CN106380485A - 一种dopo改性的环磷腈阻燃剂及其制备和应用 - Google Patents
一种dopo改性的环磷腈阻燃剂及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种DOPO改性的环磷腈阻燃剂及其制备和应用，结构式为：其中制备：DOPO的羟甲基衍生物DOPO‑CH2OH、六氯环三磷腈及缚酸剂在溶剂中反应，即得。DOPO改性的环磷腈阻燃剂作为共混添加型阻燃剂在热固性或热塑性聚合物中应用，或作为后整理用阻燃剂在纺织品阻燃整理中应用。本发明制备的阻燃剂为磷氮系阻燃剂，具有阻燃性能好、不含卤素、有利于环保等优点。
Description
技术领域
本发明属于阻燃剂材料及其制备和应用领域，特别涉及一种DOPO改性的环磷腈阻燃剂及其制备和应用。
背景技术
DOPO及其衍生物是一类无卤含磷阻燃剂，具有优异的阻燃性能。DOPO衍生物常作为环氧树脂的共混添加型阻燃剂或作为环氧树脂的固化剂，制备阻燃环氧树脂；也可以共聚或共混方式制备阻燃聚酯。一般共混添加型阻燃剂添加量较大，会影响基质的物理机械性能等；作为后整理用的阻燃剂也存在用量大，利用率不高的问题。因此需要提高阻燃剂的阻燃效率，减少阻燃剂的用量。某些含氮化合物与含磷阻燃剂结合时会产生磷氮协同效应，提高含磷阻燃剂的阻燃效果。环磷腈是一类分子结构中含–P＝N–键的阻燃剂，同时含有含磷阻燃剂良好的阻燃性能和含氮化合物的阻燃增效作用。
发明内容
本发明所要解决的技术问题是提供一种DOPO改性的环磷腈阻燃剂及其制备和应用，本发明制备的阻燃剂为磷氮系阻燃剂，具有阻燃性能好、不含卤素、有利于环保等优点。
本发明的一种DOPO改性的环磷腈阻燃剂，所述DOPO改性的环磷腈阻燃剂的结构式为：
其中
本发明的一种DOPO改性的环磷腈阻燃剂的制备方法，包括：
(1)将DOPO、甲醛和溶剂混合，反应，得到DOPO的羟甲基衍生物DOPO-CH2OH；
(2)将DOPO-CH2OH、六氯环三磷腈及缚酸剂在溶剂中反应，即得DOPO改性的环磷腈阻燃剂。
所述步骤(1)中甲醛为多聚甲醛或质量百分浓度为36～38％的甲醛水溶液；溶剂为甲醇、乙醇、甲苯、二甲苯、四氢呋喃中的一种或几种。
所述步骤(1)中DOPO与甲醛摩尔比为1:1～2。
步骤(1)中具体为：DOPO和溶剂混合加热至60-70℃，然后搅拌滴加入甲醛，加热至70-80℃，保温反应4-24h，抽滤，洗涤，烘干，得到DOPO的羟甲基衍生物DOPO-CH2OH。
所述步骤(2)中缚酸剂为三乙胺、吡啶、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾中的一种或几种；溶剂为氯仿、二氯甲烷、四氢呋喃、二氧六环、乙腈中的一种或几种。
所述步骤(2)中DOPO-CH2OH与六氯环三磷腈摩尔比为6～8:1；缚酸剂与六氯环三磷腈的摩尔比为3～10:1。
步骤(2)具体为：溶剂中加入DOPO-CH2OH、六氯环三磷腈，加热至25-65℃，然后滴加入缚酸剂，搅拌反应6-48h，提纯，洗涤，烘干。
本发明的一种DOPO改性的环磷腈阻燃剂的应用，DOPO改性的环磷腈阻燃剂作为共混添加型阻燃剂在热固性或热塑性聚合物中应用，或作为后整理用阻燃剂(将其做成阻燃分散体系)在纺织品阻燃整理中应用。
所述共混添加型阻燃剂为：DOPO改性的环磷腈阻燃剂与聚酯颗粒在双螺杆挤出机中混合挤出，然后经过压片制得共混添加型阻燃剂；其中DOPO改性的环磷腈阻燃剂与聚酯颗粒的质量比为5-20：80-95。
所述作为后整理用阻燃剂(将其做成阻燃分散体系)在纺织品阻燃整理中应用：具体为：(1)DOPO改性的环磷腈阻燃剂、木质素磺酸钠、5％(质量百分浓度)的羟乙基纤维素和水加入到球磨机中研磨8-24h，得到平均粒径约为1～2μm的黄棕色阻燃分散体系；其中DOPO改性的环磷腈阻燃剂、木质素磺酸钠、5％的羟乙基纤维素、水的质量比为10-40:3-6:1-4:50-85。(2)涤纶织物阻燃整理
整理液处方：阻燃分散体系100-200g/L，渗透剂JFC 0.5-2g/L；
工艺：涤纶织物二浸二轧阻燃分散体系整理液(带液率60-85％)，然后烘干(85℃，3min)焙烘(200℃，1.5min)。
本发明采用在DOPO衍生物上引入环磷腈的措施，设计合成单个阻燃剂分子中同时含有DOPO和环磷腈，以期通过P-N协同效应，提高阻燃效率，减少阻燃剂用量。
有益效果
(1)本发明制备的阻燃剂为磷氮系阻燃剂，具有阻燃性能好、不含卤素、有利于环保等优点；
(2)本发明制备的阻燃剂适用范围广，可用作热固性或热塑性聚合物等的添加型阻燃剂，也可作为纺织品后整理用阻燃剂；
(3)本发明制备的磷氮阻燃剂，能通过P-N协同效应，更高效地发挥阻燃作用。
附图说明
图1为实施例1所制得的DOPO改性的环磷腈阻燃剂的核磁共振氢谱(1H-NMR)。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
DOPO-CH2OH的制备
将DOPO 216g(1.0mol)与乙醇600mL加入到装有机械搅拌器、回流冷凝管、加液漏斗和温度计的四口烧瓶(1L)中，反应混合物加热至70℃，在搅拌下逐滴加入36～38％甲醛水溶液90g(1.1mol)，30min左右加完。反应物加热至80℃，保温反应6h，冷却后抽滤，洗涤，烘干得到白色固体产物。
(2)DOPO改性的环磷腈阻燃剂(DOPO-TPN)的制备
将三氯甲烷100ml加入带有机械搅拌器、温度计、回流冷凝管和滴液漏斗的四口烧瓶(250mL)中，再向其中加入DOPO-CH2OH 14.76g(0.06mol)和六氯环三磷腈3.48g(0.01mol)，反应混合物加热至65℃回流。逐滴加入三乙胺(Et3N)6.06g(0.05mol)，1h左右加完，保持回流状态继续搅拌反应24h。反应结束后旋转蒸发仪除去三氯甲烷，得到黏稠状物，加入丙酮析出固体物质，抽滤得到白色固体，蒸馏水洗涤，在烘箱中100℃烘8h得到白色固体产物(12.05g,产率75％)。
实施例2
(1)DOPO-CH2OH的制备
将DOPO 216g(1.0mol)与甲醇500mL加入到装有机械搅拌器、回流冷凝管、加液漏斗和温度计的四口烧瓶(1L)中，反应混合物加热至70℃，在搅拌下逐滴加入甲醛水溶液90g(1.1mol)，30min左右加完。反应物加热至80℃，保温反应6h，冷却后抽滤，洗涤，烘干得到白色固体产物。
(2)DOPO-TPN的制备
将四氢呋喃200ml加入带有机械搅拌器、温度计、回流冷凝管和滴液漏斗的四口烧瓶中，再向其中加入DOPO-CH2OH 14.76g(0.06mol)和六氯环三磷腈3.48g(0.01mol)，反应混合物加加热至65℃回流。加入K2CO3 5.0g(0.036mol)保持在回流下继续搅拌反应48h。反应结束后过滤除去未反应的物质，用旋转蒸发仪除去四氢呋喃，得到黏稠状物，加入丙酮析出固体物质，抽滤得到白色固体，蒸馏水洗涤，在烘箱中100℃烘8h得到白色固体产物(10.45g,产率65％)。
实施例3
将实施例1所制备的DOPO-TPN 5g与聚酯颗粒95g在双螺杆挤出机中混合挤出，然后经过压片制得阻燃剂含量约为5％的共混阻燃聚酯切片。
实施例4
将实施例1所制备的DOPO-TPN 10g与聚酯颗粒90g在双螺杆挤出机中混合挤出，然后经过压片制得阻燃剂含量约为10％的共混阻燃聚酯切片。
实施例5
将实施例1所制备的DOPO-TPN 15g与聚酯颗粒85g在双螺杆挤出机中混合挤出，然后经过压片制得阻燃剂含量约为15％的共混阻燃聚酯切片。
实施例6
(1)阻燃分散体系的制备
实施例1所制备的DOPO-TPN或DOPO 20g、木质素磺酸钠5g、5％的羟乙基纤维素4g和水71g加入到球磨机中研磨12h，得到平均粒径约为1～2μm的黄棕色阻燃分散体系。
(2)涤纶织物阻燃整理
整理液处方：阻燃分散体系200g/L，渗透剂JFC 2g/L
工艺：涤纶织物二浸二轧阻燃分散体系整理液(带液率80％左右)—烘干(85℃，3min)—焙烘(200℃，1.5min)。
阻燃性能测定
1测试方法
氧指数(LOI)：共混阻燃聚酯切片的氧指数按“GB/T 2406.2-2009塑料用氧指数法测定燃烧行为第2部分：室温试验”测定。
垂直燃烧性能：共混阻燃聚酯切片的垂直燃烧性能按“UL 94:设备和电器部件塑料材料的可燃性能试验”测定。阻燃织物垂直燃烧性能按“GB/T 5455-1997纺织品燃烧性能试验垂直法”测定。
2测定结果
表1为实施例3～5得到的共混阻燃处理后试样的氧指数及垂直燃烧性能。
表1：
注：t1为第一次余焰时间，t2为第二次余焰时间，t3为第二次余燃时间。
由表1可知，本发明制备的DOPO-TPN作为聚酯添加型阻燃剂能赋予聚酯优良的阻燃性能。当阻燃剂添加量为5％时阻燃聚酯垂直燃烧性能就能达到UL-94V-0级，极限氧指数达到34％，进一步提高阻燃剂用量，极限氧指数能达45％以上，阻燃效果极佳。
表2为实施例6阻燃整理涤纶织物的极限氧指数及垂直燃烧性能。
表2：
由表2可知，本发明制备的DOPO-TPN采用后整理的方式用于涤纶织物阻燃整理，同样能赋予整理品优良的阻燃性能，阻燃效果优于DOPO。
Claims (9)
1.一种DOPO改性的环磷腈阻燃剂，其特征在于：所述DOPO改性的环磷腈阻燃剂的结构式为：其中
2.一种如权利要求1所述的DOPO改性的环磷腈阻燃剂的制备方法，包括：
(1)将DOPO、甲醛和溶剂混合，反应，得到DOPO的羟甲基衍生物DOPO-CH2OH；
(2)将DOPO-CH2OH、六氯环三磷腈及缚酸剂在溶剂中反应，即得DOPO改性的环磷腈阻燃剂。
3.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：所述步骤(1)中甲醛为多聚甲醛或质量百分浓度为36～38％的甲醛水溶液；溶剂为甲醇、乙醇、甲苯、二甲苯、四氢呋喃中的一种或几种。
4.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：所述步骤(1)中DOPO与甲醛摩尔比为1:1～2。
5.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：步骤(1)中反应具体为：DOPO和溶剂混合加热至60-70℃，然后搅拌滴加入甲醛，加热至70-80℃，保温反应4-24h，抽滤，洗涤，烘干，得到DOPO的羟甲基衍生物DOPO-CH2OH。
6.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：所述步骤(2)中缚酸剂为三乙胺、吡啶、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾中的一种或几种；溶剂为氯仿、二氯甲烷、四氢呋喃、二氧六环、乙腈中的一种或几种。
7.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：所述步骤(2)中DOPO-CH2OH与六氯环三磷腈摩尔比为6～8:1；缚酸剂与六氯环三磷腈的摩尔比为3～10:1。
8.根据权利要求2所述的一种DOPO改性的环磷腈阻燃剂的制备方法，其特征在于：步骤(2)反应具体为：溶剂中加入DOPO-CH2OH、六氯环三磷腈，加热至25-65℃，然后滴加入缚酸剂，搅拌反应6-48h，提纯，洗涤，烘干。
9.一种如权利要求1所述的DOPO改性的环磷腈阻燃剂的应用，其特征在于：DOPO改性的环磷腈阻燃剂作为共混添加型阻燃剂在热固性或热塑性聚合物中应用，或作为后整理用阻燃剂在纺织品阻燃整理中应用。
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