CN115197388A - 一种导热系数可变的形状记忆泡沫及其制备方法 - Google Patents

一种导热系数可变的形状记忆泡沫及其制备方法 Download PDF

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CN115197388A
CN115197388A CN202210708438.XA CN202210708438A CN115197388A CN 115197388 A CN115197388 A CN 115197388A CN 202210708438 A CN202210708438 A CN 202210708438A CN 115197388 A CN115197388 A CN 115197388A
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钱建中
汪乐春
沙浩鹏
严毅凡
翟滢浩
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Abstract

本发明公开的属于化学合成技术领域，具体为一种导热系数可变的形状记忆泡沫及其制备方法，其技术方案是：包括多元醇A组分和异氰酸酯B组分，多元醇A组分的原料为结晶聚酯多元醇、聚醚多元醇、扩链剂、交联剂、发泡剂、泡沫稳定剂、催化剂，导热填料。异氰酸酯B组分的原料为结晶聚酯多元醇、异氰酸酯；本发明所述的形状记忆泡沫中加入了导热填料，一种导热系数可变的形状记忆泡沫及其制备方法的有益效果是：采用高结晶的聚酯多元醇和聚醚多元醇搭配，形状记忆泡沫的软段结晶完善，在0‑20℃条件下，链段结晶凝结，当形状记忆泡沫在压缩成无泡孔状态时，形状保持率为100％，在较宽的温度条件下(0‑50℃)均可以保持压缩形状不回复。

Description

一种导热系数可变的形状记忆泡沫及其制备方法
技术领域
本发明涉及化学合成技术领域，具体涉及一种导热系数可变的形状记忆泡沫及其制备方法。
背景技术
保温和导热是在材料特性中往往是相反的两面，保温材料通常是导热性能差的材料，而导热性能好的材料通常无法保温，但在生产生活中常常遇到需要材料在保温和导热之间切换的使用场景，如汽车动力电池领域，锂电池的特性导致温度对电池材料的活性和充放电性能的影响较大；锂电池在低温下工作时需求保温材料来保证电池的能量效率，但在其高功率运作过程中却又希望导热材料将电池放出的热量很好的传导出去；为了解决该问题，许多动力电池厂商都在电池包中采用温度智能管理系统，通过加热，液冷等方式来管理温度，但也因此消耗了大量的能量，影响了电池的效能。
为了很好地平衡保温和导热同时又能节约能源，人们进行了很多研究，大部分研究和专利都采用在材料中添加相变材料；但相变材料的热量吸收和释放与其热容大小有关，当热量过大时，超过了相变材料的热量吸收极限，这时相变材料往往无法发挥作用；材料在保温和导热的特性与材料的导热系数有关；当导热系数改变时，材料的保温和导热的特性随之改变；形状记忆泡沫材料可以在压缩的无空隙形态到回复的低密度泡沫形态间切换，不同形态的导热系数不同，因而具备了导热系数可变的特性；当需要导热时，将形状记忆泡沫材料在较低的温度下压缩，得到导热系数较高的高密度形态；当需要保温时，撤去外力并施加一定的温度，形状记忆泡沫材料即可回复成低导热系数的低密度泡沫形态；但现有的形状记忆泡沫的导热系数变化范围不大，且有回复时间过长，回复需要的温度过高的问题。
因此，发明一种导热系数可变的形状记忆泡沫及其制备方法很有必要。
发明内容
为此，本发明提供一种导热系数可变的形状记忆泡沫及其制备方法，解决了现有的形状记忆泡沫的导热系数变化范围不大，且有回复时间过长，回复需要的温度过高的问题。
为了实现上述目的，本发明提供如下技术方案：一种导热系数可变的形状记忆泡沫，包括多元醇A组分和异氰酸酯B组分，所述多元醇A组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：20-40份、聚醚多元醇：0-15份、扩链剂：2.0-6.0 份、交联剂：0.8-4.0份、泡沫稳定剂：0.5-2.0份、催化剂：0.2-2.0份、发泡剂：0.5-2.0份、导热填料：50-80份；
所述异氰酸酯B组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：10-20份、二苯基甲烷二异氰酸酯(MDI)：50-70份、液化MDI：10-30份。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述的聚醚多元醇的官能度为2-3，优选的是官能度2-2.5，聚醚多元醇的分子量为1000-5000。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述交联剂为大于等于3官能度的小分子醇或小分子胺。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述结晶聚酯多元醇的官能度为2，结晶温度为30-70℃。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述结晶聚酯多元醇的数均分子量为1000-4000。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述聚醚多元醇为聚四氢呋喃二醇，聚丙二醇，环氧乙烷环氧丙烷嵌段共聚多元醇。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述的非支链的小分子二元醇，可在0-50℃结晶。
作为本发明所述的一种导热系数可变的形状记忆泡沫的一种优选方案，其中：所述导热填料为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅、氢氧化铝和氢氧化镁中的一种或多种。
一种导热系数可变的形状记忆泡沫的制备方法，具体包括以下步骤：
S1，制备多元醇A组分：
将结晶聚酯多元醇、聚醚多元醇、扩链剂、交联剂加入到反应釜中搅拌，然后加入所述催化剂、泡沫稳定剂、导热填料在80℃下搅拌至均匀后，加入发泡剂继续搅拌均匀后保温保存；
S2，制备异氰酸酯B组分：
将所述结晶聚酯多元醇与二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入液化MDI在反应釜中搅拌均匀，得到异氰酸酯B组分；
S3，将多元醇A组分和异氰酸酯B组分进行高速混合，注入25mm厚的模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫。
本发明的有益效果是：
1、本发明在形状记忆泡沫中加入导热填料，使其导热特性可在高导热系数(0.6-1.0W/(m·k))和低导热系数(0.05-0.08W/(m·k))间转换，本发明的形状记忆泡沫可以很好的应用于需要切换导热和保温使用场景的设备或仪器组件中；
2、采用高结晶的聚酯多元醇和聚醚多元醇搭配，形状记忆泡沫的软段结晶完善，在0-20℃条件下，链段结晶凝结，当形状记忆泡沫在压缩成无泡孔状态时，形状保持率为100％，在较宽的温度条件下(0-50℃)均可以保持压缩形状不回复；
3、当放置在70-90℃环境下，撤去外力，形状记忆泡沫可快速回复成泡沫形态，形状回复率可达100％。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
本发明提供的一种导热系数可变的形状记忆泡沫，包括多元醇A组分和异氰酸酯B组分，所述多元醇A组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：20-40份、聚醚多元醇：0-15份、扩链剂：2.0-6.0 份、交联剂：0.8-4.0份、泡沫稳定剂：0.5-2.0份、催化剂：0.2-2.0份、发泡剂：0.5-2.0份、导热填料：50-80份；
所述异氰酸酯B组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：10-20份、二苯基甲烷二异氰酸酯(MDI)：50-70份、液化MDI：10-30份；
进一步地，所述的聚醚多元醇的官能度为2-3，优选的是官能度2-2.5，聚醚多元醇的分子量为1000-5000，优选的是1500-4000；
进一步地，所述交联剂为大于等于3官能度的小分子醇或小分子胺，优选的是三羟甲基丙烷、三乙醇胺、二乙醇胺，三异丙醇胺、季戊四醇中的任意一种或多种。
进一步地，所述结晶聚酯多元醇的官能度为2，结晶温度为30-70℃，优选的是40-70℃。
进一步地，所述结晶聚酯多元醇的数均分子量为1000-4000，优选的是 2000-3000。
进一步地，所述聚醚多元醇为聚四氢呋喃二醇，聚丙二醇，环氧乙烷环氧丙烷嵌段共聚多元醇。
进一步地，所述的非支链的小分子二元醇，可在0-50℃结晶。
进一步地，所述导热填料为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅、氢氧化铝和氢氧化镁中的一种或多种，更优选为氮化铝和氧化铝。
实施例1：
将25.5kg 3000分子量聚己内酯二元醇、12.0kg 2000分子量聚四氢呋喃二醇，2.0kg扩链剂1,4丁二醇，0.8kg交联剂三羟甲基丙烷加入到反应釜中搅拌，然后加入0.02kg催化剂T-12、0.5kg催化剂DABCO S-25，1.5kg泡沫稳定剂DC198，加入55kg80目球形氧化铝和5kg800目球形氧化铝在80℃下搅拌2h，加入1.5kg蒸馏水搅拌0.5h，密封保存，得到多元醇A组份。
将10kg2000分子量聚癸二酸己二醇酯二元醇与70KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入20kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：35用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫。泡沫的密度为110kg/m3，25℃固化7天后达到最终固化效果。
实施例2：
将20.2kg 3000分子量聚碳酸酯二元醇、15.0kg 3000分子量聚丙二醇， 6.0kg扩链剂1,6己二醇，1.5kg交联剂三羟甲基丙烷加入到反应釜中搅拌，然后加入0.03kg dabcoBL-11、0.5kg催化剂DABCO 1028，1.5kg泡沫稳定剂DC198，加入70.5kg80目球形氧化铝在80℃下搅拌2h，加入1.0kg蒸馏水搅拌0.5h，密封保存，得到多元醇A组份。
将20kg2000分子量聚癸二酸己二醇酯二元醇与60KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入20kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：39用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫；泡沫的密度为230kg/m3，25℃固化7天后达到最终固化效果。
实施例3：
将39.8kg 2000分子量聚癸二酸己二醇酯二元醇，4.5kg扩链剂1,4丁二醇，2.0kg交联剂三乙醇胺加入到反应釜中搅拌，然后加入0.05kg催化剂 T-12、0.2份dabco S-25，1.5kg泡沫稳定剂B8461，加入40.5kg80目球形氧化铝和10kg80目氮化铝，在80℃下搅拌2h，加入0.7kg蒸馏水搅拌1h，密封保存，得到多元醇A组份。
将10kg2000分子量聚己二酸己二醇酯二元醇与60KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入30kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：38用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫；泡沫的密度为400kg/m3，25℃固化7天后达到最终固化效果。
实施例4：
将22.3kg 3000分子量聚己二酸丁二醇酯二元醇、8.8kgTED28,2kg、6kg 扩链剂1，4-环己烷二甲醇，3.5kg交联剂三异丙醇胺加入到反应釜中搅拌，然后加入0.01kg催化剂T-12、2.0份dabco S-25、1.0kg泡沫稳定剂B8461, 0.5kg泡沫稳定剂B8715，加59.6kg80目球形氧化铝和20kg800目氮化铝在 80℃下搅拌2h，加入0.4kg蒸馏水搅拌1h，密封保存，得到多元醇A组份。
将20kg2000分子量聚碳酸酯二元醇与70KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入10kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：30用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫。泡沫的密度为560kg/m3，25℃固化7天后达到最终固化效果。
对比例1
将90.7kg 3000分子量聚碳酸酯二元醇、15.0kg 3000分子量聚丙二醇， 6.0kg扩链剂1,6己二醇，1.5kg交联剂三羟甲基丙烷加入到反应釜中搅拌，然后加入0.03kg催化剂dabco BL-11、0.5kg催化剂DABCO 1028，1.5kg泡沫稳定剂DC198，在80℃下搅拌2h，加入1.0kg蒸馏水搅拌0.5h，密封保存，得到多元醇A组份。
将20kg2000分子量聚癸二酸己二醇酯二元醇与60KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入20kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：50用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫。泡沫的密度为230kg/m3，25℃固化7天后达到最终固化效果。
对比例2
将20.2kg非结晶聚酯二元醇2000分子量邻苯二甲酸二乙二醇酯二元醇、 15.0kg3000分子量聚丙二醇，6.0kg扩链剂1,6己二醇，1.5kg交联剂三羟甲基丙烷加入到反应釜中搅拌，然后加入0.03kg dabco BL-11、0.5kg催化剂DABCO 1028，1.5kg泡沫稳定剂DC198，加入70.5kg80目球形氧化铝在80℃下搅拌2h，加入1.0kg蒸馏水搅拌0.5h，密封保存，得到多元醇A组份。
将20kg2000分子量聚癸二酸己二醇酯二元醇与60KG二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入20kg液化MDI得到的异氰酸酯B组份。
将多元醇A组分和异氰酸酯B组分按照A:B＝100：39用高速搅拌器混合均匀，注入25mm厚的钢制模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫；泡沫的密度为230kg/m3，25℃固化7天后达到最终固化效果。
性能检测指标如下表：
Figure BDA0003706251380000081
泡沫体密度参照GB/T 6343—2009测试。
形状固定率、形变恢复率、回复时间测试：样品均为25mm×25mm× 25mm的立方体，划标线间距为L0；将样品加热至80℃，施加外力压缩至原体积的10-30％，实际高度记为L1；降温至0℃保持形状10min，在 25℃或50℃放置30min测定高度，记为L2；加热样品至80℃，记录回复后的高度为L3，并记录回复到最高高度所需的时间t。按下列公式计算：形状固定率Rg＝[(L0－L2)/(L0－L1)]×100％形变恢复率Rh＝[(L3 －L2)/(L0－L2)]×100％
由实施例与对比例可以看出：
对比例1与实施例1相比，未添加导热填料，原始形态和压缩形态的导热系数变化不大。
对比例2与实施例1相比，采用非结晶聚酯多元醇替换结晶聚酯多元醇，泡沫无形状记忆能力。
且提高实验发现：在A组份中添加了聚醚多元醇后，制得的形状记忆泡沫相对于未添加聚醚多元醇的泡沫形状固定率提高，形状恢复率也同样提高了，在高温下(70-90℃)形状恢复速度也提高了；一个值得信服的理由是聚酯多元醇和聚醚多元醇是热力学不相容的物质，两种多元醇同时用于制备聚氨酯形状记忆泡沫时，聚氨酯形状记忆泡沫可以当作聚醚型聚氨酯与聚酯型聚氨酯的互穿网络结构；聚醚多元醇链段与聚酯多元醇链段间的相互影响较小，聚醚多元醇不但不会阻碍聚酯多元醇的结晶，相反的结晶聚酯多元醇可以在聚醚多元醇所形成的软段分子链中自由结晶，结晶聚酯多元醇链段的结晶更完善，形状固定率高；同时聚醚多元醇的分子链回弹性好，可以加快高温下的形状回复速度，提高了形状恢复率。
以上所述，仅是本发明的较佳实施例，任何熟悉本领域的技术人员均可能利用上述阐述的技术方案对本发明加以修改或将其修改为等同的技术方案。因此，依据本发明的技术方案所进行的任何简单修改或等同置换，尽属于本发明要求保护的范围。

Claims (9)

1.一种导热系数可变的形状记忆泡沫，其特征在于，包括多元醇A组分和异氰酸酯B组分，所述多元醇A组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：20-40份、聚醚多元醇：0-15份、扩链剂：2.0-6.0份、交联剂：0.8-4.0份、泡沫稳定剂：0.5-2.0份、催化剂：0.2-2.0份、发泡剂：0.5-2.0份、导热填料：50-80份；
所述异氰酸酯B组分当中，以重量份计算，包括如下组分：
结晶聚酯多元醇：10-20份、二苯基甲烷二异氰酸酯：50-70份、液化MDI：10-30份。
2.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述的聚醚多元醇的官能度为2-3，优选的是官能度2-2.5，聚醚多元醇的分子量为1000-5000。
3.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述交联剂为大于等于3官能度的小分子醇或小分子胺。
4.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述结晶聚酯多元醇的官能度为2，结晶温度为30-70℃。
5.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述结晶聚酯多元醇的数均分子量为1000-4000。
6.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述聚醚多元醇为聚四氢呋喃二醇，聚丙二醇，环氧乙烷环氧丙烷嵌段共聚多元醇。
7.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述的非支链的小分子二元醇，可在0-50℃结晶。
8.根据权利要求1所述的一种导热系数可变的形状记忆泡沫，其特征在于：所述导热填料为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、碳化硅、氢氧化铝和氢氧化镁中的一种或多种。
9.制备权利要求1-8中任项所述导热系数可变的形状记忆泡沫的方法，其特征在于：具体包括以下步骤：
S1，制备多元醇A组分：
将结晶聚酯多元醇、聚醚多元醇、扩链剂、交联剂加入到反应釜中搅拌，然后加入所述催化剂、泡沫稳定剂、导热填料在80℃下搅拌至均匀后，加入发泡剂继续搅拌均匀后保温保存；
S2，制备异氰酸酯B组分：
将所述结晶聚酯多元醇与二苯基甲烷二异氰酸酯在反应釜中75℃～85℃反应2～3小时，加入液化MDI在反应釜中搅拌均匀，得到异氰酸酯B组分；
S3，将多元醇A组分和异氰酸酯B组分进行高速混合，注入25mm厚的模具中；5-6min脱模后得到导热系数可变的形状记忆泡沫。
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Application publication date: 20221018