CN109438756B - 阻燃剂三聚o,o-2-螺环苯基亚膦酸二酯丙撑磷腈化合物及其制备方法 - Google Patents
阻燃剂三聚o,o-2-螺环苯基亚膦酸二酯丙撑磷腈化合物及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种阻燃剂三聚O,O‑2‑螺环苯基亚膦酸二酯丙撑磷腈化合物及其制备方法,该化合物的结构如下式所示:
Description
技术领域
本发明涉及一种阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物及其制备方法,该化合物含有磷、氮协同阻燃元素,可用作聚酯、聚酰胺、聚氨酯、环氧树脂、不饱和树脂、聚乙烯醇和涂料等的阻燃剂。
背景技术
近年来,随着对阻燃技术要求的提高和环保意识的增强,阻燃剂的无卤化、抑烟无毒已经成为当今阻燃剂研究领域的前沿性课题。相比传统的阻燃剂,由于其存在添加量大、发烟量大和产生有毒、腐蚀性气体等严重缺点,人们正在寻找新的环保型阻燃剂替代品。磷氮系阻燃剂具有高效,低毒,无腐蚀性以及与材料相容性好等优点,因此磷氮系阻燃剂已成为研究开发的重点。
本发明阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物属多磷多氮结构,磷含量高,还含有阻燃元素氮,双元素协同阻燃效能高。该产品结构对称性好,芳性稳定,分解温度高,与高分子材料相容性好,能适应材料的高温加工,且原料廉价易得,应用范围广,市场蕴藏着很好的开发前景。
发明内容
本发明的目的之一在于提出一种阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物,其物化性能稳定,无毒,阻燃效能高,与高分子材料相容性好,可克服现有技术中的不足。
为实现上述发明目的,本发明采用了如下技术方案:
一种阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物,其特征在于,该化合物的结构如下式所示:
本发明的另一目的在于提出一种阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物的制备方法,其工艺简单,易于规模化生产,且原料廉价易得,设备投资少,成本低廉,该方法为:
将季戊四醇分散溶解于有机溶剂中,再分三批加入六氯环三磷腈,控制六氯环三磷腈和季戊四醇摩尔比为1∶3,升温至90℃反应4h,至无氯化氢放出;降低温度至30℃,滴加与季戊四醇等摩尔量的苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后,升温至100℃~130℃,反应7~10小时,至无氯化氢产生;降温至30℃以下,减压蒸馏出有机溶剂(回收利用),再加入相产物对理论质量克数2~3倍体积毫升数的蒸馏水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈。
如上所述的有机溶剂为二氧六环、甲苯、乙二醇二乙醚和氯苯,其有机溶剂的体积毫升数与六氯环三磷腈和季戊四醇的质量克数总和之比是3∶1~5∶1。
本发明的三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈为白色固体,分解温度为345±5℃,产率为88.4%~92.8%,可用作聚酯、聚酰胺、环氧树脂、不饱和树脂、聚乙烯醇和涂料等的阻燃剂。该阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物的制备原理如下式所示:
与现有技术相比,本发明的有益之处在于:
①本发明阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物结构新颖,磷含量为21.8%,氮含量为4.9%,阻燃元素总含量为26.7%。结构对称好,稳定性高,能适用于多种工程塑料的高温加工,氮、磷双元素协同阻燃效能高,具有很好的增塑性;
②本发明阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈不含卤素,有利于环保,属膨胀型环境友好阻燃剂;
③本发明阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈的制备方法工艺简单,合成过程无需添加催化剂不引入杂质;设备简单,成本低廉,适于规模化生产,有很好的应用开发前景。
附图说明
为了进一步说明产品的结构和性能特给出如下附图。
图1是阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈的红外光谱图:图1表明,在3066.4cm-1处为苯环上C-H键的伸缩振动峰,2946.2cm-1为亚甲基上C-H的伸缩振动吸收峰,1389.6cm-1处为亚甲基C-H键的弯曲振动峰,1228.7cm-1为磷腈骨架P=N的伸缩振动吸收峰,1001.2cm-1为磷腈骨架上P-N的伸缩振动吸收峰,1241.7cm-1和997.2cm-1处为P-O键的伸缩振动峰,826.4cm-1处为C-P键的伸缩振动峰。
图2是阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈的核磁光谱图:图2表明,氘代氯仿做溶剂,δ7.26为氘代氯仿峰,δ3.30-3.46为与氧相连的亚甲基氢峰,δ7.22-7.27为苯环上的氢峰。
具体实施方式
以下结合具体实施方式对本发明的技术方案做进一步说明。
实施例1 在装有搅拌器、温度计、高效回流冷凝管并在冷凝管上口接有氯化氢吸收装置的250mL四口烧瓶中,用氮气赶尽瓶内的空气,加入12.24g(0.09mol)季戊四醇和120mL二氧六环,搅拌使季戊四醇充分分散溶解。再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,缓慢升温至90℃,保温反应4h,至无氯化氢放出;而后降温至30℃,滴加16.11g(0.09mol)苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后升温至100℃,反应10h,至无氯化氢放出;降温至30℃以下,减压蒸馏除去二氧六环(回收使用),再加入50mL水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈,分解温度为345±5℃,产率为88.4%。
实施例2 在装有搅拌器、温度计、高效回流冷凝管并在冷凝管上口接有氯化氢吸收装置的250mL四口烧瓶中,用氮气赶尽瓶内的空气,加入12.24g(0.09mol)季戊四醇和120mL甲苯,搅拌使季戊四醇充分分散溶解。再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,缓慢升温至90℃,保温反应4h,至无氯化氢放出;而后降温至30℃,滴加16.11g(0.09mol)苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后升温至110℃,反应9h,至无氯化氢放出;降温至30℃以下,减压蒸馏除去甲苯(回收使用),再加入50mL水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈,分解温度为345±5℃,产率为90.3%。
实施例3 在装有搅拌器、温度计、高效回流冷凝管并在冷凝管上口接有氯化氢吸收装置的250mL四口烧瓶中,用氮气赶尽瓶内的空气,加入12.24g(0.09mol)季戊四醇和120mL乙二醇二乙醚,搅拌使季戊四醇充分分散溶解。再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,缓慢升温至90℃,保温反应4h,至无氯化氢放出;而后降温至30℃,滴加16.11g(0.09mol)苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后升温至120℃,反应8h,至无氯化氢放出;降温至30℃以下,减压蒸馏除去乙二醇二乙醚(回收使用),再加入50mL水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈,分解温度为345±5℃,产率为92.8%。
实施例4 在装有搅拌器、温度计、高效回流冷凝管并在冷凝管上口接有氯化氢吸收装置的250mL四口烧瓶中,用氮气赶尽瓶内的空气,加入12.24g(0.09mol)季戊四醇和120mL氯苯,搅拌使季戊四醇充分分散溶解。再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,搅拌反应1h;再加入3.48g(0.01mol)六氯环三磷腈,缓慢升温至90℃,保温反应4h,至无氯化氢放出;而后降温至30℃,滴加16.11g(0.09mol)苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后升温至130℃,反应7h,至无氯化氢放出;降温至30℃以下,减压蒸馏除去氯苯(回收使用),再加入50mL水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈,分解温度为345±5℃,产率为91.5%。
表1 制备例主要工艺参数
本案发明人还将上述合成的阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈应用于PET中,按照一定的配比与PET均匀混合,再用XJ-01型挤出机挤出制成尺寸为直径3mm,长度15cm的样条。参照:GB/T2406-2008《塑料燃烧性能试验方法-氧指数法》测样条的极限氧指数。试验结果如表2所示:
表2 三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈在PET中阻燃性能
一般认为阻燃材料的极限氧指数达到27以上即有较好的阻燃性能。由表2可知,随着三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈的增加,极限氧指数升高很快,加入20份时,LOI为31,其表明该产品有很高的阻燃效能,并有很好的成炭性能;因而可以看出阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈对PET具有较好的阻燃效能。
Claims (3)
2.根据权利要求1所述的阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物的制备方法,其特征在于,该方法为:
将季戊四醇分散、溶解于有机溶剂中,再分三批加入六氯环三磷腈,升温至90℃反应4h,至无氯化氢放出,滴加过程中控制六氯环三磷腈和季戊四醇摩尔比为1∶3;降低温度至30℃,滴加与季戊四醇等摩尔量的苯基二氯化磷,滴加过程控制温度不高于45℃,滴完后,升温至100℃~130℃,反应7~10小时,至无氯化氢产生;降温至30℃以下,减压蒸馏出有机溶剂,再加入相对产物理论质量克数2~3倍体积毫升数的蒸馏水,搅拌使其固体产品分散于水中,过滤,抽干,滤饼真空干燥,得白色固体三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈。
3.根据权利要求2所述的阻燃剂三聚O,O-2-螺环苯基亚膦酸二酯丙撑磷腈化合物的制备方法,其特征在于:所述的有机溶剂为二氧六环、甲苯、乙二醇二乙醚和氯苯,其有机溶剂的体积毫升数与六氯环三磷腈和季戊四醇的质量克数总和之比是3∶1~5∶1。
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