CN104231309B - 一种氧杂膦菲阻燃剂、氧杂膦菲阻燃剂的制备方法及其应用 - Google Patents
一种氧杂膦菲阻燃剂、氧杂膦菲阻燃剂的制备方法及其应用 Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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Abstract
一种氧杂膦菲阻燃剂及其制备方法和应用,该结构含杯[4]芳环结构,在K2CO3与乙腈作用下,对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛制得中间体Ⅰ,中间体Ⅰ与DOPO反应得到目标化合物,该化合物外观为白色,熔点为198‑200℃,该产品热稳定好,阻燃率高,纯度达98.5%;本发明所使用的原料易得、工艺先进、易于工业化生产。该阻燃剂既可作为反应型阻燃剂,将其接入到环氧树脂、聚氨酯等热固性树脂中使用,又可作为添加型阻燃剂,用于满足对阻燃剂耐热性要求较高的工程塑料。
Description
技术领域
本发明属于DOPO阻燃性化合物技术领域,具体涉及一种含杯[4]芳环结构的氧杂膦菲阻燃剂,该阻燃剂作为环氧树脂、聚氨酯阻燃添加剂的应用,又可作为添加型阻燃剂用于工程塑料中。
背景技术
多数含卤阻燃材料燃烧时存在多烟、有毒或腐蚀性气体放出等二次危害,对人身安全构成了严重威胁,其应用受到限制。以DOPO为代表的阻燃剂已成为环保无卤阻燃剂研发与应用的热点,此类化合物具有无卤、低毒、不易水解、不易挥发、不易析出、与聚合物相容性好、阻燃性能持久的优点。
发明内容
本发明的目的在于克服上述现有技术中的不足之处,提供一种工艺简单、生产成本低、阻燃性能优良的一种含杯[4]芳环结构的氧杂膦菲阻燃剂及其的制备方法和应用。
本发明的目的是这样实现:一种氧杂膦菲阻燃剂,该化合物含杯[4]芳环结构,具有如下化学结构式:
含杯[4]芳环结构的氧杂膦菲阻燃剂的制备方法:
A:将对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛按物质的量比取量,加入到乙腈、K2CO3的反应器中回流反应48h,TLC检测原料基本反应完毕。减压蒸去溶剂,残余物用氯仿萃取,有机层用碳酸氢钠溶液洗涤,分出有机层,无水硫酸镁干燥,过滤,浓缩,用适量氯仿和甲醇混合溶剂重结晶得中间体Ⅰ;
B:再将制得的中间体Ⅰ与DOPO按物质的量比取量,与有机溶剂一并加入到反应器中,搅拌、回流、冷却、过滤、重结晶、干燥得到含杯[4]芳环结构的氧杂膦菲阻燃剂。
步骤A中,对叔丁基杯[4]芳烃、对甲苯磺酸酯基乙氧基对苯甲醛与K2CO3的物质的量之比为1:1.8-2.3:2.6-5.5,乙腈的重量为对叔丁基杯[4]芳烃、对甲苯磺酸酯基乙 氧基对苯甲醛与K2CO3总重量的12-20倍。
步骤B中,中间体Ⅰ与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的物质的量比为1:2.0-2.4,有机溶剂的重量为中间体Ⅰ与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)总重量的10-18倍。
所述的有机溶剂为甲醇-氯仿、甲醇-四氢呋喃、甲醇-DMF中的任一种。其中乙醇与氯苯的体积比为1:1;甲醇与氯苯的体积比为1:1;四氢呋喃与氯苯的体积比为1:1。
本发明制备化合物的化学反应式为:
所述的氧杂膦菲阻燃剂作为环氧树脂、聚氨酯阻燃添加剂的应用。
本发明的有益效果如下:
(1)本发明提供的含杯[4]芳环结构的氧杂膦菲阻燃剂,操作简单,工艺先进,溶剂可回收利用;
(2)本发明提供的阻燃剂是将杯[4]芳环结构结构单元引入到氧杂膦菲化合物中,具有较高磷含量和高温成炭率,既可以作为反应型阻燃剂,将其接入到环氧树脂、聚氨酯等热固性树脂中使用,又可以作为添加型阻燃剂,用于满足对阻燃剂耐热性要求较高工程塑料的无卤阻燃;
(3)本发明合成的产品,热稳定好,阻燃率高,纯度达98.5%;
(4)本发明所使用的原料易得、工艺先进、易于工业化生产。
具体实施方式
实施例1:
一种氧杂膦菲阻燃剂的制备方法,步骤为:
在装有150mL乙腈的三口瓶中加入对叔丁基杯[4]芳烃(2.96g,4mmol)、对甲苯磺酸酯基乙氧基对苯甲醛(2.56g,8mmol)和碳酸钾(2.20g,16mmol),搅拌下回流45h,TLC检测原料基本反应完毕,减压蒸去溶剂,残余物分别用盐酸、氯仿萃取,有机层用碳酸氢钠溶液洗涤。分出有机层,无水硫酸镁干燥,过滤,浓缩有大量沉淀生成,适量氯仿-甲醇混合溶剂重结晶得中间体Ⅰ(白色固体),收率85.6%。
中间体I9.44g(10mmol)和DOPO4.32g(20mmol)置于烧瓶中,再加氯仿100mL和无水甲醇100mL,回流反应24h。减压蒸去溶剂,加入少量氯仿-甲醇,放置过夜让沉淀充分析出,过滤、干燥得到白色的固体目标化合物,收率84.3%,熔点为198-200℃。
本发明制得的化合物外观为白色晶体,熔点为198-200℃;其热稳定性较好,当温度达到270℃时,失重1%,当温度达到500℃时,失重为10%,850℃成炭率为44%;该化合物能溶于二甲亚砜、N,N-二甲基甲酰胺等溶剂。
本发明制得的一种含杯[4]芳环结构的氧杂膦菲阻燃剂的分析结果如下:
化合物其外观为白色固体,熔点为198-200℃,红外光谱分析结果:FT-IR(KBr),v/cm-1:3315附近为O-H伸缩振动峰,3018附近为苯环C-H伸缩振动峰,,1220,1103附近为P-O-Ph伸缩振动峰,1260附近为P=N伸缩振动峰;核磁共振氢谱分析结果:1H NMR(DMSO-d6,400MHz):δ7.5(d,J=8.1,2H,ArH),7.31(d,J=8.2,2H,ArH),7.3(d,J=7.9,4H,Ar),7.2(t,J=7.6,2H,ArH),7.14(d,J=8.3,4H,ArH),7.05(d,J=8.1,4H,ArH),6.88(t,J=7.9,2H,ArH),6.79(s,6H,ArH),6.73(s,4H,ArH),5.0(s,2H,ArOH),4.5(d,2H,ArCH),3.94(t,J=8.1,4H,ArOCH2),3.81(s,8H,ArCH2Ar),2.55(t,J=8.2,4H,ArCH2),2.04(m,4H,CH2),2.0(s,2H,CH2OH),1.34(s,36H,CCH3)
为了研制出阻燃效率更高的阻燃剂,将杯[4]芳烃环与氧杂膦菲的核心结构片断进行合理组装和修饰,合成出含杯[4]芳烃结构氧杂膦菲复合型阻燃剂。
以下结合实施例对本发明作进一步说明,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例2:
将对甲苯磺酸酯基乙氧基对苯甲醛增大至2.62g(8.2mmol),其它同实例一,制得中间体Ⅰ的收率86.8%。
实施例3:
将对甲苯磺酸酯基乙氧基对苯甲醛增大至2.94g(9.2mmol),其它同实例一,制得中间体Ⅰ的收率88.2%。
实施例4:
将对甲苯磺酸酯基乙氧基对苯甲醛增大至3.07g(9.6mmol),其它同实例一,制得中间体Ⅰ的收率87.9%。
实施例5:
溶剂换成甲醇100mL和四氢呋喃100mL中,其它同实例一,其目标化合物收率82.5%,熔点为198-200℃。
实施例6:
溶剂换成甲醇100mL和DMF100mL中,其它同实例一,其目标化合物收率80.6%,熔点为197-199℃。
实施例7:
将DOPO的量增大至4.54g(21mmol),其它同实例一,其目标化合物收率85.9%,熔点为198-200℃。
实施例8:
将DOPO的量增大至4.76g(22mmol),其它同实例一,其目标化合物收率88.6%,熔点为198-200℃。
实施例9:
将DOPO的量增大至4.97g(23mmol),其它同实例一,其目标化合物收率87.8%,熔点为198-200℃。
本发明提供的含杯[4]芳环结构的氧杂膦菲阻燃性剂在环氧树脂、聚氨酯阻燃添加剂上的应用如下:
按照绝缘层压板燃烧性能测试标准制成样条,分别用JF-3型氧指数测定仪进行限氧指数(LOI)测试,FZ-5401型垂直燃烧仪进行UL94垂直燃烧性能测试,测定结果如下表1-2。
表1 本发明阻燃剂对环氧树脂的阻燃效果
表2 本发明阻燃剂对聚氨酯的阻燃效果
Claims (7)
1.一种氧杂膦菲阻燃剂,其特征在于,其化学结构式如下:
该氧杂膦菲阻燃剂含杯[4]芳环结构。
2.制备权利要求1所述的氧杂膦菲阻燃剂的方法,其特征在于:包括以下步骤:
A:将对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛按物质的量比取量混合后,加入装有到乙腈、K2CO3的反应器中回流反应45-48h,TLC检测原料基本反应完毕后,减压蒸去溶剂,残余物用氯仿萃取,有机层用碳酸氢钠溶液洗涤,分出有机层,无水硫酸镁干燥,过滤,浓缩,采用氯仿和甲醇混合溶剂重结晶得中间体Ⅰ,
B:再将制得的中间体Ⅰ与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)按物质的量比取量混合后,与有机溶剂一并加入到反应器中,搅拌、回流、冷却、过滤、重结晶、干燥得到氧杂膦菲阻燃剂,
3.根据权利要求2所述的氧杂膦菲阻燃剂的制备方法,其特征在于:步骤A中,对叔丁基杯[4]芳烃、对甲苯磺酸酯基乙氧基对苯甲醛与K2CO3的物质的量之比为1:1.8-2.3:2.6-5.5,乙腈的重量为对叔丁基杯[4]芳烃、对甲苯磺酸酯基乙氧基对苯甲醛与K2CO3总重量的12-20倍。
4.根据权利要求2所述的氧杂膦菲阻燃剂的制备方法,其特征在于:步骤B中,中间体Ⅰ与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的物质的量比为1:2.0-2.4,有机溶剂的重量为中间体Ⅰ与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)总重量的10-18倍。
5.根据权利要求2或4所述的氧杂膦菲阻燃剂的制备方法,其特征在于:所述的有机溶剂为甲醇-氯仿、甲醇-四氢呋喃、甲醇-DMF中的任一种。
6.根据权利要求5所述的氧杂膦菲阻燃剂的制备方法,其特征在于:甲醇与氯仿的体积比为1:1;甲醇与四氢呋喃的体积比为1:1;甲醇与DMF的体积比为1:1。
7.权利要求1所述的氧杂膦菲阻燃剂在环氧树脂、聚氨酯阻燃添加剂上的应用。
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