CN105111399A - 一种耐水压水性聚氨酯树脂 - Google Patents

一种耐水压水性聚氨酯树脂 Download PDF

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CN105111399A
CN105111399A CN201510602882.3A CN201510602882A CN105111399A CN 105111399 A CN105111399 A CN 105111399A CN 201510602882 A CN201510602882 A CN 201510602882A CN 105111399 A CN105111399 A CN 105111399A
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史星照
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YIXING HUAXIA CHEMICAL MATERIAL CO Ltd
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Abstract

本发明公开了一种耐水压水性聚氨酯树脂，该树脂由以下重量份数的各组分制成：多元醇50～100份、多异氰酸酯20～30份、亲水胺类扩链剂10～25份、酸5～8份、终止剂0.5～5份、稳定剂2～5份、有机溶剂40～70份、有机铋0.08～0.1份。本发明材料具有良好的耐候性，透湿好，耐水解性、节能、成本低、安全、不污染环境等良好的综合性能和突出的环保性；使用普通树脂涂层的织物耐水压强度可达9000～10000Pa，使用本涂层的织物耐水压强度高于12000Pa，使用本发明所提供的树脂的织物的抗粘连性良好，本发明树脂的透湿度为19000g/m2.24h。

Description

一种耐水压水性聚氨酯树脂
技术领域
本发明涉及一种聚氨酯树脂，具体为一种耐水洗、耐低温的水性聚氨酯树脂。
背景技术
聚氨酯是一种新型的合成材料，由于其特殊的分子结构，兼具了橡胶的高弹性和塑料的高强度，因而近几十年无论在应用范围还是使用数量上都得到了快速的发展。聚氨酯合成革具有光泽柔和、自然、手感柔软，真皮感强的外观，具有与基材粘结性能优异，抗磨损、耐挠曲、抗老化、抗霉菌性好等优异的性能，同时还具备耐寒性好、透气、可洗涤、加工方便、价格优廉等优点，是天然皮革的最为理想的替代品，广泛应用于服装、制鞋、箱包、家具、体育等行业
聚氨酯树脂主链是由玻璃化温度低于室温的柔性链段和玻璃化温度高于室温的链段组成。柔性链段比较长，常采用聚醚类多元醇化合物，，醚基低温柔软性好，在低温下醚键仍能自由旋转，因此采用聚醚类多元醇制造的聚氨酯材料非常适合用于低温面料表面防水透湿处理。
在一些地区冬季气温非常低，普通的聚氨酯防水透湿材料在低温下容易发脆，***，穿着不舒适，耐剥离强度也低，耐水洗性也差，因此必须对聚氨酯进行改性，增进其低温柔韧性，使聚氨酯防水透湿材料在零下40℃时仍然具有良好的柔软性，和面料有紧密的结合性，制作出适合用在寒冷地带服装面料的防水透气透湿涂层使用。
以水为分散介质时，可以制得具有不燃、节能、成本低、安全、不污染环境等良好的综合性能和突出的环保性，但是高分子量、分散均匀的稳定阳离子水性聚氨酯的制造工艺复杂且成本较高。
发明内容
本发明要解决的技术问题是克服现有的水性聚氨酯树脂制造工艺复杂、成本较高，且耐水性、耐寒性较低的缺陷，提供一种耐水洗、耐低温的水性聚氨酯树脂。
为了解决上述技术问题，本发明提供了如下的技术方案：
一种耐水压水性聚氨酯树脂，该树脂由以下重量份数的各组分制成：
多元醇50～100份、多异氰酸酯20～30份、亲水胺类扩链剂10-25份、酸5～8份，终止剂0.5～5份、稳定剂2～5份、有机溶剂40～70份、有机铋0.08～0.1份。
进一步的，所述多元醇由以下重量份数的各组分组成：聚氧化丙烯二醇40～60份、聚乙二醇己二酸酯二醇5～20份、聚四氢呋喃醚二醇5～20份。
进一步的，所述的亲水胺类扩链剂为：异佛尔酮二胺、二乙醇胺，三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺和N-苄基二乙醇胺中的一种或多种。
进一步的，所述多异氰酸酯包括异氟尔酮二异氰酸酯5～10份以及六亚甲基-1,6-己二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和环己基甲烷二异氰酸酯三者的混合物共15～20份，且三者混合物中三者的重量比为1:3:2。
进一步的，所述终止剂是甲醇、丁醇、异丁醇和丙二醇甲醚中的一种或多种。
进一步的，所述稳定剂是UV-327、UV-531、UV-1165和UV-510中的一种或多种。
进一步的，所述的有机溶剂是甲苯、二甲基乙酰胺中和二甲基甲酰胺，三者的重量比为甲苯、二甲基乙酰胺和二甲基甲酰胺＝1.5:1：2。
优选的，所述的酸为磷酸。
本发明还公开了该水性聚氨酯树脂的制造方法，包括以下四个步骤：
1)、将多元醇在80～100℃下真空处理3～4个小时；
2)、加入多异氰酸酯、亲水胺类扩链剂、有机铋、有机溶剂，固含量控制在40～65％，在50～80℃反应4～8小时；
3)、然后加入酸和终止剂，快速搅拌，在60～80℃反应1～2h；
4)、真空下脱除有机溶剂，高速搅拌下加入去离子水，搅拌0.5h得到水性聚氨酯树脂。
本发明的水性聚氨酯树脂的分子量为40000～80000g/mol，树脂的固含量在40～60％。通过本方法得到的水性聚氨酯树脂经刮涂法涂覆在基布上，经烘干后具有高耐水压，通过《GA362-2009警服材料防水透湿复合布》-40℃的耐低温冲击试验。本法制造的涂层手感柔软滑爽，耐水洗，耐-40℃低温，非常适合高寒地带使用的织物的防水透湿透气织物的直接涂层和转移涂层处理。涂层后所得材料用ISO811.1981法测得的耐水压可大于14000mmH20，JISL1099方法B-1:2006测得的数值高达9000g/m2/24h。
与现有技术比较本发明的有益效果：本发明材料具有良好的耐候性，透湿好，耐水解性、节能、成本低、安全、不污染环境等良好的综合性能和突出的环保性；按照《涂层织物抗渗水性的测定(FZ/T01004-2008)》方法进行测试，使用普通树脂涂层的织物耐水压强度可达9000～10000Pa，使用本涂层的织物耐水压强度高于12000Pa。按照《涂层织物抗粘连性的测定(FZ/T01063-2008)》方法进行测试，使用本发明所提供的树脂的织物的抗粘连性良好。按照日本JISL1099法B-1:2006的织物涂层的透湿度测试，本发明树脂的透湿度为19000g/m2.24h。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1
一种耐水压水性聚氨酯树脂，由以下重量份数的各组分组成：多元醇50份、多异氰酸酯20份、N-甲基二乙醇胺10份、磷酸5份，甲醇0.5份、UV-3272份、有机溶剂40份、有机铋0.08份。
所述多元醇由以下重量份数的各组分组成：聚氧化丙烯二醇40份、聚乙二醇己二酸酯二醇5份、聚四氢呋喃醚二醇5份。
所述异氰酸酯为异氟尔酮二异氰酸酯5份，以及六亚甲基-1,6-己二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和环己基甲烷二异氰酸酯三者的混合物共15份，且三者混合物中三者的重量比为1:3:2。
所述的有机溶剂是甲苯、二甲基乙酰胺和二甲基甲酰胺，三者的重量比为甲苯、二甲基乙酰胺：二甲基甲酰胺＝1.5:1：2。
该水性聚氨酯树脂采用以下方法制备：
1)、将多元醇在80～100℃下真空处理3～4个小时；
2)、加入多异氰酸酯、亲水胺类扩链剂、有机铋、有机溶剂，固含量控制在40～65％，在50～80℃反应4～8小时；
3)、然后加入酸和终止剂，快速搅拌，在60～80℃反应1～2h；
4)真空下脱除有机溶剂，高速搅拌下加入去离子水，搅拌0.5h得到水性聚氨酯树脂。
实施例1的材料固含量为40％，分子量为60000g/mol。
对实施例1制得的材料按照以下方法进行涂布：在底布上先进行底胶的刮涂，底胶上胶量为18～30克/平方米，涂底胶的布料在120℃烘箱中烘60s。在烘干底胶的布料上涂上面胶，面胶的量为20～30克/平方米。涂完面胶后在160℃烘箱中烘烤60s。测材料的断裂伸长率、透湿和耐压性。断裂伸长率为1000％，透湿为10500g/m2.24h，耐水压为12000mmH20。通过《GA362-2009警服材料防水透湿复合布》-40℃的耐低温冲击试验。
实施例2
一种耐水压水性聚氨酯树脂，由以下重量份数的各组分组成：多元醇100份、多异氰酸酯30份、N-乙基二乙醇胺和异佛尔酮二胺25份、磷酸8份，丁醇5份、UV-5315份、有机溶剂70份、有机铋0.1份。
多元醇由以下重量份数的各组分组成：聚氧化丙烯二醇60份、聚乙二醇己二酸酯二醇20份、聚四氢呋喃醚二醇20份。
所述异氰酸酯为异氟尔酮二异氰酸酯7份，以及六亚甲基-1,6-己二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和环己基甲烷二异氰酸酯三者的混合物共20份，且三者混合物中三者的重量比为1:3:2。
有机溶剂是甲苯、二甲基乙酰胺和二甲基甲酰胺，三者的重量比为甲苯、二甲基乙酰胺和二甲基甲酰胺＝1.5:1：2。
制备方法同实施例1，制得实施例2，固含量为60％，材料的分子量为70000g/mol。
对实施例2制得的材料按照实施例1的方法进行涂布，测材料的断裂伸长率和透湿，耐压。断裂伸长率为1200％，透湿为12500g/m2.24h，耐水压为14000mmH20。通过《GA362-2009警服材料防水透湿复合布》-40℃的耐低温冲击试验。
实施例3
一种耐水压水性聚氨酯树脂，由以下重量份数的各组分组成：多元醇80份、多异氰酸酯25份、异佛尔酮二胺和和N-苄基二乙醇胺20份、磷酸6份，丙二醇甲醚3份、UV-1165和UV-5104份、有机溶剂55份、有机铋0.09份。
多元醇醇由以下重量份数的各组分组成：聚氧化丙烯二醇55份、聚乙二醇己二酸酯二醇13份、聚四氢呋喃醚二醇12份。
所述异氰酸酯为异氟尔酮二异氰酸酯6份，以及六亚甲基-1,6-己二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和环己基甲烷二异氰酸酯三者的混合物共18份，且三者混合物中三者的重量比为1:3:2。
有机溶剂是甲苯、二甲基乙酰胺和二甲基甲酰胺，三者的重量比为甲苯、二甲基乙酰胺和二甲基甲酰胺＝1.5:1：2。
该水性聚氨酯树脂的制备方法同实施例1，制的实施例3，调整固含量为50％，材料的分子量为80000g/mol。
对实施例3制得的材料按照实施例1的方法进行涂布测材料的断裂伸长率和透湿，耐压。断裂伸长率为1400％，透湿为14500g/m2.24h，耐水压为18000mmH20。通过《GA362-2009警服材料防水透湿复合布》-40℃的耐低温冲击试验。
最后应说明的是：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 (9)

1.一种耐水压水性聚氨酯树脂，其树脂特征在于，该树脂由以下重量份数的各组分制成：多元醇50～100份、多异氰酸酯20～30份、亲水胺类扩链剂10-25份、酸5～8份、终止剂0.5～5份、稳定剂2～5份、有机溶剂40～70份、有机铋0.08～0.1份。
2.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述多元醇由以下重量份数的各组分组成：聚氧化丙烯二醇40～60份、聚乙二醇己二酸酯二醇5～20份、聚四氢呋喃醚二醇5～20份。
3.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述的亲水胺类扩链剂为：异佛尔酮二胺、二乙醇胺，三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺和N-苄基二乙醇胺中的一种或多种。
4.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述多异氰酸酯为异氟尔酮二异氰酸酯5～10份；六亚甲基-1,6-己二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和环己基甲烷二异氰酸酯共15～20份，且三者的重量比为1:3:2。
5.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述终止剂是甲醇、丁醇、异丁醇和丙二醇甲醚中的一种或多种。
6.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述稳定剂是UV-327、UV-531、UV-1165和UV-510中的一种或多种。
7.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述的有机溶剂是甲苯、二甲基乙酰胺中和二甲基甲酰胺，且三者的重量比为甲苯、二甲基乙酰胺和二甲基甲酰胺＝1.5:1：2。
8.如权利要求1所述的一种耐水压水性聚氨酯树脂，其树脂特征在于，所述的酸为磷酸。
9.一种权利要求1所述的一种耐水压水性聚氨酯树脂的制造方法，其特征在于，包括以下四个步骤：
1)、将多元醇和聚醚多元醇在80～100℃下真空处理3～4个小时；
2)、加入多异氰酸酯、亲水胺类扩链剂、有机铋、有机溶剂，固含量控制在65～75％，在50～80℃反应4～8小时；
3)、然后加入酸和终止剂，快速搅拌，在60～80℃反应1～2h；
4)真空下脱除有机溶剂，高速搅拌下加入去离子水，搅拌0.5h得到水性聚氨酯树脂。
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CN107857858A (zh) * 2017-11-29 2018-03-30 朱树彪 水合萜二醇改性聚氨酯、其制备方法及含有该聚氨酯的涂料组合物
CN107857858B (zh) * 2017-11-29 2021-05-25 黄山佳杰新材料科技有限公司 水合萜二醇改性聚氨酯、其制备方法及含有该聚氨酯的涂料组合物
TWI695779B (zh) * 2019-04-25 2020-06-11 財團法人中華民國紡織業拓展會 具有高耐水壓性之彈性體薄膜的製備方法
CN110684172A (zh) * 2019-11-12 2020-01-14 东莞市米儿塑胶原料有限公司 一种耐水压水性聚氨酯树脂
CN112227083A (zh) * 2020-09-30 2021-01-15 京准化工技术(上海)有限公司 一种织物耐水压提升剂及其制备方法
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CN113152110A (zh) * 2021-05-18 2021-07-23 广东欧美斯家具有限公司 一种绿色环保沙发家具用聚氨酯合成革及其制备方法

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