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Polynaphthylene : Development and Function of Precisely Nano-Structure Controlled Polymer

聚亚萘基：精密纳米结构控制聚合物的开发与功能

基本信息

批准号：
15350066
负责人：
HABAUE Shigeki
金额：
$ 9.73万
依托单位：
Yamagata University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

The asymmetric oxidative coupling polymerization (AOCP) leading to polybinaphthols in a highly cross-coupling selective or stereocontrolled manner was attained. The reaction of 2-naphthol and 3-hydroxy-2-naphthoate derivatives with the CuCl-(S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline) [(S)Phbox] catalyst proceeded in a highly cross-coupling selective manner with a moderate enantioselectivity. The AOCP of methyl 6,6'-dihydroxy-2,2'-binaphthalene-7-carboxylate with the CuCl-(S)Phbox catalyst gave a polymer with a high cross-coupling selectivity (head-to-tail regioselectivity). The copolymerization of 6,6'-dihydroxy-2,2'-binaphthalene and dihexyl 6,6'-dihydroxy-2,2'-binaphthalene-7,7'-dicarboxylate also afforded a polymer with the high cross-coupling selectivity, that is, a copolymer with a mainly alternating structure. Novel catalyst system, VOSO_4-(R)Phbox, for the AOCP of 2,3-dihydroxy-naphthalene (DHN) was developed. The enantioselectivity during the polymerization was evaluated to be 80% ee (S), a value much higher than that observed for the polymerizations with the copper(I)-based catalyst systems and the typical oxovanadium(IV) catalysts reported for the asymmetric oxidative homo-coupling producing the 1,1'-bi-2-naphthol derivatives. The OCP of DHN was also accomplished by the novel designed catalyst system, dinuclear copper(II) complexes. The polymerization proceeded under mild conditions to produce a polymer in a good yield.

通过不对称氧化偶联聚合（AOCP），以高度交叉偶联选择性或立体可控的方式合成了聚联萘酚。在CuCl-（S）-2，2 '-异亚丙基双（4-苯基-2-恶唑啉）[（S）Phbox]催化剂作用下，2-萘酚和3-羟基-2-萘甲酸酯衍生物的反应具有较高的交叉偶联选择性和中等的对映选择性.在CuCl-（S）Phbox催化剂作用下，6，6 '-二羟基-2，2'-联萘-7-甲酸甲酯的AOCP得到了具有高交叉偶联选择性（头-尾区域选择性）的聚合物。6，6 ′-二羟基-2，2 ′-联萘与6，6 ′-二羟基-2，2 ′-联萘-7，7 ′-二羧酸二己酯的共聚反应也得到了具有高交叉偶联选择性的聚合物，即具有主要交替结构的共聚物。开发了用于2，3-二羟基萘（DHN）AOCP的新型催化剂体系VOSO_4-（R）Phbox。聚合过程中的对映选择性被评估为80%ee（S），该值远高于用铜（I）基催化剂体系和报道的用于不对称氧化均偶联产生1，1 ′-联-2-萘酚衍生物的典型氧钒（IV）催化剂的聚合所观察到的值。设计了双核铜配合物催化体系，实现了DHN的OCP反应。聚合反应在温和条件下进行，以良好的产率生产聚合物。