CN109232847B - 一种阻燃聚氨酯泡沫塑料及其制备方法 - Google Patents
一种阻燃聚氨酯泡沫塑料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种阻燃聚氨酯泡沫塑料，所述阻燃聚氨酯泡沫塑料各组份质量份为：甲苯二异氰酸酯35‑50份、聚醚多元醇52‑65份、水1.5‑2.5份、三乙醇胺0.24‑0.4份、二月桂酸二丁基锡0.4‑0.45份、甲基硅油201型0.45‑0.5份、阻燃剂20‑30份；本发明是采用一步法发泡工艺，工艺操作简单、可控性佳、成本低，易实现工业化生产。
Description
技术领域
本发明涉及阻燃聚氨酯泡沫塑料领域，特别是涉及一种阻燃聚氨酯泡沫塑料及其制备方法。
背景技术
聚氨酯泡沫塑料由于具有多孔性，密度较低，同时还具有优异的机械性能、光电化学性能、耐化学腐蚀性等性能，被广泛应用于生产生活中的多个领域，是聚氨酯产品中使用范围最广的产品之一。然而，聚氨酯泡沫塑料在给人们带来方便的同时，因其自身燃点低，极易燃烧的缺点亦给人们的生命财产安全带来了巨大的威胁。为了提高人们生命财产的安全，阻燃型聚氨酯泡沫塑料应运而生，并获得快速发展。
聚氨酯泡沫塑料的阻燃主要有添加型阻燃和反应型阻燃两种。添加型阻燃剂相对价廉易得，制备工艺简单，对聚氨酯泡沫塑料的阻燃效果很好。但添加型阻燃燃剂由于与聚氨酯泡沫基材的相容性有限，在泡沫基体中阻燃性会随着时间的流逝而效果变差，造成添加型阻燃聚氨酯泡沫塑料不宜长期存放。另外添加型阻燃剂单一品种使用阻燃效果有限，只有多种复配使用时阻燃效果才明显。反应型阻燃剂与聚氨酯泡沫塑料基体相容性相对较好，阻燃性不易消失，阻燃性持久。但是反应型阻燃剂的制备较复杂繁琐，成本相对较高，实际应用效果不如添加型阻燃剂。
木质素主要来源于工业制浆造纸黑液，含羟基基团并具有很好成炭性，用其替代部分多元醇制备聚氨酯泡沫塑料，不仅能提高聚氨酯泡沫塑料的阻燃性，还能降低成本，实现木质素资源化利用。陆伟苗等用木质素代替部分多元醇制备了木质素基硬质聚氨酯泡沫材料，当木质素含量为15%时所得泡沫材料的氧指数为20.4%（不加木质素的硬质聚氨酯泡沫材料的氧指数为18%）。因木质素在聚氨酯泡沫材料中相容性差，体系分布不均，所得聚氨酯泡沫材料的阻燃性能提高幅度并不大。聚磷酸铵是一种阻燃性能优异、低烟、低毒膨胀型阻燃剂组分，对聚氨酯泡沫塑料具有非常好的催化增效作用。张晓光等用聚磷酸铵为阻燃剂制备了聚磷酸铵/硬质聚氨酯泡沫，当聚磷酸铵的添加量为20%时，所得泡沫材料的氧指数为27.5%，压缩强度不到0.5MPa（不加聚磷酸铵的硬质聚氨酯泡沫的氧指数约为20.0%，压缩强度约为1.0MPa）。因聚磷酸铵与聚氨酯泡沫塑料基材的相容性不佳，导致所得聚氨酯泡沫材料的压缩强度大幅下降，阻燃性能不持久。
发明内容
本发明针对上述问题，提供一种阻燃效果好、阻燃性能持久、价格低廉、高强度的阻燃聚氨酯泡沫塑料及其制备方法。
为实现上述目的，本发明所提供的技术方案为：一种阻燃聚氨酯泡沫塑料，所述阻燃聚氨酯泡沫塑料各组份质量份为：甲苯二异氰酸酯35-50份、聚醚多元醇52-65份、水1.5-2.5份、三乙醇胺0.24-0.4份、二月桂酸二丁基锡0.4-0.45份、甲基硅油201 0.45-0.5份、阻燃剂20-30份；
阻燃剂的各组份质量比为：木质素：二异氰酸酯：聚磷酸铵=1：0.1-0.3：1-1.2；将木质素、二异氰酸酯、聚磷酸铵及催化剂加入反应器中，60℃~80℃搅拌反应4~8小时后，冷却、碾磨即得；聚磷酸铵为含-OH或-NH-基团的聚磷酸铵；
上述配方的制备工艺为：采用一步法发泡工艺，将上述配方一次性加入反应器中，加入催化剂，催化剂为有机锡类催化剂，在高速搅拌条件下混合后发泡，待泡体定型后，制得阻燃聚氨酯泡沫塑料；发泡定型时间为10-60s，常温发泡。
所述的阻燃剂的各组份质量比为：木质素：二异氰酸酯：聚磷酸铵=1：0.2-0.25：1-1.2。
二异氰酸酯可采用多亚甲基多苯基多异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、萘二异氰酸酯、苯二亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种替代。
本发明的原理和有益效果如下：
木质素含有大量-OH，所用聚磷酸铵亦含-OH或-NH-，将二者通过二异氰酸酯链接后，得到含有-NH-COO-或-CO-NH-的木质素-二异氰酸酯-聚磷酸铵复合膨胀型阻燃剂。木质素-二异氰酸酯-聚磷酸铵复合阻燃剂在聚氨酯泡沫塑料制备过程中因含-NH-COO-或-CO-NH-基团能与基材原料发生一定程度的反应，与基材具有很好的相容性，亦能在基材中分散均匀。所以引入木质素-二异氰酸酯-聚磷酸铵阻燃剂的聚氨酯泡沫塑料的阻燃性非常优异且持久。
由于本发明所使用的木质素-二异氰酸酯-聚磷酸铵阻燃剂中的木质素属于无定形刚性材料，具有增强作用，所以木质素-二异氰酸酯-聚磷酸铵阻燃剂的引入亦能增加聚氨酯泡沫塑料的强度。
由于本发明所使用的木质素-二异氰酸酯-聚磷酸铵阻燃剂中的木质素是一种生物质材料，具有很好的生物降解性，因此木质素-二异氰酸酯-聚磷酸铵阻燃剂亦具有一定的降解性，属于一种绿色环保阻燃剂，它的使用符合国家绿色经济发展的要求。
由于本发明所使用的木质素-二异氰酸酯-聚磷酸铵阻燃剂中的木质素中含有大量吸收紫外光的基团，所以引入木质素-二异氰酸酯-聚磷酸铵阻燃剂的聚氨酯泡沫塑料还具有一定的抗紫外老化性能。
由于本发明是采用一步法发泡工艺，工艺操作简单、可控性佳、成本低，易实现工业化生产。
本发明在整个生产过程中无“三废”产生，对环境不产生任何污染，低碳环保。
具体实施方式
为使本发明的目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是本发明能够以很多不同于在此描述的其他方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
实施例1
二苯基甲烷二异氰酸酯48份、聚醚多元醇52份、水2份、三乙烯二胺0.24份、二月桂酸二丁基锡0.4份、甲基硅油201 0.5份、木质素-二异氰酸酯-聚磷酸铵（木质素/二异氰酸酯/聚磷酸铵的质量比为1：0.2：1）20份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
实施例2
甲苯二异氰酸酯35份、聚醚多元醇65份、水1.5份、三乙醇胺0.4份、二月桂酸二丁基锡0.45份、甲基硅油201 0.45份、木质素-二异氰酸酯-聚磷酸铵（木质素/二异氰酸酯/聚磷酸铵的质量比为1：0.25：1.1）30份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
实施例3
六亚甲基二异氰酸酯40份、聚醚多元醇60份、水2.5份、三乙醇胺0.35份、二月桂酸二丁基锡0.42份、甲基硅油201 0.45份、木质素-二异氰酸酯-聚磷酸铵（木质素/二异氰酸酯/聚磷酸铵的质量比为1：0.2：1.2）35份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
实施例4
多亚甲基多苯基多异氰酸酯50份、聚醚多元醇50份、水2份、三乙醇胺0.3份、二月桂酸二丁基锡0.4份、甲基硅油201 0.5份、木质素-二异氰酸酯-聚磷酸铵（木质素/二异氰酸酯/聚磷酸铵的质量比为1：0.3：1.2）10份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
实施例5
甲苯二异氰酸酯35份、聚醚多元醇65份、水1.5份、三乙烯二胺0.4份、二月桂酸二丁基锡0.42份、甲基硅油201 0.4份、木质素-二异氰酸酯-聚磷酸铵（木质素/二异氰酸酯/聚磷酸铵的质量比为1：0.1：1）15份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
对比例1
多亚甲基多苯基多异氰酸酯40份、聚醚多元醇60份、水2份、三乙醇胺0.3份、二月桂酸二丁基锡0.4份、甲基硅油201 0.5份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
对比例2
二苯基甲烷二异氰酸酯50份、聚醚多元醇50份、水2.0份、三乙烯二胺0.3份、二月桂酸二丁基锡0.45份、甲基硅油201 0.5份、木质素20份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
对比例3
六亚甲基二异氰酸酯35份、聚醚多元醇65份、水1.8份、三乙醇胺0.35份、二月桂酸二丁基锡0.4份、甲基硅油201 0.45份、聚磷酸铵15份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
对比例4
甲苯二异氰酸酯42份、聚醚多元醇58份、水1.5份、三乙醇胺0.3份、二月桂酸二丁基锡0.4份、甲基硅油201 0.5份、木质素5份、聚磷酸铵5份一次性加入反应器中，在高速搅拌条件下混合、发泡后得阻燃聚氨酯泡沫塑料。
对实施例和对比例所制得的阻燃聚氨酯泡沫塑料进行氧指数、UL-94燃烧及压缩试验，试验结果如表1所示。从表1可知，实施例相较于对比例，氧指数、UL-94燃烧级别及压缩强度得到明显增加，说明本发明的阻燃聚氨酯泡沫塑料的阻燃性及压缩强度得到大幅改善。
表1
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (2)
1.一种阻燃聚氨酯泡沫塑料，其特征在于：所述阻燃聚氨酯泡沫塑料各组份质量份为：甲苯二异氰酸酯35-50份、聚醚多元醇52-65份、水1.5-2.5份、三乙醇胺0.24-0.4份、二月桂酸二丁基锡0.4-0.45份、甲基硅油201 0.45-0.5份、阻燃剂20-30份；
阻燃剂的各组份质量比为：木质素：二异氰酸酯：聚磷酸铵=1：0.1-0.3：0.8-1.2；将木质素、二异氰酸酯、聚磷酸铵及催化剂加入反应器中，60℃~80℃搅拌反应4~8小时后，冷却、碾磨即得；聚磷酸铵为含-OH或-NH-基团的聚磷酸铵；
上述配方的制备工艺为：采用一步法发泡工艺，将上述配方一次性加入反应器中，加入催化剂，催化剂为有机锡类催化剂，在高速搅拌条件下混合后发泡，待泡体定型后，制得阻燃聚氨酯泡沫塑料；发泡定型时间为10-60s，常温发泡。
2.根据权利要求1所述的一种阻燃聚氨酯泡沫塑料，其特征在于：阻燃剂的各组份质量比为：木质素：二异氰酸酯：聚磷酸铵=1：0.2-0.25：1-1.2。
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