CN112142948A - 一种鞋垫用高吸湿抑菌聚氨酯泡沫材料及其制备方法 - Google Patents

一种鞋垫用高吸湿抑菌聚氨酯泡沫材料及其制备方法 Download PDF

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CN112142948A
CN112142948A CN202011110856.6A CN202011110856A CN112142948A CN 112142948 A CN112142948 A CN 112142948A CN 202011110856 A CN202011110856 A CN 202011110856A CN 112142948 A CN112142948 A CN 112142948A
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何卫东
姜志国
孙运强
陈苏婷
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Suqian Jiahe Plastic Metal Products Co ltd
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Abstract

本发明公开一种鞋垫用高吸湿抑菌聚氨酯泡沫材料及其制备方法。本发明聚氨酯高吸水抑菌泡沫材料组成成分按质量份计如下：基料树脂15‑25份；交联剂30‑50份；扩链剂0.2‑5份；聚酯催化剂0.1‑0.5份；发泡催化剂0.2‑1份；匀泡剂0.2‑5份；发泡剂1‑5份；抑菌剂1‑8份。本发明选择聚氨酯为基材，加入一定量扩链剂、聚酯催化剂、发泡催化剂、匀泡剂和发泡剂，特别加入了抑菌剂，采用超临界发泡技术进行发泡，制得高吸湿抑菌聚氨酯泡沫材料。本发明产品所用原料环保，产品无异味，生产工艺简单，生产成本低，具有优异的吸湿性能和抑菌性能，从根本上解决脚汗和脚臭的问题。

Description

一种鞋垫用高吸湿抑菌聚氨酯泡沫材料及其制备方法
技术领域
本发明涉及特种聚氨酯材料的应用，具体涉及一种鞋垫用高吸湿抑菌聚氨酯泡沫材料及其制备方法。
背景技术
随着生活水平的不断提高，人们对鞋子的舒适度和味道有了更高的要求。在夏天或运动后，由于脚心汗腺多，容易出汗，汗液里除含水分、盐分外，还含有乳酸及尿素。在多汗条件下，脚上的细菌大量繁殖并分解角质蛋白，再加上汗液中的尿素、乳酸，很容易导致脚臭现象。目前解决脚臭鞋臭的问题，主要是利用具有特殊性能的鞋垫，如在鞋垫中加入吸湿和抑菌的材料，从根本上抑制脚臭现象的发生。
目前吸湿鞋垫一般采用两种基材，传统鞋垫采用乙烯-乙酸乙烯酯共聚物（EVA）材质，但是该类材料采用偶氮二甲酰胺为发泡剂，材料本身具有氨臭味，并且具有吸湿性能差和使用寿命短等缺点；新型鞋垫采用聚氨酯为基材，但是其产品所用原料价格较高，并且性能较为单一，不利于市场推广。
发明内容
为解决现有技术性能较差、价格较高及性能单一等问题，本发明选择聚氨酯为基材，加入一定量扩链剂、聚酯催化剂、发泡催化剂、匀泡剂和发泡剂，特别添加一种抑菌剂，采用超临界发泡技术进行发泡，制得制得高吸湿抑菌聚氨酯泡沫材料，本发明所用均为环保无毒原料。
本发明的技术解决方案：
一种鞋垫用高吸湿抑菌聚氨酯泡沫材料，组成成分按如下质量比计：基料树脂15-25份；交联剂30-50份；扩链剂0.2-5份；聚酯催化剂0.1-0.5份；发泡催化剂0.2-1份；匀泡剂0.2-5份；发泡剂 1-5份；抑菌剂1-8份。
优选的，所述基料树脂为植物基多元醇与聚乙二醇共混、植物基多元醇与一缩二乙二醇共混、三羟甲基丙烷、植物基多元醇与季戊四醇共混、植物基多元醇与1,4-丁二醇共混中的一种或多种组成。
优选的，所述交联剂为液态MDI、氢化MDI、TDI、三羟甲基乙烷、聚丙二醇缩水甘油醚中的一种或多种组成。
优选的，所述扩链剂为1,4-丁二醇、1,6-己二醇、二甘醇(DEG)、甘油、三羟甲基丙烷、三甘醇、新戊二醇(NPG)、山梨醇中的一种或多种组成。
优选的，所述聚酯催化剂为辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯、柠檬酸钛、二丁基羟基氧化锡的一种或多种组成。
优选的，所述发泡催化剂为双-(2-二甲氨基乙基)醚、二乙烯三胺、五甲基二亚乙基三胺、N,N-二甲基环己胺、4-甲氧基乙基吗啉中的一种或多种组成。
优选的，所述匀泡剂为美国迈图高回弹硅油Y-10366。
优选的，所述发泡剂为碳酸钙、碳酸氢钙、碳酸镁、碳酸氢钠、水、正戊烷、正己烷中的一种或多种组成。
优选的，所述抑菌剂为(三甲氧基硅基丙基)十八烷基二甲基氯化铵。
鞋垫用高吸湿抑菌聚氨酯泡沫材料的制备方法，包括以下步骤：
（1）按上述质量份比，将基料树脂与交联剂按1:2的比例加入反应釜中搅拌共混，在27-70℃条件下，保持600-3000r/min转速，搅拌20-300秒；
（2）向步骤（1）的反应釜中加入扩链剂、聚酯催化剂、发泡催化剂、匀泡剂、发泡剂和抑菌剂，在15-85℃条件下搅拌0.5-5小时；
（3）将步骤（2）的混合液导入超临界发泡机中，设定温度为40-190℃，压力5-15MPa,发泡1-15分钟，挤出得到白色鞋垫用高吸湿抑菌聚氨酯泡沫材料。
本发明所使用各原料均为市售所得。
本发明的有益效果：本发明针对鞋垫用EVA材料味道大、性能差及寿命短等缺点，以及现有聚氨酯材料成本高、性能单一等缺点，选择微孔高吸湿聚氨酯为基材，加入一定量扩链剂、聚酯催化剂、发泡催化剂、匀泡剂和发泡剂，特别加入抑菌剂，采用超临界发泡技术进行发泡，制得鞋垫用高吸湿抑菌聚氨酯泡沫材料。本发明产品采用环保发泡技术，材料无味，提高了力学性能和使用寿命，在提高吸湿性能的同时，大大提高材料的抑菌性能，从根本上解决汗脚和臭脚的问题。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步说明，但不限于此。
实施例1
一种鞋垫用高吸湿抑菌聚氨酯泡沫材料，组成成分按如下质量比计：
植物基多元醇与季戊四醇共混的基料树脂16份；液态MDI32份；1,4-丁二醇4份；二丁基羟基氧化锡0.2份；4-甲氧基乙基吗啉0.3份；美国迈图高回弹硅油Y-103660.5份；碳酸氢钙2份；(三甲氧基硅基丙基)十八烷基二甲基氯化铵4份。
鞋垫用高吸湿抑菌聚氨酯泡沫材料的制备方法，包括以下步骤：
（1）按上述质量份比，将植物基多元醇与季戊四醇共混的基料树脂与液态MDI按1:2的比例加入反应釜中搅拌共混，在60℃条件下，保持600r/min转速，搅拌100秒；
（2）向步骤（1）的反应釜中加入1,4-丁二醇、二丁基羟基氧化锡，在75℃条件下搅拌0.5小时；
（3）将步骤（2）的混合液导入超临界发泡机中，加入4-甲氧基乙基吗啉、高回弹硅油Y-10366、碳酸氢钙和(三甲氧基硅基丙基)十八烷基二甲基氯化铵，设定温度为140℃，压力5MPa，发泡8分钟，挤出得到白色鞋垫用高吸湿抑菌聚氨酯泡沫材料。
实施例2
一种鞋垫用高吸湿抑菌聚氨酯泡沫材料，组成成分按如下质量比计：植物基多元醇与聚乙二醇共混的基料树脂20份；TDI40份；1,6-己二醇0.8份；辛酸亚锡0.3份；双-(2-二甲氨基乙基)醚0.3份；美国迈图高回弹硅油Y-103662份；水2份；(三甲氧基硅基丙基)十八烷基二甲基氯化铵6份。
鞋垫用高吸湿抑菌聚氨酯泡沫材料的制备方法，包括以下步骤：
（1）按上述质量份比，将植物基多元醇与聚乙二醇共混的基料树脂与TDI按1:2的比例加入反应釜中搅拌共混，70℃条件下，保持800/min转速，搅拌200秒；
（2）向步骤（1）的反应釜中加入1,6-己二醇、辛酸亚锡，在65℃条件下搅拌2小时；
（3）将步骤（2）的混合液导入超临界发泡机中，加入双-(2-二甲氨基乙基)醚、高回弹硅油Y-10366、水和(三甲氧基硅基丙基)十八烷基二甲基氯化铵，设定温度为150℃，压力7MPa,发泡7分钟，挤出得到白色鞋垫用高吸湿抑菌聚氨酯泡沫材料。
实施例3
一种鞋垫用高吸湿抑菌聚氨酯泡沫材料，组成成分按如下质量比计：植物基多元醇与1,4-丁二醇共混的基料树脂25份；聚丙二醇缩水甘油醚50份；1,4-丁二醇5份；钛酸异丙酯0.2份；N,N-二甲基环己胺0.2份；美国迈图高回弹硅油Y-103661.7份；水1.7份；(三甲氧基硅基丙基)十八烷基二甲基氯化铵7份。
鞋垫用高吸湿抑菌聚氨酯泡沫材料的制备方法，包括以下步骤：
（1）按上述质量份比，将植物基多元醇与1,4-丁二醇共混的基料树脂与聚丙二醇缩水甘油醚按1:2的比例加入反应釜中搅拌共混，在70℃条件下，保持600r/min转速，搅拌70秒；
（2）向步骤（1）的反应釜中加入1,4-丁二醇、钛酸异丙酯、在65℃条件下搅拌2小时；
（3）将步骤（2）的混合液导入超临界发泡机中，加入N,N-二甲基环己胺、高回弹硅油Y-10366、水和(三甲氧基硅基丙基)十八烷基二甲基氯化铵，设定温度为160℃，压力11MPa,发泡10分钟，挤出得到白色鞋垫用高吸湿抑菌聚氨酯泡沫材料。
吸水倍率 密度（g/cm<sup>3</sup>） 吸湿快干率（%） 永久压缩变形率（%） 金黄色葡萄球菌抑菌率（%）
S1 9 0.029 92.17 5.7 95
S2 11 0.037 92.32 5.5 96
S3 12 0.042 92.56 5.2 96
表1 实施例1-3高吸湿抑菌聚氨酯泡沫材料性能参数列表
由表1可见，本发明方法制备的高吸湿抑菌聚氨酯泡沫材料，其吸水倍率达到12，密度达到0.042 g/cm3，吸湿快干率达到92.56%，永久压缩变形率<6%，各项性能均优于市场同类鞋垫材料，通过抑菌性能测试，本发明所制备的材料具有良好的抑菌性能。
应当理解的是，本发明并不局限于上面已经描述的流程，并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。

Claims (10)

1.一种鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：按质量比，组成成分如下：
基料树脂15-25份；
交联剂份30-50份；
扩链剂0.2-5份；
聚酯催化剂0.1-0.5份；
发泡催化剂0.2-1份；
匀泡剂0.2-5份；
发泡剂 1-5份；
抑菌剂1-8份。
2.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述基料树脂为植物基多元醇与聚乙二醇共混、植物基多元醇与一缩二乙二醇共混、三羟甲基丙烷、植物基多元醇与季戊四醇共混、植物基多元醇与1,4-丁二醇共混中的一种或多种组成。
3.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述交联剂为液态MDI、氢化MDI、TDI、三羟甲基乙烷、聚丙二醇缩水甘油醚中的一种或多种组成。
4.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述扩链剂为1,4-丁二醇、1,6-己二醇、二甘醇(DEG)、甘油、三羟甲基丙烷、三甘醇、新戊二醇(NPG)、山梨醇中的一种或多种组成。
5.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述聚酯催化剂为辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯、柠檬酸钛、二丁基羟基氧化锡的一种或多种组成。
6.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述发泡催化剂为双-(2-二甲氨基乙基)醚、二乙烯三胺、五甲基二亚乙基三胺、N,N-二甲基环己胺、4-甲氧基乙基吗啉中的一种或多种组成。
7.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述匀泡剂为美国迈图高回弹硅油Y-10366。
8.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述发泡剂为碳酸钙、碳酸氢钙、碳酸镁、碳酸氢钠、水、正戊烷、正己烷中的一种或多种组成。
9.根据权利要求1所述鞋垫用高吸湿抑菌聚氨酯泡沫材料，其特征在于：所述抑菌剂为(三甲氧基硅基丙基)十八烷基二甲基氯化铵。
10.一种鞋垫用高吸湿抑菌聚氨酯泡沫材料制备方法，其特征在于：包括以下步骤：
（1）按上述质量份比，将基料树脂与交联剂胺1:2的比例加入反应釜中搅拌共混，在27-70℃条件下，保持600-3000r/min转速，搅拌20-300秒；
（2）向步骤（1）的反应釜中加入扩链剂、聚酯催化剂、发泡催化剂、匀泡剂、发泡剂和抑菌剂，在15-85℃条件下搅拌0.5-5小时；
（3）将步骤（2）的混合液导入超临界发泡机中，设定温度为40-190℃，压力5-15MPa,发泡1-15分钟，挤出得到白色鞋垫用高吸湿抑菌聚氨酯泡沫材料，所述聚氨酯泡沫材料具有优异的吸湿性能和力学性能：密度：0.025-0.045g/m2；吸水倍率>8；永久压缩变形率<6%抑菌性能优异：对大肠杆菌、白色念珠菌、金黄色葡萄球菌的抑菌率高达96%以上；水洗五遍之后抑菌率降低不多，依然高达94%以上。
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