CN107501859B - 一种用于环氧树脂体系的dopo型固化剂及其应用 - Google Patents
一种用于环氧树脂体系的dopo型固化剂及其应用 Download PDFInfo
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Abstract
本发明公开了一种新型化合物10‑((4‑氨基苯基)(羟基)甲基)‑9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物作为固化剂、阻燃剂在环氧树脂体系中的应用方法,该方法具体为:将其与环氧树脂混合,并加入有机溶剂、促进剂和填料,搅拌使之混合均匀;将混合物加热至60‑80℃预固化1‑2h使之成型,继续加热至120~160℃固化2‑6h,使固化剂充分固化环氧树脂,最后升温至180~200℃继续固化2‑4h完成固化,最终形成交联网状固化物。该新型化合物与环氧树脂具有较好的相容性,既可固化环氧树脂又能用于环氧树脂的阻燃,并且不含卤素,低烟低毒,符合新型绿色环保型固化剂的要求。
Description
技术领域
本发明涉及环氧树脂材料技术领域,具体涉及DOPO型化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物及其在环氧树脂体系中的应用。
背景技术
环氧树脂具有优良的机械性能、耐化学腐蚀性、电绝缘性、加工性能、粘接性能,并且收缩率低,广泛应用于社会各行各业。环氧树脂固化剂是环氧树脂体系中不可缺少的一部分,目前市场上环氧树脂固化剂品种繁多,性能也各异。前人已在此方面进行了诸多研究,主要针对环氧树脂的缺点以及不同用途,对其固化剂进行了改性,常见的有增韧、阻燃等,或是用于低温、增加黏度等方面。
环氧树脂极限氧指数(LOI)只有19.8%,属易燃材料,会限制其在某些特殊场合的应用。而DOPO是新型阻燃剂中间体,其结构中含有P-H键,对烯烃、环氧键和羰基极具活性,可反应生成许多衍生物。因此,将DOPO与以上官能团反应,制备可反应型环氧树脂固化剂,一方面可用于环氧树脂的固化,另一方面亦可用于环氧树脂的阻燃。
发明内容
本发明的目的在于提供一种新型化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,及其作为新型固化剂、阻燃剂在环氧树脂体系中的应用。该新型化合物的结构式如下所示:
所述10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物在环氧树脂体系中的应用方法,具体包括以下步骤:按一定比例将10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与环氧树脂混合,再加入有机溶剂、促进剂和填料,搅拌混合均匀;将混合物注入模具中预固化成型,升温后固化,继续升温完成后固化,最终得到交联网状固化物。
上述方案中,10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的用量为环氧树脂质量的10~15%。
上述方案中,所述促进剂的用量为环氧树脂质量的1~3%。
上述方案中,所述环氧树脂为E44、E51、CYD127、CYD128、E20、E12中的任意一种,或其中几种按任意比例混合形成的混合物。
上述方案中,所述促进剂为DMP-30或咪唑中的一种。
上述方案中,所述有机溶剂为乙醇、丙酮、二甲苯、四氢呋喃、N’N-二甲基甲酰胺(DMF)中的一种。
上述方案中,预固化成型温度为60-80℃,所需时间1-2h。预固化成型的主要目的是使之成型。
上述方案中,固化温度为120-160℃,所需时间2-6h。固化阶段的主要目的是使反应型阻燃环氧树脂固化剂充分固化环氧树脂。
上述方案中,后固化温度为180-200℃,所需时间2-4h。后固化阶段的主要目的是消除内应力,提高粘接强度,提高环氧树脂固化物的综合性能。
与现有技术相比,本发明的有益效果在于:(1)所使用化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物既可固化环氧树脂,亦可用于环氧树脂阻燃;(2)化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与环氧树脂相容性较好;(3)所用的化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物不含卤素,低烟低毒,符合新型绿色环保型固化剂的要求。
附图说明
图1为本发明制备的新型化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的1H-NMR谱图;
图2为10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物固化环氧树脂的机理图。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果,以下结合具体实施例进行进一步说明。
本发明制备化合物10-(3-氨基-2-甲基-3-氧代丙基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物所涉及到的反应如下所示:
化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的合成方法,具体步骤如下:
1.在N2氛围下,向装有温度计、冷凝回流、磁力搅拌和N2通入的250mL三口烧瓶中加入DOPO(0.01mol)、对硝基苯甲醛(0.01mol)和乙醇(10mL),开始加热并搅拌使其完全溶解,然后升温至60℃,在N2保护氛围下反应8h。
2.待反应结束后,冷却至室温,抽滤得到粗产品,再用去离子水冲洗,重复3次,最后在真空干燥箱中于80℃下干燥24h,得到中间产物。
3.将步骤(2)所得中间产物(0.01mol)、铁粉(0.035mol)和盐酸溶液(含0.065mol的氯化氢)混合,在室温下搅拌便能很快反应,然后加入稀NaOH溶液中和,用乙酸乙酯萃取提纯得到最终产物。
制得的新型化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的1H-NMR谱图如图1所示。图1中相关峰位的化学位移及归属说明参见表1,从产生的羟基碳氢以及与其相连的碳氢的化学位移,可证实得到的产物为10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物。
表1实施例1产物的1H-NMR谱图解析表
实施例1
新型化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物在环氧树脂中的应用方法,其具体步骤如下:
1.选取环氧树脂CYD127,将其与10wt%的化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,1wt%的DMP-30或咪唑(均以环氧树脂质量计,下同),有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至60℃预固化1h,使之成型;
3.将混合物加热至120℃固化2h,使固化剂充分固化环氧树脂,然后继续升温至180℃后固化2h,以便消除内应力提高胶接强度和环氧树脂固化物的综合性能。
利用10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物固化环氧树脂的机理参见图2。在适当的条件下,10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物上的伯氨基首先和环氧基反应,环氧基开环反应成羟基,伯胺失去一个活泼H成仲胺,然后仲氨基继续和环氧基反应生成叔氨基,生成的羟基同时也和环氧基反应,反应持续进行,生成的羟基具有加速固化的倾向。
实施例2
1.选取环氧树脂E51,将其与15wt%的化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,3wt%的DMP-30或咪唑,有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至60℃预固化1h,使之成型;升温至120℃固化2h,继续升温至180℃后固化2h。
实施例3
1.选取环氧树脂CYD128,将其与15wt%的化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,3wt%的DMP-30或咪唑,有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至80℃预固化1h,使之成型;升温至160℃固化2h,继续升温至200℃后固化2h。
实施例4
1.选取环氧树脂E51,将其与15wt%的化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,3wt%的DMP-30或咪唑,有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至80℃预固化2h,使之成型;升温至160℃固化6h,继续升温至200℃后固化4h。
对比例1
1.选取环氧树脂CYD127,将其与10wt%的化合物DOPO,1wt%的DMP-30或咪唑(均以环氧树脂质量计,下同),有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至60℃预固化1h,使之成型;
3.将混合物加热至120℃固化2h,使固化剂充分固化环氧树脂,然后继续升温至180℃后固化2h,以便消除内应力提高胶接强度和环氧树脂固化物的综合性能。
对比例2
1.选取环氧树脂E51,将其与15wt%的化合物苯胺,3wt%的DMP-30或咪唑,有机溶剂DMF和填料混合均匀;
2.将上述混合液注入自制的硅胶模具中,加热至60℃预固化1h,使之成型;升温至120℃固化2h,继续升温至180℃后固化2h。
将以上各实施例和对比例固化物制备成尺寸为130mm×13mm×3.2mm的标准样条各5根,测试UL94级别和极限氧指数取其平均值,测试结果如下表:
表2各样条的UL94级别和极限氧指数测试结果表
由表2可以看出,在其他参数相同的条件下,仅仅因为固化剂种类的不同使得最终样品阻燃等级和极限氧指数均有较大幅度的改善,证明该新型化合物不仅能够固化环氧树脂还能提升环氧树脂的阻燃性能。
Claims (1)
1.化合物10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物作为固化剂、阻燃剂在环氧树脂体系中的应用方法,其特征在于,包括以下步骤:按照10%-15%的质量比将10-((4-氨基苯基)(羟基)甲基)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与环氧树脂混合,再加入有机溶剂、促进剂和填料,搅拌混合均匀;将混合物注入模具中预固化成型,升温后固化,继续升温完成后固化,最终得到交联网状固化物;其中预固化成型温度为60-80℃,所需时间1-2h;固化温度为120-160℃,所需时间2-6h;后固化温度为180-200℃,所需时间2-4h;所述环氧树脂为E44、E51、CYD127、CYD128、E20、E12中的任意一种,或其中几种按任意比例混合形成的混合物;所述促进剂为DMP-30或咪唑中的一种,其加入量相当于环氧树脂质量的1%-3%;所述有机溶剂为乙醇、丙酮、二甲苯、四氢呋喃、N’N-二甲基甲酰胺中的一种。
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