CN106008916B - 一种阻燃聚氨酯泡沫塑料的制备方法 - Google Patents
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Abstract
本发明公开了一种阻燃聚氨酯泡沫塑料的制备方法,该方法通过将无卤环保有机硅阻燃剂与无机阻燃剂相结合后并加入到原料中制备出抑烟、低毒效果更为显著的聚氨酯泡沫塑料。本发明和传统聚氨酯泡沫塑料相比,抑烟、低毒效果更为显著。传统聚氨酯泡沫塑料阻燃的最高温度约5000℃左右,本发明的阻燃最高温度达到700℃左右,压缩强度可达398.7kPa,本发明可以达到自熄级别,其保留量可达91.2%,标准泡沫塑料样品的保留量只有67.3%;燃烧产生有毒气体和烟尘仅为标准聚氨酯泡沫塑料的30%‑50%。
Description
技术领域
本发明属于高分子材料技术领域,尤其涉及一种阻燃聚氨酯泡沫塑料的制备方法。
背景技术
聚氨酯具有优异耐磨、耐温、耐擦伤、耐溶剂、耐辐射、低温弹性,具有优异力学性能和分子设计性,广泛应用于泡沫塑料、橡胶、纤维、涂料、油墨、粘合剂、皮革等领域。大部分聚氨酯都为易燃材料,为保护人们生命财产安全,近年来开发阻燃聚氨酯成为热点。目前主要通过添加阻燃剂达到阻燃目的,而小分子阻燃剂存在易迁移、阻燃效果不持久等缺点,甚至会破坏聚氨酯树脂本身物理性能。近年来,在聚氨酯制备时,加入部分带阻燃元素单体,可以制备本征阻燃聚氨酯,能够克服添加型阻燃聚氨酯的缺点,同时赋予聚氨酯树脂优异综合性能。
硬质聚氨酯泡沫塑料具有质轻、隔热保温、吸音缓冲等性质,广泛应用于国民经济各行业,包括建筑、交通、包装、国防等各领域。但是一般硬质聚氨酯泡沫塑料压缩强度低,力学性能较差,作为结构材料使用受到很大限制。与绝大多数高分子材料一样,硬质聚氨酯泡沫塑料可燃,燃烧时释放一氧化碳、氢氰酸等剧毒物质,因此制备阻燃聚氨酯泡沫塑料迫在眉睫。传统方法是添加卤系物进行阻燃,但卤系物在燃烧时生成较多的烟雾、腐蚀性气体和有毒气体,对人体和环境造成危害。
发明内容
针对现有聚氨酯泡沫存在的问题,本发明的目的是提供一种阻燃聚氨酯泡沫塑料的制备方法,本发明通过将无卤环保有机硅阻燃剂与无机阻燃剂相结合后并加入到原料中制备出抑烟、低毒效果更为显著的聚氨酯泡沫塑料。
为了实现上述发明目的,本发明采用如下所述的技术方案:
一种阻燃聚氨酯泡沫塑料的制备方法,具体包括以下步骤:
第一步,按质量比计算,将1.7~4.3份发泡剂、1.0份泡沫稳定剂、0.2~1.8份催化剂、1.4~3.5份有机阻燃剂、0~2.1无机阻燃剂和20.0份蔗糖聚醚多元醇加入塑料烧杯中,在室温下,用高速分散机混合均匀,转速为4500r/min,搅拌时间为3min,得到质地均一的乳白色粘稠状液态混合物A;
第二步,将35.5~41.5份多亚甲基多苯基多异氰酸酯快速倒入到所述混合物A所在烧杯中,混合搅拌10~15 s,搅拌转速为4500r/min,得到混合物B;
第三步,当混合物B所在烧杯中有气泡冒出、混合物B发白时,立即将混合物B倒入模温为45℃的模具中进行发泡成型;
第四步,在模具中成型1Omin后,脱模,将制得的泡沫放置于85℃的烘箱中4小时,进行后熟化;
第五步,将泡沫按照相关标准在泡沫切割机上裁成合适的尺寸和形状,待用;
其中,所述有机阻燃剂为C18H37O4Psi,其结构如下:
;
所述无机阻燃剂为有机改性蒙脱土,所述催化剂为二甲基环己胺,所述发泡剂为环戊烷,所述泡沫稳定剂为有机硅稳定剂。
由于采用上述技术方案,本发明具有以下优越性:
本发明和传统聚氨酯泡沫塑料相比,抑烟、低毒效果更为显著。传统聚氨酯泡沫塑料阻燃的最高温度约5000℃左右,本发明的阻燃最高温度达到700℃左右,压缩强度可达398.7kPa,本发明可以达到自熄级别,其保留量可达91.2%,标准泡沫塑料样品的保留量只有67.3% ;燃烧产生有毒气体和烟尘仅为标准聚氨酯泡沫塑料的30%-50%。
具体实施方式
下面通过实施例对本发明的技术方案作进一步详细的说明。
下面通过制作9组实施例来具体说明本发明的技术方案,该9组实施例中各个组分的配比关系如下表所示:
所述阻燃聚氨酯泡沫塑料的制备方法,具体包括以下步骤:
第一步,按质量比计算,将发泡剂、泡沫稳定剂、催化剂、有机阻燃剂、无机阻燃剂和蔗糖聚醚多元醇按照上述9组实施例中各组分的配比关系加入塑料烧杯中,在室温下,用高速分散机混合均匀,转速为4500r/min,搅拌时间为3min,得到9组质地均一的乳白色粘稠状液态混合物A;
第二步,将9组实施例中相对应的多亚甲基多苯基多异氰酸酯分别快速倒入到各自对应的混合物A所在烧杯中,混合搅拌10~15 s,搅拌转速为4500r/min,得到9组混合物B;
第三步,当混合物B所在烧杯中有气泡冒出、混合物B发白时,立即将混合物B倒入模温为45℃的模具中进行发泡成型;
第四步,在模具中成型1Omin后,脱模,将制得的泡沫放置于85℃的烘箱中4小时,进行后熟化;
第五步,将泡沫按照相关标准在泡沫切割机上裁成合适的尺寸和形状,待用;
其中,上述表格中组份1为有机阻燃剂,C18H37O4PSi,其结构如下:
;
组份2为无机阻燃剂,有机改性蒙脱土,该有机改性蒙脱土是指聚合物/蒙脱石纳米复合材料;所述催化剂为二甲基环己胺,所述发泡剂为环戊烷,所述泡沫稳定剂为有机硅稳定剂。
对本发明的阻燃聚氨酯泡沫塑料进行测试:
测试其阻燃温度、压缩强度、保留量;
测试结果:
本发明能够达到AQ1044-2007标准;和传统防灭火材料相比,抑烟、低毒效果更为显著,传统聚氨酷泡沫塑料阻燃的最高温度约500 0C左右,新型材料阻燃的最高温度达到700℃左右,压缩强度可达398.7 kPa,添加新型阻燃剂的泡沫塑料可以达到自熄级别,其保留量可达91.2%,标准泡沫塑料样品的保留量只有67.3% ;燃烧产生有毒气体和烟尘仅为标准聚氨酯泡沫塑料的30%-50%。阻燃性能测试表明,采用3、4、5、6使硬质PU阻燃泡沫分别通过TB117和FMVSS302的测试。
需要说明的是,所述有机阻燃剂C18H37O4PSi的制备方法如下:
(1)在250mL三口烧瓶上,配置搅拌器、恒压滴液漏斗和带有CaCl2干燥管的回流冷凝管;
(2)向三口烧瓶中置入镁屑,用20mL四氢呋喃浸没,搅拌下,先滴入5mL 25%3-氯丙醇四氢呋喃溶液,加入1~2小粒碘晶,并微微加热,片刻,碘的颜色开始渐渐消褪,溶液变混浊,反应即开始,停止加热;
(3)继续将3-氯丙醇四氢呋喃溶液滴入反应瓶中,滴速以维持反应液平稳沸腾为宜,加毕,用加热回流约半小时,使反应完全,即得产物A;
(4)降低温度至零下40℃,向所述产物A内缓慢滴加二环己基氯化磷的四氢呋喃溶液,保持温度在零下40℃,液相检测反应结束,升温至0℃,滴加水淬灭反应,用EA萃取,有机相干燥、旋干,减压蒸馏,得产物B;
(5)产物B、三甲氧基氯硅烷、催化剂、甲苯,回流过夜反应,反应完毕旋干、萃取、减压蒸馏,得目标产物。
对目标产物进行分析:
(1)核磁共振分析:
在298K的条件下用氘代氯仿溶解产物,然后在Bruker Avance-400核磁共振仪上以300 MHz进行测试,其核磁共振谱图如图1所示:
(2)元素分析
采用德国ELEMENTAR公司的VARIO元素分析仪测试合成产物DPTP的C, H,N, Si三种元素的含量,其结果如下表所示:
通过对比C, H, O, Si,P五种元索的理论计算值和通过元索分析仪测试测得合成产物中四种元素实测值,从数据表中我们可以看出,各元素的百分含量的实验测试值和理论计算值相差不大,虽然也存在一定的偏差,但是在可以接受的误差范围内。因此,可以推断合成的产物的化学式为:C18H37O4PSi。
通过对产物进行元素分析并结合核磁共振谱图分析可以确定合成的目标产物的结构为:
Claims (1)
1.一种阻燃聚氨酯泡沫塑料的制备方法,其特征是:具体包括以下步骤:
第一步,按质量比计算,将1.7~4.3份发泡剂、1.0份泡沫稳定剂、0.2~1.8份催化剂、1.4~3.5份有机阻燃剂、0~2.1无机阻燃剂和20.0份蔗糖聚醚多元醇加入塑料烧杯中,在室温下,用高速分散机混合均匀,转速为4500r/min,搅拌时间为3min,得到质地均一的乳白色粘稠状液态混合物A;
第二步,将35.5~41.5份多亚甲基多苯基多异氰酸酯快速倒入到所述混合物A所在烧杯中,混合搅拌10~15 s,搅拌转速为4500r/min,得到混合物B;
第三步,当混合物B所在烧杯中有气泡冒出、混合物B发白时,立即将混合物B倒入模温为45℃的模具中进行发泡成型;
第四步,在模具中成型10min后,脱模,将制得的泡沫放置于85℃的烘箱中4小时,进行后熟化;
第五步,将泡沫按照相关标准在泡沫切割机上裁成合适的尺寸和形状,待用;
其中,所述有机阻燃剂为C18H37O4PSi,其结构如下:
;
所述无机阻燃剂为有机改性蒙脱土,所述催化剂为二甲基环己胺,所述发泡剂为环戊烷,所述泡沫稳定剂为有机硅稳定剂。
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