不同阴离子亲水扩链剂合成的水性聚氨酯性能比较Performance comparison of waterborne polyurethane synthesized by different anionic hydrophilic chain extenders
叶留留,张昕,范浩军,李成祥,黄军江
YE Liuliu,ZHANG Xin,FAN Haojun,LI Chengxiang,HUANG Junjiang
摘要(Abstract):
以二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)、二羟基磺酸盐(GS-7Q)为亲水扩链剂,采用单因素法合成一系列阴离子水性聚氨酯。通过比较乳液的粒径以及胶膜的耐水性、热稳定性、机械性能等,研究了不同的亲水扩链剂对合成的水性聚氨酯性能的影响。结果表明:DMBA作为亲水扩链剂合成水性聚氨酯(WPUB)相比于DMPA合成的水性聚氨酯(WPUP)反应时间缩短40%;获得稳定的水性聚氨酯乳液时,GS-7Q的用量比DMPA更少,仅需8%(扩链剂占所有—OH摩尔分数)即可维持乳液稳定。DMBA合成的水性聚氨酯的粒径较DMPA型的更细,其薄膜低温柔顺性更好; GS-7Q磺酸型水性聚氨酯(WPUH)薄膜的拉伸强度是羧酸型的4倍,耐热性能优于羧酸型水性聚氨酯,但低温柔顺性却不如羧酸型水性聚氨酯(WPUB,WPUP)。
Dihydroxy methyl propionic acid (DMPA),Dihydroxy methyl butyric acid (DMBA) and Dihydroxy sulfonate (GS-7Q) were used as hydrophilic chain extenders,a series of anionic waterborne polyurethanes (WPU)were synthesized and the effect of different hydrophilic chain extenders on the performances of WPU,such as the particle size of the final emulsion,water resistance,thermal stability and mechanical properties of film and so on were investigated in detail. The results indicate that reaction time of DMBA is 40% less than that of DMPA in the synthesis of polyurethane. The consume of GS-7Q is used less than DMPA to obtained a stable waterborne polyurethane,even 8%molar fraction of chain extenders account for all —OH of GS-7Q can maintain the stability of waterborne polyurethane. Particle size of WPUB is smaller than that of WPUP and low temperature flexibility is also superior to WPUP.The tensile strength of sulfonate waterborne polyurethane (WPUH) is four times that of carboxylic acid-based polyurethane. WPUH is superior to carboxylic acid type waterborne polyurethane in heat resistance,but low temperature flexibility is not as good as carboxylic acid type waterborne polyurethane (WPUB,WPUP).
关键词(KeyWords):
水性聚氨酯;二羟甲基丙酸;二羟甲基丁酸;二羟基磺酸;亲水扩链剂;性能
waterborne polyurethane;dihydroxy methyl propionic acid;dihydroxy methyl butyric acid;dihydroxy sulfonate;hydrophilic chain extender;performance
基金项目(Foundation): 十三五国家重点研发计划项目资助(2017YFB0308600)
作者(Author):
叶留留,张昕,范浩军,李成祥,黄军江
YE Liuliu,ZHANG Xin,FAN Haojun,LI Chengxiang,HUANG Junjiang
DOI: 10.13536/j.cnki.issn1001-6813.2018-011-003
参考文献(References):
- [1]许戈文.水性聚氨酯材料[M].北京:化学工业出版社,2007.
- [2]Yuse K,Guyomar D,Kanda M,et al.Development of largestrain and low-powered electro-active polymers(EAPs)using conductive fillers[J].Sensors and Actuators A:Physical,2011,165(2):147-154.
- [3]张伟,邢凤荣,李慧妮,等.一种新型非离子水性聚氨酯的合成[J].中国涂料,2012,27(4):44-48.
- [4]Dong J,Xu H,Zhang G,et al.Synthesis ofδlayered sodium disilicate with high framework stability[J].Tenside Surfactants Detergents,2004,41(6):274-277.
- [5]Saha S,Kocaefe D,Krause C,et al.Effect of titania and zinc oxide particles on acrylic polyurethane coating performance[J].Progress in Organic Coatings,2011,70(4):170-177.
- [6]张海龙,杨伟平,黄毅萍,等.新型离子水性聚氨酯的制备及性能研究[J].涂料工业,2011,41(6):46-50.
- [7]韩朝晖,王一中,余鼎声.扩链剂对水性聚氨酯乳液的影响[J].北京化工学报,2001,28(1):48.
- [8]林金河,孙亚飞.磺酸型亲水扩链剂及其制备方法[P]:CN,101240057.2008-8-13.
- [9]刘新迁,屠晓华,徐欣欣,等.高固含量羧酸/磺酸盐型水性聚氨酯乳液的合成[J].涂料工业,2013,43(3):17-20.
- [10]卫晓利,张发兴.用磺酸型亲水扩链剂制备高固含量聚氨酯乳液[J].合成橡胶工业,2010,33(1):29-32.
- [11]梁志彬.以均苯四甲酰四二乙醇胺为核的超支化聚酯的合成与表征[D].哈尔滨:东北林业大学,2011.
- [12]陈二霞.2,2-二羟甲基丁酸的制备研究[D].天津:天津大学,2009.
- [13]Lee D K,Yang Z D,Tsai H B,et al.Polyurethane dispersions derived from polycarbonatediols and m-di(2-isocyanatopropyl)benzene[J].Polymer Engineering&Science,2009,49(49):2 264-2 268.
- [14]侯薇,凌有道,陈龙,等.DMBA的合成及在水性聚氨酯中的应用研究[J].聚氨酯工业,2007,22(2):12-16.
- [15]曾俊,王武生,阮德礼,等.DMBA与DMPA聚氨酯乳液主要性能比较[J].皮革化工,1999(5):19-22.
- [16]D J David,H B Staley.Analytical chemist of polyurethanes[M].Wiley/Interscience,New York,1969.
- [17]Saalah S,Abdullah L C,Min M A,et al.Waterborne polyurethane dispersions synthesized from jatropha oil[J].Industrial Crops&Products,2015,64:194-200.
- [18]Tielemans M,Roose P,Groote P D,et al.Colloidal stability of surfactant-free radiation curable polyurethane dispersions[J].Progress in Organic Coatings,2006,55(2):128-136.
- [19]Bullermann J,Friebel S,Salthammer T,et al.Novel polyurethane dispersions based on renewable raw materials-stability studies by variations of DMPA content and degree of neutralization[J].Prog.Org.Coatings,2013,76(4):609-615.
- [20]袁腾,杨卓鸿,周显宏,等.羧酸盐/磺酸盐复合型WPU胶黏剂的制备与表征[J].化工学报,2015,66(10):4 258-4 267.
- [21]张发兴,卫晓利,肖忠良,等.亲水扩链剂含量对磺酸型高固含量聚氨酯乳液及胶膜性能的影响[J].塑料,2009,38(4):67-69.
- [22]赖小娟,王磊,杨燕.基于羧酸-磺酸盐的聚氨酯高分子表面活性剂的合成及性能研究[J].中国皮革,2011,40(17):19-21,25.
- [23]林璟,杨秋转,文秀芳,等.耐热性聚氨酯新型材料热稳定性研究进展[J].化工新型材料,2011,39(6):8-10.
- [24]张晓镭,高富堂,张哲,等.超细纤维合成革玻璃化温度影响因素的探讨[J].中国皮革,2005,34(7):29-31.
- [25]何曼君,陈维孝,董西侠.高分子物理-修订版[M].上海:复旦大学出版社,1990.
- 水性聚氨酯
- 二羟甲基丙酸
- 二羟甲基丁酸
- 二羟基磺酸
- 亲水扩链剂
- 性能
waterborne polyurethane - dihydroxy methyl propionic acid
- dihydroxy methyl butyric acid
- dihydroxy sulfonate
- hydrophilic chain extender
- performance