CN112979915A - 一种超软质低表面能改性聚氨酯树脂及其制备方法 - Google Patents

一种超软质低表面能改性聚氨酯树脂及其制备方法 Download PDF

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CN112979915A
CN112979915A CN202110301870.2A CN202110301870A CN112979915A CN 112979915 A CN112979915 A CN 112979915A CN 202110301870 A CN202110301870 A CN 202110301870A CN 112979915 A CN112979915 A CN 112979915A
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polyurethane resin
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antioxidant
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钟招亨
范石有
杨家淳
徐德胜
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Zhangzhou Jialian Chemical Co ltd
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Abstract

本发明涉及一种超软质低表面能改性聚氨酯树脂及其制备方法，该树脂原料包括以下重量份的组分：100重量份醇类混合物、10‑30重量份二异氰酸酯类化合物、1‑10重量份扩链剂、0.05‑1重量份稳定剂、0.05‑1重量份终止剂、0.01‑0.2重量份抗氧剂、9‑55重量份有机溶剂、1‑5重量份氟化聚乙烯。与现有技术相比，本发明产品表面能较低，涂布时涂层更薄，产品更轻，经实验对比涂布米数高于市场现有聚氨脂树脂25％以上，生产出的产品附着力强、致密性高，柔软性佳等特点，同时又节约了产品生产成本和运输成本，提高市场竞争力。

Description

一种超软质低表面能改性聚氨酯树脂及其制备方法
技术领域
本发明属于高分子材料领域，具体涉及一种超软质低表面能改性聚氨酯树脂及其制备方法。
背景技术
改性聚氨酯树脂作为一种具有高强度、耐水解、抗撕裂、防水透气和耐磨等特性的高分子材料，广泛应用于日常生活、工农业生产、医学、建筑等领域。
超软质高水压聚氨酯树脂广泛应用于生产服装面料、防护服及对性能要求严格的户外冲锋衣、建筑外墙材料等。随着社会不断进步、人民生活水平的不断提高,现在市场上流行的超软质高水压聚氨酯树脂均存在使用年限较短，手感硬或耐寒性差等各种不同的缺点。但是一般的树脂的柔软性均以牺牲耐水压或耐磨性来实现，容易造成手感虽然柔软，但树脂加工后表面发粘，耐水压低，耐磨性差等缺点。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种手感柔软、低表面能、耐高水压和耐寒性优异的超软质低表面能改性聚氨酯树脂及其制备方法，来满足人们日常生活对高性能布料的需求。
本发明的目的可以通过以下技术方案来实现：一种超软质低表面能改性聚氨酯树脂，该树脂原料包括以下重量份的组分：100重量份醇类混合物、10-30重量份二异氰酸酯类化合物、1-10重量份扩链剂、0.05-1重量份稳定剂、0.05-1重量份终止剂、0.01-0.2重量份抗氧剂、9-55重量份有机溶剂、1-5重量份氟化聚乙烯。
该超软质低表面能改性聚氨酯树脂平均分子量在80000～140000，粘度为140000～160000cps(25℃)，树脂的固体含量在60～80％。
进一步地，所述的醇类混合物为聚碳酸酯二醇、聚己内酯多元醇、己二酸-二甘醇多元醇类按重量比6:1:3～2:1:7组合而成，醇类混合物的平均分子量在850-5000。
所述的二异氰酸酯类化合物为异佛尔酮二异氰酸酯与六亚甲基-1，6二异氰酸酯按重量比1:1～3:2组成的混合物。其中异佛尔酮二异氰酸酯IPDI，属于脂肪族二异氰酸酯，是一种环脂肪族二异氰酸酯，六亚甲基-1，6二异氰酸酯(HDI)，也是一种脂肪族多异氰酸酯，将IPDI与HDI按特定比例混合，与上述醇类组合物进行反应，制成的聚氨酯胶黏剂具有优秀的耐光学稳定，耐化学药品性，不黄变，而且柔韧性较好，可以制造耐磨、耐水解聚氨酯弹性体，也可用于制造不黄变微孔聚氨酯泡沫塑料等。
所述的扩链剂为二甘醇、1,6-己二醇、1,3-丁二醇、1,4-丁二醇、二乙醇胺、乙二醇中的一种或几种组合。
所述的稳定剂为UV-292、UV-77ODF、UV-994、UV-1084中的一种或几种组合。
所述的终止剂为甲基丙二醇、甲醇、1,2丙二醇中的一种或几种。
所述的抗氧剂为抗氧剂BHT、抗氧剂1010、抗氧剂168、抗氧剂DLTP的一种或几种。
所述的有机溶剂为碳酸二甲酯、丁酮、环己酮、二甲基甲酰胺、醋酸乙酯中的一种或几种组合。
一种超软质低表面能改性聚氨酯树脂的制备方法，包括以下步骤：将醇类混合物，二异氰酸酯类化合物、抗氧剂、有机溶剂、扩链剂、氟化聚乙烯混合投入反应釜，反应温度控制在50-80℃，反应4-8小时，检测粘度合格后加入终止剂，继续搅拌1～2小时，然后加入稳定剂，混合均匀得到产品。
所述检测粘度合格是指用溶剂调整固含至60-80％，粘度调整至140000-160000cps(25℃)。
与现有技术相比，本发明具有以下有益效果：
1.本产品采用的聚碳酸酯二醇具有优异的耐水解性、耐候性和耐磨性，聚己内酯玻璃化温度为-60℃，且非常柔软，具有极大的伸展性，可增强材料低温的柔软性，己二酸-二甘醇制得的制品价格低廉、柔软，再加上氟化聚乙烯具有的低表面能，本发明把四者性能有机结合互补，制得的产品综合性能优异。
2.本发明材料采用的混合醇和二异氰酸酯通过羟基(-OH)与异氰酸酯基团(-NCO)的反应，生成端羟基聚氨酯。在工业上使用时，这个聚氨酯的端羟基再与异氰酸酯基团反应，并结合具有低表面能的氟化聚乙烯，施工后形成的漆膜就具有耐水压高、耐水解好、剥离强度大、耐黄变好、柔软性好、附着力好等优异性能。
3.本发明材料具有手感柔软、低表面能产生耐高水压、耐寒性优异、耐水解、耐黄变、附着力强等特点。参照Caurtaulds method和ISO 105-X18:2007耐黄变测试方法，本产品耐黄变等级5级，基本不黄变。按照《织物涂层抗渗水性的测定FZ/T 01004-2008》方法进行测试，普通树脂涂层的织物耐水压强度在6000～8000mmH2O，使用本树脂涂层的织物耐水压强度在15000～22000mmH2O范围内。对比织物涂层市场上常用树脂，相同工艺条件下，由于本产品表面能较低，涂布时涂层更薄，产品更轻，经实验对比涂布米数高于市场现有聚氨脂树脂25％以上，生产出的产品附着力强、致密性高，柔软性佳等特点，同时又节约了产品生产成本和运输成本，提高市场竞争力。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
本发明采用的各原料均为市售产品，或者按照已公开的方法制备而成，如
聚碳酸酯二醇可选择日本宇部兴产株式会社生产的UH-200。
聚己内酯多元醇可选择日本大赛璐生产的PCL-308。
己二酸-二甘醇多元醇为本公司自制多元醇，其制备方法为:
依次将二甘醇、己二酸按质量比70～80:100加入反应釜中熔融、通入氮气保护、升温至150℃脱水、釜内生成低聚酯混合物、随着水分的蒸出、继续升温至230℃，持续真空反应6H，检测其酸值达到0.2～0.5mgKOH/g、羟值达到22～24mgKOH/g，合格后降温、出料。
氟化聚乙烯可选择美国陶氏生产的400500E。
实施例1
超软质低表面能改性聚氨酯树脂，通过以下方法获得：
(1)原料组成如下：
醇类混合物：聚碳酸酯二醇(2000分子量):50.0g，聚己内酯(850分子量)10.0g，聚己二酸-二甘醇(分子量5000)40.0g；
二异氰酸酯类化合物：IPDI(异佛尔酮二异氰酸酯)6.3g，HDI(六亚甲基-1,6二异氰酸酯)6.3g；
抗氧剂：BHT 0.016g；
扩链剂：1,6-己二醇3.2g，1,4-丁二醇1.9g；
终止剂：甲醇0.18g；
稳定剂：(UV-292)0.05g；
有机溶剂：二甲基甲酰胺9.0g；
氟化聚乙烯：2g。
(2)按配方量依次加入醇类混合物、二异氰酸酯类化合物、抗氧剂、扩链剂、有机溶剂，氟化聚乙烯；开始搅拌，反应温度控制在80±5℃，常压下持续反应7～8h，用NDJ-8S粘度计检测物料粘度，粘度合格后加入终止剂终止反应，继续搅拌1～1.5h后加入稳定剂。经过滤，得到超软质低表面能聚氨酯树脂。
实施例2：
超软质低表面能改性聚氨酯树脂，通过以下方法获得：
(1)原料组成如下：
醇类混合物：聚碳酸酯二醇(2000分子量):20.0g，聚己内酯(850分子量)10g.0，聚己二酸-二甘醇(分子量5000)70.0g，
二异氰酸酯类化合物：IPDI(异佛尔酮二异氰酸酯)15g，HDI(六亚甲基-1，6二异氰酸酯)5g，
抗氧剂BHT 0.018g，
扩链剂：1,6-己二醇2.2g，1,4-丁二醇4.6g，
终止剂：甲醇0.07g，
稳定剂：(UV-770DF)1.0g，
有机溶剂：二甲基甲酰胺32.0g，醋酸乙酯18.0g。
氟化聚乙烯：3g。
(2)按配方量依次加入醇类混合物、二异氰酸酯类化合物、抗氧剂、扩链剂、有机溶剂，氟化聚乙烯；开始搅拌，反应温度控制在75±5℃，常压下持续反应6～7h，用NDJ-8S粘度计检测物料粘度，粘度合格后加入终止剂终止反应，继续搅拌1～1.5h后加入稳定剂。经过滤，得到超软质低表面能聚氨酯树脂。
实施例3：
超软质低表面能改性聚氨酯树脂，通过以下方法获得：
(1)原料组成如下：
醇类混合物：聚碳酸酯二醇(2000分子量)60.0g，聚己内酯(850分子量)10.0g，聚己二酸-二甘醇(分子量5000)30.0g，
二异氰酸酯类化合物：IPDI(异佛尔酮二异氰酸酯)15.0g，HDI(六亚甲基-1，6二而异氰酸酯)15.0g，
抗氧剂：抗氧剂1010 0.01g，
扩链剂：1,6-己二醇0.5g，乙二醇0.5g，
终止剂：甲基丙二醇0.017g，
稳定剂：(UV-994)0.08g，
有机溶剂：二甲基甲酰胺18.0g，碳酸二甲酯23.0g；
氟化聚乙烯：1g。
(2)按配方量依次加入醇类混合物、二异氰酸酯类化合物、抗氧剂、扩链剂、有机溶剂，氟化聚乙烯；开始搅拌，反应温度控制在70±5℃，常压下持续反应6～7h，用NDJ-8S粘度计检测物料粘度，粘度合格后加入终止剂终止反应，继续搅拌1～1.5h，降温至60℃以下后加入稳定剂。经过滤，得到低表面能改性聚氨酯树脂。
实施例4：
超软质低表面能改性聚氨酯树脂，通过以下方法获得：
(1)原料组成如下：
醇类混合物：聚碳酸酯二醇(2000分子量)21.8g，聚己内酯(850分子量)8.2g，聚己二酸-二甘醇(分子量5000)70.0g，
二异氰酸酯类化合物：IPDI(异佛尔酮二异氰酸酯)5.0g，HDI(六亚甲基-1，6二异氰酸酯)5.0g，
抗氧剂:BHT0.2g，
扩链剂：1,4-丁二醇5.0g，乙二醇5.0g，
终止剂：1,2丙二醇0.20g，
稳定剂：(UV-1084)0.6g，
有机溶剂：二甲基甲酰胺25.0g，碳酸二甲酯30.0g，
氟化聚乙烯：5g。
(2)按配方量依次加入醇类混合物、二异氰酸酯类化合物、抗氧剂、扩链剂、有机溶剂，氟化聚乙烯；开始搅拌，反应温度控制在70±5℃，常压下持续反应7～8h，用NDJ-8S粘度计检测物料粘度，粘度合格后加入终止剂终止反应，继续搅拌1～1.5h，1降温至60℃以下，加入稳定剂。经过滤，得到超软质低表面能聚氨酯树脂。
应用上述实施例1-4得到的低表面能改性聚氨酯树脂得到的物性检测结果如表1:
表1物性检测结果
Figure BDA0002986590910000061
通过表1对本发明制得的产品的各项物性测试结果得出，无论耐水压、耐水解、剥离强度、耐黄变、柔软性、附着力等性能均表现优异，对比市场现有产品，其适用性更好，可以满足不同基布对各种性能的要求。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种超软质低表面能改性聚氨酯树脂，其特征在于，该树脂原料包括以下重量份的组分：100重量份醇类混合物、10-30重量份二异氰酸酯类化合物、1-10重量份扩链剂、0.05-1重量份稳定剂、0.05-1重量份终止剂、0.01-0.2重量份抗氧剂、9-55重量份有机溶剂、1-5重量份氟化聚乙烯。
2.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的醇类混合物为聚碳酸酯二醇、聚己内酯多元醇、己二酸-二甘醇多元醇类按重量比6:1:3～2:1:7组合而成，醇类混合物的平均分子量在850-5000。
3.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的二异氰酸酯类化合物为异佛尔酮二异氰酸酯与六亚甲基-1，6二异氰酸酯按重量比1:1～3:2组成的混合物。
4.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的扩链剂为二甘醇、1,6-己二醇、1,3-丁二醇、1,4-丁二醇、二乙醇胺、乙二醇中的一种或几种组合。
5.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的稳定剂为UV-292、UV-77ODF、UV-994、UV-1084中的一种或几种组合。
6.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的终止剂为甲基丙二醇、甲醇、1,2丙二醇中的一种或几种。
7.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的抗氧剂为抗氧剂BHT、抗氧剂1010、抗氧剂168、抗氧剂DLTP的一种或几种。
8.根据权利要求1所述的超软质低表面能改性聚氨酯树脂，其特征在于，所述的有机溶剂为碳酸二甲酯、丁酮、环己酮、二甲基甲酰胺、醋酸乙酯中的一种或几种组合。
9.一种如权利要求1-8中任一所述的超软质低表面能改性聚氨酯树脂的制备方法，其特征在于，包括以下步骤：将醇类混合物，二异氰酸酯类化合物、抗氧剂、有机溶剂、扩链剂、氟化聚乙烯混合投入反应釜，反应温度控制在50-80℃，反应4-8小时，检测粘度合格后加入终止剂，继续搅拌1～2小时，然后加入稳定剂，混合均匀得到产品。
10.根据权利要求9所述的超软质低表面能改性聚氨酯树脂的制备方法，其特征在于，所述检测粘度合格是指用溶剂调整固含至60-80％，粘度调整至140000-160000cps(25℃)。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254399A (zh) * 2013-05-22 2013-08-21 宜兴市华夏化工材料有限公司 一种高耐水压耐寒聚氨酯树脂及其制备方法
CN105111399A (zh) * 2015-09-21 2015-12-02 宜兴市华夏化工材料有限公司 一种耐水压水性聚氨酯树脂
CN105732936A (zh) * 2014-12-10 2016-07-06 田建频 一种聚氨酯树脂
CN108504273A (zh) * 2018-04-10 2018-09-07 苏州中来光伏新材股份有限公司 一种涂覆太阳能电池背板的聚氨酯基涂料及其制备方法
CN109880143A (zh) * 2019-02-18 2019-06-14 东莞市和域战士纳米科技有限公司 一种氟化聚乙烯复合超疏水防水纳米膜
CN111019450A (zh) * 2018-10-09 2020-04-17 通用汽车环球科技运作有限责任公司 具有含非氟化域的氟化连续相的多相防污溶剂型聚合物涂层

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254399A (zh) * 2013-05-22 2013-08-21 宜兴市华夏化工材料有限公司 一种高耐水压耐寒聚氨酯树脂及其制备方法
CN105732936A (zh) * 2014-12-10 2016-07-06 田建频 一种聚氨酯树脂
CN105111399A (zh) * 2015-09-21 2015-12-02 宜兴市华夏化工材料有限公司 一种耐水压水性聚氨酯树脂
CN108504273A (zh) * 2018-04-10 2018-09-07 苏州中来光伏新材股份有限公司 一种涂覆太阳能电池背板的聚氨酯基涂料及其制备方法
CN111019450A (zh) * 2018-10-09 2020-04-17 通用汽车环球科技运作有限责任公司 具有含非氟化域的氟化连续相的多相防污溶剂型聚合物涂层
CN109880143A (zh) * 2019-02-18 2019-06-14 东莞市和域战士纳米科技有限公司 一种氟化聚乙烯复合超疏水防水纳米膜

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
丁绍兰等: "《革制品材料学》", 31 January 2019, 中国轻工业出版社 *
杨铁军主编: "《产业专利分析报告 第26册 氟化工》", 31 May 2014, 知识产权出版社 *

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