FUNDAMENTAL STUDIES ON RADICAL POLYMERIZATION OF RODLIKE MACROMONOMERS

棒状大分子自由基聚合的基础研究

• 批准号: 16550105
• 负责人: KAWAGUCHI Seigo
• 金额: $ 2.37万
• 依托单位: Yamagata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550105/
• 关键词: RODLIKE POLYMER; MACROMONOMER; GRAFT POLYMER; REACTIVITY RATIO; LIVING RADICAL POLYMERIZATION; LIGHT SCATTERING; HELICAL POLYMER; SOLUTION PROPERTIES; 櫛形高分子; ポリイソシアナート; 共重合反応性; 小角X-線散乱

Styryl- and methacrylate-ended rodlike macromonomers consisting of poly(n-hexyl isocyanate) (VB-HIC-n and MA-HIC-n) with relatively narrow molecular weight distribution (Mw/Mn < 1.2) have successfully been prepared in CH_2Cl_2 at room temperature by living coordination polymerization of n-hexyl isocyanate (HIC) using 4-vinylbenzyloxy- and 2-methacrylate ethyloxy-dichloro(cyclopentadienyl)titanium(IV) as initiator, respectively. The radical copolymerization behavior of the rodlike macromonomers with corresponding low molecular weight monomers such as styrene or MMA has been studied and summarized as a function of degree of polymerization of HIC. In the copolymerization of VB-HIC-n with styrene, the apparent copolymerizabilities of the rodlike macromonomer (1/r_1) seem to be almost equivalent to the styrene, suggesting that the reactivity is mainly determined by the chemical reactivity of the ended double bond. On the other hand, in the copolymerization of MA-HIC-n macromonomers with MMA the value of 1/r_1 is almost constant for total monomer concentration and degree of polymerization but lower than that of MMA, most likely due to the incompativility between MA-HIC-n and PMMA propagating chain.Radical homopolymerization of the macromonomers affords novel well-defined comblike, cylindrical brushes consisting of the rods as a branched chain. The dimensional properties of the brushes have been studied by means of light scattering, SAXS, and viscometry. The molecular weight dependence of radius of gyration of the brushes in dilute solution is analyzed in terms of wormlike chain model and rationalized as a function of the side chain length of the rods. The Kuhn statistical length of the brushes is found to linearly increase with the rod length.

苯乙烯基和甲基丙烯酸酯封端的由聚（异氰酸正己酯）分子量分布相对较窄的（VB-HIC-n和MA-HIC-n）在CH_2Cl_2中，以4-乙烯基苄氧基-和2-甲基丙烯酸乙酯氧基-二氯为单体，通过活性配位聚合反应，成功地合成了分子量为1.2 ~ 1.2的聚（甲基丙烯酸甲酯）-N-异丙基苯甲酸酯（HIC）（3）钛（IV）为引发剂。研究了棒状大分子单体与苯乙烯、甲基丙烯酸甲酯等低分子量单体的自由基共聚合行为，总结了HIC聚合度对自由基共聚合行为的影响。在VB-HIC-n与苯乙烯的共聚反应中，棒状大分子单体的表观共聚反应速率（1/r_1）与苯乙烯的表观共聚反应速率几乎相等，表明其反应活性主要取决于末端双键的化学反应活性。另一方面，在MA-HIC-n大分子单体与MMA的共聚反应中，由于MA-HIC-n大分子单体与PMMA增长链之间的不相容性，其1/r_1值与单体浓度和聚合度基本保持不变，但低于MMA的1/r_1值，大分子单体的自由基均聚反应形成了由棒状支链组成的梳状圆柱刷。通过光散射、小角X射线散射和粘度计研究了刷的尺寸特性。的分子量的依赖性的旋转半径的刷在稀溶液中的蠕虫状链模型进行了分析，并合理化作为一个功能的侧链长度的杆。发现电刷的Kuhn统计长度随杆长线性增加。

项目成果

高分子電解質の水溶液物性

聚合物电解质的水溶液性质

• 发表时间: 2004
• 期刊: 高分子 58
• 作者: Goto;H;Akagi;K;H.Imahori;川口正剛
• 通讯作者: 川口正剛

基礎高分子科学

高分子基础科学

• 发表时间: 2006
• 作者: Tomonori;YAMADA;Naoki;TSUKAMOTO;Hironori;KAJI;Fumitaka;HORII;梶 弘典(分担執筆);梶 弘典(分担執筆);梶 弘典(分担執筆);梶 弘典 (分担執筆);梶 弘典 (分担執筆);梶 弘典(分担執筆);梶 弘典(分担執筆)
• 通讯作者: 梶 弘典(分担執筆)

(Review) Solution Properties of Polyelectrolyts

（综述）聚电解质的溶液性质

• 发表时间: 2004
• 期刊: Kobunshi 58
• 作者: A.V.Sesha Sainath;T.Inoue;Y.Hatakeyama;S.Kawaguchi;S.Kuriyama;K.Koyama;S.Kawaguchi
• 通讯作者: S.Kawaguchi

(Text Book) New Science of Dispersion and Emulsion and Their Advance in Their Application

（教材）分散乳化新科学及其应用进展

• 发表时间: 2006
• 作者: A.V.Sesha Sainath;T.Inoue;Y.Hatakeyama;S.Kawaguchi;S.Kuriyama;K.Koyama;S.Kawaguchi;S.Kawaguchi et al.
• 通讯作者: S.Kawaguchi et al.

高分子分析化学ハンドブック

高分子分析化学手册

• 作者: 川口正剛;他多数
• 通讯作者: 他多数