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Dienes and diamondoids: poly(2‐[1‐adamantyl]‐1,3‐butadiene) and random copolymers with isoprene via redox‐emulsion polymerization and their hydrogenation
Author(s) -
Hill Connor J.,
McDonald Armando G.,
Roll Mark F.
Publication year - 2021
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.50711
Subject(s) - isoprene , comonomer , polymer chemistry , polymerization , cationic polymerization , monomer , copolymer , emulsion polymerization , diene , materials science , polymer , glass transition , chemistry , organic chemistry , natural rubber
A novel route to adamantane substituted diene copolymers is demonstrated using emulsion polymerization, with an improved monomer synthesis. Heterogenous dehydration of 2‐(1‐adamantyl)‐3‐buten‐2‐ol using Amberlyst®‐15 cationic exchange resin at ambient temperature gave 2‐(1‐adamantyl)‐1,3‐butadiene ( 1 ) in excellent yield and presents an attractive alternative monomer synthesis route. Emulsion polymerization of 1 and mixtures of 1 and isoprene was carried out at room temperature using redox pair, hydroperoxide initiator. All poly( 1 ) and poly( 1 ‐ ran ‐isoprene) samples were soluble in common organic solvents and exhibited high 1,4‐microstructure. A continuous increase in glass transition temperature from −63 to 172°C was observed by increasing the ratio of 1 in the comonomer feed of poly( 1 ‐ ran ‐isoprene), and T g values were in good agreement with the Fox equation. After complete hydrogenation to poly(1‐vinyladamantane‐ alt ‐ethylene‐ ran ‐propylene‐ alt ‐ethylene), a continuous increase in T g was observed from −55 to 152°C. The high solubility and improved access to 2‐(1‐adamantyl)‐1,3‐butadiene opens the door to exploration of diene polymers with enhanced high temperature properties.