硅烷改性聚氨酯树脂的制备及性能研究  

Preparation and properties of silane modified polyurethane resin

作　　者：郭志强[1] 吴林志[1] 武金笔 刘兴江[1] Guo Zhiqiang;Wu Linzhi;Wu Jinbi;Liu Xingjiang(School of Chemistry and Molecular Engineering,Zhengzhou University,Zhengzhou 450001,Henan,China;Henan Duonaibao New Material Co.,Ltd.,Jiaozuo 454100,Henan,China)

机构地区：[1]郑州大学化学学院,河南郑州450001 [2]河南多耐保新材料有限公司,河南焦作454100

出　　处：《中国胶粘剂》2024年第12期8-17,56,共11页China Adhesives

基　　金：郑州大学青年人才企业合作创新团队项目。

摘　　要：以聚四氢呋喃二元醇(PTMEG-1000)、二苯基甲烷二异氰酸酯(MDI-50)、二(3-三甲氧基甲硅烷基丙基)胺(TMSPMA,牌号GX-1170)和N-苯基-3-氨基丙基三甲氧基硅烷(牌号Y-9669)为原料,以二月桂酸二丁基锡(DBTDL)为催化剂,对聚氨酯(PU)预聚体进行封端处理,制备了一系列硅烷改性聚氨酯(SPU)树脂。在室温下进行湿气固化,并对固化后的弹性体性能进行结构和性能表征。研究结果表明:(1)结构表征说明氨基硅烷接枝到了PU体系上,证实了SPU树脂的成功合成。(2)通过对固化后的弹性体进行力学测试发现,SPU-40的力学强度最高。对固化后的SPU-40和PU弹性体进行热重分析表明,SPU-40的失重50%温度比PU提高了约32.6℃,表明硅烷的引入使得PU的热稳定性得到了提升。(3)随着Y-9669含量的增加,聚合物分子规整性逐渐降低,分子间缠绕加剧,玻璃化转变温度(T_(g))会逐渐升高。(4)随着Y-9669比例的增大,SPU树脂的黏度在逐渐升高,邵A硬度逐渐降低。(5)在硅氧烷进行交联固化过程中,仍然有一部分Si—OH裸露在聚合物表面上,并没有达到完全的交联。(6)随着GX-1170硅烷比例含量的减少,SPU弹性体表面的水接触角逐渐减小,逐渐由疏水变为亲水性。(7)硅烷加入量对于最终SPU弹性体的吸水率会有影响,进一步影响其表干时间及其固化时间。(8)由于GX-1170的氨基硅烷具有规整性,而Y-9669的氨基硅烷却不具有规整性,随着Y-9669的氨基硅烷增加,进一步增加不规整性,衍射峰逐渐变宽,因此SPU薄膜的软硬段条理性差,难以结晶。(9)随着GX-1170硅烷比例的下降,SPU弹性体的拉伸强度呈现出先上升后下降的趋势,而断裂伸长率是逐渐上升的。最佳条件下SPU-40弹性体的力学强度高达8.67MPa,断裂伸长率为75.1%。(10)在湿热老化条件下,透射率没有明显的下降,但是其力学强度在逐渐下降。经过硅烷改性后的聚氨酯保留了本身良好的耐酸碱性能,A series of silane modified polyurethane(SPU)resins were prepared by using polytetramethylene glycol(PTMEG-1000),diphenylmethane diisocyanate(MDI-50),bis(3-trimethoxysilylpropyl)amine(TMSPMA,brand GX-1170),and N-phenyl-3-aminopropyltrimethoxysilane(brand Y-9669)as raw materials,and dibutyltin dilaurate(DBTDL)as a catalyst for the end-capping treatment of polyurethane(PU)prepolymers.It was cured by moisture at room temperature,and the structure and properties of the cured elastomer were characterized.The research results showed that,(1)The structural characterization indicated that aminosilane was grafted onto the PU system,confirming the successful synthesis of SPU resin.(2)Through mechanical testing of the cured elastomer,it was found that SPU-40 had the highest mechanical strength.Thermogravimetric analysis of the cured SPU-40 and PU elastomers showed that the 50%weight loss temperature of SPU-40 was about 32.6℃higher than that of PU,indicating that the introduction of silane improved the thermal stability of PU.(3)As the content of Y-9669 increased,the regularity of polymer molecules gradually decreased,intermolecular entanglement intensified,and the glass transition temperature(T_(g))gradually increased.(4)As the proportion of Y-9669 increased,the viscosity of SPU resin gradually increased and the Shore A hardness gradually decreased.(5)During the crosslinking and curing process of siloxane,there was still a portion of Si—OH exposed on the surface of the polymer,and complete crosslinking has not been achieved.(6)As the proportion of GX-1170 silane decreased,the water contact angle on the surface of SPU elastomer gradually decreased,gradually changing from hydrophobic to hydrophilic.(7)The amount of silane added had an impact on the water absorption rate of the final SPU elastomer,further affecting its surface drying time and curing time.(8)Due to the regularity of the amino silane in GX-1170,while the amino silane in Y-9669 did not have regularity,as the amino silane in Y-9669 increased,the irregularity f

关 键 词：聚氨酯 硅烷改性 湿气固化 

分 类 号：TQ433.43[化学工程]