Synthesis of Multifunctionalized Graft‐Type Polyolefin‐Based Elastomers with a High Utility Temperature

Abstract

A novel polyolefin‐based elastomer of polyolefin‐graft‐poly(t‐butylstyrene) is synthesized from styrene moieties via graft‐from anionic living polymerization. The afforded elastomer comprises a soft poly(ethylene‐t‐1‐hexene‐t‐divinylbenzene) segment and a hard poly(t‐butylstyrene) [P(t‐BS)] segment. The polymerization proceeds via complete lithiation of the pendent styrene groups (polyolefin elastomer) and subsequent graft anionic polymerization of 4‐tert‐butylstyrene (2000–10 000 g mol−1). The graft‐from living anionic polymerization controls the grafting size with excellent efficiency by increasing the monomer concentration. To introduce functional groups into the polymer chain‐end, vinyl isoprene units are introduced into the polyolefin‐graft‐poly(t‐butylstyrene) anion to form polyolefin‐graft‐[poly(t‐butylstyrene)‐block‐polyisoprene] via living block copolymerization. Subsequent graft chain‐end multicarboxyl functionalization via thiol‐ene “click” reactions introduces carboxyl groups into the [P(t‐BS)] graft chain‐end. The water contact angle of this multicarboxyl functionalized product exhibits a sharper decrement, which affects its hydrophilicity significantly. This process produces a novel, well‐defined functionalized graft‐type polyolefin‐based elastomer with a high utility temperature and excellent mechanical properties.

Enzymatic and Chemical Approaches for Post‐Polymerization Modifications of Diene Rubbers: Current state and Perspectives

“…Moreover, the thiol-ene reactions are frequently employed to introduce "clickable" functional groups in the polymer backbone. Rubber functionalization through thiol-ene click reactions also include modulation of the polymer hydrophobicity by introduction of polar groups, [142][143][144] introduction of inorganic materials, [63,145] improvement of the dispersion of nanomaterials, [137,146,147] polymer coating, [148] introduction of biomolecules, [149][150][151][152] synthesis of patterned microstructures, [153,154] linking of ionic liquids, [155] and introduction of dynamic hydrogen bonds for self-healing properties. [143,[156][157][158] Some biological applications include preparation of antibacterial materials, [159,160] surface preparation to protein adsorption [161] and synthesis of chiral materials by introduction of chiral amino acids.…”