CN109438755A - 反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物及其制备方法 - Google Patents
反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物及其制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
本发明涉及一种反应型阻燃剂烯丙氧基五苯胺基环三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
本发明涉及一种反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物及其制备方法,该化合物是含有磷、氮双元素阻燃的化合物,可用作不饱和树脂、苯乙烯、丙烯酸酯、聚酯、聚氨酯、环氧树脂、聚乙烯醇和涂料等的阻燃剂。
背景技术
随着三大合成材料在电子电器,交通运输,家具,室内装饰等领域的广泛应用,其易燃性带来的火灾隐患也越来越多,因此促进了阻燃剂工业的发展。具有成炭膨胀性的磷、氮阻燃剂具有显著的阻燃效能。因此,该类阻燃剂在阻燃研究中越来越受到重视。
本发明公开的反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物属多磷、多氮结构,磷、氮含量高,双元素协同阻燃效能高。它还带有活性烯丙基官能团,可作为反应型阻燃剂使用,也可作为添加型阻燃剂使用。该产品结构芳性稳定,分解温度高,燃烧过程中不会释放有毒气体,为绿色环保型阻燃剂。且原料廉价易得,应用范围广,具有市场急需性,有很好的应用和开发前景。
发明内容
本发明的目的之一在于提出一种反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物,该化合物带有活性烯丙基官能团,可作为反应型阻燃剂用于不饱和树脂、苯乙烯、丙烯酸酯等的聚合得到本体阻燃树脂,阻燃剂不迁移、不影响材料的力学性能;也可作为添加型阻燃剂用于聚酯、聚氨酯、环氧树脂、聚乙烯醇和涂料等的阻燃。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:
一种反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物,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反应型阻燃剂烯丙氧基五苯胺基环三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:
将六氯环三磷腈溶于有机溶剂中,加入缚酸剂,控制六氯环三磷腈、烯丙醇、苯胺及缚酸剂的摩尔比为1∶1∶5∶6反应,冰水浴冷却下,滴加烯丙醇,反应1h;滴加六氯环三磷腈5倍摩尔的苯胺,升温至60~110℃,保温反应4~7h;降温至30℃以下,抽滤除去生成的缚酸剂盐酸盐,减压蒸馏出有机溶剂(回收利用),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洗涤两次,分出下层有机相,加入相对产物理论质量克数2~3倍体积毫升数的乙酸乙酯,用无水硫酸钠进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得浅黄色液体烯丙氧基五苯胺基环三磷腈。
如上所述的缚酸剂为三乙胺、N,N-二甲基苯胺或吡啶。
如上所述的有机溶剂为四氢呋喃、乙腈、二氧六环或甲苯,其有机溶剂的体积毫升数与六氯环三磷腈的质量克数之比是3∶1~5∶1。
本发明的反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物为浅黄色液体,闪点(开口杯):182±5℃,密度:1.427g/cm3(25℃),折光率:nD 25=1.3614。产率为89.2%~94.5%,可用作不饱和树脂、苯乙烯、丙烯酸酯、聚酯、聚氨酯、环氧树脂、聚乙烯醇和涂料等的阻燃剂。该反应型阻燃剂烯丙氧基五苯胺基环三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本发明反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物结构新颖,磷含量高达14.3%,氮含量高达17.3%,阻燃元素总含量高达31.6%。结构共轭稳定,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本发明反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物带有活性烯丙基官能团,可作为反应型阻燃剂用于不饱和树脂、苯乙烯等的聚合得到本体阻燃树脂,阻燃剂不迁移、不影响材料的力学性能,特别是用于不饱和树脂后添加达到添加反应型的目的,根据需要可以随意调节阻燃剂的量,达到不同的阻燃等级,非常方便;也可作为添加型阻燃剂用于聚酯、聚酰胺、聚氨酯、环氧树脂、聚乙烯醇和涂料等的阻燃。
③本发明反应型阻燃剂烯丙氧基五苯胺基环三磷腈不含卤素,有利于环保,属膨胀型环境友好阻燃剂;
④本发明反应型阻燃剂烯丙氧基五苯胺基环三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是反应型阻燃剂烯丙氧基五苯胺基环三磷腈的红外光谱图:图1表明,在3402cm-1和3390cm-1为N-H的伸缩振动峰;3014cm-1为苯环C-H吸收峰,1489cm-1为苯环骨架变形振动吸收峰;1596cm-1为烯丙基上C=C双键的吸收峰;1204cm-1为烯丙基上C-O键的吸收峰。1099cm-1和1201cm-1为环三磷腈的P-N键的吸收振动峰,969cm-1和701cm-1处为P-O-C的特征吸收峰。
图2是反应型阻燃剂烯丙氧基五苯胺基环三磷腈的核磁光谱图:图2表明,以氘代DMSO作为溶剂,δ4.10-4.15处为CH2=CH-CH2-O上与氧相连的亚甲基氢峰;δ4.89-5.01处为ph-NH上胺基的氢峰;δ5.04-5.23处为CH2=CH-CH2-O上双键亚甲基的氢峰;δ5.89-6.02处为CH2=CH-CH2-O上-CH-的氢峰;δ6.44-6.90处为苯环上的氢峰。
图3是反应型阻燃剂烯丙氧基五苯胺基环三磷腈的热分析图:图3表明,温度为311℃开始失重;随后,失重速率明显加快,409℃时候,失重率达到50%,但当温度升到800℃后,仍有23%的剩炭率,说明该阻燃剂具有良好的热稳定性。
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、温度计和冷凝管,并在冷凝管上口装有干燥管的250mL三口瓶中,用氮气置换掉瓶内的空气,加入6.95g(0.02mol)六氯环三磷腈、120mL四氢呋喃和12.12g(0.12mol)三乙胺,搅拌使六氯环三磷腈溶解后,冰水浴冷却下,滴加1.16g(0.02mol)烯丙醇,控制温度不超过30℃,反应1h;滴加9.30g(0.10mol)苯胺,升温至60℃,反应7h;降温至30℃以下,抽滤除去生成的三乙胺盐酸盐,滤液减压蒸馏除去四氢呋喃(回收利用),分别加入25mL水洗涤两次,分出下层有机相,加入20mL乙酸乙酯,用1g无水硫酸镁进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得浅黄色液体烯丙氧基五苯胺基环三磷腈。产率为89.2%,闪点(开口杯):182±5℃,密度:1.427g/cm3(25℃),折光率:nD 25=1.3614。
实施例2在装有搅拌器、温度计和冷凝管,并在冷凝管上口装有干燥管的250mL三口瓶中,用氮气置换掉瓶内的空气,加入6.95g(0.02mol)六氯环三磷腈、120mL乙腈、12.12g(0.12mol)三乙胺,搅拌使六氯环三磷腈溶解后,冰水浴冷却下,滴加1.16g(0.02mol)烯丙醇,控制温度不超过30℃,反应1h;滴加9.30g(0.10mol)苯胺,升温至80℃,反应6h;降温至30℃以下,抽滤除去生成的三乙胺盐酸盐,滤液减压蒸馏除去乙腈(回收利用),分别加入25mL水洗涤两次,分出下层有机相,加入20mL乙酸乙酯,用1g无水硫酸镁进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得浅黄色液体烯丙氧基五苯胺基环三磷腈。产率为91.9%,闪点(开口杯):182±5℃,密度:1.427g/cm3(25℃),折光率:nD 25=1.3614。
实施例3在装有搅拌器、温度计和冷凝管,并在冷凝管上口装有干燥管的250mL三口瓶中,用氮气置换掉瓶内的空气,加入6.95g(0.02mol)六氯环三磷腈、120mL二氧六环、14.52g(0.12mol)N,N-二甲基苯胺,搅拌使六氯环三磷腈溶解后,冰水浴冷却下,滴加1.16g(0.02mol)烯丙醇,控制温度不超过30℃,反应1h;滴加9.30g(0.10mol)苯胺,升温至100℃,反应5h;降温至30℃以下,抽滤除去生成的N,N-二甲基苯胺盐酸盐,滤液减压蒸馏除去二氧六环(回收利用),分别加入25mL水洗涤两次,分出下层有机相,加入20mL乙酸乙酯,用1g无水硫酸镁进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得浅黄色液体烯丙氧基五苯胺基环三磷腈。产率为94.5%,闪点(开口杯):182±5℃,密度:1.427g/cm3(25℃),折光率:nD 25=1.3614。
实施例4在装有搅拌器、温度计和冷凝管,并在冷凝管上口装有干燥管的250mL三口瓶中,用氮气置换掉瓶内的空气,加入6.95g(0.02mol)六氯环三磷腈、120mL甲苯、9.48g(0.12mol)吡啶,搅拌使六氯环三磷腈溶解后,冰水浴冷却下,滴加1.16g(0.02mol)烯丙醇,控制温度不超过30℃,反应1h;滴加9.30g(0.10mol)苯胺,升温至110℃,反应4h;降温至30℃以下,抽滤除去生成的吡啶盐酸盐,滤液减压蒸馏除去甲苯(回收利用),分别加入25mL水洗涤两次,分出下层有机相,加入20mL乙酸乙酯,用1g无水硫酸镁进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得浅黄色液体烯丙氧基五苯胺基环三磷腈。产率为93.4%,闪点(开口杯):182±5℃,密度:1.427g/cm3(25℃),折光率:nD 25=1.3614。
表1制备例主要工艺参数
本案发明人还将上述合成的反应型阻燃剂烯丙氧基五苯胺基环三磷腈应用于191不饱和树脂中,将烯丙氧基五苯胺基环三磷腈与191不饱和树脂、过氧化环己酮和环烷酸钴按照下列表格中的配比混合均匀后,倒入铺有玻璃丝布的模具中,制成长15cm、宽0.7cm、厚0.3cm的改性树脂样条。然后对其进行阻燃性能测定,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反应型阻燃剂烯丙氧基五苯胺基环三磷腈在不饱和树脂中阻燃性能
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可知当烯丙氧基五苯胺基环三磷腈在191不饱和树脂中的质量分数为20%时,LOI为30;因而可以看出反应型阻燃剂烯丙氧基五苯胺基环三磷腈对191不饱和树脂具有较好的阻燃效能。
Claims (4)
1.一种反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物,其特征在于,该化合物的结构如下式所示:
2.根据权利要求1所述的反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物的制备方法,其特征在于,该方法为:
将六氯环三磷腈溶于有机溶剂中,加入缚酸剂,控制六氯环三磷腈、烯丙醇、苯胺及缚酸剂的摩尔比为1∶1∶5∶6反应,冰水浴冷却下,滴加烯丙醇,反应1h;滴加六氯环三磷腈5倍摩尔的苯胺,升温至60~110℃,保温反应4~7h;降温至30℃以下,抽滤除去生成的缚酸剂盐酸盐,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洗涤两次,分出下层有机相,加入相对产物理论质量克数2~3倍体积毫升数的乙酸乙酯,用无水硫酸钠进行干燥,抽滤,滤液减压蒸馏除去乙酸乙酯,得黄色液体烯丙氧基五苯胺基环三磷腈。
3.根据权利要求2所述的反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物的制备方法,其特征在于:所述的缚酸剂为三乙胺、N,N-二甲基苯胺或吡啶。
4.根据权利要求2和3所述的反应型阻燃剂烯丙氧基五苯胺基环三磷腈化合物的制备方法,其特征在于:所述的有机溶剂为四氢呋喃、乙腈、二氧六环或甲苯,其有机溶剂的体积毫升数与六氯环三磷腈的质量克数之比是3∶1~5∶1。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101597308A (zh) * | 2009-06-30 | 2009-12-09 | 广东榕泰实业股份有限公司 | 六苯胺基环三磷腈及无卤阻燃环氧树脂组合物的制备方法 |
CN102719206A (zh) * | 2012-05-31 | 2012-10-10 | 四川东材科技集团股份有限公司 | 一种无卤环保阻燃丙烯酸酯压敏胶的制备方法 |
CN105461751A (zh) * | 2014-08-27 | 2016-04-06 | 青岛鑫润土苗木专业合作社 | 一种高效环保型阻燃剂的制备方法 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101597308A (zh) * | 2009-06-30 | 2009-12-09 | 广东榕泰实业股份有限公司 | 六苯胺基环三磷腈及无卤阻燃环氧树脂组合物的制备方法 |
CN102719206A (zh) * | 2012-05-31 | 2012-10-10 | 四川东材科技集团股份有限公司 | 一种无卤环保阻燃丙烯酸酯压敏胶的制备方法 |
CN105461751A (zh) * | 2014-08-27 | 2016-04-06 | 青岛鑫润土苗木专业合作社 | 一种高效环保型阻燃剂的制备方法 |
Non-Patent Citations (1)
Title |
---|
王锐: ""环磷腈衍生物的制备及其在环氧树脂中的阻燃研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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