CN110511351A - 无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法 - Google Patents
无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法，组成如下：聚酯聚醚多元醇80‑95份；纳米蒙脱土5‑20份；降粘剂2‑20份；胺类催化剂1‑4份；锡类催化剂0‑1份；发泡剂1‑5份；匀泡剂1‑10份；先将聚酯聚醚多元醇、纳米蒙脱土、降粘剂三种原料按重量比置入容器内搅拌混合，加热抽真空使其脱水，再加入催化剂，混合均匀后，再加入发泡剂，匀泡剂，然后充分搅拌混合制备出组合料；再加入异氰酸酯充分搅拌；所述发泡剂为水。本发明物料流动性好；热导率高；基材粘接力好，解决了现有技术中的不足。
Description
技术领域
本发明属于高分子材料领域，特别涉及一种以水为发泡剂的无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法。
背景技术
传统的硬质泡沫塑料的制备方法是以含有多羟基官能度在3以上、分子量在300-350的聚醚或聚酯为主要原材料，加入催化剂、发泡剂（包括物理或化学两种）匀泡剂、与异氰酸酯发生合成反应成型。尤其聚氨酯硬质泡沫塑料具有良好的绝热性（导热系数低）和较强的结构强度，具有容重低、隔音、防震、耐油、耐酸 ，吸水率低，室温化学稳定性好的特点，以做为独特的保温材料应用于电冰箱，冷藏库中的隔热材料以及石油液化气和化工冷冻设备管道保温，建筑工业的隔墙板、屋顶及地板的绝热材料等，发展速度很快。
由于在发聚氨酯硬质泡沫过程中释放大量的含氯氟羟的气体，使大气臭层遭到破坏，不利于环保。正在寻求可替代CFCS的替代物，现有技术中相应的替代物大常用的有4种：1.141b. 2.环戊烷.3.二氧化碳4.水。其中以水做为发泡剂的方案是最为理想的，但现有技术中，以水作为发泡还存在如下缺点：
1.原料体系粘度大，物料流动性差；
2.产品泡孔粗，热导率高；
3.泡沫较脆，基材粘接力差等。
发明内容
本发明的目的是提供一种无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法，它不仅保持聚氨酯硬质泡沫塑料性能和特点，真正做到全水无氟的同时，还有效能解决现有技术中水发泡存在的缺点。
本发明的目的是这样实现的：一种无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法，其特征在于：所述无氟纳米蒙脱土聚氨酯硬质泡沫塑料包括如下重量份数的各组分：聚酯聚醚多元醇80-95份；纳米蒙脱土5-20份；降粘剂2-20份；胺类催化剂1-4份；锡类催化剂0-1份；发泡剂1-5份；匀泡剂1-10份；
其制备方法如下：首先将聚酯聚醚多元醇、纳米蒙脱土、降粘剂三种原料按重量比置入容器内搅拌混合，加热抽真空使其脱水，生成纳米蒙脱土聚酯聚醚多元醇复合材料，再加入重量份为1-4份的胺类催化剂和0-1份的锡类催化剂，混合均匀后，再加入重量份为1-5份的发泡剂，1-10份的匀泡剂，然后充分搅拌混合制备出组合料；再加入NCO指数为1-2的粗MDI或PAPI的异氰酸酯充分搅拌，搅拌速度3000转/分，搅拌时间7-10秒，熟化时间10-15分，环境温度大于15℃，物料温度为22-25℃；
所述发泡剂为水。
进一步的：所述聚酯聚醚多元醇，是以低分子聚酯为起始剂与环氧丙烷合成的聚酯聚醚多元醇；或者是由相溶性良好的低分子量聚酯与低分子量聚醚组成的混合物。
进一步的：所述降粘剂是邻苯二甲酸二乙烯丙酯或NDI-101或有机硅烷偶联剂。
进一步的：所述粗MDI或PAPI的NCO指数为1.4-1.6。
本发明的优点是：
本发明所述方案中，采用纳米级的蒙脱土材料，在反应过程中，纳米材料可有效进入聚酯聚醚多元醇结构单元，纳米尺度的粒子介于宏观物质与微观原子分子的中间，物质的局限性及巨大的表面积效应使物质性能发生质变，呈现整个以水为发泡剂的纳米蒙脱土聚氨酯硬质泡沫塑料中，它以聚酯聚醚为连续相，其分散相中至少有一维小于100nm；和传统聚酯聚醚相比，由于纳米粒子带来的效应和纳米粒子与基面的界面相互作用，使纳米蒙脱土聚酯聚醚复合接触面积增大，使反应更完善，从而大大提高其性能。在100份聚酯聚醚多元醇中溶入1-5份的水，传统以水为发泡剂时，将其溶解在聚酯聚醚中，由于分散的不好，所得到的硬质泡沫泡孔大；本方案中，将聚酯聚醚多元醇复合一定量的纳米蒙脱土，对聚酯聚醚进行插层反应，在发泡过程中由于纳米效应，以更小水滴分布在聚酯聚醚中，和纳米粒子于基面相互作用，使之溶入的水分随着聚酯聚醚被插层反应而分割的更小，分散在聚酯聚醚的水也又一次被分割成更小的水滴，从而解决了水发泡造成泡孔粗大的问题，增加了绝热功能，使导热率接近或达到传统泡沫的性能。
此外，在原料配方中我们利用聚酯部分溶解足够量的水分，在制作聚氨酯硬质泡沫中反应产所生CO2气体可供发泡使用。
具体实施方式
本发明公开了一种无氟纳米蒙脱土聚氨酯硬质泡沫塑料，其包括如下重量份数(下同)的各组分：聚酯聚醚多元醇80-95份；纳米蒙脱土5-20份；降粘剂2-20份；胺类催化剂1-4份；锡类催化剂0-1份；发泡剂1-5份；匀泡剂1-10份；
其制备方法如下：首先将聚酯聚醚多元醇、纳米蒙脱土、降粘剂三种原料按重量比置入容器内搅拌混合，加热抽真空使其脱水，生成纳米蒙脱土聚酯聚醚多元醇复合材料，再加入重量份为1-4份的胺类催化剂和0-1份的锡类催化剂，混合均匀后，再加入重量份为1-5份的发泡剂，1-10份的匀泡剂，然后充分搅拌混合制备出组合料；再加入NCO指数为1-2的粗MDI或PAPI的异氰酸酯充分搅拌，搅拌速度3000转/分，搅拌时间7-10秒，熟化时间10-15分，环境温度大于15℃，物料温度为22-25℃；
所述发泡剂为水。
优选的：所述聚酯聚醚多元醇，是以低分子聚酯为起始剂与环氧丙烷合成的聚酯聚醚多元醇；或者是由相溶性良好的低分子量聚酯与低分子量聚醚组成的混合物。
优选的：所述降粘剂是邻苯二甲酸二乙烯丙酯或NDI-101或有机硅烷偶联剂。
优选的：所述粗MDI或PAPI的NCO指数为1.4-1.6。
本发明所述方案中，采用纳米级的蒙脱土材料，在反应过程中，纳米材料可有效进入聚酯聚醚多元醇结构单元，纳米尺度的粒子介于宏观物质与微观原子分子的中间，物质的局限性及巨大的表面积效应使物质性能发生质变，呈现整个以水为发泡剂的纳米蒙脱土聚氨酯硬质泡沫塑料中，它以聚酯聚醚为连续相，其分散相中至少有一维小于100nm；和传统聚酯聚醚相比，由于纳米粒子带来的效应和纳米粒子与基面的界面相互作用，使纳米蒙脱土聚酯聚醚复合接触面积增大，使反应更完善，从而大大提高其性能。同时，也解决了原料体系粘度大，物料流动性差的问题。在100份聚酯聚醚多元醇中溶入1-5份的水，传统以水为发泡剂时，将其溶解在聚酯聚醚中，由于分散的不好，所得到的硬质泡沫泡孔大；本方案中，将聚酯聚醚多元醇复合一定量的纳米蒙脱土，对聚酯聚醚进行插层反应，在发泡过程中由于纳米效应，以更小水滴分布在聚酯聚醚中，和纳米粒子于基面相互作用，使之溶入的水分随着聚酯聚醚被插层反应而分割的更小，分散在聚酯聚醚的水也又一次被分割成更小的水滴，从而解决了水发泡造成泡孔粗大的问题，增加了绝热功能，使导热率接近或达到传统泡沫的性能。
此外，在原料配方中我们利用聚酯部分溶解足够量的水分，在制作聚氨酯硬质泡沫中反应产所生CO2气体可供发泡使用。
本方案中，在制备无氟纳米蒙脱土聚氨酯硬质泡沫塑料时，以水与异氰酸酯反应生成的小分子缩二脲是硬链段，存在泡沫中蒙脱土是刚性粒子；再加上聚醚与异铝酸酯也可产生少部分硬链段；而同时，配比中聚酯则为软链段物质，二者相互协调，从而获得较好的泡沫体，解决了泡沫较脆，基材粘接力差等问题。
由于选择了聚酯聚醚，它能充分溶解发泡剂水。聚酯聚醚中复合了一定比例的纳米蒙脱土，使在合成聚氨基酸甲酯反应时在纳米效应作用下，使发泡剂水在更小微粒下与异氰酸酯反应，它不但产生的CO2气泡更小，更均匀从而使水与异氰酸酯反应生成硬链段缩二脲以更小的链可均匀中存在泡沫的结构中，使泡沫体软硬链分配更合理，可大大改善其脆性，也提高了对基面粘接性，实现了无氟发泡，保护了大气臭氧层。
下面通过具体实施例对本发明作进一步说明：
实施例1，制作保温车库门板：
将门板模具加热至20℃备用。首先将10份的有机纳米蒙脱土与90份的聚酯聚醚多元醇及2份的降粘酯类化合物同入一容器内加热至70-90℃并抽真空0.5小时，加入胺类催化剂1-4份，1-5份的水及1-4份的匀泡剂，后充分搅拌混合制备出组合料备用。取一定量的组合料，置于容器内再加入NCO指数为1-1.6份的粗MDI或粗PAPI搅拌7秒（搅拌速度3000转每分）倒入模具内。要求环境温度11℃以上，物料温度20-22℃，模具温度30-35℃，熟化6分钟，即制得保温车库门板所需的泡沫，即本发明无氟纳米蒙脱土聚氨酯硬质泡沫塑料。该泡沫基面粘接牢固泡沫充满，泡沫硬有弹性有良好的保温效果。
将上述材料按GB10800-89要求进行检测，其结果如下：密度37 kg/m3，压缩性能122 KPg，尺寸稳定3%，导热系数0.021。
本实例中，原料温度10－25℃，熟化温度常温，搅拌速度3000转/分，搅拌时间7-15秒，乳白时间10-17秒，拉丝时间27秒，固化时间60秒。
实施例2，制作两步黄夹克保温管：
将预制的黄夹克管的塑料套与要保温的铁管串在一起封堵两端，在塑料套中间打料孔备用。首先将重量份为95的聚酯聚醚多元醇及3份的降粘剂酯类化合物置入同一容器内加热70-90℃，抽真空0.5小时脱水并复合。加入胺催化剂1-4份，再加入锡类催化剂0.1-1份，再加入1-4份水，再加入复合匀泡剂2-3份充分搅拌混合制备出组合聚醚。利用低压发泡机，按要求注入定量的异氰酸酯，和组合聚醚混合液后，封闭注料口3-5分钟泡沫充满，拆除两端封堵，得一根合格的黄夹克保温管。
实施例3，制做耐150℃管壳：
首先将重量份数为10的纳米级有机蒙脱土与90份的聚酯聚醚多元醇以及3份降粘剂化合物，置入同一容器加热70-90℃，抽真空0.5小时进行脱水并复合，加入油酸钾0.8份，三聚催化剂4.0份，匀泡剂3-5份，水2-4份，后充分搅拌混合制备出组合料。取一定量的组合料按配方量加入NCO指数1.0-2.0的粗MD1或PAP1，要求搅拌转数3000转/分，搅拌7秒后倒入模具内合模5-15分钟开模，即得耐高温150℃的管壳。
Claims (4)
1.一种无氟纳米蒙脱土聚氨酯硬质泡沫塑料的制备方法，其特征在于：所述无氟纳米蒙脱土聚氨酯硬质泡沫塑料包括如下重量份数的各组分：聚酯聚醚多元醇80-95份；纳米蒙脱土5-20份；降粘剂2-20份；胺类催化剂1-4份；锡类催化剂0-1份；发泡剂1-5份；匀泡剂1-10份；
其制备方法如下：首先将聚酯聚醚多元醇、纳米蒙脱土、降粘剂三种原料按重量比置入容器内搅拌混合，加热抽真空使其脱水，生成纳米蒙脱土聚酯聚醚多元醇复合材料，再加入重量份为1-4份的胺类催化剂和0-1份的锡类催化剂，混合均匀后，再加入重量份为1-5份的发泡剂，1-10份的匀泡剂，然后充分搅拌混合制备出组合料；再加入NCO指数为1-2的粗MDI或PAPI的异氰酸酯充分搅拌，搅拌速度3000转/分，搅拌时间7-10秒，熟化时间10-15分，环境温度大于15℃，物料温度为22-25℃；
所述发泡剂为水。
2.根据权利要求1所述的无氟纳米蒙脱土聚氨酯硬质泡沫塑料，其特征在于：所述聚酯聚醚多元醇，是以低分子聚酯为起始剂与环氧丙烷合成的聚酯聚醚多元醇；或者是由相溶性良好的低分子量聚酯与低分子量聚醚组成的混合物。
3.根据权利要求1所述的无氟纳米蒙脱土聚氨酯硬质泡沫塑料，其特征在于：所述降粘剂是邻苯二甲酸二乙烯丙酯或NDI-101或有机硅烷偶联剂。
4.根据权利要求1所述的无氟纳米蒙脱土聚氨酯硬质泡沫塑料，其特征在于：所述粗MDI或PAPI的NCO指数为1.4-1.6。
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