Synthesis and properties investigation of hydroxyl functionalized polyisoprene prepared by cobalt catalyzed co-polymerization of isoprene and hydroxylmyrcene

Abstract

Controlled copolymerization of isoprene and hydroxylmyrcene afforded well-defined hydroxyl functionalized polyisoprene. Blends of functionalized polyisoprene/SiO2 displayed enhanced miscibility, and remarkable vulcanization and mechanical properties.

Anionic Polymerization of Terpene Monomers: New Options for Bio-Based Thermoplastic Elastomers

“…Terpenoids offer a possibility to overcome the lack of functional 1,3-diene monomers for the living anionic polymerization, caused by synthetic difficulties due to the high reactivity of the 1,3-diene entity. By protection of the hydroxyl groups of terpenoids like β-myrcenol with appropriate protective groups for the living anionic polymerization (e.g., silyl groups), a novel type of monomer is obtained. , Furthermore, in recent work myrcenol was copolymerized with β-myrcene or isoprene by using reversible addition–fragmentation chain transfer (RAFT) polymerization or neodymium- or cobalt-catalyst based polymerization. − …”

“…Furthermore, protecting functional groups is mandatory to prevent proton abstraction by the living carbanionic chain end, which results in immediate termination of the polymerization . Relying on coordination polymerization, there are several recent works by Gong et al in which a hydroxylmyrcene derivative (2-methyl-6-methyleneoct-7-en-2-ol) was copolymerized with β-myrcene or isoprene, applying neodymium or cobalt catalyst systems for polymerization. , Furthermore, Gong et al polymerized functionalized myrcene derivatives by RAFT polymerization, albeit with rather low monomer conversions of 40–80%. In comparison, complete monomer conversion is generally obtained by living anionic polymerization techniques .…”

Stereoregular Polymerization of Acyclic Terpenes

“…Further investigation by the same research group on the synthesis of cobalt complexes (49 and 50), supported by a 2oxazoline-pyridine (N,N) ligand bearing a labile 6-(di-tert-butylphosphine oxide) moiety (Figure 12), and on their ability to copolymerize I with M derivative 2-methyl-6-methyleneoct-7en-3-ol (M-OH) were disclosed. [66] In presence of an excess of AlEt 2 Cl and various masking agents such as MAO, AlEt 3 , Al i Bu 3 , Al i Bu 2 H, AlEt 2 Cl or Al i Bu 2 Cl, 49 and 50 ([AlEt 2 Cl]/[Co] = 300, 1-3 h, 30 °C, toluene) allowed the synthesis of a poly(I-co-M-OH) with M-OH incorporation from 4.4 mol% to 31.5 mol%, M n of 23-453 kg mol À 1 and Ð of 1.2-2.6 (cis-1,4 selectivity up to 72.5 %). The DSC thermograms of samples showed a single transition with T g values (from À 52.6 to 10.5 °C) increasing by increasing the incorporation of higher hydroxyl content.…”

cis-1,4 Selective Coordination Polymerization of 1,3-Butadiene and Copolymerization with Polar 2-(4-Methoxyphenyl)-1,3-butadiene by Acenaphthene-Based α-Diimine Cobalt Complexes Featuring Intra-Ligand π-π Stacking Interactions

“…Similar to polar polyolefin materials, functionalized Polymers 2021, 13, 3329 2 of 11 polydienes elastomers are also of great significance because the incorporated functional groups can greatly improve the compatibility between the polydienes matrix and reinforce polar fillers, such as carbon black, silica, etc., which therefore produces well-performing elastomers with good modulus, tensile strength, and other dynamic mechanical properties [13]. However, research n copolymerization with polar copolymers in this field o is very limited [14,15]. In the present research, a series copolymerizations of 1,3-butadiene with polar comonomer 2-(4-methoxyphenyl)-1,3-butadiene (2-MOPB) is conducted, and the corresponding catalytic performances and microstructures of the resulting copolymers are discussed.…”