Highly efficient cis-1,4 polymerisation of isoprene using simple homoleptic amido rare earth-based catalysts

Martins, Nuno M. R.; Bonnet, Fanny; Visseaux, Marc

doi:10.1016/j.polymer.2014.07.056

Cited by 27 publications

(22 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The growing interest in rare-earth metal-based catalytic systems for the polymerization of 1,3-conjugated dienes, such as 1,3-butadiene, isoprene and terpenes, to produce high-performance rubbers is due to their high catalytic activity and a high degree of stereoregulation [1][2][3][4][5]. The polymers obtained using these types of catalytic systems are characterized by broad molecular weight distributions, as a result of the formation of catalytic species with different activity, and also because of the irreversibility of chain transfer reactions during the polymerization.…”

Section: Introductionmentioning

confidence: 99%

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Ubaldo-Alarcón¹,

Soriano‐Corral²,

Córdova³

et al. 2022

Polymers

View full text Add to dashboard Cite

The interest in the Coordinative Chain Transfer Polymerization (CCTP) of a family of naturally occurring hydrocarbon monomers, namely terpenes, for the production of high-performance rubbers is increasing year by year. In this work, the synthesis of poly(β-myrcene) via CCTP is introduced, using neodymium versatate (NdV3), diisobutylaluminum hydrade (DIBAH) as the catalytic system and dimethyldichlorosilane (Me2SiCl2) as the activator. A bimodal distribution in the GPC signal reveals the presence of two populations at low conversions, attributable to dormants (arising from reversible chain transfer reactions) and dead chains (arising from termination and irreversible chain transfer reactions); a unimodal distribution is generated at medium and high conversions, corresponding to the dominant species, the dormant chains. Additionally, a mathematical kinetic model was developed based on the Method of Moments to study a set of selected experiments: ([β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1, 885:1:2:1, and 533:1:2:1). In order to estimate the kinetic rate constant of the systems, a minimization of the sum of squared errors (SSE) between the model predicted values and the experimental measurements was carried out, resulting in an excellent fit. A set of the Arrhenius parameters were estimated for the ratio [β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1 in a temperature range between 50 to 70 °C. While the end-group functionality (EGF) was predominantly preserved as the ratio [β-myrcene]0:[NdV3]0 was decreased, higher catalytic activity was obtained with a high ratio.

show abstract

Section: Introductionmentioning

confidence: 99%

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Ubaldo-Alarcón¹,

Soriano‐Corral²,

Córdova³

et al. 2022

Polymers

View full text Add to dashboard Cite

show abstract

“…Neodymium‐based catalytic systems have been successfully applied in isoprene polymerization due to their high activity and high selectivity . Neodymium carboxylates are usually employed in industry; from the academic point of view, however, neodymium alkyls are assumed to be the sensitive intermediates in the catalytic process . Besides the neodymium carboxylates mentioned above, neodymium alkoxylates also initiate the polymerization of 1,3‐butadiene, and, activated with AlEt 3 , lead to cis ‐1,4‐stereospecific polymers ( ca 96%) with high molecular weights ( ca 10 5 g mol −1 ) .…”

Section: Introductionmentioning

confidence: 99%

Highly cis‐1,4‐selective polymerization of isoprene achieved using neodymium chloride 8‐hydroxyquinolines

Wang

Qian

Zhang

et al. 2015

Polymer International

View full text Add to dashboard Cite

Isoprene polymerization was conducted in the cis-1,4-selective manner by combining neodymium chloride with 8-hydroxyquinoline derivatives and activating the system with triisobutylaluminium. The neodymium-based complex pre-catalysts with 8-hydroxyquinoline derivatives were synthesized and characterized as well as the molecular structure of a representative complex using single-crystal X-ray diffraction. All complexes exhibited high activity and stereospecificity (up to 97.3%) towards isoprene polymers with high molecular weight (10 5 g mol −1 ). The Al/Nd and isoprene/Nd molar ratios, reaction temperature and influence of 8-hydroxyquinoline substituents were investigated for correlations with catalytic activities and molecular weights of the polyisoprenes obtained.

show abstract

“…Rare-earth metal-based catalysts have been reported for their efficiency to polymerize 1,3-dienes with high catalytic activities, yielding polymers with good control in both their stereoregularity and molecular weight characteristics. [10][11][12][13][14] The potential of such catalytic systems has lately been extended to the polymerization of unconventional bio-terpenes, such as b-myrcene, 15,16 b-farnesene, 17,18 and (E)-a-ocimene, 18,19 obtained from renewable resources. Although the aforesaid monomers produce bio-elastomers with low carbon footprint and acceptable performance, they fall short when compared to conventional petroleum-based materials in terms of cost-efficiency and performance.…”

Section: Introductionmentioning

confidence: 99%

Bio-elastomers based on polyocimene synthesizedviacoordination polymerization using neodymium-based catalytic systems

et al. 2020

View full text Add to dashboard Cite

show abstract

Highly efficient cis-1,4 polymerisation of isoprene using simple homoleptic amido rare earth-based catalysts

Cited by 27 publications

References 36 publications

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling

Highly cis‐1,4‐selective polymerization of isoprene achieved using neodymium chloride 8‐hydroxyquinolines

Bio-elastomers based on polyocimene synthesizedviacoordination polymerization using neodymium-based catalytic systems

Contact Info

Product

Resources

About