CN116396332A - 氮-磷-硼阻燃剂、阻燃抗融滴聚氨酯弹性体及其制备方法 - Google Patents
氮-磷-硼阻燃剂、阻燃抗融滴聚氨酯弹性体及其制备方法 Download PDFInfo
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Abstract
本发明公开一种氮‑磷‑硼阻燃剂、阻燃抗融滴聚氨酯弹性体及其制备方法,属于聚氨酯弹性体技术领域。该氮‑磷‑硼阻燃剂的制备方法,包括:将一乙醇胺硼酸酯和糠醛溶于无水乙醇中,通入氮气,在45‑55℃下搅拌反应,得到中间产物;将磷杂菲DOPO溶液与中间产物混合在70‑80℃搅拌反应得到氮‑磷‑硼阻燃剂。该改性聚氨酯弹性体,包括:70%‑80%的聚醚二醇,0.5‑3%氮化硼纳米复合物,16%‑22%的甲苯‑2,4‑二异氰酸酯,8%‑10%的二甲基甲苯二胺,0.5‑1%的紫外光稳定剂和0.5‑3%的氮‑磷‑硼阻燃剂。本发明提出的氮‑磷‑硼阻燃剂提高了聚氨酯弹性体阻燃性、抗融滴性,以及力学性能。
Description
技术领域
本发明涉及聚氨酯弹性体技术领域,具体涉及一种氮-磷-硼阻燃剂、阻燃抗融滴聚氨酯弹性体及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是一种可加热塑化的弹性体材料。分子结构是由二异氰酸酯和多元醇缩聚形成的线型高分子,在使用温度下可以形成物理交联网络,因而具有很好的弹性。TPU由于其优良的力学性质,如高强度、高弹性、卓越的耐磨性,以及良好的耐油、耐老化等特性,已经被广泛的应用于工业、生活、医疗以及军工等方面。虽然TPU性能优点众多,易于成型加工,但它也有着明显的缺陷,即是易燃且熔滴严重。其极限氧指数仅为16%~18%,遇火会迅速燃烧,并产生大量融滴,加快火势蔓延。因此,TPU材料的阻燃改性也显得非常重要。目前市场上的TPU材料大多采用添加含卤素或含磷元素的阻燃剂,卤素由于燃烧时会产生大量有害气体,环境污染严重,慢慢已被磷系阻燃剂取代。但常规磷系阻燃剂并不能解决TPU燃烧时融滴的问题。因此,同时赋予TPU材料阻燃和抗融滴特性是目前对TPU阻燃改性研究的重点。
氮化硼是由氮原子和硼原子所组成的晶体,具有4种不同晶型结构:六方氮化硼、菱方氮化硼、立方氮化硼和纤维矿氮化硼。期中,六方氮化硼结构与性能与石墨极为相似,可剥离为二维纳米片层,具有很强的刚度以及高温润滑性,研究表明六方氮化硼纳米片可以明显提高聚合物力学性能,同时还能增强聚合物阻燃性。因此,将氮化硼纳米片引入TPU中有望提高其抗融滴性。但将氮化硼纳米片直接将氮化硼纳米片应用于聚合物中,由于极性原因很难在聚合物中均匀分散,影响其性能的充分发挥。
发明内容
本发明的目的在于克服上述技术不足,提供一种氮-磷-硼阻燃剂、以及阻燃抗融滴聚氨酯弹性体及其制备方法,解决现有技术中如何同时提高聚氨酯弹性体阻燃性、抗融滴性,以及力学性能的技术问题。
为达到上述技术目的,本发明的技术方案提供一种氮-磷-硼阻燃剂、以及阻燃抗融滴聚氨酯弹性体及其制备方法。
本发明提出的氮-磷-硼阻燃剂的制备方法,包括以下步骤:
将一乙醇胺硼酸酯和糠醛溶于无水乙醇中,通入氮气,在45-55℃下搅拌反应,得到中间产物;
将磷杂菲DOPO溶液与所述中间产物混合在70-80℃搅拌反应得到所述氮-磷-硼阻燃剂。
进一步地,本发明还提出一种氮-磷-硼阻燃剂,由以上制备方法制得。
进一步地,本发明为了配合新型阻燃剂提高TPU抗熔滴性,还发明了一种氮化硼纳米复合物。
该氮化硼纳米复合物的制备方法,包括以下步骤:将聚多巴胺包覆氮化硼纳米片与DMF溶剂混合形成悬浊液;之后向所述悬浊液中加入4,4’-二苯基甲烷二异氰酸酯继续搅拌,之后升温至50-60℃加入催化剂继续反应得到异氰酸酯化的氮化硼纳米复合物。
进一步地,所述催化剂为二月桂酸二丁基锡;和/或,所述反应的时间为10-12h;和/或,按照所述聚多巴胺包覆氮化硼纳米片与所述4,4’-二苯基甲烷二异氰酸酯的质量比(1-2):(50-60)加入所述4,4’-二苯基甲烷二异氰酸酯;和/或,所述聚多巴胺包覆氮化硼纳米片由以下步骤制得:将氮化硼纳米片与水搅拌,得到氮化硼悬浮液,之后加入Tris缓冲液搅拌,继续调节pH至8-9,之后加入多巴胺盐酸盐继续搅拌得到所述聚多巴胺包覆氮化硼纳米片。
此外,本发明还提出一种改性聚氨酯弹性体,按照质量百分比计算,原料包括:70%-80%的聚醚二醇,0.5-3%所述的氮化硼纳米复合物,16%-22%的甲苯-2,4-二异氰酸酯,8%-10%的二甲基甲苯二胺,0.5-1%的紫外光稳定剂和0.5-3%的氮-磷-硼阻燃剂。
进一步地,所述聚醚二醇为聚氧化丙烯醚二醇和四氢呋喃均聚醚二醇中的一种或者两种;和/或,所述紫外光稳定剂为2-(2-羟基-3,5-二叔戊基苯基)苯并三唑。
此外,本发明还提出一种上述改性聚氨酯弹性体的制备方法,包括以下步骤:
S1、将氮化硼纳米复合物、聚醚二醇在80-85℃混合,之后在45-50℃下加入甲苯-2,4-二异氰酸酯混合,之后在85-90℃下搅拌反应得到改性聚氨酯预聚体;
S2、将步骤S1制得的改性聚氨酯预聚体、二甲硫基甲苯二胺、紫外光稳定剂、氮-磷-硼阻燃剂在110-120℃下搅拌混合,之后固化得到所述改性聚氨酯弹性体。
进一步地,在步骤S2中,所述固化包括:在100-105℃下固化,成型后在95-100℃保温得到所述改性聚氨酯弹性体。
进一步地,在步骤S1中,所述搅拌反应的时间为1.5-2h。
进一步地,在步骤S2中,所述搅拌混合的时间为5-10min。
与现有技术相比,本发明的有益效果包括:新型氮-磷-硼阻燃剂的高效阻燃性,即在添加量很少的情况下(3%以下)即可达到理想阻燃效果(UL94-V0级),同时聚多巴胺包覆氮化硼纳米片可以高效的与4,4’-二苯基甲烷二异氰酸酯进行接枝,制备出具有异氰酸酯特征的高分散的氮化硼纳米复合物,使其可以参与下一步与聚醚多元醇的聚合固化过程,不仅可以很好地解决氮化硼纳米片在聚氨酯基体中的分散问题,同时还可通过化学键将分散的纳米氮化硼接入聚氨酯弹性体树脂分子链中,提高改性聚氨酯弹性体的力学性能和燃烧抗熔滴性。
附图说明
图1是本发明制得的氮-磷-硼阻燃剂的核磁氢谱图;
图2是本发明实施例1制得的氮化硼纳米复合物的SEM图。
图3是六方氮化硼粉体在有机溶剂DMF中的分散图(左图),以及实施例1制得的氮化硼纳米复合物有机溶剂DMF中的分散图(右图)。
具体实施方式
本具体实施方式提供一种氮化硼纳米复合物的制备方法,包括以下步骤:将聚多巴胺包覆氮化硼纳米片与DMF溶剂混合形成悬浊液;之后向所述悬浊液中加入4,4’-二苯基甲烷二异氰酸酯继续搅拌,之后升温至50-60℃加入催化剂继续反应10-12h得到异氰酸酯化的氮化硼纳米复合物;所述催化剂为二月桂酸二丁基锡;和/或,按照所述聚多巴胺包覆氮化硼纳米片与所述4,4’-二苯基甲烷二异氰酸酯的质量比(1-2):(50-60)加入所述4,4’-二苯基甲烷二异氰酸酯;和/或,所述聚多巴胺包覆氮化硼纳米片由以下步骤制得:将氮化硼纳米片与水搅拌,得到氮化硼悬浮液,之后加入Tris缓冲液搅拌,继续调节pH至8-9,之后加入多巴胺盐酸盐继续搅拌得到所述聚多巴胺包覆氮化硼纳米片;
所述氮化硼纳米片由以下步骤制得:将六方氮化硼粉体与蔗糖晶体混合,在500rpm转速下固相球磨10-12h,将所得球磨氮化硼在水中超声搅拌,然后离心过滤,重复以上搅拌离心过滤步骤三次得氮化硼纳米片,室温干燥20-24h;所述六方氮化硼粒径为15-50μm,六方氮化硼与蔗糖晶体质量比为1:(4-5)。
本具体实施方式还提出一种氮化硼纳米复合物,由上述制备方法制备得到。
本具体实施方式还提出一种改性聚氨酯弹性体,按照质量百分比计算,原料包括:70%-80%的聚醚二醇,0.5-3%的氮化硼纳米复合物,16%-22%的甲苯-2,4-二异氰酸酯,8%-10%的二甲基甲苯二胺,0.5-1%的紫外光稳定剂及0.5-3%的氮-磷-硼阻燃剂;所述聚醚二醇为聚氧化丙烯醚二醇和四氢呋喃均聚醚二醇中的一种或者两种;和/或,所述紫外光稳定剂为2-(2-羟基-3,5-二叔戊基苯基)苯并三唑。
此外,本具体实施方式还提出一种改性聚氨酯弹性体的制备方法,包括以下步骤:
S1、将氮化硼纳米复合物、聚醚二醇在80-85℃混合,之后在45-50℃下加入甲苯-2,4-二异氰酸酯混合,之后在85-90℃下搅拌反应1.5-2h得到改性聚氨酯预聚体;
S2、将步骤S1制得的改性聚氨酯预聚体、二甲硫基甲苯二胺、紫外光稳定剂、氮-磷-硼阻燃剂在110-120℃下搅拌混合5-10min,之后在100-105℃下固化1-1.5h,成型后放入烘箱中95-100℃保温24h-28h得到所述改性聚氨酯弹性体;
本具体实施方式中的氮-磷-硼阻燃剂由以下步骤制得:
将一乙醇胺硼酸酯和糠醛溶于无水乙醇中,通入氮气,在45-55℃下搅拌反应,得到中间产物;
将磷杂菲DOPO溶液与所述中间产物混合在70-80℃搅拌反应得到所述氮-磷-硼阻燃剂。
常规磷系阻燃剂如聚磷酸铵类,要达到理想阻燃效果,添加量都相对较大(质量百分比10%以上),且燃烧时有烟雾,一般硼系阻燃剂虽然具有一定抑烟功效,但其树脂相容性差且易受湿度和温度影响。本发明所合成的氮-磷-硼阻燃剂MFD,从分子层面结合了磷系阻燃剂与硼系阻燃剂的优势,将硼酸酯结构与磷杂菲结构DOPO通过席夫碱化学键结合在一起,同时引入了有阻燃效果的N元素,大大提高了阻燃剂的阻燃效率,且与树脂的相容性好,在较少的添加量下(0.5%-3%)即可达到对聚氨酯弹性体高效的阻燃和抑烟协同效果。
通过在氮化硼纳米片的表面包覆聚多巴胺,得到表面改性的氮化硼纳米材料,由于聚多巴胺表面富含羟基活性位点,相对于未改性的氮化硼,聚多巴胺包覆氮化硼纳米片可以高效的与4,4’-二苯基甲烷二异氰酸酯进行接枝,制备出具有异氰酸酯特征的高分散的氮化硼纳米复合物,很好地解决了氮化硼纳米片在聚氨酯基体中的分散问题,同时聚多巴胺也具有一定的阻燃性。以异氰酸酯化的氮化硼纳米复合物,聚醚二醇,甲苯-2,4-二异氰酸酯为反应物合成的聚氨酯弹性体预聚物进一步与二甲硫基甲苯二胺反应将氮-磷-硼阻燃剂均匀包埋其中,制备得到的聚氨酯弹性体具有优良的阻燃性,抗融滴性以及力学性能。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
下述实施例中的氮-磷-硼阻燃剂(MFD)由以下步骤制得:
将0.05mol的一乙醇胺硼酸酯和0.05mol的糠醛分别溶于50ml无水乙醇加入三口烧瓶中,通入氮气,在50℃下搅拌反应4h,得到中间产物(MF);
将0.05mol溶于50ml无水乙醇的磷杂菲DOPO加入上述反应三口烧瓶中,升温至80℃搅拌12h;反应结束后过滤沉淀,并用无水乙醇洗涤三遍,60℃真空干燥12h,最终得到淡黄色固体粉末,即为氮-磷-硼阻燃剂(MFD),合成所得氮-磷-硼阻燃剂MFD核磁氢谱图如图1所示。
反应式为:
另外需要说明的是,所用市售药品均为分析纯,其中,聚四氢呋喃醚二醇分子量2000,氮化硼粒径15-50μm。
实施例1
本实施例提出一种氮化硼纳米复合物,由以下步骤制得:
1)将4g六方氮化硼粉体与16g蔗糖晶体混合,在500rpm转速下固相球磨12h,将所得球磨氮化硼在去离子水中超声搅拌,然后离心过滤,重复以上搅拌离心过滤步骤三次得氮化硼纳米片,室温干燥24h;
2)将1g氮化硼纳米片加入100mL去离子水中超声搅拌,得到氮化硼悬浮液,然后加入12.5mLTris缓冲液,继续超声处理30min;加入适量的6mol/L的NaOH溶液调节溶液pH至8.5,随后向以上溶液体系中加入1.0g多巴胺盐酸盐,在室温搅拌反应24h;反应结束后,以5000rpm离心5min,用去离子水多次洗涤,直到离心上层溶液的pH变为中性,最后,将包覆多巴胺聚合物的氮化硼纳米片在真空烘箱中在80℃下干燥24h;
3)将1g包覆多巴胺聚合物的氮化硼纳米片加入溶剂200mLDMF中超声搅拌,形成悬浊液,向上述悬浊液中加入55g4,4’-二苯基甲烷二异氰酸酯继续搅拌,升温到55℃,加入7-8滴催化剂二月桂酸二丁基锡,继续反应10h,过滤,抽真空除去溶剂得异氰酸酯化的氮化硼纳米复合物,从图2可以看出,还是保留了其片状形貌,从图3可以看出氮化硼纳米复合物能够在有机溶剂DMF中分散均匀,而没有改性的六方氮化硼粉体不能在有机溶剂DMF中分散。
本实施例还提出一种聚氨酯弹性体,由以下步骤制得:
1)将0.5g的本实施例制得的异氰酸酯化的氮化硼纳米复合物加入至70g聚四氢呋喃醚二醇搅拌升温至80℃反应0.5h,然后降温到50℃加入20g甲苯-2,4-二异氰酸酯中,继续搅拌升温到90℃反应1.5h,抽真空除泡得到改性聚氨酯预聚体;
2)将上述反应所得改性聚氨酯预聚体、8g二甲硫基甲苯二胺、0.5g紫外光稳定剂2-(2-羟基-3,5-二叔戊基苯基)苯并三唑、1g氮-磷-硼阻燃剂混合,然后转移到密炼机中混炼5min,混炼温度110℃;之后将混炼样品倒入模具中,在100℃下反应固化1.5h,成型后放入烘箱中100℃保温24h,得到阻燃抗融滴聚氨酯弹性体样品;其中,氮化硼纳米复合物质量百分比含量为0.5%,氮-磷-硼阻燃剂MFD含量为1%。
实施例2
本实施例提出一种氮化硼纳米复合物,由以下步骤制备得到:
1)将4g六方氮化硼粉体与20g蔗糖晶体混合,在500rpm转速下固相球磨12h,将所得球磨氮化硼在去离子水中超声搅拌,然后离心过滤,重复以上搅拌离心过滤步骤三次得氮化硼纳米片,室温干燥24h;
2)将2g氮化硼纳米片加入200mL去离子水中超声搅拌,得到氮化硼悬浮液,之后加入25mLTris缓冲液,继续超声处理30min;之后加入适量的6mol/L的NaOH溶液调节溶液pH至8.5;之后向以上溶液体系中加入3g多巴胺盐酸盐;在室温搅拌反应24h;反应结束后,通过以5000rpm离心5min,用去离子水多次洗涤,直到离心上层溶液的pH变为中性;最后,将包覆多巴胺聚合物的氮化硼纳米片在真空烘箱中在80℃下干燥24h。
3)将2g包覆多巴胺聚合物的氮化硼纳米片加入溶剂200mLDMF中超声搅拌,形成悬浊液,向上述悬浊液中加入100g4,4’-二苯基甲烷二异氰酸酯继续搅拌,升温到55℃,加入14-15滴催化剂二月桂酸二丁基锡,继续反应12h,过滤,抽真空除去溶剂得异氰酸酯化的氮化硼纳米复合物。
本实施例还提出一种改性聚氨酯弹性体,由以下步骤制得:
1)将1.5g的本实施例制得的氮化硼纳米复合物加入80g聚四氢呋喃醚二醇搅拌升温80℃反应0.5h,然后降温到50℃加入15g甲苯-2,4-二异氰酸酯中,继续搅拌升温到90℃反应1.5h,抽真空除泡得到改性聚氨酯预聚体;
2)将上述反应所得改性聚氨酯预聚体、10g二甲硫基甲苯二胺、0.8g紫外光稳定剂2-(2-羟基-3,5-二叔戊基苯基)苯并三唑、2g氮-磷-硼阻燃剂混合,然后转移到密炼机中混炼5min,混炼温度110℃;然后将混炼样品倒入模具中,在100℃下反应固化1.5h,成型后放入烘箱中100℃保温24h,得到阻燃抗融滴聚氨酯弹性体样品。其中,氮化硼纳米复合物质量百分比含量为1.3%,氮-磷-硼阻燃剂MFD含量为1.8%。
实施例3
本实施例提出一种氮化硼纳米复合物,由以下步骤制得:
1)将3g六方氮化硼粉体与15g蔗糖晶体混合,在500rpm转速下固相球磨12h,将所得球磨氮化硼在去离子水中超声搅拌,然后离心过滤,重复以上搅拌离心过滤步骤三次得氮化硼纳米片,室温干燥24h;
2)将2g氮化硼纳米片加入200mL去离子水中超声搅拌,得到氮化硼悬浮液,然后加入25mLTris缓冲液,继续超声处理30min;加入适量的6mol/L的NaOH溶液调节溶液pH至8.5;随后向以上溶液体系中加入3g多巴胺盐酸盐,在室温搅拌反应24h;反应结束后,通过以5000rpm离心5min,用去离子水多次洗涤,直到离心上层溶液的pH变为中性;最后,将包覆多巴胺聚合物的氮化硼纳米片在真空烘箱中在80℃下干燥24h;
3)将2g包覆多巴胺聚合物的氮化硼纳米片加入溶剂200mLDMF中超声搅拌,形成悬浊液,向上述悬浊液中加入100g4,4’-二苯基甲烷二异氰酸酯继续搅拌,升温到55℃,加入14-15滴催化剂二月桂酸二丁基锡,继续反应12h,过滤,抽真空除去溶剂得异氰酸酯化的氮化硼纳米复合物。
本实施例还提出一种改性聚氨酯弹性体,由以下步骤制得:
1)将2g本实施例制得的氮化硼纳米复合物加入70g聚四氢呋喃醚二醇搅拌升温80℃反应0.5h,然后降温到50℃加入16g甲苯-2,4-二异氰酸酯中,继续搅拌升温到90℃反应2h,抽真空除泡得到改性聚氨酯预聚体;
2)将上述反应所得改性聚氨酯预聚体、10g二甲硫基甲苯二胺、0.6g紫外光稳定剂2-(2-羟基-3,5-二叔戊基苯基)苯并三唑、3g新型氮-磷-硼阻燃剂混合,然后转移到密炼机中混炼5min,混炼温度110°C;然后将混炼样品倒入模具中,在100℃下反应固化1.5h,成型后放入烘箱中100℃保温24h,得到阻燃抗融滴聚氨酯弹性体样品。其中,氮化硼纳米复合物质量百分比含量为2%氮-磷-硼阻燃剂MFD含量为3%。
对比例
实验所用对比例是在实施例1的组成基础上进行变动所得。与实施例1不同之处在于,用相同质量的常规改性氮化硼以及常规阻燃剂APP(聚磷酸铵)替代氮化硼纳米复合物以及氮-磷-硼阻燃剂,其他反应步骤和反应条件均与实施例1相同。实施例1以及对比例1-1,1-2,1-3,1-4,1-5,组成如下表1所述(质量百分含量)。
表1实施例1及各对比例聚氨酯弹性体成分表
对实施例以及对比例进行阻燃性能测试以及力学测试,结果如下表2所示。
阻燃性能测试:垂直燃烧(UL94);极限氧指数LOI(IOS4589-2)。
力学性能测试:拉伸性能测试(电子万能拉伸试验机,拉伸速率250mm/min)。
表2实施例1-3及各对比例聚氨酯弹性体测试性能表
对比表2中数据可以明显发现,氮化硼纳米复合物的引入明显改善聚氨酯弹性体的燃烧滴落问题,且本发明制得的阻燃剂阻燃效果优于常规阻燃剂聚磷酸铵。同时力学性能方面,加入氮化硼纳米复合物的聚氨酯弹性体也优于加入聚磷酸铵或未改性氮化硼的体系。原因可能是改性氮化硼纳米在聚氨酯基体之间分散均匀且有化学键结合,可以很好的发挥纳米增强效应,提高聚氨酯强度。
本发明制备的改性聚氨酯弹性体不仅阻燃性能优异,且力学性能好,具有良好的应用前景。
以上所述本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内。
Claims (10)
1.一种氮-磷-硼阻燃剂的制备方法,其特征在于,包括以下步骤:
将一乙醇胺硼酸酯和糠醛溶于无水乙醇中,通入氮气,在45-55℃下搅拌反应,得到中间产物;
将磷杂菲DOPO溶液与所述中间产物混合在70-80℃搅拌反应得到所述氮-磷-硼阻燃剂。
2.一种氮-磷-硼阻燃剂,其特征在于,由权利要求1所述的制备方法制得。
3.一种阻燃抗融滴聚氨酯弹性体,其特征在于,按照质量百分比计算,原料包括:70%-80%的聚醚二醇,0.5-3%氮化硼纳米复合物,16%-22%的甲苯-2,4-二异氰酸酯,8%-10%的二甲基甲苯二胺,0.5-1%的紫外光稳定剂和0.5-3%的权利要求2所述的氮-磷-硼阻燃剂。
4.根据权利要求3所述的阻燃抗融滴聚氨酯弹性体,其特征在于,所述聚醚二醇为聚氧化丙烯醚二醇和四氢呋喃均聚醚二醇中的一种或者两种;和/或,所述紫外光稳定剂为2-(2-羟基-3,5-二叔戊基苯基)苯并三唑。
5.一种权利要求3-4任一项所述的阻燃抗融滴聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
S1、将氮化硼纳米复合物、聚醚二醇在80-85℃混合,之后在45-50℃下加入甲苯-2,4-二异氰酸酯混合,之后在85-90℃下搅拌反应得到改性聚氨酯预聚体;
S2、将步骤S1制得的改性聚氨酯预聚体、二甲硫基甲苯二胺、紫外光稳定剂、氮-磷-硼阻燃剂在110-120℃下搅拌混合,之后固化得到所述改性聚氨酯弹性体。
6.根据权利要求5所述的制备方法,其特征在于,在步骤S2中,所述固化包括:在100-105℃下固化,成型后在95-100℃保温得到所述改性聚氨酯弹性体。
7.根据权利要求5所述的制备方法,其特征在于,在步骤S1中,所述搅拌反应的时间为1.5-2h。
8.根据权利要求7所述的制备方法,其特征在于,在步骤S2中,所述搅拌混合的时间为5-10min。
9.根据权利要求5所述的制备方法,其特征在于,所述氮化硼纳米复合物由以下步骤制得:将聚多巴胺包覆氮化硼纳米片与DMF溶剂混合形成悬浊液;之后向所述悬浊液中加入4,4’-二苯基甲烷二异氰酸酯继续搅拌,之后升温至50-60℃加入催化剂继续反应得到异氰酸酯化的氮化硼纳米复合物。
10.根据权利要求9所述的制备方法,其特征在于,所述催化剂为二月桂酸二丁基锡;和/或,所述继续反应的时间为10-12h;和/或,按照所述聚多巴胺包覆氮化硼纳米片与所述4,4’-二苯基甲烷二异氰酸酯的质量比(1-2):(50-60)加入所述4,4’-二苯基甲烷二异氰酸酯;和/或,所述聚多巴胺包覆氮化硼纳米片由以下步骤制得:将氮化硼纳米片与水搅拌,得到氮化硼悬浮液,之后加入Tris缓冲液搅拌,继续调节pH至8-9,之后加入多巴胺盐酸盐继续搅拌得到所述聚多巴胺包覆氮化硼纳米片。
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