Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene

Fu, Tingting; Jiang, Lei; Sun, Hanyang; Hou, Zhaomin; Guo, Fang

doi:10.1039/d2py00290f

Cited by 4 publications

(3 citation statements)

References 56 publications

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“…These properties lead to exclusive formation of the alternating o ‐StPPh 2 ‐St copolymer (poly( o ‐StPPh 2 ‐ alt ‐St)) before all the o ‐StPPh 2 was consume and also leads to formation of alternating and block copolymers poly( o ‐StPPh 2 ‐ alt ‐St)‐ b ‐ s PS after all the o ‐StPPh 2 was consume (Scheme 1). [14–16,22,24,26] …”

Section: Resultsmentioning

confidence: 99%

Phosphine‐Functionalized Syndiotactic Polystyrenes: Synthesis and Application to Immobilization of Transition Metal Nanoparticle Catalysts

Jiang

Wang

Sun

et al. 2022

Chemistry A European J

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The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of high performance materials, but studies toward this goal have met with only limited success to date. The coordination polymerization of diphenylphosphinostyrene (p-StPPh 2 and o-StPPh 2 ) and its copolymerization with styrene (St) by (C 5 Me 4 SiMe 3 )Sc(CH 2 C 6 H 4 NMe 2 -o) 2 have been achieved for the first time to afford a new series of phosphine functionalized syndiotactic polystyrene. By the design of the polymer structure, the copolymer of o-StPPh 2 and St (poly(o-StPPh 2 -alt-St)-b-sPS) containing o-StPPh 2 and St atactic alternating copolymer block and syndiotactic polystyrene block (sPS) showed excellent thermal stability and chemical resistance. The simple combination of the triphenylphosphine and syndiotactic polystyrene realized the stable immobilization of metal nanoparticles to afford highly robust metal@poly(o-StPPh 2 -alt-St)-b-sPS nanocatalysts at high temperature and various atmospheres. The Cu@poly(o-StPPh 2 -alt-St)-b-sPS catalyst can serve as a highly efficient heterogeneous catalyst for the synthesis of quinoline derivatives by acceptorless dehydrogenative coupling of o-aminobenzylalcohol with ketones.

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Section: Resultsmentioning

confidence: 99%

Phosphine‐Functionalized Syndiotactic Polystyrenes: Synthesis and Application to Immobilization of Transition Metal Nanoparticle Catalysts

Jiang

Wang

Sun

et al. 2022

Chemistry A European J

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“…For example, the co-ordination copolymerization of polar diphenylphosphine styrene ( p -StPPh 2 ) and IP was conducted using a half-sandwich scandium (C 5 Me 4 SiMe 3 ) Sc (CH 2 C 6 H 4 NMe 2 - o ) 2 catalyst. Notably, p-StPPh 2 was incorporated into the polymer chains after the almost complete depletion of IP, resulting in the synthesis of phosphine-functionalized 1,4/3,4-isoprene-styrene block copolymers [ 21 ]. The recent study also presents examples of 3,4-PI- b -polycaprolactone block copolymers prepared through the sequential addition of hard ε -caprolactone to the living lutetium (Lu)−PI active species, followed by ring-opening polymerization [ 22 ].…”

Section: Introductionmentioning

confidence: 99%

Preparation and Characterization of Soft-Hard Block Copolymer of 3,4-IP-b-s-1,2-PBD Using a Robust Iron-Based Catalyst System

Zhao,

Xu,

et al. 2024

Polymers

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A series of well-defined diblock copolymers, namely, 3,4-polyisoprene-block-syndiotactic-1,2-polybutadiene (3,4-PI-b-s-1,2-PBD), with a soft–hard block sequence were synthesized via an in situ sequential polymerization process using a robust iron-based catalytic system Fe(acac)3/(isocyanoimino) triptenylphosphorane (IITP)/AliBu3. This catalyst exhibits vigorous activity and temperature tolerance, achieving a polymerization activity of 5.41 × 106 g mol(Fe)−1 h−1 at 70 °C with a [IP]/[Fe] ratio of 15,000. Moreover, the quasi-living polymerization characteristics of the catalyst were verified through kinetic experiments. The first-stage polymerization of isoprene (IP) is performed at 30 °C to give a soft 3,4-PI block, and then a quantitative amount of 1,3-butadiene was added in situ to the quasi-living polymerization system to produce a second hard s-1,2-PBD. The s-1,2-PBD segments in block copolymers display a rodlike morphology contrasting with the spherulitic morphology characteristic of s-1,2-PBD homopolymers. The precise tunability of the length of the soft and hard chain segments of these novel elastic materials with the feed ratio of IP and BD, endowing them with outstanding mechanical properties and excellent dynamic mechanical properties, which are expected to be promising high-performance rubber materials.

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“…Currently, in the research on polar monomer insertion reaction, a significant amount of successful experimental work has been carried out. Hou et al [22][23][24][25][26] demonstrated that cationic half-sandwich rare earth metal aminobenzyl complexes are highly effective in catalyzing the insertion reactions of halogenated or amino-containing styrene monomers. Cui et al [27][28][29][30][31] developed constrained-geometry-configuration rare-earth metal complexes that effectively catalyze the insertion reactions of methoxystyrene monomers, ethyl vinyl ether, and other polar monomers, showing high catalytic activity and stereoselectivity.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex

Wen,

Ren,

Zhang

et al. 2024

Inorganics

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This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG≠), respectively. The results indicate that ΔΔE and ΔG≠ can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation.

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Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene

Cited by 4 publications

References 56 publications

Phosphine‐Functionalized Syndiotactic Polystyrenes: Synthesis and Application to Immobilization of Transition Metal Nanoparticle Catalysts

Phosphine‐Functionalized Syndiotactic Polystyrenes: Synthesis and Application to Immobilization of Transition Metal Nanoparticle Catalysts

Preparation and Characterization of Soft-Hard Block Copolymer of 3,4-IP-b-s-1,2-PBD Using a Robust Iron-Based Catalyst System

Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex

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