Copolymerization of Butadiene with Styrene by Nd(vers)3–Al(i‐Bu)3–CHCl3Catalyst System

Zhang, Qisheng; Ni, Xufeng; Shen, Zhiquan

doi:10.1081/ma-120027175

Cited by 8 publications

(2 citation statements)

References 24 publications

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“…In addition, the PS content showed a tendency to decrease with increasing the [Al]/[Nd] ratio. The decrease in conversion and PS content due to an increase in [Al]/[Nd] ratio from 20 to 30 is in agreement with Zhang et al [20] who carried out the copolymerization of 1,3-butadiene with styrene in equimolar concentrations using the catalyst system NdV 3 /TIBA/CHCl 3 . Such behavior was attributed to a change of active site, which might only contain active sites for the polymerization of 1,3-butadiene.…”

Section: Effect Of [Al]/[nd] and [Cl]/[nd]supporting

confidence: 90%

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

León¹,

Soriano‐Corral²,

Enríquez-Medrano³

et al. 2016

International Journal of Polymer Science

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In a first step, 1,3-butadiene was selectively polymerized at 60°C in styrene as solvent using NdV3/DIBAH/EASC as the catalyst system. The catalyst system activation process, the addition order of monomers and catalyst components, and the molar ratios [Al]/[Nd] and [Cl]/[Nd] were studied. The catalyst system allowed the selective 1,3-butadiene polymerization, reaching conversions between 57.5 and 88.1% with low polystyrene contents in the order of 6.3 to 15.4%. Molecular weights ranging from 39,000 to 150,000 g/mol were obtained, while cis-1,4 content was found in the interval of 94.4 to 96.4%. On the other hand, the glass transition temperatures of synthesized materials were established in the range of −101.9 to −107.4°C, explained by the presence of polystyrene segments in the polybutadiene chains; in the same sense, the polybutadienes did not show the typical melting endotherm of high cis-polybutadienes. In a second step, the resulting styrene/high cis-1,4 polybutadiene solutions were used to synthesize ABS (adding a fraction of acrylonitrile monomer) and HIPS via in situ bulk polymerizations and the results were discussed in terms of morphological development, molecular parameters, dynamical mechanical behavior, and mechanical properties.

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Section: Effect Of [Al]/[nd] and [Cl]/[nd]supporting

confidence: 90%

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

León¹,

Soriano‐Corral²,

Enríquez-Medrano³

et al. 2016

International Journal of Polymer Science

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“…Phenyl functionalized butadienes, which can be polymerized through ionic, emulsion, or Ziegler–Natta type methods, allow for synthesis of ES copolymers with greater microstructural control by eliminating statistical comonomer distributions compared to SBR. − However, utilization of these polymerization methods to synthesize ES copolymers also presents challenges. Namely, this polymerization method often results in 1,2 or 3,4 addition rather than 1,4 (especially with 1-phenylbutadiene), which limits the full scope of microstructural possibilities. − ,,,− Furthermore, phenyl functionalized butadiene polymers obtained that contain 3,4 addition can undergo intramolecular cyclization. ,,, High content of 1,4 cis addition (>99%) of 2-phenylbutadiene has been obtained with emulsion polymerization and with certain Ziegler–Natta catalysts; however, material properties of the hydrogenated polymer were not investigated. , …”

Section: Introductionmentioning

confidence: 99%

Viscoelastic, Mechanical, and Glasstomeric Properties of Precision Polyolefins Containing a Phenyl Branch at Every Five Carbons

Kieber

Neary

Kennemur

2018

Ind. Eng. Chem. Res.

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Mechanical and viscoelastic properties of precision polyolefins, poly(4-phenylcyclopentene) (P4PCP) and its hydrogenated analog (H2-P4PCP) containing atactic phenyl branches at exactly every five carbons along the backbone are explored. Both materials are amorphous with a glass transition temperature of ∼17 ± 3 °C. Rheological investigations determined that P4PCP has an entanglement molar mass (M e = 10.0 kg mol–1) much higher and closer to polystyrene than H2-P4PCP (M e = 3.6 kg mol–1). Both materials have elastomeric and shape memory properties at ambient temperatures, which were further explored through strain hysteresis measurements. H2-P4PCP has an elastic recovery of ∼95% at max strain values up to 500% as determined by uniaxial tensile testing. Time–temperature superposition analysis, Williams–Landel–Ferry constants, and further mechanical analysis are discussed and compared to previously reported ethylene–styrene copolymers of similar phenyl-branch content within the microstructure.

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Styrene–butadiene block copolymer with high cis‐1,4 microstructure

Zhu

Zhao

et al. 2007

J of Applied Polymer Sci

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ABSTRACT:The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i-Bu) 3 (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, 1 H NMR, 13 C NMR, and TEM. The results show that styrenebutadiene diblock copolymer with high cis-1,4 microstructure of butadiene units ( 97 mol %) was synthesized. The cis-selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase-separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS-b-cis-PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis-PB blends.

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Copolymerization of Butadiene with Styrene by Nd(vers)₃–Al(i‐Bu)₃–CHCl₃Catalyst System

Cited by 8 publications

References 24 publications

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

Viscoelastic, Mechanical, and Glasstomeric Properties of Precision Polyolefins Containing a Phenyl Branch at Every Five Carbons

Styrene–butadiene block copolymer with high cis‐1,4 microstructure

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