聚酯/聚硅氧烷复合型自交联水性聚氨酯的制备及性能  

Preparation and performance of polyester/polysiloxane composite self-crosslinking waterborne polyurethane

作　　者：代文斗 范淑红[1] 王正祥[1] 宋婕 李佳新 DAI Wendou;FAN Shuhong;WANG Zhengxiang;SONG Jie;LI Jiaxin(School of Packaging&Materials Engineering,Hunan University of Technology,Zhuzhou 421007,China)

机构地区：[1]湖南工业大学包装与材料工程学院,湖南株洲421007

出　　处：《工程塑料应用》2024年第11期35-44,共10页Engineering Plastics Application

摘　　要：为了制备能够应用在双向拉伸聚丙烯(BOPP)和聚对苯二甲酸乙二酯(PET)薄膜上的水性油墨连接料。以乙二胺和双丙酮丙烯酰胺为原料,合成了N,N'-二双丙酮丙烯酰胺基乙二胺(DDA)扩链剂,然后以DDA、双羟甲基硅油(PDMS-OH)、聚碳酸酯二元醇、二羟甲基丙酸等原料,制备了一系列聚酯/聚硅氧烷复合型自交联水性聚氨酯(WPU)分散体,并制备了WPU固化膜(WPU-1~WPU-5)。通过傅里叶变换红外光谱、紫外可见分光光度计、差示扫描量热、热重、接触角、固体质量分数、吸水率、表面自由能以及拉伸性能等检测,对WPU进行了表征。结果表明,成功制备了DDA功能性扩链剂,以及含有聚硅氧烷特征官能团、酮羰基官能团及酮肼交联反应官能团的目标聚合物;聚硅氧烷链段的嵌入,以及酮羰基官能团质量分数的增加明显提高了WPU固化膜的相分离程度和交联度,相反固化膜的透明性逐渐变差。交联度的增加改善了固化膜的拉伸强度,降低了断裂伸长率,并且柔性聚硅氧烷的引入增大了固化膜的断裂伸长率;随着交联度的增加固化膜的玻璃化转变温度也随之增加,WPU固化膜均表现出较好的热稳定性;同时,固化膜的耐水性能增加,且含聚硅氧烷链段的WPU耐水性能更好;除WPU-1外,其余分散体均在BOPP和PET薄膜上表现出良好的黏附性能。当PDMS-OH质量分数为5%,DDA质量分数为9%时,WPU-4展现出最优异的综合性能:可见光透过率在70%以上;水接触角为68.32°,吸水率降低到5.62%;初始分解温度和失重为5%时分解温度分别达到131.2,220.7℃;拉伸强度达到21.27 MPa;WPU-4对BOPP和PET薄膜有较低的界面张力、较大的黏附能以及铺展系数,表现出优异的黏附性能,有望作为BOPP和PET薄膜印刷用WPU油墨的连接料。To prepare aqueous ink linkers suitable for application on BOPP(biaxially oriented polypropylene)films and PET(Polyethylene terephthalate)films.N,N'-dibis(acetone acrylamido)ethylenediamine(DDA)chain extender was synthesized using ethylenediamine and dibasic acetone acrylamide as raw materials.Subsequently,a series of polyester/polysiloxane composite selfcrosslinking waterborne polyurethane(WPU)dispersions were prepared using DDA,bis(hydroxymethyl)silicone oil(PDMS-OH),polycarbonate diol,and dihydroxymethylpropionic acid as raw materials.The cured films of WPU(WPU-1~WPU-5)were also fabricated and characterized by Fourier transform infrared spectrometer,ultraviolet-visible spectrophotometer,differential scanning calorimeter,thermogravimetry,contact angle,solid mass fraction,water absorption,surface free energy,and tensile properties.The results indicate that DDA functional chain extender and target polymers containing polysiloxane functional groups,ketocarbonyl functional groups,and ketohydrazide cross-linking reaction functional groups are successfully synthesized.Furthermore,the incorporation of polysiloxane chain segments and the increase of the content of ketocarbonyl functional groups significantly enhance the phase separation and cross-linking degree of cured WPU films.However,this result in a gradual reduction in the transparency of the cured films.The increase in the degree of cross-linking improve the tensile strength of the cured films while decreasing the elongation at break.Conversely,the introduction of flexible polysiloxane enhance the elongation at break of the cured films.Additionally,the glass transition temperature of the cured films increase with the degree of cross-linking,leading to improved thermal stability for all polyurethane cured films.Simultaneously,the water resistance of the cured films is improved,with WPU containing polysiloxane chain segments demonstrating superior water resistance.Excluding WPU-1,the remaining WPUs exhibite better water resistance compared to polyurethanes without

关 键 词：扩链剂 双羟甲基硅油 自交联 改性 水性聚氨酯 

分 类 号：TQ322.44[化学工程—合成树脂塑料工业]