CN114921088B - 一种用于冷链物流的改性聚氨酯保温材料及其制备方法 - Google Patents
一种用于冷链物流的改性聚氨酯保温材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于冷链物流的改性聚氨酯保温材料的制备方法，首先在反应容器中加入15~25份聚醚多元醇4110、聚醚多元醇H3006、苯酐聚酯多元醇中的一种或两种以上，0.5~1份去离子水，0.003~0.007份叔胺类催化剂混合均匀后，再加入6~12份气凝胶纳米泡沫稳定剂混合均匀作为A料，然后将1~1.3份B料加入到1份A料中，混合后迅速倒入模具中发泡，冷却至室温，即可得到气凝胶改性聚氨酯保温材料；所述B料为二苯基甲烷二异氰酸酯、多苯基多亚甲基异氰酸酯中的一种或两种以上。本发明改性后的聚氨酯泡沫热稳定性提高、压缩强度提高、阻燃系数提高，达到难燃或不燃的等级，同时导热系数大幅降低。
Description
技术领域
本发明涉及保温材料技术领域，特别是涉及一种用于冷链物流的改性聚氨酯保温材料及其制备方法。
背景技术
目前，我国的冷藏运输率（即易腐货物采用冷藏运输所占的比例）仅能达到 10%～20%，远远不能满足冷链运输的要求；并且现有冷链运输过程中损耗高，整个物流费用占到易腐物品成本的70%，超过国际规定的易腐物品物流成本最高不超过其总成本的50%。
市场上冷链运输箱的保温材料大部分采用有机泡沫类材料，如EPS、XPS、PU等，它们具有质轻、保温、施工简便等优点。然而这些有机泡沫保温材料的阻燃性差、易老化、易燃烧、不耐高温、安全环保性差等缺点引发了人们对冷链物流防火安全性能的思考。针对冷链物流需求，探寻一种隔热性能更好、阻燃性能强、热稳定性能高的保温材料已迫在眉睫。
近年来，通过对有机泡沫保温材料的改性并且将其与纳米无机材料复合来提高保温材料的阻燃性能成为当前保温材料领域的一个研究热点。有机/无机杂化聚氨酯泡沫材料结合了多种材料的优异性能，具有很好的应用前景，复合后的机械性能、热稳定性和阻燃性都有所提高。
目前市面上被用于与聚氨酯复合的无机材料一般有空心微珠、有机改性纳米蒙脱土、可膨胀性石墨、纳米SiO2、有机改性粘土等，虽然这些无机材料的加入克服了聚氨酯阻燃性能差的缺陷，但是这类纳米材料的导热系数较高，密度较大，吸水率较高，加入后使得聚氨酯泡沫导热系数升高，保温性能下降。
由此可见，上述现有的用于冷链物流的保温材料仍存在有不便与缺陷，亟待加以进一步改进。如何能创设一种新的用于冷链物流的改性聚氨酯保温材料及其制备方法，使其能兼具有机保温材料的低导热系数，又具有无机保温材料的防火阻燃性能、热稳定性，提升用于冷链物流的保温材料的综合性能，成为当前业界极需改进的目标。
发明内容
为解决上述技术问题，本发明提供一种用于冷链物流的改性聚氨酯保温材料及其制备方法，使其既具有机保温材料的低导热系数，又具有无机保温材料的防火阻燃性能、热稳定性，提升用于冷链物流的保温材料的综合性能，从而克服现有的用于冷链物流的保温材料的不足。
本发明的技术方案如下：
一种用于冷链物流的改性聚氨酯保温材料，其特征在于，所述改性聚氨酯保温材料为纳米孔隙结构的气凝胶改性聚氨酯保温材料。
进一步的，所述纳米孔隙结构的气凝胶内部空隙尺度范围为2纳米--69纳米，优选为30-60纳米。
进一步的，所述纳米孔隙结构的气凝胶为无机氧化物气凝胶、金属氧化物产气凝胶、高分子气凝胶的一种或两种以上。
进一步的，所述纳米孔隙结构的气凝胶为氧化物气凝胶。
一种用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，所述制备方法为：首先在反应容器中加入15~25份聚醚多元醇4110、聚醚多元醇H3006、苯酐聚酯多元醇中的一种或两种以上，0.5~1份去离子水，0.003~0.007份叔胺类催化剂混合均匀后，再加入6~12份气凝胶纳米泡沫稳定剂混合均匀作为A料，然后将1~1.3份B料加入到1份A料中，混合后迅速倒入模具中发泡，冷却至室温，即可得到气凝胶改性聚氨酯保温材料；
所述B料为二苯基甲烷二异氰酸酯、多苯基多亚甲基异氰酸酯中的一种或两种以上。
进一步的，所述气凝胶纳米泡沫稳定剂的制备方法为：在密封反应釜中加入20份正己烷和4~8份硅烷化试剂，搅拌混合，控制反应釜温度为5~15℃，再加入5~10份气凝胶，将2~4份端氨基聚醚与2~5份环己烷混合均匀后加入到上述反应釜中，继续反应2h；反应完成后，向反应釜中缓慢加入5~8份三乙胺，中和生成HCL，旋转蒸发除去正己烷，即可得到所述气凝胶纳米泡沫稳定剂。
进一步的，所述硅烷化试剂为三甲基氯硅烷、六甲基二硅氧烷、六甲基二硅氮烷中的一种或两种以上。
进一步的，加入所述气凝胶的粒度介于20μm～150μm之间，孔隙率介于30％～99.9％之间，堆积密度3～500g/L。
进一步的，加入所述气凝胶的粒度介于500μm～100μm之间，孔隙率介于90％～99.9％之间，堆积密度10～50g/L。
进一步的，所述密封反应釜内物料液面的上方位置设有一带过滤网的排气口，所述过滤网空隙尺度小于20微米。
与现有技术相比，本发明的有益效果体现在：
1、气凝胶是目前已知固体物质中最轻并且性能最好的隔热材料，其体积的90%以上都是极微小的纳米孔洞，其余部分由三维纳米网状孔壁构成，具有隔热、隔音、透明、憎水、防火、质轻等多项优异性能；将气凝胶与聚氨酯复合，不仅可以降低聚氨酯导热系数，大幅提升其保温隔热性能，还可能提高聚氨酯的力学性能、热稳定性和阻燃性能；
2、气凝胶为载体制备了纳米泡沫稳定剂，通过反应将聚硅氧烷、聚氧化烯烃类结构接枝到气凝胶上，该类结构对调节聚氨酯泡孔、提高闭孔率有明显效果；加入气凝胶纳米泡沫稳定剂后，聚氨酯泡沫壁厚增加、泡孔缺陷减少、泡孔均匀性提高，泡沫闭孔率提高，从而泡沫的压缩强度、热稳定性得以提高，导热系数降低；
3、采用将聚氨酯与气凝胶复合制备出性能指标优于传统聚氨酯体系，改性后的聚氨酯泡沫热稳定性提高、压缩强度提高、阻燃系数提高，达到难燃或不燃的等级，同时导热系数大幅降低。
4，由于所采用气凝胶的比重只有0.2克/立方厘米以下，与比重0.8克/立方厘米以上的聚氨酯差别很大，所以在将气凝胶加入到密封反应釜时极易飘浮四散，本专利独创的釜内负压进料装置科学地解决了这一难题。
具体实施方式
本发明气凝胶改性聚氨酯保温材料与传统工艺制备的聚氨酯相比提高了保温隔热性能、热稳定性、阻燃性等，导热系数由0.030降低到0.015，热稳定性通过热分解温度反应，气凝胶改性后热分解温度提高了70℃，阻燃性通过极限氧指数反应，极限氧指数由27.2%提高到34.5%，压缩强度提高了25%。
下面结合示例性实施例来详细说明本发明。
本申请中，在制备气凝胶纳米泡沫稳定剂时使用的所述密封反应釜，内部物料液面上方的位置有一个带过滤网的排气口，所述过滤网空隙尺度小于20微米，该排气口外部连接有带阀门的排气管，排气管连接有向外排气的排气泵，该排气泵为气动驱动或防爆电机驱动。
实施例1
在密封的反应釜中加入20克正己烷、4.6克六甲基二硅氮烷，搅拌混合，控制反应釜温度为10℃，加入5克气凝胶。将3克端氨基聚醚与5克环己烷混合均匀，加入到反应釜中，继续反应2h。反应完成后，向反应釜中缓慢加如5克三乙胺中和生成的HCL。旋转蒸发除去正己烷，即可得到气凝胶纳米泡沫稳定剂1。
在容器中加入20克聚醚多元醇4110，0.5克去离子水，0.003克叔胺类催化剂混合均匀后，再加入6克气凝胶纳米泡沫稳定剂1混合均匀作为A料，B料为二苯基甲烷二异氰酸酯，将1.18份B料加入到1份A料中在2000rpm转速下混合10s后迅速倒入模具中发泡，冷却至室温，即可得到气凝胶改性聚氨酯材料1。
实施例2
在密封的反应釜中加入20克正己烷、6克三甲基氯硅烷，搅拌混合，控制反应釜温度为5~15℃，加入5克气凝胶。将3.5端氨基聚醚与5克环己烷混合均匀，加入到反应釜中，继续反应2h。反应完成后，向反应釜中缓慢加如5克三乙胺中和生成的HCL。旋转蒸发除去正己烷，即可得到气凝胶纳米泡沫稳定剂2。
在容器中加入20克苯酐聚酯多元醇，1克去离子水，0.003克叔胺类催化剂混合均匀后，再加入8份气凝胶纳米泡沫稳定剂2混合均匀作为A料，B料为多苯基多亚甲基异氰酸酯，将1克B料加入到1克A料中在2000rpm转速下混合10s后迅速倒入模具中发泡，冷却至室温，即可得到气凝胶改性聚氨酯材料2。
对比例1
在容器中加入20克聚醚多元醇4110，0.5克去离子水，0.003克叔胺类催化剂混合均匀后作为A料，B料为二苯基甲烷二异氰酸酯，将1.18份B料加入到1份A料中在2000rpm转速下混合10s后迅速倒入模具中发泡，冷却至室温，即可得到聚氨酯材料对比例1。
表1 性能参数对比表格
从表1中可以看出，本发明气凝胶改性聚氨酯保温材料与传统工艺制备的聚氨酯相比提高了保温隔热性能、热稳定性、阻燃性等，导热系数由0.030降低到0.015，热稳定性通过热分解温度反应，气凝胶改性后热分解温度提高了70℃，阻燃性通过极限氧指数反应，极限氧指数由27.2%提高到34.5%，压缩强度提高了25%。
Claims (10)
1.一种用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，所述制备方法为：首先在反应容器中加入15～25份聚醚多元醇4110、聚醚多元醇H3006、苯酐聚酯多元醇中的一种或两种以上，0.5～1份去离子水，0.003～0.007份叔胺类催化剂混合均匀后，再加入6～12份气凝胶纳米泡沫稳定剂混合均匀作为A料，然后将1～1.3份B料加入到1份A料中，混合后迅速倒入模具中发泡，冷却至室温，即可得到气凝胶改性聚氨酯保温材料；
所述B料为二苯基甲烷二异氰酸酯、多苯基多亚甲基异氰酸酯中的一种或两种以上；
所述气凝胶纳米泡沫稳定剂的制备方法为：在密封反应釜中加入20份正己烷和4～8份硅烷化试剂，搅拌混合，控制反应釜温度为5～15℃，再加入5～10份气凝胶，将2～4份端氨基聚醚与2～5份环己烷混合均匀后加入到上述反应釜中，继续反应2h；反应完成后，向反应釜中缓慢加入5～8份三乙胺，中和生成HCL，旋转蒸发除去正己烷，即可得到所述气凝胶纳米泡沫稳定剂。
2.如权利要求1所述的用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，所述硅烷化试剂为三甲基氯硅烷、六甲基二硅氧烷、六甲基二硅氮烷中的一种或两种以上。
3.如权利要求2所述的用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，加入所述气凝胶的粒度介于20μm～150μm之间，孔隙率介于30％～99.9％之间，堆积密度3～500g/L。
4.如权利要求3所述的用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，加入所述气凝胶的孔隙率介于90％～99.9％之间，堆积密度10～50g/L。
5.如权利要求1所述的用于冷链物流的改性聚氨酯保温材料的制备方法，其特征在于，所述密封反应釜内物料液面的上方位置设有一带过滤网的排气口，所述过滤网空隙尺度小于20微米。
6.权利要求1-5任一项所述的制备方法得到的用于冷链物流的改性聚氨酯保温材料，所述改性聚氨酯保温材料为纳米孔隙结构的气凝胶改性聚氨酯保温材料。
7.如权利要求6所述的用于冷链物流的改性聚氨酯保温材料，其特征在于，所述纳米孔隙结构的气凝胶内部空隙尺度范围为2纳米-69纳米。
8.如权利要求6所述的用于冷链物流的改性聚氨酯保温材料，其特征在于，所述纳米孔隙结构的气凝胶内部空隙尺度范围为30-60纳米。
9.如权利要求6所述的用于冷链物流的改性聚氨酯保温材料，其特征在于，所述纳米孔隙结构的气凝胶为无机氧化物气凝胶、金属氧化物气凝胶、高分子气凝胶的一种或两种以上。
10.如权利要求6所述的用于冷链物流的改性聚氨酯保温材料，其特征在于，所述纳米孔隙结构的气凝胶为氧化物气凝胶。
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