Synthesis of Regioblock Polybutadiene with CoCl<sub>2</sub>-Based Catalyst via Reversible Coordination of Lewis Base

Cai, Zhengguo; Shinzawa, Masahito; Nakayama, Yuushou; Shiono, Takeshi

doi:10.1021/ma901886b

Cited by 42 publications

(36 citation statements)

References 11 publications

(10 reference statements)

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“…This result showed randomly distributed trans and cis sequences in the obtained polymer and the occurrence of interconversion between cis-specific and trans-specific active species via disproportionation (Figure 3). The increase of cis-specificity along with the Al/Mg ratio showed that the neutral active species with trans-specificity was gradually converted to a cationic cis-specific one by the increasing amount of dMMAO, similar to Nd(BH 4 ) 3 (thf) 3 -catalyzed isoprene polymerization previously reported. 3).…”

Section: Resultssupporting

confidence: 80%

“…This result showed randomly distributed trans and cis sequences in the obtained polymer and the occurrence of interconversion between cis-specific and trans-specific active species via disproportionation (Figure Scheme 1. Synthesis of stereoblock polyisoprene using Nd(BH 4 ) 3 (thf) 3 as a catalyst precursor. dMMAO: trialkylaluminum-depleted modified methylaluminoxane.…”

Section: Resultsmentioning

confidence: 99%

“…Butadiene solution in toluene were purchased from Tokyo Chemical Industry Co. Ltd. (Tokyo, Japan) and used as received. Nd(BH 4 ) 3 (thf) 3 and Cp*Nd(BH 4 ) 2 (thf) 2 was prepared according to the literature and used immediately after the preparation [19]. Other materials were used without further purifications.…”

Section: Generalmentioning

confidence: 99%

“…Some synthetic examples of stereoblock polymers are reported using Ni [2], Co [3,4] and Fe [5] catalysts with additional ligands, or rare-earth metal catalysts with chain transfer reagent [6]. However, these stereoblock polymers always contain atactic blocks or short stereoregular blocks consist of less than 10 repeating units.…”

Section: Introductionmentioning

confidence: 99%

“…This is based on the idea that a simple neodymium catalyst system such as Nd(BH 4 ) 3 (thf) 3 /Bu 2 Mg and (C 3 H 5 )NdCl 2 /methylaluminoxane (MAO) can promote trans-and cis-specific polymerization of isoprene and butadiene in a living manner, respectively ( Figure 1) [8][9][10][11][12][13][14]. The stereospecificity is basically strongly affected by the metal charge; namely, neutral systems give trans-polymer and cationic systems give cis-polymer, and the change of the metal charge from neutral to cationic during the polymerization with Lewis acid gave stereodiblock polymer.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

et al. 2017

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Butadiene polymerization, in both a highly cis-and trans-specific manner, was achieved by using a Cp*Nd(BH 4 ) 2 (thf) 2 -Bu 2 Mg system as an initiator. The cis-/trans-ratio can be tuned by the amount of trialkylaluminum-depleted modified methylaluminoxane (dMMAO). The cis-regularity of the polymer was much higher than those obtained by Nd(BH 4 ) 3 (thf) 3 . The molecular weight of cis-regular polymer was increased according to polymer yield, showing that there was no termination or chain transfer reaction during the polymerization. Synthesis of stereodiblock polybutadiene, which showed a high melting temperature (T m ) compared with stereodiblock polyisoprene, was also performed by the addition dMMAO during the polymerization.

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Section: Resultssupporting

confidence: 80%

“…This result showed randomly distributed trans and cis sequences in the obtained polymer and the occurrence of interconversion between cis-specific and trans-specific active species via disproportionation (Figure Scheme 1. Synthesis of stereoblock polyisoprene using Nd(BH 4 ) 3 (thf) 3 as a catalyst precursor. dMMAO: trialkylaluminum-depleted modified methylaluminoxane.…”

Section: Resultsmentioning

confidence: 99%

Section: Generalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

et al. 2017

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Polymerization of isoprene, myrcene, and butadiene catalyzed by cobalt complexes supported with 2‐acetyl‐6‐iminopyridine ligand

You,

Chen,

Gong

2023

Applied Organom Chemis

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Cobalt complexes carrying 2‐acetyl‐6‐iminopyridine ligand are synthesized and characterized. Single‐crystal X‐ray diffraction reveals the cobalt ion is chelated with two nitrogen atoms and an acetyl oxygen atom additionally. A significant prolonged Co–O distance (2.3960(57) Å) is found, indicative of a labile character. Activated by diethylchloroaluminum, all complexes show high conversion rates for isoprene and myrcene polymerizations, affording cis‐1,4/3,4 regulated 1,3‐diene polymers. The polymerization of butadiene, interestingly, gives predominant cis‐1,4 selectivity (>99.2%) with moderate activity. The substituent at ortho‐position of arylimine plays a minor role in controlling activity and selectivity as well as the molecular weight of the resultant polymers. The properties of resultant poly(1,3‐diene)s are stable even in a wide range of operational conditions, such as [Al]/[Co] varied from 20 to 600, temperature spanning from 0°C to 60°C, and monomer–catalyst ratio from 1000 to 4000. These additional benefits of minimum fluctuation in catalytic performances may be suitable for industrial polymerization process.

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Synthesis of a Multiblock Copolymer of cis‐1,4‐Polybutadiene and Poly(3‐buten‐1‐ol)

Tanaka

Kasai

Shinzawa

et al. 2014

Macro Chemistry & Physics

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Synthesis of a multiblock copolymer composed of cis‐1,4‐polybutadiene (PBd) segments and poly(3‐buten‐1‐ol) segments is performed via successive hydroboration and oxidation of cis‐1,4/syn‐1,2‐multiblock PBd. The ratio of functionalization can be controlled by changing the amount of the borane reagent. The obtained polymer shows two distinctive glass‐transition temperatures, which correspond to the cis‐1,4‐PBd block and the poly(3‐buten‐1‐ol) block. These thermal properties clearly show that the functionalization of the PBd proceeds keeping the elastic property derived from cis‐1,4 segment.

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Synthesis of Regioblock Polybutadiene with CoCl₂-Based Catalyst via Reversible Coordination of Lewis Base

Cited by 42 publications

References 11 publications

Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

Polymerization of isoprene, myrcene, and butadiene catalyzed by cobalt complexes supported with 2‐acetyl‐6‐iminopyridine ligand

Synthesis of a Multiblock Copolymer of cis‐1,4‐Polybutadiene and Poly(3‐buten‐1‐ol)

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Synthesis of Regioblock Polybutadiene with CoCl2-Based Catalyst via Reversible Coordination of Lewis Base

Cited by 42 publications

References 11 publications

Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst

Polymerization of isoprene, myrcene, and butadiene catalyzed by cobalt complexes supported with 2‐acetyl‐6‐iminopyridine ligand

Synthesis of a Multiblock Copolymer of cis‐1,4‐Polybutadiene and Poly(3‐buten‐1‐ol)

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Synthesis of Regioblock Polybutadiene with CoCl₂-Based Catalyst via Reversible Coordination of Lewis Base