Surface Structure and Dynamics of Functional Block Copolymer

功能嵌段共聚物的表面结构和动力学

• 批准号: 03044059
• 负责人: NAKAHAMA Seiichi
• 金额: $ 4.8万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 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-03044059/
• 关键词: Hydrophobic-hydrophilic block copolymer; Surface structure; Anionic living polymerization; Contact angle; Transmission electron microscopy; XPS; Surface reconstruction; SIMS

Hydrophilic-hydrophobic block copolymers, poly(2,3-dihydroxypropyl methacrylate) (PDIMA)-b-polystyrene, PDIMA-b-poly(4-octylstyrene), and PDIMA-b-polyisoprene, have been synthesized by anionic living polymerization. The weight % of PDIMA was around 50 %. The surface structures of the block copolymers were investigated by transmission electron miroscopic(TEM) observation, XPS and contact angle(CA) measurements.The specimens for TEM observation were cast from 3% DMF or THF/methanol solution. The dry and wet samples were fixed and stained with OsO4 vapor solution, respectively. The sample embedded in epoxy resin were cut into the ultra thin sections. The specimens for XPS and CA measurements were prepared by spin-coating onto a glass disk. After treatment of the film under various conditions, as-cast, soaking in water, and annealing at 100^ﾟC in air after soaking in water, CA of water was measured.TEM observation of the as-cast film of PDIMA-b-polystyrene showed that the outermost surface was completely covered with polystyrene layer. After soaking in water for 30 min, the top layer of polystyrene was completely disappeared to lead hydrophilic surface. In the case of PDIMA-b-polyisoprene, the hydrated morphology was also observed inside of the film. The XPS measurement gave the consistent results with those of the TEM observation. The contact angle measurement was successful for the PDIMA-b-polystyrene film, but not for the PDIMA-b-poly(4-octylstyrene) and PDIMA-b-polyisoprene films. This is because of rapid rearrangement of the surface structure at the water-polymer interface.

采用阴离子活性聚合法合成了聚甲基丙烯酸2，3-二羟丙酯（PDIMA）-b-聚苯乙烯、PDIMA-b-聚（4-辛基苯乙烯）和PDIMA-b-聚异戊二烯等亲水-疏水嵌段共聚物。PDIMA的重量%为约50%。用透射电子显微镜（TEM）、XPS和接触角（CA）研究了嵌段共聚物的表面结构。干燥和湿样品分别用OsO 4蒸气溶液固定和染色。将环氧树脂包埋的样品切成超薄切片。用于XPS和CA测量的样品通过旋涂到玻璃盘上来制备。在各种条件下对膜进行处理后，如铸态、在水中浸泡以及在水中浸泡后在空气中在100 ℃下退火，测量水的CA。PDIMA-b-聚苯乙烯铸态膜的TEM观察表明，最外表面完全被聚苯乙烯层覆盖。在水中浸泡30 min后，聚苯乙烯的顶层完全消失，导致亲水表面。在PDIMA-b-聚异戊二烯的情况下，在膜内部也观察到水合形态。XPS测量结果与TEM观察结果一致。PDIMA-b-聚苯乙烯膜的接触角测量是成功的，但PDIMA-b-聚（4-辛基苯乙烯）和PDIMA-b-聚异戊二烯膜的接触角测量不是成功的。这是因为在水-聚合物界面处的表面结构的快速重排。

项目成果

K.Iwasaki: "Morphology of blends of poly(3-(2-propenyl)aniline-b-styrene-b-3-(2-propenyl)aniline)with,-dicarboxy poly(ethylene oxide)" New Polymeric Mater.4. 53-70 (1993)

K.Iwasaki：“聚(3-(2-丙烯基)苯胺-b-苯乙烯-b-3-(2-丙烯基)苯胺)与,-二羧基聚(环氧乙烷)共混物的形态”新聚合物材料.4

T.Ishizone,J.Tsuchiya,A.Hirao,S.Nakahama: "Anionic Polymerization of Monomers Containing Functional Groups.4.Anionic Living Polymerization of N,N-Dialkyl-4-vinylbenzenesulfonamides" Macromolecules. 25. 4840-4847 (1992)

T.Ishizone，J.Tsuchiya，A.Hirao，S.Nakahama：“含有官能团的单体的阴离子聚合。4.N,N-二烷基-4-乙烯基苯磺酰胺的阴离子活性聚合”大分子。

H.Mori: "Protection and Polymerization of Functional Monomers.23.Synthesis of Well-Defined Poly-(2-hydroxyethyl methacrylate)by Means of Anionic Living Polymerization of Protected Monomers" Macromolecular Chemistry and Physics. (1994)

H.Mori：“功能单体的保护和聚合。23.通过受保护单体的阴离子活性聚合来合成明确的聚-(2-羟乙基甲基丙烯酸酯)”高分子化学和物理。

中浜 精一 他共著: "高分子機能材料シリーズ1 高分子の分成と反応(1)" 共立出版, 554 (1992)

中滨诚一等合着：《高分子功能材料系列1高分子组成与反应(1)》共立出版，554(1992)

S.Nakahama: "Synthesis of telechelic and block polymers with functional groups and formation of the ordered structures in the blends of the polymers" New Functionality Materials. C. 307-314 (1993)

S.Nakahama：“具有官能团的遥爪和嵌段聚合物的合成以及聚合物共混物中有序结构的形成”新功能材料。