CN106496514A - 一种水性聚氨酯树脂 - Google Patents

一种水性聚氨酯树脂 Download PDF

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CN106496514A
CN106496514A CN201610841013.0A CN201610841013A CN106496514A CN 106496514 A CN106496514 A CN 106496514A CN 201610841013 A CN201610841013 A CN 201610841013A CN 106496514 A CN106496514 A CN 106496514A
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polyurethane resin
waterborne polyurethane
chain extender
polyol
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徐顺乐
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Nantong Wanshun Chemical Technology Co Ltd
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Abstract

本发明涉及一种水性聚氨酯树脂，所述水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20～40份，聚醚多元醇60～80份，多异氰酸酯12～16份，扩链剂4～10份，成盐剂1～5份，有机铋催化剂1～2份和水200～400份；其中，聚氨酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚醚多元醇为四氟呋喃‑氧化丙烯共聚二醇，扩链剂是由乙二醇和异氟尔酮二胺的混合而成。本发明的优点在于：本发明通过调整配方中的组分以及各组分的配比，使得水性聚氨酯树脂能够耐寒，且该水性聚氨酯树脂进行服装革贴面时，贴合层具有柔软的手感、高的剥离强度及优良的耐水性能。

Description

一种水性聚氨酯树脂
技术领域
本发明涉及高分子聚合物技术领域，特别涉及一种水性聚氨酯树脂。
背景技术
合成革可分为聚氨酯服装革、鞋用合成革、汽车革和沙发革。不同领域对革的性能要求不尽相同，其中服装革对舒适性和功能性的要求较高。例如要求革具有较好的透气性、肉感、柔软的手感、耐水解性、耐磨耐刮性和伸展性等。此外，在开发服装革产品时，必须追求革性能和价格的平衡，以满足市场上的皮革服装要求。
水性聚氨酯树脂是以水为分散介质，在加工过程中无需有机溶剂，而且产品体系中不含有有毒份NCO基团，避免了对环境的污染和对操作人员的健康危害。但是收到水性聚氨酯树脂本身的物理化学性质的限制，将其批量应用于服装革上还没有成功的先例。在现有制革生产过程中，采用水性聚氨酯树脂作为粘合层有致命的劣势。其以水为溶剂，粘合层在面层和基布之间更不利于水分的烘干，且在烘干过程中需要蒸发热较高，因此制革过程的烘烤时间延长，烘烤温度提高，造成生产效率低下。
现有技术中如公开号为CN 103351456 A 的发明申请公开了一种服装革用湿法聚氨酯树脂，通过设计具有特定分子结构和分子量的酯醚共聚物多元醇，同时通过先合成一种粘度及固含量的聚氨酯树脂中间体，然后将该中间体加入到最终的聚氨酯树脂中，获得了有较好柔软度、湿滑感、丰满的手感，较强的真皮感，具有服装领域所要求的耐水解、高剥离和超柔软等性能要求的产品；但是，这种聚氨酯树脂的配方中含有占配方比重50%以上的有机溶剂，生产过程及所制备的产品不能够满足环保要求。
针对上述现象，专利CN 105061722 A公开了一种水性聚氨酯树脂，所述水性聚氨酯树脂包括以下原料组分及重量份：多元醇120-170份，多异氰酸酯10-30份，第一扩链剂4-10份，第二扩链剂0.6-2份，三乙胺2-6份，有机铋催化剂0.2-0.6份和水260-400份。本发明的用于服装革半干贴工艺的底料水性聚氨酯树脂，其在合成过程中与传统的水性聚氨酯异氰酸酯过量不同，在合成过程中羟基过量，直接以羟基封端。该水性聚氨酯在进行服装革贴面时，加热至半干状态进行贴面，贴出来的革手感极柔软和高的剥离强度，但这种水性聚氨酯树脂极不耐寒，不能满足低温环境要求。
发明内容
本发明要解决的技术问题是提供一种水性聚氨酯树脂，通过调整配方中的组分以及各组分的配比，使得水性聚氨酯树脂能够耐寒，且该水性聚氨酯树脂进行服装革贴面时，贴合层具有柔软的手感、高的剥离强度及优良的耐水性能。
为解决上述技术问题，本发明的技术方案为：一种水性聚氨酯树脂，其创新点在于：所述水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20～40份，聚醚多元醇60～80份，多异氰酸酯12～16份，扩链剂4～10份，成盐剂1～5份，有机铋催化剂1～2份和水200～400份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，且聚己内酯多元醇和聚碳酸酯多元醇的质量比为1.7～2.1:1；聚醚多元醇为四氟呋喃-氧化丙烯共聚二醇；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，且乙二醇和异氟尔酮二胺的质量比为1:1.5～2。
进一步地，所述的多异氰酸酯为异氟尔酮二异氰酸酯。
进一步地，所述的成盐剂为三乙胺和乙酸的混合物，且三乙胺和乙酸的质量比为1.3～1.7:1。
本发明的优点在于：
（1）本发明水性聚氨酯树脂，配方中聚醚多元醇采用四氟呋喃-氧化丙烯共聚二醇，该共聚醚成本比纯聚四氢呋喃二醇便宜，而其制品性能近似于纯聚四氢呋喃二醇，进而使制得的水性聚氨酯树脂具有优良的耐寒性；同时，聚酯多元醇采用聚己内酯多元醇和聚碳酸酯多元醇混合物，扩链剂采用乙二醇和异氟尔酮二胺的混合物，通过混合物的中和，使得水性聚氨酯树脂的性能大大提升，同时，各组分通过严格的配比控制，使得水性聚氨酯树脂进行服装革贴面时，贴合层手感的柔软度、剥离强度及耐水性能都有显著的提高；
（2）本发明水性聚氨酯树脂，多异氰酸酯选用异氟尔酮二异氰酸酯，避免了使用4,4-二苯基甲烷2-异氰酸酯或甲苯二异氰酸酯，不会出现苯环在紫外线下发生异变而导致物料黄变的现象；此外，成盐剂选用三乙胺和乙酸的混合物，且三乙胺和乙酸的质量比为1.3～1.7:1，避免了碱性过强，导致水性聚氨酯树脂性能下降的现象。
具体实施方式
下面的实施例可以使本专业的技术人员更全面地理解本发明，但并不因此将本发明限制在所述的实施例范围之中。
实施例1
本实施例水性聚氨酯树脂，该水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20份，四氟呋喃-氧化丙烯共聚二醇80份，异氟尔酮二异氰酸酯16份，扩链剂10份，成盐剂5份，有机铋催化剂2份和水400份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚己内酯多元醇12.6份，聚碳酸酯多元醇7.4份；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，乙二醇4份，异氟尔酮二胺6份；成盐剂为三乙胺和乙酸的混合物，三乙胺2.83份，乙酸2.17份。
实施例2
本实施例水性聚氨酯树脂，该水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20份，四氟呋喃-氧化丙烯共聚二醇80份，异氟尔酮二异氰酸酯16份，扩链剂10份，成盐剂5份，有机铋催化剂2份和水400份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚己内酯多元醇13.55份，聚碳酸酯多元醇6.45份；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，乙二醇3.33份，异氟尔酮二胺6.67份；成盐剂为三乙胺和乙酸的混合物，三乙胺3.15份，乙酸1.85份。
实施例3
本实施例水性聚氨酯树脂，该水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20份，四氟呋喃-氧化丙烯共聚二醇80份，异氟尔酮二异氰酸酯16份，扩链剂10份，成盐剂5份，有机铋催化剂2份和水400份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚己内酯多元醇13.1份，聚碳酸酯多元醇6.9份；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，乙二醇3.64份，异氟尔酮二胺6.36份；成盐剂为三乙胺和乙酸的混合物，三乙胺3份，乙酸2份。
下表1为实施例1-3中聚酯多元醇中聚己内酯多元醇和聚碳酸酯多元醇，扩链剂中乙二醇和异氟尔酮，成盐剂中三乙胺和乙酸的质量比对比表格：
将上述实施例1～3中的水性聚氨酯树脂按常规步骤制备聚氨酯服装革，对制得的聚氨酯服装革进行性能测试，测试结构见表2。
注：1.耐寒测试按IS05423-1992、IS0-4643：1992、SATRAPM-25-1002测试，具体为-100℃下8万次测试；
2.耐UV黄变按HG/T3689-2001测试；
3.剥离强度按GB/T8949-1995测试；
4.耐折牢度按照QB/T1646-2007标准规定进行，分别将各组试样在23℃±2℃和-10℃±2℃下，将试样正面向里折叠，观察正、反两面受折部分的变化；
5.耐磨性测试方法：按照QB/T2726-2005的规定进行，荷重为1000g，选用H-22号磨轮，设定转速为500r/min，试验结束后观察受测试样表面的变化。
结论：由上表可以看出，实施例1-3的水性聚氨酯树脂用于服装革时，各性能都有了显著的提高，尤其是耐寒性能，即-100℃下8万次无裂痕；此外，实施例1-3进行相互对比，可以看出，实施例3的各项测试性能均优于其他两个实施例，因而实施例3为最佳实施例。
实施例4
本实施例水性聚氨酯树脂，该水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇40份，四氟呋喃-氧化丙烯共聚二醇60份，异氟尔酮二异氰酸酯12份，扩链剂4份，成盐剂1份，有机铋催化剂1份和水200份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚己内酯多元醇26.2份，聚碳酸酯多元醇13.8份；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，乙二醇1.45份，异氟尔酮二胺2.55份；成盐剂为三乙胺和乙酸的混合物，三乙胺0.6份，乙酸0.4份。
实施例5
本实施例水性聚氨酯树脂，该水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇30份，四氟呋喃-氧化丙烯共聚二醇70份，异氟尔酮二异氰酸酯14份，扩链剂7份，成盐剂3份，有机铋催化剂1.5份和水300份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，聚己内酯多元醇19.66份，聚碳酸酯多元醇10.34份；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，乙二醇2.55份，异氟尔酮二胺4.45份；成盐剂为三乙胺和乙酸的混合物，三乙胺1.8份，乙酸1.2份。
下表3为实施例3-5的各组分配比对比表格：
表3 实施例3-5的重量配比
将上述实施例3～5中的水性聚氨酯树脂按常规步骤制备聚氨酯服装革，对制得的聚氨酯服装革进行性能测试，测试结构见表4。
注：1.耐寒测试按IS05423-1992、IS0-4643：1992、SATRAPM-25-1002测试，具体为-100℃下8万次测试；
2.耐UV黄变按HG/T3689-2001测试；
3.剥离强度按GB/T8949-1995测试；
4.耐折牢度按照QB/T1646-2007标准规定进行，分别将各组试样在23℃±2℃和-10℃±2℃下，将试样正面向里折叠，观察正、反两面受折部分的变化；
5.耐磨性测试方法：按照QB/T2726-2005的规定进行，荷重为1000g，选用H-22号磨轮，设定转速为500r/min，试验结束后观察受测试样表面的变化。
结论：由上表可以看出，实施例3-5的水性聚氨酯树脂用于服装革时，各性能都有了显著的提高，尤其是耐寒性能，即-100℃下8万次无裂痕；此外，实施例3-5进行相互对比，可以看出，实施例5的各项测试性能均优于其他两个实施例，因而实施例5为最佳实施例。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。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 (3)

1.一种水性聚氨酯树脂，其特征在于：所述水性聚氨酯树脂包括以下原料组分及重量份：聚酯多元醇20～40份，聚醚多元醇60～80份，多异氰酸酯12～16份，扩链剂4～10份，成盐剂1～5份，有机铋催化剂1～2份和水200～400份；其中，聚酯多元醇是由聚己内酯多元醇和聚碳酸酯多元醇混合而成的，且聚己内酯多元醇和聚碳酸酯多元醇的质量比为1.7～2.1:1；聚醚多元醇为四氟呋喃-氧化丙烯共聚二醇；扩链剂是由乙二醇和异氟尔酮二胺的混合而成，且乙二醇和异氟尔酮二胺的质量比为1:1.5～2。
2.根据权利要求1所述的水性聚氨酯树脂，其特征在于：所述的多异氰酸酯为异氟尔酮二异氰酸酯。
3.根据权利要求1所述的水性聚氨酯树脂，其特征在于：所述的成盐剂为三乙胺和乙酸的混合物，且三乙胺和乙酸的质量比为1.3～1.7:1。
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