CN107722231A - 氢键吸附型聚氨酯泡沫材料及其制备方法 - Google Patents

氢键吸附型聚氨酯泡沫材料及其制备方法 Download PDF

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CN107722231A
CN107722231A CN201711060275.4A CN201711060275A CN107722231A CN 107722231 A CN107722231 A CN 107722231A CN 201711060275 A CN201711060275 A CN 201711060275A CN 107722231 A CN107722231 A CN 107722231A
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杜江
张季冰
陈松雄
周川泉
晋齐怀
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Jihua 3537 Shoe Making Co Ltd
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/7621Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/4804Two or more polyethers of different physical or chemical nature
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    • C08G18/6688Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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Abstract

本发明公开了一种氢键吸附型聚氨酯泡沫材料及其制备方法。本发明设计了一种含特殊链节——多氢键型聚氨酯高分子长链,使之对于水分或潮气具与环境适应的吸附特性,并且具有自我解吸附的能力,实现自我还原再生功能重复性,将这种聚合物加工成为开孔型泡沫材料后制作成鞋垫,由于泡沫的开孔结构使得人脚产生的潮气或汗液有自由扩散的通道,而孔的内壁具有氢键吸附作用,能吸收并容纳潮气或汗液,达到保持鞋内环境的干爽,但又不致于过度吸附。该材料制作的鞋垫有吸湿、解潮的循环往复的再生功能,达到有效的吸湿排汗的效果。所制作的鞋垫既具有“尿不湿”的长处,又能反复再生还原,实现鞋垫重复使用永保干爽。

Description

氢键吸附型聚氨酯泡沫材料及其制备方法
技术领域
本发明涉及橡胶加工技术领域,特别是一种氢键吸附型聚氨酯泡沫材料及其制备方法。
背景技术
保持鞋内干爽,不湿脚,是每一个鞋类消费者极其关注的事项。然而,迄今为止,还没有一套切实可行的方法使消费者彻底摆脱脚湿、脚臭,以及由此带来的脚气等疾病的困扰。尽管几乎每一个鞋类的制造商或销售商都宣称自己的产品“抗菌防臭”,但由于缺乏相应功能的鞋垫材料,所以对于消费者的承诺终究言过其实。
鞋在穿着过程中是否“抗菌防臭”,其决定性的因素是鞋内微环境的潮湿程度。由于每一个人的脚汗腺的分泌能力,以及新陈代谢所产生的皮屑的蛋白质的构成千差万别,滋生的微生物都各不相同,不解决鞋内微环境潮湿的问题,单靠使用抗菌素往往事倍功半。
因此,研究一种鞋垫材料,对人脚运动或行走过程中产生的脚汗水分或潮气具有特殊的吸附能力又能实现自然还原再生,达到优异的吸湿排汗效果,实现对鞋内微生物滋生的条件釜底抽薪,对于鞋类消费者的舒适和健康,无论在理论上和实践上都具有重要的意义。
发明内容
本发明所要解决的技术问题是:提供一种氢键吸附型聚氨酯泡沫材料及其制备方法,它对鞋内产生的潮气或水分具有充分的吸附、再生能力,以克服现有技术的不足。
本发明的是这样实现的:氢键吸附型聚氨酯泡沫材料,其特征在于:按质量份数计算,按照重量份计算,包括通用型聚醚三元醇30-65份,聚氧化乙烯三元醇30-65份,水1-2份,三乙醇胺4-6份,二乙基乙醇胺0.4-0.6份以及液化MDI 1-1.1份为制备原料。
按照上述质量份数取各组分,之后按照聚氨酯泡沫塑料的生产方法进行生产。
众所周知的“尿不湿”是一种高吸水性树脂,虽然在保持干爽方面性能卓越,但由于对水分或潮气过度强烈的吸附能力,吸水后不易再生还原,只能实现一次性使用的功能,而且这种材料也不具有弹性,不宜制作质轻的开孔型泡沫材料,因而不适宜制作鞋垫。
一般地,泡沫塑料的结构成分主要由有机多异氰酸酯(如甲苯二异氰酸酯(TDI)经缩聚反应交联而成,或二苯基甲烷二异氰酸酯(MDI))和多元醇(聚酯多元醇或聚醚多元醇)经缩聚反应交联而成。本发明采用聚醚多元醇,为了避免环境污染问题,多异氰酸酯采用沸点很高,气味和毒性均很小的二苯基甲烷二异氰酸酯。
聚氨酯泡沫塑料对水分或潮气的吸附能力很差,原因是通用型聚醚多元醇的分子链上的氧化丙烯链节上带有甲基基团,而甲基基团是一个疏水基团,不具有吸水功能。本发明采用了氧化乙烯链节结构的多元醇(以下称聚氧化乙烯多元醇)和通用型的聚醚多元醇按不同比例共混,形成共混多元醇,由此按功能目标设计的发泡配方所制得的聚氨酯开孔型泡沫塑料,由于聚合物分子链上含有氧化乙烯链节,获得了对水分或潮气的氢键吸附能力,制作的鞋垫具有优异的吸湿排汗功能,同时,又可以反复再生,重复功能使用。
根据使用环境条件差异,以目标为导向,改变聚氧化乙烯多元醇和通用型聚醚多元醇的比例关系,可以随意调节聚氨酯泡沫塑料对水分或潮气的氢键吸附能力大小,使所制作的鞋垫能满足不同吸湿排汗要求场合的使用要求。对于普通的休闲鞋,由于出汗不严重,对吸汗功能要求不强,可采用较少量的聚氧化乙烯多元醇(聚氧化乙烯多元醇和通用型聚醚多元醇的比例按3:7),所制作的泡沫塑料的氢键吸附能力一般,只适用于制作常规的吸湿排汗功能鞋垫。而对于运动较为激烈,出汗较多的场合,如运动鞋,登山鞋,士兵穿着的军用训练鞋,则采用加大氧化乙烯链节的比例(聚氧化乙烯多元醇和通用型聚醚多元醇的比例可按7:3进行),制作具有很强的氢键吸附能力的泡沫塑料,达到高强的吸湿排汗效果。
本发明所采用的多异氰酸酯为液化二苯基甲烷二异氰酸酯(MDI-50),MDI分子结构中含有两个苯环,相对分子质量为250.26,比TDI大;由于蒸汽压很低,挥发性很小,对人体毒害较小。一般纯的MDI主要是指4,4’-MDI,又称MDI-100,常温下它是白色至浅黄色固体,熔化后是无色至浅黄色液体,可溶于丙酮,四氯化碳,苯,氯苯,硝基苯,二氧六环等。高2,4’-MDI含量的MDI产品与4,4’-MDI相比具有较低的反应活性和熔点,2,4’-MDI和4,4’-MDI各含50%的产品叫MDI-50,室温下为无色或微黄色的液体。
本发明所采用的通用型聚醚多元醇以聚氧化丙烯多元醇为主,以氢氧化钾为催化剂,以丙二醇,甘油或蔗糖等小分子多元醇为起始剂,以氧化丙烯或氧化丙烯与氧化乙烯的混合物为单体,在一定的温度或压力下进行开环聚合而得。
与现有技术相比,本发明设计了一种含特殊链节——多氢键型聚氨酯高分子长链,使之对于水分或潮气具与环境适应的吸附特性,并且具有自我解吸附的能力,实现自我还原再生功能重复性,将这种聚合物加工成为开孔型泡沫材料后制作成鞋垫,由于泡沫的开孔结构使得人脚产生的潮气或汗液有自由扩散的通道,而孔的内壁具有氢键吸附作用,能吸收并容纳潮气或汗液,达到保持鞋内环境的干爽,但又不致于过度吸附。该材料制作的鞋垫有吸湿、解潮的循环往复的再生功能,达到有效的吸湿排汗的效果。所制作的鞋垫既具有“尿不湿”的长处,又能反复再生还原,实现鞋垫重复使用永保干爽。
具体实施方式
本发明的实施例1:氢键吸附型聚氨酯泡沫材料,按质量份数计算,按照重量份计算,包括通用型聚醚三元醇65份,聚氧化乙烯三元醇30份,水1.5份,三乙醇胺5份,二乙基乙醇胺0.5份以及液化MDI1-1.05份为制备原料;按照上述质量份数取各组分,之后按照聚氨酯泡沫塑料的生产方法进行生产。其生产工艺的参数如表1所示。
表1
所制得的泡沫塑料性能如表2所示:
表2.按表1所示配方和工艺所制得的泡沫塑料的性能
实施例1中聚氧化乙烯三元醇的用量不大,质量份数只有30份,而通用型聚醚多元醇用量为65份,制作的聚氨酯泡沫塑料适合于对吸湿排汗要求不苛刻的场合。制得的鞋垫经充分吸湿后(如洗涤后)很容易晾干,25℃时泡孔内吸附水的饱和蒸气压较高,约为3.5KPa。在南方的冬天需2-3天,夏天只需2天左右。
本发明的实施例2:氢键吸附型聚氨酯泡沫材料,按质量份数计算,按照重量份计算,包括通用型聚醚三元醇35份,聚氧化乙烯三元醇60份,水1.5份,三乙醇胺5份,二乙基乙醇胺0.5份以及液化MDI1-1.05份为制备原料;按照上述质量份数取各组分,之后按照聚氨酯泡沫塑料的生产方法进行生产。其生产工艺的参数如表3所示。
表3
所制得的泡沫塑料性能如表4所示:
表4,按表3所示配方和工艺所制得的泡沫塑料的性能
实施例2中,聚氧化乙烯三元醇用量很大,质量份数达60份,比通用型聚醚多元醇的35份,大将近一倍,制作的聚氨酯泡沫塑料适合于对吸湿排汗要求非常苛刻的场合。制得的鞋垫经充分吸湿后(如洗涤后)不太容易晾干,25℃时泡孔内吸附水的饱和蒸气压较低,约为1.5KPa,尤其是在冬天,这个问题更为突出,建议烘烤干燥。

Claims (2)

1.一种氢键吸附型聚氨酯泡沫材料,其特征在于:按质量份数计算,按照重量份计算,包括通用型聚醚三元醇30-65份,聚氧化乙烯三元醇30-65份,水1-2份,三乙醇胺4-6份,二乙基乙醇胺0.4-0.6份以及液化MDI 1-1.1份为制备原料。
2.根据权利要求1所述的在氢键吸附型聚氨酯泡沫材料的制备方法,其特征在于:按照上述质量份数取各组分,之后按照聚氨酯泡沫塑料的生产方法进行生产。
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