Polyisoprene Bearing Dual Functionalized Mini-Blocky Chain-Ends Prepared from Neodymium-mediated Coordinative Chain Transfer Polymerizations

Wang, Weixin; Zhao, Wenpeng; Dong, Jing; Zhang, Hua-Qiang; Wang, Rui; Liu, Heng; Zhang, Xuequan

doi:10.1007/s10118-023-2953-z

Cited by 4 publications

(4 citation statements)

References 31 publications

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“…The authors suggested a sturdy kinetic model, which can cover the wide range of polyisoprene properties obtained by CTTP mechanism, applying various reaction conditions . The same catalytic system, Nd(versatate) 3 ( 22 )/Al( i -Bu) 2 H/Me 2 SiCl 2 , further enabled the CCTcoP of isoprene with polar comonomer (2-(ω-hydroxypropyl)-1,3-butadiene), that was protected by Al( i -Bu) 2 H, resulting in the formation of polyisoprenes containing hydroxyl side groups …”

Section: Coordinative Chain Transfer Polymerizationmentioning

confidence: 99%

“…33 The same catalytic system, Nd-(versatate) 3 (22)/Al(i-Bu) 2 H/Me 2 SiCl 2 , further enabled the CCTcoP of isoprene with polar comonomer (2-(ω-hydroxypropyl)-1,3-butadiene), that was protected by Al(i-Bu) 2 H, resulting in the formation of polyisoprenes containing hydroxyl side groups. 34 CCTcoP of 1,3-butadiene with isoprene was achieved, using well established catalytic system Nd(Oi-Pr) 3 (21, Figure 7)/i-Bu 2 AlH/Me 2 SiCl 2 . 35 CCTcoP showed living/character allowing precise tailoring of molar mass and monomer composition, while 4−6 polymer chains were generated per Nd center (Table 1), demonstrating reasonable atom economy.…”

Section: Coordinative Chain Transfer Polymerizationmentioning

confidence: 99%

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Coordinative Chain Transfer and Chain Shuttling Polymerization

Mundil,

Bravo,

Merle

et al. 2023

Chem. Rev.

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Coordinative chain transfer polymerization, CCTP, is a degenerative chain transfer polymerization process that has a wide range of applications. It allows a highly controlled synthesis of polyolefins, stereoregular polydienes, and stereoregular polystyrene, including (stereo)block as well as statistical copolymers thereof. It also shows a green character by allowing catalyst economy during the synthesis of such polymers. CCTP notably allows the end functionalization of both the commodity and stereoregular specialty polymers aforementionned, control of the composition of statistical copolymers without adjusting the feed, and quantitative formation of 1-alkenes from ethene. A one-pot one-step synthesis of the original multiblock microstructures and architectures by chain shuttling polymerization (CSP) is also an asset of CCTP. This methodology takes advantage of the simultaneous presence of two catalysts of different selectivity toward comonomers that produce blocks of different composition/microstructure, while still allowing the chain transfer. This affords the production of highly performant functional polymers, such as thermoplastic elastomers and adhesives, among others. This approach has been extended to cyclic esters' and ethers' ring-opening polymerization, providing new types of multiblock microstructure. The present Review provides the state of the art in the field with a focus on the last 10 years.

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Section: Coordinative Chain Transfer Polymerizationmentioning

confidence: 99%

Section: Coordinative Chain Transfer Polymerizationmentioning

confidence: 99%

Coordinative Chain Transfer and Chain Shuttling Polymerization

Mundil,

Bravo,

Merle

et al. 2023

Chem. Rev.

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“…still limits their widespread application. By contrast, a CCTP strategy can overcome such a shortage, because it demonstrates a highly atom-economic characteristic, that is, one Nd atom can produce multiple polydienyl chains, which therefore serves as an effective strategy to reduce the cost of a Nd-based precatalyst [27][28][29][30][31][32][33][34][35][36][37][38]. Based on this consideration, much of our recent research has looked to explore any factors that could have an influence on CCTP behaviors [28][29][30]34,36,39].…”

Section: Introductionmentioning

confidence: 99%

“…By contrast, a CCTP strategy can overcome such a shortage, because it demonstrates a highly atom-economic characteristic, that is, one Nd atom can produce multiple polydienyl chains, which therefore serves as an effective strategy to reduce the cost of a Nd-based precatalyst [27][28][29][30][31][32][33][34][35][36][37][38]. Based on this consideration, much of our recent research has looked to explore any factors that could have an influence on CCTP behaviors [28][29][30]34,36,39]. Of all the possible factors, heteroatom-based external donors are of great importance, because they are often used to disassociate the clustered structure of the neodymium precatalyst or to facilitate the formation of active species [40][41][42][43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Neodymium-Mediated Coordinative Chain Transfer Polymerization of Isoprene in the Presence of External Donors

Ding,

Fang,

Zhang

et al. 2023

Molecules

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Nd-based polydiene elastomers, including NdIR and NdBR, are regarded as indispensable key raw materials in preparing green tires with excellent performance capabilities, but their wide application is still limited by the relative higher cost of Nd precatalysts. Nd-mediated coordinative chain transfer polymerization (CCTP) of diene provides an effective strategy to reduce the precatalyst cost, because this method involves very high atom economy, i.e., each Nd molecule can generate multiple polymer chains. Nevertheless, all possible factors that could influence such CCTP behaviors are still mostly unexplored to date. In this report, the basic chemistry on the influence of external donors on the overall CCTP behaviors of isoprene was established for the first time. It was found that increasing the amount of external donors had a negative influence on the chain transfer efficiencies, resulting in gradually decreasing atom economies. Catalyst addition order studies revealed that the coordination of donors with cationic Nd active species, rather than alkylaluminium CTAs, contributed mostly to such decreased efficiencies. Moreover, it was found that when the ratio of donors and Nd compounds was higher than 1.0, the CCTP behaviors were corrupted, resulting in polymers with broad distributions, as well as resulting in low atom economies; nevertheless, when the ratio was lower than 0.5, the system still displayed CCTP characteristics, implying that the critical ratio for maintaining the CCTP was 0.5. Additionally, when such a ratio was 0.01, the high atom economy was almost the same as donor-free CCTP systems. Detailed kinetic studies at such a ratio demonstrated that the donor-contained system proceeded in a well-controlled manner, as concluded from the good linear relationship between the Mn of the PIps against the polymer yields, as well as the good linearity between the Mn against the (IP)/(Nd) ratios. Such maintained CCTP properties also allowed for seeding two-step polymerizations to prepare diblock copolymers with precisely controlled molecular weights. Expanding the types of donors to more phosphine, oxygen, and nitrogen containing compounds showed that they also affected the CCTP behaviors depending on their steric and electronic properties.

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Neodymium‐Mediated Coordinative Chain Transfer Homopolymerization of Bio‐Based Myrcene and Copolymerization With Butadiene and Isoprene

Li,

Zhang,

Wang

et al. 2024

J of Applied Polymer Sci

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Coordinative chain transfer polymerization (CCTP) has emerged as a powerful strategy in controlling the polymerization behavior of petroleum‐based diene monomers of butadiene (BD) and isoprene (Ip) and has been extensively studied in the past few years. Nevertheless, for the bio‐based terpene monomer of myrcene (My), its polymerization performance is rarely disclosed. Herein, by using a neodymium‐based Ziegler–Natta catalytic system of Nd(vers)3/Al(i‐Bu)2H/AlEt3/EASC, the CCTP of My was systematically evaluated. In order to concrete the CCTP characteristic, more evidence was provided, including its comprehensive comparison with the Ip system, kinetic studies, and seeding polymerization. All these results have led to the conclusion that, despite the long alkenyl substitute in the My monomer, CCTP properties were still demonstrated, albeit with relative lower chain transfer efficiency. Coordinative chain transfer copolymerization (CCTcoP) of My with BD or Ip was also studied, in which, similar to My homopolymerization, well‐controlled polymerization behaviors were also revealed that gave narrow polydispersities, high atom economies, as well as controlled copolymer compositions. Monomer reactivity ratio studies by Fineman‐Ross plot revealed that, for CCTcoP of My and BD, rMy and rBD were determined as 0.62 and 0.27, whereas for My/Ip system, rMy and rIp values were 0.74 and 0.24, respectively, implying both two systems preferred to undergo cross‐polymerization to give copolymers rather than homopolymer sequences.

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Polyisoprene Bearing Dual Functionalized Mini-Blocky Chain-Ends Prepared from Neodymium-mediated Coordinative Chain Transfer Polymerizations

Cited by 4 publications

References 31 publications

Coordinative Chain Transfer and Chain Shuttling Polymerization

Coordinative Chain Transfer and Chain Shuttling Polymerization

Neodymium-Mediated Coordinative Chain Transfer Polymerization of Isoprene in the Presence of External Donors

Neodymium‐Mediated Coordinative Chain Transfer Homopolymerization of Bio‐Based Myrcene and Copolymerization With Butadiene and Isoprene

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