乙烯与乙烯基五甲基二硅氧烷的配位共聚  

Coordination Copolymerization of Ethylene with Vinyl Pentamethyldisiloxane

作　　者：张丹枫[1] 高春旋 黄海林 ZHANG Danfeng;GAO Chunxuan;HUANG Hailin(Shanghai Key Laboratory of Advanced Polymer Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,上海200237

出　　处：《高等学校化学学报》2024年第9期148-156,共9页Chemical Journal of Chinese Universities

基　　金：上海市重点学科和重点实验室项目(批准号:B502,08DZ2230500)资助.

摘　　要：后过渡金属催化剂具有独特的“链行走”机理以及对极性基团的耐毒性等特点,可用于催化α-烯烃与极性单体共聚,得到结构与性能优异的功能化聚烯烃.本文以α-二亚胺镍(Ⅱ)配合物(C1~C6)为催化剂,在倍半乙基氯化铝(EASC)作用下,以乙烯和乙烯基五甲基二硅氧烷(VPMDSO)为单体进行配位共聚,制备了一系列共聚物.考察了VPMDSO单体浓度、催化剂用量、Al/Ni摩尔比、乙烯压力、聚合时间、溶剂以及催化剂结构对配位共聚反应的影响,得到了最优的聚合条件.通过核磁共振氢谱(1H NMR)、傅里叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、热失重分析(TGA)及接触角测试等表征了聚合物的微观结构、热稳定性、硅含量和表面性能.研究结果表明,α-二亚胺镍(Ⅱ)配合物催化活性可达1.26×10^(6)g·mol_(Ni)^(-1)·h^(-1),共聚物中硅含量为0.25%~0.87%(质量分数),与聚乙烯(PE)相比,共聚物的表面能降低、疏水性提高.Owing to the unique“chain walking”mechanism and tolerance of polar groups,post-transition metal catalysts can be utilized for the copolymerization ofα-olefin with polar monomers,resulting in the production of high-quality functional polyolefins with desired structure and properties.In this study,under the activation of ethylaluminum sesquichloride,the coordination copolymerization of ethylene with vinyl pentamethyldisiloxane(VPMDSO)usingα-diimine nickel(II)complexes(C1—C6)as catalysts was performed.The effects of VPMDSO monomer concentration,catalyst dosage,Al/Ni molar ratio,ethylene pressure,polymerization time,solvent,and catalyst structure on copolymerization were examined,and the optimal polymerization conditions were obtained.The microstructures,silicon content,thermal stability and surface energy of the copolymer were characterized by proton nuclear magnetic resonance(1H NMR),Fourier transform infrared(FTIR)spectroscopy,gel permeation chromatography(GPC)analysis,thermogravimetry analysis(TGA)and contact angle measurement.The results show that the copolymerization catalytic activity ofα-diimide nickel(II)complex could reach to 1.26×10^(6)g·mol_(Ni)^(-1)·h^(-1)while the silicon content range between 0.25%to 0.87%.Compared to polyethylene,the surface energy of the copolymer films decreased and the hydrophobicity increased.

关 键 词：含硅功能化聚烯烃 α-二亚胺镍(Ⅱ)催化剂 乙烯共聚 乙烯基五甲基二硅氧烷 

分 类 号：O631[理学—高分子化学]