Polymerization of 1,3‐Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component

Friebe, Lars; Windisch, Heike; Nuyken, Oskar; Obrecht, Werner

doi:10.1081/ma-120028204

Cited by 50 publications

(52 citation statements)

References 15 publications

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“…From Table 2, an increase in the TEAL content in the system also decreased the Mw of the Co/Nd-BR since the TEAL was also used as a chain transfer agent for polymerization [17,18]. For the MWD of the Co/Nd-BR, the previous literature [19] revealed that the alkyl aluminum containing hydride moiety such as diisobutyl aluminumhydride (DIBAH) had high efficiency to control the molar mass of BR than an alkyl aluminum such as triiobutylaluminum (TIBA). This implied that the use of TEAL in the Co/Nd-based catalytic system might not effectively control the MWD of BR.…”

Section: Resultsmentioning

confidence: 98%

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Chatarsa

Prasassarakich

Rempel

et al. 2014

Polymer Engineering & Sci

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Among Ziegler‐Natta catalysts used for 1,3‐butadiene (1,3‐BD) polymerization, the advantage of a neodymium (Nd)‐based catalyst is that it provides butadiene rubber (BR) with a high content of cis−1,4 configuration and a low amount of vinyl−1,2 units. Whereas, a cobalt (Co)‐based catalyst can produce BR with a low content of trans−1,4 configuration. Thus, this research was aimed to prepare BR containing a high content of cis−1,4 configuration with low amounts of both trans−1,4 and vinyl−1,2 units using a combination of Nd‐ and Co‐based Ziegler/Natta catalysts with triethyl aluminum (TEAL) and diethyl aluminum chloride (DEAC) acting as a co‐catalyst and a chlorinating agent, respectively. The effects of the molar Co/Nd ratio, TEAL concentration, DEAC loading, 1,3‐BD content, solvent type, and reaction temperature on % conversion, microstructures, molecular weight, and molecular weight distribution of the obtained BR (Co/Nd‐BR) were evaluated. The Co/Nd‐BR having >97% of cis−1,4 configuration, <2% of trans−1,4 structure, and <1% of vinyl−1,2 unit with >80% conversion was achieved when 3.01 M of 1,3‐BD concentration was treated in a toluene/cyclohexane mixture (7/3 [w/w]). The Co/Nd‐BR exhibited no gel formation with high mechanical performance, which was equivalent to commercial BR produced from a Nd‐based catalyst system. POLYM. ENG. SCI., 55:14–21, 2015. © 2014 Society of Plastics Engineers

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Section: Resultsmentioning

confidence: 98%

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Chatarsa

Prasassarakich

Rempel

et al. 2014

Polymer Engineering & Sci

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“…In Ziegler-type systems (NdV 3 /AliBu 3 /Et 3 Al 2 Cl 3 ), increasing AliBu 3 reduces the polybutadiene molecular weight and the dispersity. 42 Reversible exchange of chains between neodymium and aluminum, more generally known as coordinative chain transfer polymerization (CCTP), 43 is proposed to account for these trends. 8,42 However, Landis and co-workers have pointed out that a hafnium-catalyzed α-olefin polymerization system, which includes a similar molecular weight regulation as in the Ziegler-type butadiene polymerization, is also effectively described by an irreversible chain transfer model (see below).…”

Section: Synthesis and Characterization Of Zwitterionic Lanthanide DImentioning

confidence: 99%

Zwitterionic Trivalent (Alkyl)lanthanide Complexes in Ziegler-Type Butadiene Polymerization

et al. 2018

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The organolanthanide complexes Ln{C(SiHMe 2) 3 } 3 (Ln = La, 1a; Ce, 1b; Pr, 1c; Nd, 1d) react with one or two equiv. of B(C 6 F 5) 3 to yield the well-defined zwitterionic species Ln{C(SiHMe 2) 3 } 2 HB(C 6 F 5) 3 (Ln = La, 2a; Ce, 2b; Pr, 2c; Nd, 2d) or LnC(SiHMe 2) 3 {HB(C 6 F 5) 3 } 2 (Ln = La, 3a; Ce, 3b; Pr, 3c; Nd, 3d), respectively. These complexes are shown to contain labile, bridging Si-H⇀Ln and oF ->Ln interactions based upon the observation of low one-bond silicon-hydrogen coupling constants (1 J SiH) in 1 H NMR spectra of 2a and 3a, the presence of one set of C 6 F 5 signals in the 19 F NMR spectra of 2a and 3a, the detection of only m-F and p-F resonances in 19 F NMR spectra of 2b-d and 3b-d, two ν SiH bands in IR spectra of 2a-d, and X-ray crystallography analyses of 2b and 3d. In addition, a hexametertoluene molecule is coordinated to neodymium in 3d. Reactions of 1a and (AlMe 3) 2 yield labile adducts with an approximate stoichiometry of 1a•3AlMe 3. Exchange between free and bound AlMe 3 groups was observed in EXSY NMR experiments with greater than 3 equiv. of AlMe 3. Compounds 2a-d and 3a-d, in the presence of AliBu 3 , are precatalysts for polymerization of butadiene. The neodymium alkyl 3d has the highest activity of the series, and its performance is consistent with chain transfer reactions with AliBu 3 .

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“…by replacing the numerical approximations presented in Equation (36) into Equation (44)(45)(46). The molecular weight averages (M n and M w ), the polydispersity (IP), the average branching frequencies per chain (B N ), and the average branching frequencies per monomer unit (B d ) can be calculated with the help of the moments as: …”

Section: Numerical Implementationmentioning

confidence: 99%

“…This is in accordance with published material, because the existence of as many as five different active sites has already been reported for this type of catalyst system. [37,[44][45][46] Based on the previous discussion and on the main effect analysis performed by Ferreira et al, [43] the kinetic parameters presented in Table 3 were estimated for a dual catalyst system, using the experimental data presented by Ferreira et al [43] The two active sites used for simulation were fundamental for proper description of the MWDs of the obtained Figure 9. Short CBD for polyethylenes produced with the nickel based catalyst.…”

Section: Mwd Of Polybutadienes Produced With a Neodymium Catalystmentioning

confidence: 99%

“…This can certainly be regarded as an indirect evidence of multiple site formation, as discussed in the literature. [37,[44][45][46] The presence of multiple active sites depends on the cocatalysts concentrations and on the catalyst/cocatalyst ratio in a complex manner, as it is believed that distinct catalyst sites can be formed through a series of reaction steps involving the neodymium and the alkylaluminum compounds. It is important to emphasize that improvement of model performance could not be obtained with manipulation of the kinetic constants, as described in the kinetic mechanism.…”

Section: Mwd Of Polybutadienes Produced With a Neodymium Catalystmentioning

confidence: 99%

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Mathematical Modeling of MWD and CBD in Polymerizations with Macromonomer Reincorporation and Chain Running

Ferreira

Nele

Costa

et al. 2010

Macro Theory & Simulations

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A model is proposed for the computation of MWD and CBD when the simultaneous formation of LCB and SCB is possible. LCBs are produced through incorporation of unsaturated polymer chains. SCBs are produced through chain running as a series of spontaneous chain transfer and reinsertion steps. The model was solved numerically with the help of orthogonal adaptive collocation techniques. It is shown that ten collocation points are sufficient to provide accurate numerical solutions for the evolution of MWDs and CBDs. The model can be used successfully to represent experimental data available for ethylene polymerizations performed with nickel catalysts and butadiene polymerizations performed with neodymium catalysts.

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Polymerization of 1,3‐Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component

Cited by 50 publications

References 15 publications

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Zwitterionic Trivalent (Alkyl)lanthanide Complexes in Ziegler-Type Butadiene Polymerization

Mathematical Modeling of MWD and CBD in Polymerizations with Macromonomer Reincorporation and Chain Running

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