CN111454426A - 环保可降解的芳香型聚氨酯发泡材料及其制备方法 - Google Patents

环保可降解的芳香型聚氨酯发泡材料及其制备方法 Download PDF

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CN111454426A
CN111454426A CN202010335978.9A CN202010335978A CN111454426A CN 111454426 A CN111454426 A CN 111454426A CN 202010335978 A CN202010335978 A CN 202010335978A CN 111454426 A CN111454426 A CN 111454426A
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foaming
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lavender
polyurethane foam
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丁永煌
伍柃眉
王斌
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Quanzhou Ximilu New Material Technology Co ltd
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Abstract

本发明具体公开一种环保可降解的芳香型聚氨酯发泡材料，由组料A和组料B混合发泡而成，其中：组料B为脂肪族异氰酸酯，组料A包括如下重量份数计的组分：80～100份的复合多元醇，4～8份的发泡剂、0.5～0.8份的催化剂、0～1份的交联剂、0.5～1份的泡沫稳定剂以及15～25份的改性薰衣草颗粒，其中所述复合多元醇由植物油基聚醚多元醇、聚环氧丙烷醚及聚氨酯鞋垫醇解产物构成。本发明采用改性薰衣草颗粒，可有效控制薰衣草香气成分的挥发，达到香气效力持久并掩盖异味，同时可增强发泡材料和制品的抗菌性能，具有除味、透气、提神醒脑、熏香兼驱虫等优点，可提高薰衣草利用率，减少废弃物的浪费并提高降解程度，绿色环保。

Description

环保可降解的芳香型聚氨酯发泡材料及其制备方法
技术领域
本发明属于发泡材料技术领域，具体涉及一种环保可降解的芳香型聚氨酯发泡材料及其制备方法。
背景技术
聚氨酯泡沫是以异氰酸酯和聚醚为主要原料，在发泡剂、催化剂等多种助剂的作用下，通过专用设备混合，经高压喷涂现场发泡而成的高分子聚合物。聚氨酯海绵或多或少带有化工材料的刺鼻性异味，部分异味是氨气的气味，异味会刺激到使用产品的人们，影响人们使用的舒适度。
薰衣草，被称为“百草之王”，香气清新优雅，性质温和，是公认为最具有镇静，舒缓，催眠作用的植物，可舒缓紧张情绪、镇定心神，平息静气，舒缓压力等功效，而制作成香包可代替樟脑丸放在橱柜内熏香兼驱虫。
中国公开专利文献(CN109262936A)公开了一种增加聚氨酯发泡产品香味的方法，其特征在于，该方法包括以下步骤：S1：配好聚氨酯发泡原料的基本原料，并在聚氨酯发泡原料中加入已碾碎为粉末状的香精，并初步混合得到发泡混合物；香精为薰衣草香精、桂花香精、茉莉花香精、兰花香精、玫瑰香精、果味香精和风油精中的一种；S2：将S1中获得的发泡混合物投入到聚氨酯发泡机中开始充分混合发泡；S3：待S3对发泡混合物开始发泡时，向聚氨酯发泡机内通入香气，使香气进入聚氨酯发泡机内与发泡混合物一起发泡，使发泡混合物内的泡沫充满香气；S4：待S3完成发泡混合物发泡后，利用发泡后的产物制作产品。本发明通过在聚氨酯发泡原料中加入粉末状的香精，使制成的聚氨酯发泡产品带有香味；通过向聚氨酯发泡机内通入香气，使香气进入聚氨酯发泡机内与发泡混合物一起发泡，使制成的聚氨酯发泡产品带有香味。
但是，薰衣草粉的香气挥发较快，存在持久效力问题，同时降解性不佳。另外，聚氨酯海绵或多或少带有化工材料的刺鼻性异味，部分异味是氨气的气味，异味会刺激到使用产品的人们，影响人们使用的舒适度。
发明内容
鉴于现有技术的不足，本发明所要解决的技术问题是提供一种环保可降解的芳香型聚氨酯发泡材料。
为解决上述技术问题，本发明采用的技术方案是：
环保可降解的芳香型聚氨酯发泡材料，由组料A和组料B混合发泡而成，其中：组料B为脂肪族异氰酸酯，组料A包括如下重量份数计的组分：80～100份的复合多元醇，4～8份的发泡剂、0.5～0.8份的催化剂、0～1份的交联剂、0.5～1份的泡沫稳定剂以及15～25份的改性薰衣草颗粒，其中所述复合多元醇由质量百分比为50％～65％的植物油基聚醚多元醇、20％～30％的聚环氧丙烷醚及15％～25％的聚氨酯鞋垫醇解产物构成。
优选地，所述植物油基聚醚多元醇为蓖麻油多元醇；所述聚环氧丙烷醚以山梨醇为起始剂，羟值430～470mgKOH/g，官能度4.4。
优选地，所述发泡剂是甲酸甲酯，所述泡沫稳定剂为二甲基硅油；所述催化剂为五甲基二亚乙基三胺、N,N-二甲基环己胺、三乙烯二胺按质量比为0.3～0.5:0.8～1.2:0.2～0.4复配而成；所述交联剂为乙二醇或二乙醇胺。
优选地，所述聚氨酯鞋垫醇解产物的制备过程具体为：将聚氨酯鞋垫、小分子二元醇、催化剂加入到反应釜中；所述聚氨酯鞋垫和小分子二元醇的质量比为100:10～15；然后加热，控制反应温度为180～230℃，反应时间1～3小时，出料即得；其中，所述催化剂为乙醇胺、二乙醇胺、三乙醇胺中一种或多种的混合物，所述小分子二元醇为乙二醇、丙二醇、二乙二醇中的一种或多种的混合物。
优选地，所述改性薰衣草颗粒由如下重量份数的组分制成：20-30份的纳米薰衣草粉末、5-8份的水性聚氨酯树脂、0.3-0.5份的poly foam发泡剂、2.5-3份的抗坏血酸、1-2份的纳米氧化锌和2.5-3.0份的聚N-乙烯基乙酰胺。
所述改性薰衣草颗粒的制备方法具体如下：
a)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入纳米薰衣草粉末、polyfoam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺，低温超声分散均匀得到在纳米薰衣草粉末表面包裹水性聚氨酯树脂、poly foam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺的反应液；
b)、将步骤a)的反应液注入发泡模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，然后粉碎、研磨成微米级发泡颗粒；
c)、将步骤b)的微米级发泡颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
d)、将步骤c)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
本发明还提供一种环保可降解的芳香型聚氨酯发泡材料的制备方法，按照配方配备好各原料，然后将组料A中的各组分搅拌混合后与组料B经高压发泡机混合均匀进行发泡反应。
与现有技术相比，本发明具有以下有益效果：
1、本发明采用改性薰衣草颗粒，通过poly foam发泡剂在薰衣草粉末表面微孔发泡形成具有一定形状开孔的多孔泡孔结构，从而降低材料的密度、硬度，并形成独特外观表面效果，这样可有效控制薰衣草香气成分的挥发，达到香气效力持久并掩盖异味，同时利用比表面积大以及聚N-乙烯基乙酰胺，可很好地吸附纳米氧化锌，避免纳米氧化锌易团聚问题，而纳米氧化锌具有光催化抗菌效果可增强发泡材料和制品的抗菌性能，同时还起到对薰衣草粉末的热保护作用，发泡效果好。
2、本发明组料B采用脂肪族异氰酸酯，不含有芳香族，可避免由于芳香族官能团的耐候性不佳和易于被氧化裂解而造成的聚氨酯发泡材料黄变现象；另本发明复合多元醇利用植物油基聚醚多元醇和聚氨酯鞋垫的醇解产物，提高聚氨酯产品的生物可降解率。
3、本发明在改性薰衣草颗粒制备中加入了抗坏血酸，在发泡过程中比表面积大的泡孔表面上的抗坏血酸也能够中和碱性的氨类形成铵盐，可大大减少发泡材料和制品中氨气的释放，从而达到除臭以及保证薰衣草香气的纯正。
4、本发明充分利用了薰衣草本身的香气特性，发泡材料及制品具有除味、透气、提神醒脑、熏香兼驱虫等优点，特别适用于鞋底、鞋垫、瑜伽垫、爬行垫等生活用品和运动器材使用，且加工中无需添加碳酸钙或者滑石粉等天然填充剂就可正常发泡，可提高薰衣草利用率，减少废弃物的浪费并提高降解程度，绿色环保，降低了生产成本，具有很好的应用价值和推广前景。
具体实施方式
本发明提供一种环保可降解的芳香型聚氨酯发泡材料，环保可降解的芳香型聚氨酯发泡材料，由组料A和组料B混合发泡而成，其中：组料B为脂肪族异氰酸酯，组料A包括如下重量份数计的组分：80～100份的复合多元醇，4～8份的发泡剂、0.5～0.8份的催化剂、0～1份的交联剂、0.5～1份的泡沫稳定剂以及15～25份的改性薰衣草颗粒，其中所述复合多元醇由质量百分比为50％～65％的植物油基聚醚多元醇、20％～30％的聚环氧丙烷醚及15％～25％的聚氨酯鞋垫醇解产物构成。
其中：所述植物油基聚醚多元醇为蓖麻油多元醇；所述聚环氧丙烷醚以山梨醇为起始剂，羟值430～470mgKOH/g，官能度4.4。
所述聚氨酯鞋垫醇解产物的制备过程具体为：将聚氨酯鞋垫、小分子二元醇、催化剂加入到反应釜中；所述聚氨酯鞋垫和小分子二元醇的质量比为100:10～15；然后加热，控制反应温度为180～230℃，反应时间1～3小时，出料即得；其中，所述催化剂为乙醇胺、二乙醇胺、三乙醇胺中一种或多种的混合物，所述小分子二元醇为乙二醇、丙二醇、二乙二醇中的一种或多种的混合物。
下面给出本发明环保可降解的芳香型聚氨酯发泡材料的几个具体实施例，同时也给出3个对比例，各实施例和对比例中的组分配比参见表1和表2。
其中，本发明实施例1-5中的环保可降解的芳香型聚氨酯发泡材料均采用如下方法制得，具体为：按照配方配备好各原料，然后将组料A中的各组分搅拌混合后与组料B经高压发泡机混合均匀进行发泡反应，其中改性薰衣草颗粒需预先制备。
本发明实施例1-5中的改性薰衣草颗粒均采用如下方法制得，具体为：
a)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入纳米薰衣草粉末、polyfoam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺，低温超声分散均匀得到在纳米薰衣草粉末表面包裹水性聚氨酯树脂、poly foam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺的反应液；
b)、将步骤a)的反应液注入发泡模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，然后粉碎、研磨成微米级发泡颗粒；c)、将步骤b)的微米级发泡颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
d)、将步骤c)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
表1：本发明实施例1-5及对比例1-3的配方表
Figure BDA0002466622790000041
表2：本发明实施例1-5及对比例1-3中改性薰衣草颗粒组成表
Figure BDA0002466622790000051
而本发明给出的对比例1-3的复合发泡材料制备方法与上述实施例1的制备方法区别仅在于改性薰衣草颗粒的制备。
其中，对比例1的改性薰衣草颗粒由如下方法制得，具体步骤为：
1a)、将纳米薰衣草粉末、抗坏血酸、纳米氧化锌和聚N-乙烯基乙酰胺加入乙醇溶液中，超声分散12-15小时得到悬浮液；
1b)、将步骤1a)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥。
其中，对比例2的改性薰衣草颗粒由如下方法制得，具体步骤为：
2a)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入纳米薰衣草粉末、polyfoam发泡剂、柠檬酸和聚N-乙烯基乙酰胺，低温超声分散均匀得到在纳米薰衣草粉末表面包裹水性聚氨酯树脂、poly foam发泡剂、柠檬酸和聚N-乙烯基乙酰胺的反应液；
2b)、将步骤2a)的反应液注入发泡模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，然后粉碎、研磨成微米级发泡颗粒；
2c)、将步骤2b)的微米级发泡颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
2d)、将步骤2c)的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥。
其中，对比例3的改性薰衣草颗粒由如下方法制得，具体步骤为：
3a)、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入纳米薰衣草粉末、polyfoam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺，低温超声分散均匀得到在纳米薰衣草粉末表面包裹水性聚氨酯树脂、poly foam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺的反应液；
3b)、将步骤3a)的反应液注入发泡模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，然后粉碎、研磨成微米级，即为对比例3的改性薰衣草颗粒。
分别取上述实施例1-5及对比例1-3制得的发泡材料进行拉伸强度、回弹值、透气量、大肠杆菌、金黄色葡萄球菌和气味等测试实验，实验结果参见表3。
表3：本发明实施例1-5及对比例1-3的物性测试结果表
Figure BDA0002466622790000061
其中：透气率测试采用透气性测试仪测试各产品的透气量，测试气体为氮气，测试时间为24小时，测试压力为0.2MPa，透气量越大表明透气率越好。
氨味检测方法参考鞋底异味标准(GB30585-2014)，具体为：制备的发泡试片1片，重126g左右，进行水洗两分钟后，将表面的水珠除尽，进行干燥，然后将试片放置进自封袋中，于室温下密封放置24h，在进行异味判别时，将自封袋封口打开15mm左右，鼻子凑近深吸进行判别。
降解程度测试采用将各例发泡材料制成薄片，将这些薄片都埋入污泥中，深度为20cm，环境温度为28℃，6个月后取出测试重量损失并观察薄片外观以薄片失重率(％)表示降解程度。
以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明创造精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (10)

1.环保可降解的芳香型聚氨酯发泡材料，其特征在于：该复合发泡材料由组料A和组料B混合发泡而成，其中：组料B为脂肪族异氰酸酯，组料A包括如下重量份数计的组分：80～100份的复合多元醇，4～8份的发泡剂、0.5～0.8份的催化剂、0～1份的交联剂、0.5～1份的泡沫稳定剂以及15～25份的改性薰衣草颗粒，其中所述复合多元醇由质量百分比为50％～65％的植物油基聚醚多元醇、20％～30％的聚环氧丙烷醚及15％～25％的聚氨酯鞋垫醇解产物构成。
2.根据权利要求1所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述植物油基聚醚多元醇为蓖麻油多元醇。
3.根据权利要求2所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述聚环氧丙烷醚以山梨醇为起始剂，羟值430～470mgKOH/g，官能度4.4。
4.根据权利要求1所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述发泡剂是甲酸甲酯，所述泡沫稳定剂为二甲基硅油。
5.根据权利要求1所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述催化剂为五甲基二亚乙基三胺、N,N-二甲基环己胺、三乙烯二胺按质量比为0.3～0.5:0.8～1.2:0.2～0.4复配而成。
6.根据权利要求1所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述交联剂为乙二醇或二乙醇胺。
7.根据权利要求1所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述聚氨酯鞋垫醇解产物的制备过程具体为：将聚氨酯鞋垫、小分子二元醇、催化剂加入到反应釜中；所述聚氨酯鞋垫和小分子二元醇的质量比为100:10～15；然后加热，控制反应温度为180～230℃，反应时间1～3小时，出料即得；其中，所述催化剂为乙醇胺、二乙醇胺、三乙醇胺中一种或多种的混合物，所述小分子二元醇为乙二醇、丙二醇、二乙二醇中的一种或多种的混合物。
8.根据权利要求1至7任一项所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述改性薰衣草颗粒由如下重量份数的组分制成：20-30份的纳米薰衣草粉末、5-8份的水性聚氨酯树脂、0.3-0.5份的poly foam发泡剂、2.5-3份的抗坏血酸、1-2份的纳米氧化锌和2.5-3.0份的聚N-乙烯基乙酰胺。
9.根据权利要求8所述的环保可降解的芳香型聚氨酯发泡材料，其特征在于：所述改性薰衣草颗粒的制备方法具体如下：
a）、将水性聚氨酯树脂溶于乙醇形成有机溶液，分别加入纳米薰衣草粉末、poly foam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺，低温超声分散均匀得到在纳米薰衣草粉末表面包裹水性聚氨酯树脂、poly foam发泡剂、抗坏血酸和聚N-乙烯基乙酰胺的反应液；
b)、将步骤a）的反应液注入发泡模具内，125℃～140℃加热发泡形成开孔球形泡孔结构，然后粉碎、研磨成微米级发泡颗粒；
c）、将步骤b）的微米级发泡颗粒及纳米氧化锌加入乙醇溶液中，然后超声分散12-15小时得到悬浮液；
d）、将步骤c）的悬浮液上半部分取出，离心分离后置于真空干燥箱中70℃～80℃干燥，得到表面负载有纳米氧化锌的改性薰衣草颗粒。
10.一种如权利要求1所述的环保可降解的芳香型聚氨酯发泡材料的制备方法，其特征在于：具体是按照配方配备好各原料，然后将组料A中的各组分搅拌混合后与组料B经高压发泡机混合均匀进行发泡反应。
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