CN103833950B - 一种硬质阻燃聚氨酯泡沫塑料 - Google Patents
一种硬质阻燃聚氨酯泡沫塑料 Download PDFInfo
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Abstract
本发明公开了一种硬质阻燃聚氨酯泡沫塑料,其原料包括如下重量份的组分:聚醚多元醇和反应型含磷阻燃剂95~110重量份、胺类催化剂2.2~3.2重量份、叔胺类催化剂0.7~2.2重量份、匀泡剂0.7~2.2重量份、发泡剂0.3~1.3重量份、异氰酸酯130~155重量份和有机金属催化剂0.03~0.11重量份;其中所述反应型含磷阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲基-二(4-羟苯基)甲烷。本发明的泡沫塑料将含有阻燃元素活性单体引入聚氨酯网络中,在不明显影响基体树脂的性能情况下,永久提高聚氨酯的阻燃性能。
Description
技术领域
本发明属于泡沫塑料技术领域,具体涉及一种硬质阻燃聚氨酯泡沫塑料。
背景技术
聚氨酯(PU)材料是目前世界上使用最广泛的高分子材料之一,具有良好的耐油、耐寒、耐潮湿以及尺寸稳定性等优点,大量运用于汽车工业和家电工业等领域。但是,聚氨酯材料在空气中易燃,并且燃烧时产生大量的烟尘,限制了发展前景,所以阻燃聚氨酯材料的研究一直是当今聚氨酯材料研究的热点。
欧洲专利EP0394769采用(RO)3P=O作为阻燃剂,其中R为C1-C3的烷基,在聚氨酯泡沫塑料中加入5%~20%的上述阻燃剂可以使泡沫塑料具有很高的绝热和阻燃性能;欧洲专利EP1219677公开了一种长碳链烷基磷酸酯,将其引入到聚氨酯中,大大提升了材料的阻燃性能和抗水性能,同时在不降低树脂物理性能的情况下改善了机械性能;中国专利CN102203186A公开了一种阻燃聚氨酯组合物,其包括(a)基于热塑性聚氨酯的树脂组分;(b)含磷阻燃剂颗粒填料,和(c)低熔化温度的含磷阻燃剂。改性后聚氨酯的阻燃性能大大提升。
添加型阻燃剂在聚氨酯材料中产生迁移、挥发而影响材料性能的稳定性,同时,为达到需要的阻燃等级,使用量大,从而影响材料本身力学等基本性能。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种硬质阻燃聚氨酯泡沫塑料。
本发明的具体技术方案如下:
一种硬质阻燃聚氨酯泡沫塑料,其原料包括如下重量份的组分:
其中所述反应型含磷阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲基-二(4-羟苯基)甲烷(DOPO-HPM),结构式为:
其制备方法参考文献(ChingHsuanLin,ShengLungChang,TsaiPeiWei.High-TgTransparentPoly(ethersulfone)sBasedonPhosphinatedBisphenols[J].Macromol.Chem.Phys.2011,212,455–464)。
制备DOPO-HPM的反应式如下:
在本发明的一个优选实施方案中,所述聚醚多元醇与所述反应型含磷阻燃剂的重量比为10~90:10~90。
在本发明的一个优选实施方案中,所述聚醚多元醇为硬泡类聚氨酯用聚醚多元醇。
在本发明的一个优选实施方案中,所述胺类催化剂为五甲基二亚烷基三胺。
在本发明的一个优选实施方案中,所述叔胺类催化剂为1,3,5-三(二甲氨基丙基)六氢三嗪。
在本发明的一个优选实施方案中,所述匀泡剂为硅碳键型匀泡剂。
在本发明的一个优选实施方案中,所述发泡剂为水。
在本发明的一个优选实施方案中,所述异氰酸酯的粘度为150~250mPa·s,NCO质量百分数含量为30.0%~32.0%。
在本发明的一个优选实施方案中,所述有机金属催化剂为辛酸亚锡。
上述硬质阻燃聚氨酯泡沫塑料的制备方法如下:
1)将反应型含磷阻燃剂、聚醚多元醇、胺类催化剂、匀泡剂、叔胺类催化剂、发泡剂混合,得到混合组分A;
2)将异氰酸酯与有机金属催化剂混合,得到混合组分B;
3)将混合组分B加入混合组份A中,倒入模具,进行发泡,熟化,脱模工序后,最终制得本发明的硬质阻燃聚氨酯泡沫塑料。
通过改变聚醚多元醇与DOPO-HPM的用量比,可制备出一系列磷含量不同的阻燃硬质聚氨酯泡沫塑料。
本发明的有益效果是:
1、本发明中的DOPO-HPM与聚醚多元醇一样以羟基封端的醇类,它能充当聚醚多元醇的功能,同时,羟基活性点之间的分子链引入阻燃元素形成了元素分子,这类化合物不仅具有无机物的阻燃性能,同时也具有有机物的弹性和塑性;
2、本发明的泡沫塑料将阻燃性能优异的DOPO基团以共价键形式引入聚氨酯网络中,避免了树脂长期贮存和使用时阻燃元素的迁移,增加了聚氨酯泡沫的有效使用年限;
3、本发明的泡沫塑料将含有阻燃元素活性单体引入聚氨酯网络中,在不明显影响基体树脂的性能情况下,永久提高聚氨酯的阻燃性能。
附图说明
图1为本发明所用的反应型含磷阻燃剂DOPO-HPM的1H核磁共振谱图;
图2为本发明所用的反应型含磷阻燃剂DOPO-HPM的31P核磁共振谱图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中的DOPO-HPM的1H和31P核磁共振谱图分别如图1和图2所示。(DMSO/TMS,δ(ppm),氢谱中数字为各化学环境中氢的积分面积)。1HNMR(ppm,DMSO-d6),δ=4.44(1H,Ha),6.63~8.16(16H,Ar-H),9.36(2H,OH).31PNMR(ppm,DMSO-d6),δ=32.8.
下述实施例中的硬泡类聚氨酯用聚醚多元醇为羟值380±20mgKOH/g的烟台亿达聚氨酯有限公司的硬泡聚醚多元醇-聚醚380。所用异氰酸酯为烟台万华聚氨酯股份有限公司生产的牌号为PM-100的异氰酸酯,其粘度为150~250mPa·s,NCO质量百分数含量为30.0%~32.0%。
实施例1:
该实施例为不添加反应型含磷阻燃剂的对比实施例
称取110g聚醚380、3.2g五甲基二亚烷基三胺、2.2g硅碳键型匀泡剂、2.2g1,3,5-三(二甲氨基丙基)六氢三嗪和1.3g水,用高速搅拌下混合均匀组成A料,快速加入B材料(155gPM-100和0.11g辛酸亚锡),室温2500r/min下高速搅拌混合均匀。观察到混合料发白时,即倒入自制模具中自由发泡,发泡完后熟化48h,脱模即得到硬质聚氨酯泡沫塑料。其氧指数为17.0(GB/T2406.1-2008)。
实施例2:
称取90g聚醚380、10gDOPO-HPM、2.2g五甲基二亚烷基三胺、0.7g硅碳键型匀泡剂、0.7g1,3,5-三(二甲氨基丙基)六氢三嗪和0.3g水,用高速搅拌下混合均匀组成A料,快速加入B材料(130gPM-100和0.03g辛酸亚锡),室温2500r/min下高速搅拌混合均匀。观察到混合料发白时,即倒入自制模具中自由发泡,发泡完后熟化48h,脱模即得到硬质聚氨酯泡沫塑料。其氧指数为18.0(GB/T2406.1-2008)。
实施例3:
称取80g聚醚380、20gDOPO-HPM、2.5g五甲基二亚烷基三胺、1.5g硅碳键型匀泡剂、1.5g1,3,5-三(二甲氨基丙基)六氢三嗪和1.0g水,用高速搅拌下混合均匀组成A料,快速加入B材料(140gPM-100和0.07g辛酸亚锡),室温2500r/min下高速搅拌混合均匀。观察到混合料发白时,即倒入自制模具中自由发泡,发泡完后熟化48h,脱模即得到硬质聚氨酯泡沫塑料。其氧指数为20.0(GB/T2406.1-2008)。
实施例4-10:
硬质阻燃聚氨酯泡沫塑料的制备方法同实施例1。改变聚醚380和DOPO-HPM的配比,制备得到一系列磷含量不同的阻燃聚氨酯,配比如表1所示:
以上所述,仅为本发明的较佳实施例而已,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 (6)
1.一种硬质阻燃聚氨酯泡沫塑料,其特征在于:其原料包括如下重量份的组分:
其中所述反应型含磷阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲基-二(4-羟苯基)甲烷,所述聚醚多元醇与所述反应型含磷阻燃剂的重量比为10~90:10~90。
2.如权利要求1所述的一种硬质阻燃聚氨酯泡沫塑料,其特征在于:所述聚醚多元醇为硬泡类聚氨酯用聚醚多元醇。
3.如权利要求1所述的一种硬质阻燃聚氨酯泡沫塑料,其特征在于:所述匀泡剂为硅碳键型匀泡剂。
4.如权利要求1所述的一种硬质阻燃聚氨酯泡沫塑料,其特征在于:所述发泡剂为水。
5.如权利要求1所述的一种硬质阻燃聚氨酯泡沫塑料,其特征在于:所述异氰酸酯的粘度为150~250mPa·s,NCO质量百分数含量为30.0%~32.0%。
6.如权利要求1所述的一种硬质阻燃聚氨酯泡沫塑料,其特征在于:所述有机金属催化剂为辛酸亚锡。
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