Binary copolymerization of 4-methyl-1,3-pentadiene with styrene, butadiene and isoprene catalysed by a titanium [OSSO]-type catalyst

Abstract

Binary copolymerization of 4‐methyl‐1,3‐pentadiene (4MPD) with styrene, butadiene and isoprene promoted by the titanium complex dichloro{1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐bis(2‐phenyl‐2‐propyl)phenoxy]}titanium activated by methylaluminoxane is reported. All the copolymers are obtained in a wide range of composition and the molecular weight distributions obtained from gel permeation chromatographic analysis of the copolymers are coherent with the materials being copolymeric in nature. The copolymer microstructure was fully elucidated by means of 1H NMR and 13C NMR spectroscopy. Differential scanning calorimetry shows an increase of glass transition temperature (Tg) with the amount of 4MPD in the copolymers with butadiene and isoprene, while in the copolymers with styrene Tg is increased on increasing the amount of styrene. © 2016 Society of Chemical Industry

Metal Catalyzed Polymerization: From Stereoregular Poly(α‐olefins) to Tailor‐Made Biodegradable/Biorenewable Polymers and Copolymers

“…[62] 4MPD was also copolymerized with S, B and I in the presence of catalyst 31/MAO obtaining copolymers with preferentially alternating microstructure. [63]…”

Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization

“…The tacticity of the PS sequences was not quantified, probably due to the fact that both complexes mostly afforded short PS homosequences. Using the same catalyst 21b , styrene and 4-methyl-1,3-pentadiene ((4Me)PD) were efficiently copolymerized [ 67 , 68 ]. Both diblock iPS- b -i(1,2)P(4Me)PD and nearly alternated iPS- co -i(1,2)P(4Me)PD copolymers were obtained.…”

Synthesis of amphiphilic diblock copolymers of isotactic polystyrene-block-isotactic poly(p-hydroxystyrene) using a titanium complex with an [OSSO]-type bis(phenolate) ligand and sequential monomer addition

“…46 Styrene stereospecic living polymerization with other olens such as butadiene, 4-methyl-1,3-pentadiene (4MPD), 46 4-methylstyrene (PMS), 47 and 4-tert-butylstyrene (PTBS) 47 was carried out by using [OSSO] titanium complexes having two cumyl bulky groups in the ortho positions. [46][47][48] The mechanism of isospecic styrene polymerization was depicted in Scheme 2. The active species were formed from the dichloro complex as a result of methyl exchange between aluminum and titanium.…”