CN113321783B - 快速自熄α-氨基膦酸酯/硬质聚氨酯材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种快速自熄的α‑氨基膦酸酯/硬质聚氨酯材料及其制备方法;首先采用绿色环保高效的“一锅式”反应法制备含磷、氮阻燃元素的α‑氨基膦酸酯(α‑APP)反应单体,然后通过化学反应的方式将α‑APP引入到硬质聚氨酯泡沫(RPUF)发泡体系中制备出α‑APP/RPUF复合材料。相比于传统磷氮反应阻燃单体制备过程复杂,涉及有毒溶剂,产率低等不足,本发明采用一步法制备α‑APP阻燃单体具有过程简便,无有毒溶剂,产率高等优点。此外,本方法制备的α‑APP/RPUF复合材料在α‑APP磷‑氮协同阻燃作用下可实现快速自熄,阻燃性能提升的同时兼顾了其固有性能。本发明对于制备绿色环保、规模化生产的阻燃硬质聚氨酯泡沫具有一定的实际意义。
Description
技术领域
本发明涉及建筑保温材料,尤其涉及快速自熄α-氨基膦酸酯/硬质聚氨酯(泡沫复合)材料及其制备方法。
背景技术
硬质聚氨酯泡沫是众多有机建筑保温材料中具有显著优势的保温材料,例如低热导率(0.024W/m·K),重量轻、耐湿、防水化学稳定性好、力学性能优异、价格低廉等优点。
此外,硬质聚氨酯泡沫不会像聚乙烯泡沫一样燃烧时发生熔融流淌的现象。
因此,硬质聚氨酯泡沫是目前国内外最理想的节能保温材料之一,已被广泛应用到保温材料的行业如工业设备、冷冻冷藏设备、汽车工业,建筑等等诸多领域。
作为建筑保温材料的硬质聚氨酯泡沫未来的市场非常的庞大。
然而,由于硬质聚氨酯泡沫其脂肪链含量大、比表面积巨大,导致与空气接触面积大,极其易燃(LOI仅为17),火焰蔓延速率极快,而且燃烧会释放大量的热量和有毒烟气,硬质聚氨酯泡沫存在极大的火灾安全隐患会对社会造成巨大的财产损失和人员伤亡,也大大限制了其扩展应用。
目前,对于改善硬质聚氨酯泡沫阻燃性能采用较多的策略是反应型阻燃策略,该策略的核心思想是设计含有磷、氮等阻燃元素的反应单体,该反应单体一般会含有羟基(—OH)或者异氰酸根(—N=C=O),其目的就是可以参与到RPUF的合成反应中,将含有官能团的有机阻燃单体通过化学反应的方式键合到RPUF的分子链段上构成阻燃硬质聚氨酯泡沫复合材料。
虽然目前的有机磷-氮系阻燃剂具有显著的阻燃效果,但是传统制备磷-氮系阻燃剂的实验过程非常复杂。
在合成目标产物前需要合成一些中间单体,实验周期较长,产率较低。此外,大部分的有机合成反应需要一些有毒机溶剂和催化剂的参与,这些试剂最终会遗留下来,产物也需要多次提纯,整个制备过程既不环保也不经济。因此,简化磷-氮系阻燃剂的制备过程,采用环保高效的合成方法制备高产率的磷-氮阻燃剂来实现硬质聚氨酯泡沫的高效阻燃是具有实际意义的。
发明内容
本发明针对传统有机磷氮阻燃剂合成过程复杂,涉及有毒溶剂,产率较低等不足,提供一种能快速自熄α-氨基膦酸酯/硬质聚氨酯材料及其制备方法。
本发明通过简便高效绿色的“一锅式”方法制备含磷氮阻燃剂APP,然后通过化学反应的方式引入硬质聚氨酯泡沫体系,制备可快速自熄的α-氨基膦酸酯/硬质聚氨酯泡沫复合材料,显著改善其阻燃性能的同时兼顾了其固有性能。
本发明通过下述技术方案实现:
α-氨基膦酸酯/硬质聚氨酯(泡沫复合)材料按重量分数由以下原料组成:
聚醚多元醇100份
异氰酸酯140~150份
发泡剂1~3份
催化剂1~3份
稳定剂1~3份
含磷氮反应阻燃单体0~20wt%(按所有原料的质量百分数)
优选地,所述聚醚多元醇型号为4110,羟值=430KOH/g,粘度(25℃)为2500~4000mPa·s。
优选地,所述异氰酸酯为二苯基甲烷二异氰酸酯(MDI5005),密度(25℃)=1.23g/cm3,粘度(25℃)=220mPa·s,NCO值=30.75%。
优选地,所述发泡剂为蒸馏水,密度(25℃)=1.00g/cm3。
优选地,所述催化剂为33wt%的三亚乙基二胺的二丙二醇溶液。
优选地,所述稳定剂为硅油(AK-8805),粘度(25℃)=600mPa·s,密度(25℃)=1.060g/cm3凝固点≤-10℃。
优选地,所述含磷氮反应阻燃单体为α-氨基膦酸酯(α-APP),由原料苯甲醛(C7H6O)、乙醇胺(C2H7NO)和亚磷酸二甲酯(C2H7O3P)在“一锅法”循环式水泵辅助法下制备,颜色为淡黄色,分子式为C11H18O4PN。α-APP的化学反应式为如下:
一种可快速自熄的α-氨基膦酸酯/硬质聚氨酯泡沫复合材料制备方法,具体包括以下步骤:
(1)将聚醚多元醇、发泡剂、催化剂、稳定剂以及含磷氮反应阻燃单体α-APP以机械搅拌的方式混合均匀,得到混合组分A;
(2)异氰酸酯作为组分B;将组分B倒入组分A中,然后用机械搅拌快速搅拌10s,倒入塑料模具中自由发泡直到发泡停止。
(3)然后泡沫放在60~80℃烘箱中固化24~30小时,脱模,即可得到可快速自熄的α-氨基膦酸酯/硬质聚氨酯泡沫复合材料。
通过改变反应阻燃单体α-APP的配比,可以制得一系列不同阻燃效果的硬质聚氨酯泡沫复合材料。
本发明相对于现有技术,具有如下的优点及效果:
本发明采用“一锅式”方法制备含磷氮反应阻燃单体具有过程简便高效,绿色无毒,产率较高等有点,此外获得α-氨基膦酸酯/硬质聚氨酯泡沫复合材料具有快速自熄的优异阻燃性能,同时也兼顾了其固有性能。
附图说明
图1:α-氨基膦酸酯的红外光谱图。
图2:α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的制备过程。
图3:α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的实物图和SEM图;
其中:图a1,a2为实施例1;图b1,b2为实施例2;图c1,c2为实施例3;图d1,d2为实施例4;实物图比例尺50mm;SEM图比例尺400μm。
图4:垂直燃烧测试;
其中,图a为实施例1;图b为实施例2;图c为实施例3;图d为实施例4。
图5:α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的锥形量热测试;
其中,图a为热释放速率曲线;图b为总释放热曲线;图c为烟释放速率曲线;图d为总烟气释放量曲线。
图6:α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的热重测试;
其中,图a为TGA曲线;图b为DTG曲线。
图7:不同点火时间燃烧图;
其中,实施例1不同点火时间燃烧图:图a1为点火2s;图a2为点火4s;图a3为点火6s;
实施例2不同点火时间燃烧图:图b1为点火2s;图b2为点火4s;图b3为点火6s。
图8:不同点火时间样品残炭截面图;
其中,图a为实施例1不同点火时间样品残炭截面图,比例尺10mm;图b实施例2不同点火时间样品残炭截面图,比例尺10mm。
图9:α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的红外热成像图;
其中,图a为实施例1的成像图;图b为实施例2的成像图;图c为实施例3的成像图;图d为实施例4的成像图。
具体实施方式
下面结合具体实施例对本发明作进一步具体详细描述。
实施例1
一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的配方为(对照组):
将聚醚多元醇100份、发泡剂2份、催化剂2份、稳定剂2份混合后搅拌均匀得到混合组分A,称取异氰酸酯145份作为组分B。
然后将组分B倒入组分A中,用手动搅拌器快速搅拌10s左右,倒入塑料模具自由发泡至停止,然后将模具放入烘箱中70℃下固化24h,最后脱模即可得到硬质聚氨酯泡沫。
实施例2
一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的配方为(对照组):
将聚醚多元醇100份、发泡剂2份、催化剂2份、稳定剂2份、10wt%反应阻燃单体α-APP混合后搅拌均匀得到混合组分A,称取异氰酸酯145份作为组分B。
然后将组分B倒入组分A中,用手动搅拌器快速搅拌10s左右,倒入塑料模具自由发泡至停止,然后将模具放入烘箱中70℃下固化24h,最后脱模即可得到一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料。
实施例3
一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的配方为(对照组):将聚醚多元醇100份、发泡剂2份、催化剂2份、稳定剂2份、15wt%反应阻燃单体α-APP混合后搅拌均匀得到混合组分A,称取异氰酸酯145份作为组分B。然后将组分B倒入组分A中,用手动搅拌器快速搅拌10s左右,倒入塑料模具自由发泡至停止,然后将模具放入烘箱中70℃下固化24h,最后脱模即可得到一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料。
实施例4
一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料的配方为(对照组):
将聚醚多元醇100份、发泡剂2份、催化剂2份、稳定剂2份、20wt%反应阻燃单体α-APP混合后搅拌均匀得到混合组分A,称取异氰酸酯145份作为组分B。
然后将组分B倒入组分A中,用手动搅拌器快速搅拌10s左右,倒入塑料模具自由发泡至停止,然后将模具放入烘箱中70℃下固化24h,最后脱模即可得到一种α-氨基膦酸酯/硬质聚氨酯泡沫复合材料。
表1α-氨基膦酸酯/硬质聚氨酯泡沫复合材料部分性能测试结果
α:第一次移去火源后样品持续燃烧的时间;β:第二次移去火源后样品持续燃烧的时间;
γ:峰值或曲线最大值;δ:样品重量损失10%时的温度;ε:样品热失重速率最大时的温度;
θ:800℃时样品的残炭率。
如上所述,便可较好地实现本发明。
相比于传统磷氮反应阻燃单体制备过程复杂,涉及有毒溶剂,产率低等不足,本发明采用一步法制备α-APP阻燃单体具有过程简便,无有毒溶剂,产率高等优点。此外,本方法制备的α-APP/RPUF复合材料在α-APP磷-氮协同阻燃作用下可实现快速自熄,阻燃性能提升的同时兼顾了其固有性能。本发明对于制备绿色环保、规模化生产的阻燃硬质聚氨酯泡沫具有一定的实际意义。
本发明的实施方式并不受上述实施例的限制,其他任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述聚醚多元醇型号为4110,羟值=430mgKOH/g,在25℃下的粘度为2500~4000 mPa•s。
3.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述的异氰酸酯为二苯基甲烷二异氰酸酯,在25℃下的密度=1.23g/cm3,在25℃下的粘度=220 mPa·s,NCO值=30.75%。
4.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述发泡剂为蒸馏水,在25℃下的密度=1.00g/cm3。
5.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述的催化剂为33wt%的三亚乙基二胺的二丙二醇溶液。
6.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述的稳定剂为硅油AK-8805,在25℃下的粘度=600mPa·s,在25℃下的密度=1.060g/cm3,凝固点≤ -10℃。
7.根据权利要求1所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料,其特征在于:
所述含磷氮反应阻燃单体为α-氨基膦酸酯,由原料苯甲醛、乙醇胺和亚磷酸二甲酯在“一锅法”循环式水泵辅助法下制备,颜色为淡黄色。
8.权利要求1-7任一项所述快速自熄α-氨基膦酸酯/硬质聚氨酯材料的制备方法,其特征在于:包括如下步骤:
步骤一:将聚醚多元醇、发泡剂、催化剂、稳定剂以及含磷氮反应阻燃单体α-氨基膦酸酯采用搅拌的方式混合均匀,得到混合组分A;
步骤二:异氰酸酯作为组分B;将组分B倒入组分A中,并采用搅拌方式混合均匀,倒入模具中自由发泡,然后在60~80oC烘箱中固化24~30小时,即得到快速自熄的α-氨基膦酸酯/硬质聚氨酯材料。
9.根据权利要求8所述的制备方法,其特征在于:步骤一和步骤二中所述搅拌,均为机械搅拌方式。
10.根据权利要求9所述的制备方法,其特征在于:步骤二所述模具为塑料模具。
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