端/侧氟烷基共改性聚氨酯杂化乳液的制备与性能  

Preparation and Performance Properties of Polyurethane Hybrid Latexes Co-modified by Terminal and Pendant Fluoroalkyl Segments

作　　者：赵婷 林云周 赵维甲 许伟 ZHAO Ting;LIN Yunzhou;ZHAO Weijia;XU Wei(Transfar Zhilian Co.Ltd.,Hangzhou 311215,China;College of Bioresources Chemical and Materials Engineering,Shaanxi University of Science and Technology,Xi'an 710021,China)

机构地区：[1]传化智联股份有限公司,浙江杭州311215 [2]陕西科技大学轻工科学与工程学院,陕西西安710021

出　　处：《皮革与化工》2021年第3期1-7,共7页Leather And Chemicals

基　　金：陕西省重点研发计划项目(2020GY-239)。

摘　　要：分别以二乙醇胺(DEOA)和甲基丙烯酸十二氟庚酯(G04)及γ-氨丙基三乙氧基硅烷(KH-550)和丙烯酸羟乙酯(HEA)间的迈克尔加成反应合成含氟扩链剂(DEFA)和含硅扩链剂(DESiA);再以异佛尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(CMA1044)、1,4-丁二醇(BDO)、2,2-二羟甲基丙酸(DMPA)、DEFA和DESiA为原料合成侧氟烷基改性聚氨酯预聚体(SiFPU);然后利用全氟己基乙醇(S104)单侧封端SiFPU制得端/侧氟烷基改性聚氨酯中间体(SiFPUF);最后利用季戊四醇(PE)交联,随后在中和乳化过程中加入不同用量的硅溶胶(SiO_(2))制得系列端/侧氟烷基共改性聚氨酯杂化乳液(FPUF-SiO_(2))。通过红外光谱(IR)、纳米粒度仪、热重分析仪(TGA)以及静态接触角测量仪等对其结构和性能进行研究。结果表明:所得产物具有预期的结构。FPUF-SiO_(2)乳液的粒径及FPUF-SiO_(2)胶膜的热稳定性随硅溶胶的引入量增大而增加;随硅溶胶的用量增加,FPUF-SiO_(2)胶膜的疏水性先增加而后略减小,FPUF-SiO_(2)-10胶膜的疏水性最好,静态接触角为119.8°,吸水率为2.49%;随硅溶胶用量的增加,FPUF-SiO_(2)胶膜的抗张强度先增大后减小,而断裂伸长率则一直减小。Fluroine-containing chain extender(DEFA)and silane-containing chain extender(DESiA)were prepared by Michael addition reaction between diethanolamine(DEOA)and dodecafluoroheptyl methacrylate(G04),γ-aminopropyl triethoxy silane(KH-550)and hydroxyethyl acrylate(HEA),respectively.Next,a series of modified polyurethane prepolymers by the fluoroalkyl side groups(SiFPU)were synthesized from isophorone diisocyanate(IPDI),Polybutylene adipate(CMA1044),1,4-butanediol(BDO),2,2-dihydroxymethylpropionic acid(DMPA),DEFA and DESiA.Then,the synergistically modified polyurethane intermediates by terminal and pendant fluoroalkyl segments(SiFPUF)were unilaterally blocked using perfluorohexyl ethanol(S104).Finally,pentaerythritol(PE)was used to react with SiFPUF and a series of the hybrid latexes were prepared by adding different amount of silica sols during the process of neutralizing and emulsifing operaions.The structure and performance properties of the resultants were characterized by IR,nanometer particle size meter,TGA,and contact angle measurements,etc.The results showed that the product had the due structure.With the increase of silica sols dosage,the average particle sizes of the FPUF-SiO_(2) latexes and thermal stability of the FPUF-SiO_(2) films were increased gradually.With the increase of silica sol dosage,the hydrophobicity of FPUF-SiO_(2) film increased first and then slightly decreased.The hydrophobicity of FPUF-SiO_(2)-10 film was the best with static contact angle of 119.8°and the water absorption of 2.49%.With the augment of silica sol content,tensile strength of the FPUF-SiO_(2) film firstly increased and then decreased,while the elongation at break always decreased.

关 键 词：聚氨酯杂化乳液 疏水性 氟硅聚合物 力学性能 

分 类 号：TS529.5[轻工技术与工程—皮革化学与工程]