CN111499829A - 一种环保无味发泡鞋底材料及其制备鞋底的方法 - Google Patents

一种环保无味发泡鞋底材料及其制备鞋底的方法 Download PDF

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CN111499829A
CN111499829A CN202010381318.4A CN202010381318A CN111499829A CN 111499829 A CN111499829 A CN 111499829A CN 202010381318 A CN202010381318 A CN 202010381318A CN 111499829 A CN111499829 A CN 111499829A
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倪益玲
朱益军
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Zhejiang Ni Ruan New Material Co Ltd
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Abstract

本发明属于聚氨酯弹性技术领域，特别涉及一种环保无味发泡鞋底材料。所述的环保无味发泡鞋底由60‑90份的醋酸酯淀粉、20‑40份的丝素蛋白、10‑30份的聚醚多元醇、50‑80份的异氰酸酯、1‑4份的交联剂、0.2‑0.8份的发泡剂、5‑10份的纳米竹纤维、5‑10份的纳米二氧化硅、5‑10份的氧化锌、1‑5份的活性炭、1‑2份的碳化硅、0.2‑0.5份的硬脂酸钠、0.1‑0.3份催化剂制成。本发明的鞋底制品具有良好的力学性能和使用稳定性，且具有生物可降解性，减少白色污染。

Description

一种环保无味发泡鞋底材料及其制备鞋底的方法
技术领域
本发明属于聚氨酯弹性技术领域，特别涉及一种环保无味发泡鞋底材料及其制备鞋底的方法。
技术背景
鞋子是人类生活的必需用品，而且随着人类文明的不断发展，鞋子的种类也不断丰富起来，例如男士皮鞋、女士皮鞋、休闲鞋、运动鞋、帆布鞋、化学鞋、凉鞋、拖鞋以及安全鞋等各种种类的鞋子。
聚氨酯全名聚氨基甲酸酯，是主链上含有重复氨基甲酸酯基团的大分子化合物的统称，是由二元或多元有机异氰酸酯与多元醇化合物相互作用而得到的高分子化合物。聚氨酯按其物理性能和用途，通常可分为硬质聚氨酯泡沫塑料、软质聚氨酯泡沫塑料、聚氨酯弹性体和聚氨酯涂料等。聚氨酯因其卓越的性能被广泛应用于建筑、汽车、轻工、纺织、石化等众多领域，是一种新兴的有机高分子材料，被誉为“第五大塑料”。
郑水蓉等在《工程塑料运用》2010年第38卷第2期47～50页发表的论文中公布了用玉米秸秆碎粉填充聚氨酯泡沫隔热塑料的方法，降低了聚氨酯泡沫隔热塑料的成本。马立国等在《聚氨酯工业》2011年第26卷第3期44～46页公布了由玉米基多元醇副产物树脂制备改性聚氨酯泡沫塑料的工艺，当玉米基副产物树脂加入量在5份左右时，制备的聚氨酯泡沫塑料可以满足保温材料的相关要求，同时大幅度降低了聚氨酯泡沫塑料的生产成本。然而由上述方法生成的聚氨酯材料力学性能较差，并不适用于鞋底制作。
专利CN110105538A公开了一种鞋底用聚氨酯弹性体材料，主体材料是75～80份聚酯多元醇、7～9份扩链剂、35～40份MDI，添加0.8～1.3份抗氧剂、0.3～0.5份催化剂、4～6份改性多壁碳纳米管、0.1～0.3份有机硅、0.2～0.4份环氧大豆油、0.2～0.5份硬脂酸钠制备而成，然而所添加的改性多壁碳纳米管为致癌物，并不利于人体健康，不符合绿色环保的要求。
发明内容
为了解决现有技术中的上述问题，本发明的目的在于提供一种环保无味发泡鞋底材料及其制备方法。
为了实现上述发明目的，本发明采用以下技术方案：一种环保无味发泡鞋底材料包括如下组分原料：60-90份的醋酸酯淀粉、20-40份的丝素蛋白、10-30份的聚醚多元醇、50-80份的异氰酸酯、1-4份的交联剂、0.2-0.8份的发泡剂、5-10份的纳米竹纤维、5-10份的纳米二氧化硅、5-10份的氧化锌、1-5份的活性炭、1-2份的碳化硅、0.2-0.5份的硬脂酸钠、0.1-0.3份催化剂。
进一步地，聚醚多元醇为甘油与环氧乙烷聚合制得官能度为2数均分子量为4000-6000的聚醚多元醇。
进一步地，异氰酸酯为2,4-二苯基甲烷二异氰酸酯，4,4-二苯基甲烷二异氰酸酯中的一种或两种混合物。
进一步地，催化剂为三乙烯二胺、三乙醇胺的一种或两种混合物。
交联剂为甘油、二乙醇胺、三乙醇胺中的一种或多种。
发泡剂为水。
本发明的一种环保无味发泡鞋底，其制备方法按照以下步骤进行：
步骤一，按上述配比，将醋酸酯淀粉、丝素蛋白、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜一中，搅拌1-2h，得混合物A；
步骤二，按上述配比，将聚醚多元醇在常温下投入反应釜二中，搅拌升温至120℃，真空条件下脱水脱气3.5小时，然后降温到60℃，加入异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按上述配比，将交联剂、纳米竹纤维、纳米二氧化硅、氧化锌、活性炭、碳化硅加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，3-5分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
与现有技术相比，本发明有以下有益效果：
采用可生物降解的醋酸酯淀粉为主体材料，使制备的聚氨酯发泡鞋底具有良好的生物可降解性，经土壤中微生物作用降解、代谢后，鞋底主体材料被分解为二氧化碳与水，减少对环境的污染。
所添加的纳米竹纤维具有良好的力学性能、抗紫外线、抑菌等特点，与纳米二氧化硅、碳化硅共同作用能够有效改善环保无味发泡鞋底材料的力学性能，延长其使用寿命。
添加的丝素蛋白具有良好的生物相容性，因此能作为交联剂与稳定剂，而其独特的氨基酸组成，与纳米竹纤维上的羟基形成分子间作用力，能够使添加丝素蛋白的环保无味发泡鞋底材料力学性能进一步提升。
而活性炭具有良好的吸附性能，与纳米竹纤维、氧化锌共同形成抑菌抗菌环境，由其制成的环保无味发泡鞋底材料能够预防脚气。
本发明的环保无味发泡鞋底材料均由能够生物降解的材料为主体材料，制备方法简单，节约能耗，生产成本低；相比于现有鞋底材料，对环境污染大幅度降低，并且耐磨性能好，穿着舒适，具有良好的经济效益。
具体实施方式
以下结合实施例对本发明做进一步说明，但本发明的保护范围不仅限于此，该领域专业人员对本发明技术方案所作的改变，均应属于本发明的保护范围内。
实施例1
一种环保无味发泡鞋底材料由以下重量的物质制成：
Figure BDA0002482106640000031
其中交联剂为甘油、二乙醇胺和三乙醇胺的混合物，按质量比为甘油：二乙醇胺：三乙醇胺＝1:1:1；
其中催化剂为三乙烯二胺与三乙醇胺的混合物，按质量比为三乙烯二胺：三乙醇胺＝2:1；
其中异氰酸酯为4,4-二苯基甲烷二异氰酸酯。
本发明的一种环保无味发泡鞋底，其制备方法按照以下步骤进行：
步骤一，按上述配比，将醋酸酯淀粉、丝素蛋白、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜一中，搅拌2h，得混合物A；
步骤二，按上述配比，将聚醚多元醇在常温下投入反应釜二中，搅拌升温至120℃，抽真空到-0.1MPa，脱水脱气3.5小时，然后降温到60℃，加入4,4-二苯基甲烷二异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按上述配比，将交联剂、纳米竹纤维、纳米二氧化硅、氧化锌、活性炭、碳化硅加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，5分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
实施例2
一种环保无味发泡鞋底材料由以下重量的物质制成：
Figure BDA0002482106640000041
其中交联剂为甘油、二乙醇胺和三乙醇胺的混合物，按质量比为甘油：三乙醇胺＝1:1；
其中催化剂为三乙烯二胺；
其中异氰酸酯为2,4-二苯基甲烷二异氰酸酯。
本发明的一种环保无味发泡鞋底，其制备方法按照以下步骤进行：
步骤一，按上述配比，将醋酸酯淀粉、丝素蛋白、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜一中，搅拌1h，得混合物A；
步骤二，按上述配比，将聚醚多元醇在常温下投入反应釜二中，搅拌升温至120℃，抽真空到-0.1MPa，脱水脱气3.5小时，然后降温到60℃，加入2,4-二苯基甲烷二异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按上述配比，将交联剂、纳米竹纤维、纳米二氧化硅、氧化锌、活性炭、碳化硅加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，4分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
实施例3
一种环保无味发泡鞋底材料由以下重量的物质制成：
Figure BDA0002482106640000051
其中催化剂为三乙烯二胺与三乙醇胺的混合物，按质量比为三乙烯二胺：三乙醇胺＝1:1；
其中异氰酸酯为2,4-二苯基甲烷二异氰酸酯与4,4-二苯基甲烷二异氰酸酯的混合物，两种的质量比为2:1。
本发明的一种环保无味发泡鞋底，其制备方法按照以下步骤进行：
步骤一，按上述配比，将醋酸酯淀粉、丝素蛋白、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜一中，搅拌1.5h，得混合物A；
步骤二，按上述配比，将聚醚多元醇在常温下投入反应釜二中，搅拌升温至120℃，抽真空到-0.1MPa，脱水脱气3.5小时，然后降温到60℃，加入异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按上述配比，将交联剂、纳米竹纤维、纳米二氧化硅、氧化锌、活性炭、碳化硅加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，3分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
对比例1
一种环保无味发泡鞋底材料由以下重量的物质制成：
Figure BDA0002482106640000061
其中交联剂为甘油、二乙醇胺和三乙醇胺的混合物，按质量比为甘油：二乙醇胺：三乙醇胺＝1:1:1；
其中催化剂为三乙烯二胺与三乙醇胺的混合物，按质量比为三乙烯二胺：三乙醇胺＝2:1；
其中异氰酸酯为4,4-二苯基甲烷二异氰酸酯。
制备方法按照以下步骤进行：
步骤一，按上述配比，将醋酸酯淀粉、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜中，搅拌2h，得混合物A；
步骤二，按上述配比，将聚醚多元醇在常温下投入反应釜中，搅拌升温至120℃，抽真空到-0.1MPa，脱水脱气3.5小时，然后降温到60℃，加入4,4-二苯基甲烷二异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按上述配比，将交联剂加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，5分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
将实施例1-3和对比例1所得聚氨酯鞋底裁剪成6mm厚的样片，进行物理性能测试，并对整个鞋底进行生物降解测试，测试方法如下：
(1)制品的拉伸强度、撕裂强度、伸长率都是由伺服拉伸试验机测定；
(2)90°曲挠是由鞋底曲挠机测定，每小时6000次90°弯折鞋底前掌部分；
(3)生物降解实验的实验条件为在含有微生物的土壤中深埋0.5m，温度10-35℃，分解2个月时间的数据。
测试结果如表1所示。
表1实施例1-3和对比例1的制品性能测试结果
Figure BDA0002482106640000071
从表1可以看出，本发明公开的鞋底材料及由此得到的鞋底(实施例1-3)，相对于对比例1，其力学性能和使用稳定性优异，这是由于加入了纳米二氧化硅、碳化硅等耐磨材料及纳米竹纤维和丝素蛋白，形成的强化作用促成的。另外，从表1还可以看出，本发明得到的鞋底，具有良好的生物降解性，对于环境影响小，符合绿色生产的要求。

Claims (4)

1.一种环保无味发泡鞋底材料，其特征在于：包括以下组分原料制成：60-90份的醋酸酯淀粉、20-40份的丝素蛋白、10-30份的聚醚多元醇、50-80份的异氰酸酯、1-4份的交联剂、0.2-0.8份的发泡剂、5-10份的纳米竹纤维、5-10份的纳米二氧化硅、5-10份的氧化锌、1-5份的活性炭、1-2份的碳化硅、0.2-0.5份的硬脂酸钠、0.1-0.3份催化剂。
2.根据权利要求1所述的环保无味发泡鞋底材料，其特征在于：聚醚多元醇为甘油与环氧乙烷聚合制得官能度为2数均分子量为4000-6000的聚醚多元醇。
3.根据权利要求1所述的环保无味发泡鞋底材料，其特征在于：异氰酸酯为2,4-二苯基甲烷二异氰酸酯与4,4-二苯基甲烷二异氰酸酯中的一种或两种混合物；催化剂为三乙烯二胺、三乙醇胺的一种或两种混合物；交联剂为甘油、二乙醇胺、三乙醇胺中的一种或多种；发泡剂为水。
4.一种利用根据权利要求1所述的环保无味发泡鞋底材料制备鞋底制品的方法，其特征在于：所述方法按照以下步骤进行：
步骤一，按原料配比，将醋酸酯淀粉、丝素蛋白、硬脂酸钠、发泡剂和催化剂，在常温下投入反应釜一中，搅拌1-2h，得混合物A；
步骤二，按原料配比，将聚醚多元醇在常温下投入反应釜二中，搅拌升温至120℃，真空条件下脱水脱气3.5小时，然后降温到60℃，加入异氰酸酯，在90℃下反应4小时，得混合物B；
步骤三，按原料配比，将交联剂、纳米竹纤维、纳米二氧化硅、氧化锌、活性炭、碳化硅加入混合物A中，混合均匀后，将该混合物与混合物B分别注入低压浇注机料罐中，在机头处混合注入70℃模具，3-5分钟后开模得到生物可降解聚氨酯发泡鞋底制品。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114073357A (zh) * 2020-08-19 2022-02-22 驰绿国际股份有限公司 环保鞋材及其制备方法
WO2023240670A1 (zh) * 2022-06-17 2023-12-21 宋伟杰 用于汽车脚垫的热塑性弹性体材料及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316208A (zh) * 2021-12-28 2022-04-12 苏州云裳电子有限公司 一种聚氨酯环保泡棉及其制备方法
CN116554673B (zh) * 2023-05-16 2023-12-19 广东技塑新材料股份有限公司 一种用于鞋材的可降解tpu及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2540182A1 (en) * 2011-07-01 2013-01-02 Puentelago Anil S.L. Compostable shoe, methodof composting organic matter and corresponding uses
CN104262573A (zh) * 2014-09-28 2015-01-07 苏州市景荣科技有限公司 高耐磨的聚氨酯鞋底材料及其制造方法
CN106674982A (zh) * 2016-12-12 2017-05-17 成都育芽科技有限公司 一种聚氨酯抗菌型生物医用复合材料及其制备方法
CN108586935A (zh) * 2018-05-14 2018-09-28 浙江工业大学之江学院 一种环保型可降解塑料

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001112501A (ja) 1999-10-21 2001-04-24 Nexta Corp 履物類
JP4938706B2 (ja) 2008-03-05 2012-05-23 庚賢 林 衝撃吸収装置
FR2937040B1 (fr) 2008-10-13 2012-07-27 Roquette Freres Compositions thermoplastiques ou elastomeriques a base d'esters d'une matiere amylacee et procede de preparation de telles compositions
US10138373B2 (en) 2013-09-04 2018-11-27 Virfex, LLC Flexible polyurethane and polyurethane/polyorganosiloxane foam materials that absorb impact energy
JP6811010B2 (ja) 2015-10-26 2021-01-13 ミヨシ油脂株式会社 樹脂に添加されるフィラー、樹脂材料とその弾性率を調整する方法および製造方法
WO2019112010A1 (ja) 2017-12-06 2019-06-13 中越パルプ工業株式会社 ナノコンポジット及びナノコンポジットの製造方法
JP6938771B2 (ja) 2018-04-05 2021-09-22 三井化学株式会社 ポリウレタンゲル材料、ポリウレタンゲル、疑似生体材料、および、ポリウレタンゲルの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2540182A1 (en) * 2011-07-01 2013-01-02 Puentelago Anil S.L. Compostable shoe, methodof composting organic matter and corresponding uses
CN104262573A (zh) * 2014-09-28 2015-01-07 苏州市景荣科技有限公司 高耐磨的聚氨酯鞋底材料及其制造方法
CN106674982A (zh) * 2016-12-12 2017-05-17 成都育芽科技有限公司 一种聚氨酯抗菌型生物医用复合材料及其制备方法
CN108586935A (zh) * 2018-05-14 2018-09-28 浙江工业大学之江学院 一种环保型可降解塑料

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
张浩: "《基于纳米结晶纤维素复合材料的性能机制研究》", 31 May 2018, 黄河水利出版社 *
汪多仁: "《绿色化工助剂》", 31 January 2006, 科学技术文献出版社 *
陈葵阳: "《纺织纤维与面料分析》", 30 April 2012, 东华大学出版社 *
马正先: "《纳米氧化锌制备原理与技术》", 30 June 2009, 中国轻工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114073357A (zh) * 2020-08-19 2022-02-22 驰绿国际股份有限公司 环保鞋材及其制备方法
WO2023240670A1 (zh) * 2022-06-17 2023-12-21 宋伟杰 用于汽车脚垫的热塑性弹性体材料及其制备方法

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