥器中保存。(2)将0.20g酸化后的碳纳米管分散于9.60g(0.0096mol)聚丙二醇1000(PPG1000)中,然后与6.85g(0.0308mol)异佛尔酮二异氰酸酯(IPDI)、0.075g二月桂酸二丁基锡(DBTDL)混合均匀,在300r/min转速下,在氮气保护下,85℃,反应4h,至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,得到聚氨酯预聚体;(3)降温至80℃,加入阴离子型扩链剂二羟甲基丙酸1.10g(0.0082mol),继续搅拌反应,加入稀释剂丙酮,反应4h,降温至60℃,加入1.00g(0.0099mol)三乙胺(TEA),中和30min;(4)在1500r/min转速下,向上述预聚体中缓慢加入37mL去离子水,乳化30min,分别加入三羟甲基氧化磷(THPO)和1,4-丁二醇(BDO)的质量为0.31g(0.0022mol)和0.80g(0.0088mol),加入反应体系,反应0.5h,减压蒸馏出丙酮,得到复配阻燃水性聚氨酯乳液。
实施例2
将步骤(1)中酸化后的碳纳米管的量改为0.40g,其他工艺流程不变,步骤(2)、(3)同实例1,将步骤(4)中三羟甲基氧化磷和1,4-丁二醇的量分别改为0.62g(0.0044mol)和0.6g(0.0066mol),其他工艺流程不变,得到复配阻燃水性聚氨酯。
实施例3
将步骤(1)中酸化后的碳纳米管的量改为0.61g,其他工艺流程不变,步骤(2)、(3)同实例1,将步骤(4)中三羟甲基氧化磷和1,4-丁二醇的量分别改为0.93g(0.0066mol)和0.40g(0.0044mol),其他工艺流程不变,得到复配阻燃水性聚氨酯。
实施例4
将步骤(1)中酸化后的碳纳米管的量改为0.83g,其他工艺流程不变,步骤(2)、(3)同实例1,将步骤(4)中三羟甲基氧化磷和1,4-丁二醇的量分别改为1.24g(0.0088mol)和0.20g(0.0022mol),其他工艺流程不变,得到复配阻燃水性聚氨酯。
实施例5
将步骤(1)中酸化后的碳纳米管的量改为1.06g,其他工艺流程不变,步骤(2)、(3)同实例1,在步骤(4)中加入三羟甲基氧化磷的质量为1.55g(0.011mol),其他工艺流程不变,得到复配阻燃水性聚氨酯。
阻燃性能测试将上述实施例中样品制备成聚氨酯膜,按ASTM D2863标准测试极限氧指数,按GB/T2794-1995测试乳液粒径,按GB/T2794-1995测试乳液粘度,按GB/T6753.3-1986测试乳液稳定性。实验结果如下表所示:
表1阻燃水性聚氨酯性能测试
Claims (3)
1.一种利用碳纳米管与磷系阻燃剂复配改性水性聚氨酯及制备方法,其特征在于:将碳纳米管与具有阻燃功能的含磷单体三羟甲基氧化磷通过化学键方式分别连接在聚氨酯分子主链上。三羟甲基氧化磷(THPO)的化学结构中含有较磷酸酯类更耐水解的C-P键,不含卤素,燃烧不产生有害气体,且其三个羟基(-CH2OH)含有活性氢,反应活性强。酸化后的碳纳米管上具有一定数量的羟基和羧基,羧基可以参与聚氨酯的合成。制备步骤如下:
(1)制备聚氨酯预聚体:以反应原料总质量为100%计,将不同比例的酸化后的碳纳米管分散于10-20%聚丙二醇1000中,然后与10-20%异佛尔酮二异氰酸酯、0.1-0.3%二月桂酸二正丁基锡混合均匀,在200-500r/min转速下,在氮气保护下,70-100℃,反应至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,得到聚氨酯预聚体;
(2)降温至60-80℃,加入1-2%阴离子型自乳化剂二羟甲基丙酸,继续搅拌反应,加入稀释剂丙酮,反应4h,降温至50-60℃,加入1.5-2.5%三乙胺溶液,中和30min;
(3)在1000-1500r/min转速下,向上述预聚体中缓慢加入55-75%去离子水,乳化后,把三羟甲基氧化磷与二元醇扩链剂按不同比例进行复配,加入反应体系,反应0.5h,减压蒸馏出溶剂,得到复配阻燃水性聚氨酯乳液。
2.根据权利要求1所述的方法,其特征在于:步骤(1)中所述的酸化后的碳纳米管在反应物中所占质量分数比为1-5%。
3.根据权利要求1所述的方法,其特征在于:步骤(3)所述的三羟甲基氧化磷物质的量在二元醇扩链剂中的比例为20-100%。
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