The monomer β‐myrcene, a renewable resource, was polymerized in cyclohexane using two different Ziegler‐Natta catalyst systems based on neodymium Nd(Oi‐Pr)3 and NdV3. The Nd(Oi‐Pr)3 was combined with [HNMe2Ph][B(C6F5)4] (or [CPh3][B(C6F5)4]) and Al(i‐Bu)3 (or Al(i‐Bu)2H). Next, the NdV3 was activated using Al(i‐Bu)3 and AlEt2Cl. Both catalyst systems exhibited high polymer yields near 100 % in the established reaction time, high polymer molecular masses, and broad molecular mass distributions. The catalyst systems gave an effective and stereospecific polymerization reaction of β‐myrcene providing high cis selectivity of 1,4‐polymyrcenes (> 92 %) with a glass transition temperature between −66 and −62 °C. The above‐mentioned features of resulting elastomers in conjunction with the polymer's molecular masses and molecular mass distributions proved to be sensitive to borane and alkylaluminum compounds molar ratios, [B]/[Nd] and [Al]/[Nd] using Nd(Oi‐Pr)3 and [Cl]/[Nd] and [Al]/[Nd] with NdV3.

In this work, we explore the statistical copolymerization of 1,3-butadiene with the terpenic monomers myrcene and farnesene, carried out via coordination polymerization using a neodymium-based ternary catalytic system.

This article proposes a method to produce bio-elastomer nanocomposites, based on polyfarnesene or polymyrcene, reinforced with surface-modified graphene oxide (GO).

The kinetics of isothermal anionic homopolymerization of ß–myrcene (MYR) and 4–methylstyrene (4MS) in cyclohexane, initiated by n–butyllithium was studied at different temperatures (55, 63, and 71 ° C). The kinetic information obtained from the homopolymerizations was used to estimate the parameters of the Eyring equation, ΔH‡= 84080 J/mol and ΔS‡= −21.9 J/mol·K for the MYR, and ΔH‡= 51250 J/mol and ΔS‡= −116.8 J/mol·K for the 4MS, to calculate the apparent propagation coefficients kpapp as a function of temperature. Finally, the parameters obtained for the Eyring equation were validated by applying them in a mathematical model representing the kinetics of nonisothermal (quasi‐adiabatic) polymerization experiments of MYR and 4MS. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2157–2165

Towards the development of eco-friendly alternatives of elastomeric materials, herein we report the synthesis of polyocimene via coordination polymerization.

This article proposes a process to prepare fully bio-based elastomer nanocomposites based on polyfarnesene and cellulose nanocrystals (CNC). To improve the compatibility of cellulose with the hydrophobic matrix of polyfarnesene, the surface of CNC was modified via plasma-induced polymerization, at different powers of the plasma generator, using a trans-β-farnesene monomer in the plasma reactor. The characteristic features of plasma surface-modified CNC have been corroborated by spectroscopic (XPS) and microscopic (AFM) analyses. Moreover, the cellulose nanocrystals modified at 150 W have been selected to reinforce polyfarnesene-based nanocomposites, synthesized via an in-situ coordination polymerization using a neodymium-based catalytic system. The effect of the different loading content of nanocrystals on the polymerization behavior, as well as on the rheological aspects, was evaluated. The increase in the storage modulus with the incorporation of superficially modified nanocrystals was demonstrated by rheological measurements and these materials exhibited better properties than those containing pristine cellulose nanocrystals. Moreover, we elucidate that the viscoelastic moduli of the elastomer nanocomposites are aligned with power–law model systems with characteristic relaxation time scales similar to commercial nanocomposites, also implying tunable mechanical properties. In this foreground, our findings have important implications in the development of fully bio-based nanocomposites in close competition with the commercial stock, thereby producing alternatives in favor of sustainable materials.

Triisobutylaluminum (TIBA), triethylaluminum (TEA), di-isobutylaluminum hydride (DIBAH) and methylaluminoxane (MAO) were evaluated as activators of neodymium chloride tripentanolate catalyst in order to investigate their influence over the catalytic activi-ty, macro- and microstructure, and thermal properties of of resulting polybutadienes. The higher catalytic activities were achieved by TEA and TIBA as co-catalysts, whereas TIBA and DIBAH led to the poly-mers with highest cis-1,4 structure content with 98.4 and 97.3% re-spectively. The catalytic activity was remarkably poor with MAO as co-catalyst, as well as low stereocontrol. Number average molecular weight values were observed in the range of 260 to 720 kg/mol.