Block copolymerization of allene derivatives with isocyanides by the coordination polymerization with π-allylnickel catalyst

✍ Scribed by Ikuyoshi Tomita; Masanori Taguchi; Koji Takagi; Takeshi Endo

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 733 KB
• Volume: 35
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(199702)35:3<431::aid-pola5>3.0.co;2-v

✦ Synopsis

A living block copolymerization of allene derivatives with 1-phenylethyI isocyanide (3) using [(ally l) NiOCOCF~]2 ( 1 ) is described. After complete polymerization of allene monomers such as rz-octyloxyallene (2A) with 1, further addition of 3 to the reaction system yielded the corresponding block copolymers in high yield. For instance, a block copolymer (4A, M" = 39,600, M. /M. = 1.20) was obtained in 96% yield by the addition of 3 ( [3]/[ 1 ] = 250) to the living solution of poly(n-octyloxy allene) (Mn = 14,400, MU/Mn = 1.03) prepared by the polymerization of 2A in the ratio of [2A]/[ 1 ] = 90. The resulting copolymer was a brownish orange gum or a solid, depending on the length of each of the segments. The volubility of the block copolymers could be controlled by the allene components. The copolymer of 2A with 3 having appropriate length of segments was soluble in rz-hexane, while that of methoxyethoxyethoxy allene (2D) with 3 was soluble in methanol. c 19% ,John Wiley & Sons, Inc.