CN106905510B - 一种含多官能团的反应型阻燃剂及其合成方法和应用 - Google Patents
一种含多官能团的反应型阻燃剂及其合成方法和应用 Download PDFInfo
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Abstract
本发明公开了一种含多官能团的反应型阻燃剂及其合成方法和应用,涉及一种阻燃剂,将对氨基酚溶于有机溶剂,在一定条件下与四羟甲基硫酸膦(THPS)、三乙胺(TEA)反应,经提纯后得到一种含多官能团的反应型阻燃剂。该阻燃剂具有抗水解性好的特点,同时在高分子基体中不会发生迁移。该反应原料简单易得,条件温和,易于工业化。
Description
技术领域
本发明涉及一种阻燃剂,尤其是一种含多官能团的反应型阻燃剂及其合成方法和应用。
背景技术
当今社会,高分子材料早已渗透到国民生活的方方面面。随着高分子材料的广泛应用,火灾的潜在危险日益增长,因而积极研究和开发新的高分子阻燃材料,提高高分子材料使用的安全性,已成为当前的研究热点。一般而言,阻燃高分子材料可分为本质阻燃高分子材料和非本质阻燃高分子材料,其中,非本质阻燃高分子材料又可分为添加型阻燃高分子材料和反应型阻燃高分子材料。本质阻燃高分子材料在很多场合可以直接使用,但由于其价格昂贵或者制造工艺复杂,应用相当有限。非本质阻燃高分子材料中,相比添加型阻燃剂,反应型阻燃剂由于具有活性官能团,其与高分子材料以化学键的方式相结合,因而可长期使用而不发生迁移,在发挥其阻燃功效的同时也不会对高分子材料的其它性能产生较大影响。因此,开发新的含多官能团的反应型阻燃剂
发明内容
本发明旨在提供一种含多官能团的反应型阻燃剂及其合成方法和应用,能够用于增强聚氨酯、环氧树脂等的阻燃性能。
本发明解决其技术问题所采用的技术方案之一是:
一种含多官能团的反应型阻燃剂,所述阻燃剂由四羟甲基硫酸膦(THPS,本发明中所采用的THPS均为质量分数75%的THPS溶液的形式)、对氨基酚(PAP)、三乙胺(TEA)反应所得。所述含多官能度反应型阻燃剂的结构式如下所示:
本发明解决其技术问题所采用的技术方案之二是:
上述含多官能团的反应型阻燃剂的合成路线如下:
上述含多官能团的反应型阻燃剂的合成方法如下:
1)氮气保护下,将对氨基酚溶于有机溶剂中,-5~50℃下搅拌溶解后,逐滴加入THPS,滴完后回流反应0.5~4h;其中对氨基酚与THPS的摩尔比为6~14:1;
2)升温至45~85℃,逐滴加入TEA,滴完后回流反应0.5~4h;
3)浓缩,沉淀,得到的固体产物以柱色谱分离,得到目标产物;所述柱色谱的固定相为硅胶,展开剂为体积比3~5:1的乙酸乙酯-石油醚混合液,且每100ml展开剂中加入4~6ml的三乙胺。
一实施例中:所述对氨基酚、THPS、TEA的摩尔比为8~12:1:2~4。
一实施例中:所述步骤1)中,有机溶剂为甲醇或乙醇。
一实施例中:所述步骤1)中,回流反应温度为0~45℃,反应时间为1~3h。
一实施例中:所述步骤2)中,回流反应温度为50~80℃,反应时间为1~3h。
一实施例中:所述步骤3)中,沉淀过程采用的沉淀剂为冰水。
本发明解决其技术问题所采用的技术方案之三是:
上述含多官能团的反应型阻燃剂在制备阻燃高分子材料中的应用。
一实施例中:所述阻燃高分子材料中的含多官能团的反应型阻燃剂的含量为1~30%。
本发明解决其技术问题所采用的技术方案之四是:
一种利用上述含多官能团的反应型阻燃剂制备阻燃环氧树脂的方法,称取环氧树脂预聚体,升温至85~100℃,搅拌20~40min;向环氧树脂预聚体内加入已预溶于溶剂中的阻燃剂,继续搅拌40~80min;除去溶剂;加入固化剂,搅拌均匀后倒入模具中,进行程序升温:110~130℃固化3~5h,然后150~170℃保温1~3h,最后在170~190℃保温1~3h,即得阻燃环氧树脂,其中所述反应型阻燃剂的含量为1~30%。
本发明所述含多官能团的阻燃剂与现有阻燃剂相比具有如下优点:
(1)本发明的阻燃剂分子结构中含有羟基和仲胺基,两者为活性官能团,可参与聚氨酯发泡或环氧树脂固化,为反应型阻燃剂,与高分子材料结合力强,使用过程中不发生迁移;
(2)本发明的阻燃剂分子结构中含有磷氮两种元素,可发挥协同阻燃作用,阻燃效率高;
(3)本发明的阻燃剂分子结构中磷碳氮原子以六元杂环结构连接,耐水解性好,热稳定性提高。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1为本发明实施例1得到的阻燃剂H1NMR谱图。
图2为本发明实施例1得到的该阻燃剂P31NMR谱图。
具体实施方式
下面通过实施例具体说明本发明的内容:
实施例1
1)在装有回流冷凝管的250mL三口瓶中加入9.81g(0.09mol)PAP,再加入100mL甲醇,通氮气保护,升温到45℃,磁力搅拌10min溶解后,通过恒压滴液漏斗逐滴加入5.4gTHPS(0.01mol),滴完后反应1h;
2)升温到70℃,再通过恒压滴液漏斗逐滴加入3.03g TEA,滴完后反应1h;
3)反应完成后将体系旋蒸浓缩至10mL左右,用冰水沉淀,得灰色固体7.21g;取适量该灰色固体产物以柱色谱进行分离得到目标产物。其中,柱色谱以硅胶为固定相,以乙酸乙酯:石油醚体积比4:1的乙酸乙酯-石油醚混合液为展开剂,且每100mL展开剂中加入5mL的三乙胺。
实施例2
1)在装有回流冷凝管的250mL三口瓶中加入10.9g(0.1mol)PAP,再加入100mL甲醇,通氮气保护,升温到45℃,磁力搅拌10min溶解后,通过恒压滴液漏斗逐滴加入5.4gTHPS(为75%的THPS溶液,下同)(0.01mol),滴完后反应1h;
2)升温到60℃,再通过恒压滴液漏斗逐滴加入3.03g TEA,滴完后反应2h;
3)反应完成后将体系旋蒸浓缩至10mL左右,用冰水沉淀,得灰色固体6.9g;取适量该灰色固体产物以柱色谱进行分离得到目标产物。其中,柱色谱以硅胶为固定相,以乙酸乙酯:石油醚体积比4:1的乙酸乙酯-石油醚混合液为展开剂,且每100mL展开剂中加入5mL的三乙胺。
实施例3
1)在装有回流冷凝管的250mL三口瓶中加入9.81g(0.09mol)PAP,再加入100mL甲醇,通氮气保护,冰浴,磁力搅拌10min溶解后,通过恒压滴液漏斗逐滴加入5.4g THPS(0.01mol),滴完后反应2h;
2)升温到50℃,通过恒压滴液漏斗逐滴加入4g TEA,滴完后反应2h;
3)反应完成后将体系旋蒸浓缩至10mL左右,用冰水沉淀,得灰色固体7.91g;取适量该灰色固体产物以柱色谱进行分离得到目标产物。其中,柱色谱以硅胶为固定相,以乙酸乙酯:石油醚体积比4:1的乙酸乙酯-石油醚混合液为展开剂,且每100mL展开剂中加入5mL的三乙胺。
实施例4
1)在装有回流冷凝管的250mL三口瓶中加入9.81g(0.09mol)PAP,再加入100mL甲醇,通氮气保护,冰浴,磁力搅拌10min溶解后,通过恒压滴液漏斗逐滴加入5.4g THPS(0.01mol),滴完后反应2h;
2)升温到60℃,通过恒压滴液漏斗逐滴加入4g TEA,滴完后反应2h;
3)反应完成后将体系旋蒸浓缩至10mL左右,用冰水沉淀,得灰色固体7.45g;取适量该灰色固体产物以柱色谱进行分离得到目标产物。其中,柱色谱以硅胶为固定相,以乙酸乙酯:石油醚体积比4:1的乙酸乙酯-石油醚混合液为展开剂,且每100mL展开剂中加入5mL的三乙胺。
实施例5
纯环氧树脂及利用本发明实施例1的阻燃剂改性的环氧树脂制备及阻燃测试步骤如下:
(1)纯环氧树脂的制备
称取25g环氧树脂E-51,升温到90℃搅拌,待无气泡后加入6.25g固化剂4,4’-二氨基二苯甲烷,搅拌均匀后倒入模具,在120℃保温4h,然后在160℃保温2h,最后在180℃保温2h。
(2)利用本发明实施例1的反应型阻燃剂改性的环氧树脂的制备
称取25g环氧树脂E-51,升温到90℃,搅拌20~40min;0.63g阻燃剂加入到适量甲醇中,待无气泡后加入到环氧树脂中,搅拌40~80min至混合物呈均一透明的状态;旋蒸除掉甲醇;加入6.02g固化剂4,4’-二氨基二苯甲烷,搅拌均匀后倒入模具,进行程序升温:在120℃固化4h,然后在160℃保温2h,最后在180℃保温2h,即得该反应型阻燃剂改性的环氧树脂,其中反应型阻燃剂的含量为2%(对应表1中EP-2%)。按此方法,分别添加1.61g、3.34g该阻燃剂制备两种改性环氧树脂,对应固化剂含量分别为5.67g、5.04g,两种改性环氧树脂中反应型阻燃剂的含量分别为5%(对应表1中EP-5%)、10%(对应表1中EP-10%)。
(3)将所得样品按照GB/T 2406.2-2009方法测试其氧指数。
表1本发明实施例1的阻燃剂改性的环氧树脂极限氧指数(LOI)测试结果
以上所述,仅为本发明较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (3)
1.一种含多官能团的反应型阻燃剂的合成方法,其特征在于:所述反应型阻燃剂的结构式如下所示:
所述合成方法包括以下步骤:
1)氮气保护下,将对氨基酚溶于有机溶剂中,-5~50℃下搅拌溶解后,逐滴加入THPS,滴完后回流反应0.5~4h;所述有机溶剂为甲醇或乙醇;
2)升温至45~85℃,逐滴加入TEA,滴完后回流反应0.5~4h;所述对氨基酚、THPS、TEA的摩尔比为8~12:1:2~4;
3)浓缩,沉淀,得到的固体产物以柱色谱分离,得到目标产物;所述沉淀过程采用的沉淀剂为冰水;所述柱色谱的固定相为硅胶,展开剂为体积比3~5:1的乙酸乙酯-石油醚混合液,且每100ml展开剂中加入4~6ml的三乙胺。
2.根据权利要求1所述的合成方法,其特征在于:所述步骤1)中,回流反应温度为0~45℃,反应时间为1~3h。
3.根据权利要求1所述的合成方法,其特征在于:所述步骤2)中,回流反应温度为50~80℃,反应时间为1~3h。
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