Synthesis of silylated polyolefin with well-defined chain structure and the application to a surface modifier

具有明确链结构的硅烷化聚烯烃的合成及其在表面改性剂中的应用

• 批准号: 03555194
• 负责人: NAKAHAMA Seiichi
• 金额: $ 11.01万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555194/
• 关键词: Block Copolymer; Alkoxysilylated Butadiene; Electronic Microscopic Observation; Silica; Silylated Polyolefin; Anionic Living Polymerization; Surface Modification; アルコキシシリル化ブタジエン

The block copolymer containing 1,4-polybutadiene and 1,4-poly(2-triisopropoxysilyl-1,3-butadiene)segments was synthesized by living anionic polymerization. The anionic living polyisoprene initiated with sec butyllityium in heptane was allowed to react with potassium tertbutoxide in THF to transform the propagating species. The sequential polymerization of 2-triisopropoxysilyl-1,3-butadiene with the resulting living polyisoprene to afford the block copolymer with desired well-defined chain structure. The hydrogenation of the block copolymer with Wilkinson catalyst gave the block polyolefin containing silyl groups. The small silica particle(200-600 nm diameter)was prepared by sol-gel method, which was modified with the silyated polyolefin and mixed with linear low density polyethylene(LLDPE) at180ﾟC.The fractured surface of the blend was observed by scanning electronic microscopy. The surface of the silica bead was completely covered with polymer. On the contrary, the fractured surface of the blend of the unmodified silica bead and LLDPE had clear beads, which did not adhered to the polymer matrix. These results suggest that the silylated polyolefin is fixed onto the silica surface tyrough siloxane linkage and that polyethylene segment attached to the surface is compatible with LLDPE.

采用活性阴离子聚合法制备了含1，4-聚丁二烯和1，4-poly(2-triisopropoxysilyl-1，3-butadiene)segments的嵌段共聚物。以仲丁基锂在正庚烷中引发的阴离子活性聚异戊二烯在四氢呋喃中与叔丁醇钾反应，转化繁殖物种。将2-三异丙氧基硅基-1，3-丁二烯与活性聚异戊二烯进行顺序聚合，得到具有良好链结构的嵌段共聚物。用Wilkinson催化剂对嵌段共聚物进行加氢反应，制得含硅基的嵌段聚烯烃。采用溶胶凝胶法制备了直径为2 0 0~6 0 0 nm的小二氧化硅粒子，用硅烷化聚烯烃对其进行改性，并在180ﾟC下与线性低密度聚乙烯共混，用扫描电子显微镜观察了共混物的断口形貌。二氧化硅微珠的表面完全被聚合物覆盖。反之，未改性白炭黑微珠与LLDPE共混物的断口表面有明显的珠粒，不附着在聚合物基质上。这些结果表明，硅烷化聚烯烃通过硅氧烷键固定在白炭黑表面，附着在表面的聚乙烯链段与LLDPE是相容的。

项目成果

K.Tsuda: "Protection and Polymerization of Functional Monomers.19.Synthesis of Well-Defined Poly(ethynylstyrene)s by Means of Anionic Living Polymerization of(Trimethylsilyl)ethynylstyrene" Macromolecules. 26. 6985-6991 (1993)

K.Tsuda：“功能单体的保护和聚合。19.通过（三甲基甲硅烷基）乙炔基苯乙烯的阴离子活性聚合来合成明确的聚（乙炔基苯乙烯）”大分子。

Hideharu Mori: "Protection and Polymerization of Functional Monomers.21.Anionic Living Polymerization of(2,2-Dimethyl-1,3-dioxolan-4-yl)methyl" Macromolecules. 27. 35-39 (1994)

Hideharu Mori：“功能单体的保护和聚合。21.(2,2-二甲基-1,3-二氧戊环-4-基)甲基”大分子的阴离子活性聚合。

市原祥次: "熱重量分析による高分子の熱分解挙動の解析" 高分子論文集. 000-000 (1994)

Shoji Ichihara：“通过热重分析分析聚合物的热分解行为”聚合物论文 000-000 (1994)。

中浜 精一: "高性能ポリマ-アロイ" 丸善, 349 (1991)

中滨诚一：“高性能聚合物合金”Maruzen，349（1991）

K.Takenaka: "Free-Radical Polymerization of 2-Silyl-substituted 1,3-Butadienes" Makromol.Chem.,. 193. 1943-1953 (1992)

K.Takenaka：“2-甲硅烷基取代的 1,3-丁二烯的自由基聚合”Makromol.Chem.,。