阳离子聚硅氧烷杂化乳液在皮革超疏水整理中的应用

Application of Cationic Polysiloxane Hybrid Emulsion in Finishing of Superhydrophobic Leather

以四甲基氢氧化铵(THMA)为催化剂,八甲基环四硅氧烷(D4)、四甲基四乙烯基环四硅氧烷(D4Vi)和甲基三乙氧基硅烷(MTES)进行阴离子聚合制备羟基封端的乙烯侧基聚硅氧烷中间体;再使此中间体与含氢硅油进行硅氢化加成反应制备疏水性交联聚硅氧烷(JPDMS);然后,在复合乳化剂(AEO3/AEO9)作用下,聚氨丙基/甲基倍半硅氧烷纳米球(PAMSQ)与JPDMS反应,制得阳离子聚硅氧烷纳米杂化聚合物(PAMSQ-JPDMS)乳液。考察了引入的PAMSQ粒径和含量及PAMSQ-JPDMS乳液用量对处理后皮革(PAMSQ-JPDMS/Lea)性能的影响;并用XPS和FESEM分别研究了皮革表面化学组成和微观形貌。结果表明,产物具有预期的结构。当PAMSQ的平均粒径为128.7 nm,含量为15%,PAMSQ-JPDMS乳液固含量为1.2%时,处理后PAMSQ-JPDMS/Lea的疏水性最优,水静态接触角163.8°,水蒸气透过率达3074.01 g/(m2·day),耐干擦牢度优良。XPS和FESEM证实了皮革表面形成的一层致密硅膜和大量仿荷叶纳米凸起是超疏水表面构筑的内因。

Under the catalyst of tetramethylammonium hydroxide（THMA）, the present work performed the anionic ringopening polymerization of octamethylcyclotetrasiloxane（D4）, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinylcyclotetrasiloxane（D4 Vi）, and methyltriethoxysilane（MTES） to prepare hydroxyls-terminated polyvinylmethylsiloxane intermediate, which was then reacted with polymethylhydrosiloxane（PHMS） via hydrosilylation to produce the hydrophobic cross-linked polysiloxane（JPDMS）. Afterwards, a cationic polysiloxane hybrid emulsion was prepared via reaction of polyaminopropylmethylsilsesquioxane（PAMSQ） and JPDMS and AEO3/AEO9 used as composite emulsifiers. The effects of the PAMSQ particle size and the amount of PAMSQ-JPDMS emulsion on performance properties of the PAMSQ-JPDMS/Lea were investigated. Chemical composition and microstructure of the leather surface were studied by XPS and FESEM,respectively. FT-IR confirmed structures of the resultants. Results showed that PAMSQ-JPDMS/Lea had the best hydrophobicity, and water static contact angle was 163.8° when average particle size of PAMSQ was 128.7 nm, its content was 15% and solid content of the PAMSQ-JPDMS emulsion was 1.2%. Moreover, water vapor transmittance rate could still attain 3074.01 g/（m^2·day）. XPS and FESEM observation confirmed that construction of superhydrophobic leather surface was mainly rooted from a layer of dense silicon film and many lotus-like nano protuberances.