CN113087954A - 环保透气聚氨酯鞋垫的制备方法 - Google Patents
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Abstract
本发明涉及环保透气聚氨酯鞋垫的制备方法，具体：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜中在氮气保护下升温酯化反应；将不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜中，加入反应助剂，在常温下搅拌反应；碳化二亚胺改性MDI与A组分混合，在氮气保护下加成聚合反应；加入青叶醇和引发剂，升温聚合反应；置于密封耐压模具内，通入超临界流体，饱和反应后降再泄压得到聚氨酯鞋垫。本发明利用聚醚、聚酯和改性MDI分子链结构赋予本发明鞋垫良好的力学性能和发泡透气性能，同时利用青叶醇在引发剂作用下与不饱和双键加成反应而获得更多的羟基支链，提高亲水吸汗并抑制异味，另外采用超临界流体发泡工艺，泡孔均匀，环保安全。
Description
技术领域
本发明属于鞋材技术领域，具体涉及一种环保透气聚氨酯鞋垫的制备方法。
背景技术
传统的EVA鞋垫透气性差，舒适性不好，穿的时间久了会导致脚臭，更严重者会引起脚部的真菌感染。欧索莱是聚氨酯发泡鞋垫的一种，一般采用模具灌注聚氨酯微发泡料模压成型，成型后切割成不同厚度的片材，与其他材料一起热压成型鞋垫。
聚氨酯材料的软段有聚酯多元醇和聚醚多元醇两种类型，为了兼具两种类型聚氨酯材料的性能，通常将聚酯型多元醇和聚醚型多元醇按照一定比列混合使用，但是两者相容性差，混合后放置出现分层，制品达不到理想的性能。
发明内容
鉴于现有技术的不足，本发明所要解决的技术问题是提供一种环保透气聚氨酯鞋垫的制备方法，透气吸汗并具有良好的力学性能。
为解决上述技术问题，本发明采用的技术方案是：
环保透气聚氨酯鞋垫的制备方法，具体包括如下步骤：
S1、制备不饱和聚醚酯多元醇：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜E中并搅拌均匀，在氮气保护下升温酯化反应，然后脱水脱醇而得不饱和聚醚酯多元醇；
S2、制备A组分：将步骤S1的不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜A中搅拌均匀，然后加入交联剂、催化剂、匀泡剂、扩链剂，在常温下反应，搅拌3-4小时即可；
S3、制备改性聚氨酯基料：以碳化二亚胺改性的MDI为B组分并投入反应釜B中，再加入步骤S2的A组分，在氮气保护下加成聚合反应至无-NC0含量检出，且在加成聚合反应过程中加入适量丁酮稀释保持溶液状态；然后加入青叶醇和引发剂并搅拌均匀，升温至80℃-90℃聚合反应4-6小时，降温即得改性聚氨酯基料；
S4、制备透气聚氨酯鞋垫：将步骤S3的改性聚氨酯基料置于密封耐压模具内，向模具内通入超临界流体，模具温度130℃～135℃，压力控制在12MPa～18MPa，饱和反应一段时间后降温至100℃～105℃再泄压，得到聚氨酯鞋垫。
优选地，所述交联剂为交联剂为三乙醇胺或二乙醇胺，所述催化剂为叔胺类催化剂，所述匀泡剂为二甲基硅油，所述扩链剂为1,4-丁二醇、1,3-丙二醇或乙二醇。
优选地，所述引发剂为过氧化苯甲酰或叔丁基过氧化氢。
与现有技术相比，本发明具有以下有益效果：
本发明利用二甘醇、甘油、顺丁烯二酸和三乙烯二胺进行酯化反应制得不饱和聚醚酯多元醇，在聚醚多元醇中引入聚酯链段以及不饱和双键，再与碳化二亚胺改性MDI聚合反应，利用聚醚、聚酯和改性MDI分子链结构赋予本发明聚氨酯鞋垫良好的力学性能和发泡透气性能，同时利用青叶醇在引发剂作用下与不饱和双键加成反应而获得更多的羟基支链，大大提高聚氨酯鞋垫的亲水吸汗性能，并利用青叶醇的青香抑制异味，另外采用超临界流体发泡工艺，发泡倍率可控且泡孔均匀，不用化学发泡，环保安全。
具体实施方式
实施例1
本实施例提供一种环保透气聚氨酯鞋垫的制备方法，具体包括如下步骤：
S1、制备不饱和聚醚酯多元醇：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜E中并搅拌均匀，在氮气保护下升温酯化反应，然后脱水脱醇而得不饱和聚醚酯多元醇；二甘醇、甘油、顺丁烯二酸的摩尔比为1:2:2.8，三乙烯二胺的用量为二甘醇、甘油、顺丁烯二酸总量的300ppm。
S2、制备A组分：按配方取步骤S1的不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜A中搅拌均匀，然后加入交联剂、催化剂、匀泡剂、扩链剂，在常温下反应，搅拌3-4小时即可；蓖麻油多元醇的伯羟基含量大于60%，交联剂为三乙醇胺，所述催化剂为三乙烯二胺，所述匀泡剂为二甲基硅油，所述扩链剂为1,4-丁二醇；不饱和聚醚酯多元醇、蓖麻油多元醇的质量比为1:2，交联剂、催化剂、匀泡剂、扩链剂的用量分别为不饱和聚醚酯多元醇和蓖麻油多元醇总量的1.5%、1%、1%、3%。
S3、制备改性聚氨酯基料：以碳化二亚胺改性的MDI为B组分并投入反应釜B中，再加入步骤S2的A组分，A组分与B组分的质量比为100:70，在氮气保护下加成聚合反应至无-NC0含量检出，且在加成聚合反应过程中加入适量丁酮稀释保持溶液状态；然后加入青叶醇和引发剂并搅拌均匀，升温至80℃-90℃聚合反应4-6小时，降温即得改性聚氨酯基料；引发剂为过氧化苯甲酰，青叶醇与不饱和聚醚酯多元醇的质量比为1:10，引发剂用量为青叶醇的2%。
S4、制备透气聚氨酯鞋垫：将步骤S3的改性聚氨酯基料置于密封耐压模具内，向模具内通入超临界二氧化碳，模具温度130℃～135℃，压力控制在15MPa，饱和反应一段时间后降温至100℃～105℃再泄压，得到聚氨酯鞋垫。
本实施例还提供由上述制备方法制得的环保透气聚氨酯鞋垫。
实施例2
本实施例提供一种环保透气聚氨酯鞋垫的制备方法，具体包括如下步骤：
S1、制备不饱和聚醚酯多元醇：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜E中并搅拌均匀，在氮气保护下升温酯化反应，然后脱水脱醇而得不饱和聚醚酯多元醇；二甘醇、甘油、顺丁烯二酸的摩尔比为1:2.5:3.2，三乙烯二胺的用量为二甘醇、甘油、顺丁烯二酸总量的250ppm。
S2、制备A组分：按配方取步骤S1的不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜A中搅拌均匀，然后加入交联剂、催化剂、匀泡剂、扩链剂，在常温下反应，搅拌3-4小时即可；蓖麻油多元醇的伯羟基含量大于60%，交联剂为二乙醇胺，所述催化剂为三乙烯二胺，所述匀泡剂为二甲基硅油，所述扩链剂为1,3-丙二醇；不饱和聚醚酯多元醇、蓖麻油多元醇的质量比为1:3，交联剂、催化剂、匀泡剂、扩链剂的用量分别为不饱和聚醚酯多元醇和蓖麻油多元醇总量的1%、2%、1.5%、2%。
S3、制备改性聚氨酯基料：以碳化二亚胺改性的MDI为B组分并投入反应釜B中，再加入步骤S2的A组分，A组分与B组分的质量比为100:75，在氮气保护下加成聚合反应至无-NC0含量检出，且在加成聚合反应过程中加入适量丁酮稀释保持溶液状态；然后加入青叶醇和引发剂并搅拌均匀，升温至80℃-90℃聚合反应4-6小时，降温即得改性聚氨酯基料；引发剂为叔丁基过氧化氢，青叶醇与不饱和聚醚酯多元醇的质量比为1:12，引发剂用量为青叶醇的3%。
S4、制备透气聚氨酯鞋垫：将步骤S3的改性聚氨酯基料置于密封耐压模具内，向模具内通入超临界氮气，模具温度130℃～135℃，压力控制在12MPa，饱和反应一段时间后降温至100℃～105℃再泄压，得到聚氨酯鞋垫。
本实施例还提供由上述制备方法制得的环保透气聚氨酯鞋垫。
实施例3
本实施例提供一种环保透气聚氨酯鞋垫的制备方法，具体包括如下步骤：
S1、制备不饱和聚醚酯多元醇：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜E中并搅拌均匀，在氮气保护下升温酯化反应，然后脱水脱醇而得不饱和聚醚酯多元醇；二甘醇、甘油、顺丁烯二酸的摩尔比为1:2.2:3，三乙烯二胺的用量为二甘醇、甘油、顺丁烯二酸总量的400ppm。
S2、制备A组分：按配方取步骤S1的不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜A中搅拌均匀，然后加入交联剂、催化剂、匀泡剂、扩链剂，在常温下反应，搅拌3-4小时即可；蓖麻油多元醇的伯羟基含量大于60%，交联剂为三乙醇胺，所述催化剂为三乙烯二胺，所述匀泡剂为二甲基硅油，所述扩链剂为乙二醇；不饱和聚醚酯多元醇、蓖麻油多元醇的质量比为1:2.5，交联剂、催化剂、匀泡剂、扩链剂的用量分别为不饱和聚醚酯多元醇和蓖麻油多元醇总量的2%、1.5%、1.2%、2.5%。
S3、制备改性聚氨酯基料：以碳化二亚胺改性的MDI为B组分并投入反应釜B中，再加入步骤S2的A组分，A组分与B组分的质量比为100:80，在氮气保护下加成聚合反应至无-NC0含量检出，且在加成聚合反应过程中加入适量丁酮稀释保持溶液状态；然后加入青叶醇和引发剂并搅拌均匀，升温至80℃-90℃聚合反应4-6小时，降温即得改性聚氨酯基料；引发剂为过氧化苯甲酰，青叶醇与不饱和聚醚酯多元醇的质量比为1:15，引发剂用量为青叶醇的1.5%。
S4、制备透气聚氨酯鞋垫：将步骤S3的改性聚氨酯基料置于密封耐压模具内，向模具内通入超临界二氧化碳，模具温度130℃～135℃，压力控制在18MPa，饱和反应一段时间后降温至100℃～105℃再泄压，得到聚氨酯鞋垫。
本实施例还提供由上述制备方法制得的环保透气聚氨酯鞋垫。
以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明创造精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
1.环保透气聚氨酯鞋垫的制备方法，其特征在于：具体包括如下步骤：
S1、制备不饱和聚醚酯多元醇：将二甘醇、甘油、顺丁烯二酸、三乙烯二胺置于反应釜E中并搅拌均匀，在氮气保护下升温酯化反应，然后脱水脱醇而得不饱和聚醚酯多元醇；
S2、制备A组分：将步骤S1的不饱和聚醚酯多元醇、蓖麻油多元醇装入反应釜A中搅拌均匀，然后加入交联剂、催化剂、匀泡剂、扩链剂，在常温下反应，搅拌3-4小时即可；
S3、制备改性聚氨酯基料：以碳化二亚胺改性的MDI为B组分并投入反应釜B中，再加入步骤S2的A组分，在氮气保护下加成聚合反应至无-NC0含量检出，且在加成聚合反应过程中加入适量丁酮稀释保持溶液状态；然后加入青叶醇和引发剂并搅拌均匀，升温至80℃-90℃聚合反应4-6小时，降温即得改性聚氨酯基料；
S4、制备透气聚氨酯鞋垫：将步骤S3的改性聚氨酯基料置于密封耐压模具内，向模具内通入超临界流体，模具温度130℃～135℃，压力控制在12MPa～18MPa，饱和反应一段时间后降温至100℃～105℃再泄压，得到聚氨酯鞋垫。
2.根据权利要求1所述的环保透气聚氨酯鞋垫，其特征在于：所述交联剂为交联剂为三乙醇胺或二乙醇胺。
3.根据权利要求1所述的环保透气聚氨酯鞋垫，其特征在于：所述催化剂为叔胺类催化剂。
4.根据权利要求1所述的环保透气聚氨酯鞋垫，其特征在于：所述匀泡剂为二甲基硅油。
5.根据权利要求1所述的环保透气聚氨酯鞋垫，其特征在于：所述扩链剂为1,4-丁二醇、1,3-丙二醇或乙二醇。
6.根据权利要求1所述的环保透气聚氨酯鞋垫，其特征在于：所述引发剂为过氧化苯甲酰或叔丁基过氧化氢。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023044944A1 (zh) * | 2021-09-27 | 2023-03-30 | 福建鸿星尔克体育用品有限公司 | 一种高回弹超轻鞋垫及其制备方法 |
| CN117186344A (zh) * | 2023-11-08 | 2023-12-08 | 山东一诺威聚氨酯股份有限公司 | 生物基环保透气鞋垫及其制备方法 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024684A (zh) * | 2007-01-29 | 2007-08-29 | 青岛科技大学 | 聚醚酯多元醇及其制备方法 |
| JP2010126659A (ja) * | 2008-11-28 | 2010-06-10 | Kawasaki Kasei Chem Ltd | ポリエステルポリオール及びポリウレタンエラストマー |
| JP2010195870A (ja) * | 2009-02-23 | 2010-09-09 | Inoac Corp | ポリウレタンフォームの製造方法、この方法により製造されたポリウレタンフォーム及びこれを用いたインソール |
| CN103555429A (zh) * | 2013-11-05 | 2014-02-05 | 湖北大学 | 一种含羧基的氢化蓖麻油多元醇的制备方法 |
| CN107353393A (zh) * | 2017-08-18 | 2017-11-17 | 江苏宝泽高分子材料股份有限公司 | 一种蓖麻油改性聚氨酯树脂及其制备方法 |
| CN108864400A (zh) * | 2018-07-10 | 2018-11-23 | 合肥科天水性科技有限责任公司 | 一种高性能阳离子型水性聚氨酯树脂及其制备方法 |
| CN111138624A (zh) * | 2019-12-16 | 2020-05-12 | 旭川化学（苏州）有限公司 | 一种高物性透气鞋垫用聚氨酯树脂及其制备方法 |
-
2021
- 2021-04-06 CN CN202110365522.1A patent/CN113087954A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024684A (zh) * | 2007-01-29 | 2007-08-29 | 青岛科技大学 | 聚醚酯多元醇及其制备方法 |
| JP2010126659A (ja) * | 2008-11-28 | 2010-06-10 | Kawasaki Kasei Chem Ltd | ポリエステルポリオール及びポリウレタンエラストマー |
| JP2010195870A (ja) * | 2009-02-23 | 2010-09-09 | Inoac Corp | ポリウレタンフォームの製造方法、この方法により製造されたポリウレタンフォーム及びこれを用いたインソール |
| CN103555429A (zh) * | 2013-11-05 | 2014-02-05 | 湖北大学 | 一种含羧基的氢化蓖麻油多元醇的制备方法 |
| CN107353393A (zh) * | 2017-08-18 | 2017-11-17 | 江苏宝泽高分子材料股份有限公司 | 一种蓖麻油改性聚氨酯树脂及其制备方法 |
| CN108864400A (zh) * | 2018-07-10 | 2018-11-23 | 合肥科天水性科技有限责任公司 | 一种高性能阳离子型水性聚氨酯树脂及其制备方法 |
| CN111138624A (zh) * | 2019-12-16 | 2020-05-12 | 旭川化学（苏州）有限公司 | 一种高物性透气鞋垫用聚氨酯树脂及其制备方法 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023044944A1 (zh) * | 2021-09-27 | 2023-03-30 | 福建鸿星尔克体育用品有限公司 | 一种高回弹超轻鞋垫及其制备方法 |
| CN117186344A (zh) * | 2023-11-08 | 2023-12-08 | 山东一诺威聚氨酯股份有限公司 | 生物基环保透气鞋垫及其制备方法 |
| CN117186344B (zh) * | 2023-11-08 | 2024-03-08 | 山东一诺威聚氨酯股份有限公司 | 生物基环保透气鞋垫及其制备方法 |
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