Functionalization at the central position of vinyl polymer chains: highly associable multipoint hydrogen bonds for complementary self-assemblies.
This paper deals with the precision introduction of a multiple hydrogen-bonding site of a high association constant at the central position of a vinyl polymer chain for complementary self-assemblies. The interactive site consists of an array of hydrogen donors (D) and acceptors (A) to induce a multiple and highly associable interaction with a complementary counterpart. A bifunctional initiator (Cl-DADDAD-Cl) for metal-catalyzed living radical polymerization is thus designed and synthesized to embed a "Hamilton receptor" (DADDAD) between two terminal chlorides (Cl). In the presence of a ruthenium complex, the dichloride gives controlled polymers (Cl∼∼∼DADDAD∼∼∼Cl, ∼ ∼ ∼: polymer backbone) of narrow molecular weight distributions (Mw/Mn < 1.2) from common monomers such as styrene and methyl methacrylate (MMA). The receptor-decorated polystyrene recognizes complementary associable molecules and polymers carrying an ADADA unit (ADADA-Anthracene and ADADA-PMMA) to form self-assemblies where the association constant is as high as K(ass) ≈ 8000 m(-1).
Department of Polymer Chemistry, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
Sang-Ho
SH
Lee
Makoto
M
Ouchi
Mitsuo
M
Sawamoto
D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D006860:Hydrogen Bonding; D020366:Methylmethacrylate / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D011137:Polystyrenes / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry; D020058:Styrene / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry*
D056831:Coordination Complexes; D011108:Polymers; D011137:Polystyrenes; D014753:Vinyl Compounds; D020366:Methylmethacrylate; D020058:Styrene; D012428:Ruthenium
bifunctional initiator; hydrogen bond; living radical polymerization; polystyrene; supramolecule