Estimation of Kinetic Parameters for the Polar‐Modified Anionic Solution Copolymerization of 1,3‐Butadiene and Styrene

McIntosh, Winnette; Hamann, E.; Oertel, Ronald; Bartke, Michael

doi:10.1002/masy.200751312

Cited by 13 publications

(4 citation statements)

References 13 publications

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“…The fit of a numerical solution of the reaction equations has the advantage that not only the ratios of the rate constants can be obtained but also their individual values. This approach has rarely been used to determine kinetic parameters , but never in combination with in situ NMR which provides a solid database for short as well as long times.…”

Section: Introductionmentioning

confidence: 99%

Determination of the Compositional Profile for Tapered Copolymers of Ethylene Oxide and 1,2-Butylene Oxide by In-situ-NMR

et al. 2013

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In this work, 1 H NMR was used to examine the anionic copolymerization kinetics of ethylene oxide and 1,2butylene oxide. The in situ NMR technique allows monitoring the concentration profiles of both monomers simultaneously. A series of polymerization experiments at different monomer and initiator concentrations were done in order to determine the copolymerization rate constants. The data were evaluated by fitting the result of a numerical solution of the kinetic differential equations to the NMR data. This procedure allowed calculating all four rate constants, k EE , k EB , k BE , and k BB , individually instead of the commonly determined reactivity ratios r E = k EE /k EB and r B = k BB /k BE . The monomer incorporation into the copolymer chains is dominated by the different reactivities of the monomers, whereas the nature of the chain ends is of minor importance. In the system investigated ethylene oxide is about 6.5 times more reactive than 1,2butylene oxide. The compositional profiles of the final copolymers can be calculated from the time-resolved concentration profiles. If both monomers are present at the start of the polymerization the compositional profiles have a sigmoidal shape with one chain end containing mainly ethylene oxide and the other chain end being formed almost exclusively of butylene oxide units. However, with the knowledge of the copolymerization rate constants it is possible to realize other compositional profiles. If the reactor is first charged with ethylene oxide the addition rates of butylene oxide can be calculated in order to obtain any other arbitrarily chosen compositional profile.

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Section: Introductionmentioning

confidence: 99%

Determination of the Compositional Profile for Tapered Copolymers of Ethylene Oxide and 1,2-Butylene Oxide by In-situ-NMR

et al. 2013

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“…The literatures2–6 contain several reports on the preparation of random and tapered SSBR using polar modifiers that increase the vinyl microstructures with an increase T g of such copolymers. In these reports, the authors have used polar modifiers such as ethers, glymes, tetrahydrofurfuryl compounds, and N ‐ N ‐ N ′‐ N ′‐tetramethylethylenediamine 2, 7–11. These polar modifiers usually randomize the styrene but also increase the vinyl structure units in the 1,3‐butadiene position resulting in high T g of SSBR copolymers and a high degree of branching via chain metallation 12–15…”

Section: Introductionmentioning

confidence: 99%

Synthesis of random or tapered solution styrene–butadiene copolymers in the presence of sodium dodecylbenzene sulfonate as a polar modifier

Halasa

Jasiunas

Hsu

et al. 2012

J of Applied Polymer Sci

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Random or tapered solution styrene-butadiene copolymer (SSBR) is very difficult to prepare in an isothermal batch process without the use of polar modifiers because of the diverse reactivity ratios of the styrene and the butadiene in hydrocarbon solvents. In the presence of polar modifiers, the random SSBR can be synthesized by anionic living polymerization with the variety of microstructures, which results in the change of glass transition temperature (T g ). This article will discuss the use of sodium dodecylbenzene sulfonate as a polar modifier in isothermal batch process that controls the microstructure of the SSBR resulting in a random as well as tapered SSBR with low T g (À67 C to À80 C). The T g of SSBR was controlled by the styrene content rather than the microstructure of polybutadiene. Physical properties of SSBR compounding were discussed for tire tread applications.

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“…Initial conditions: McIntosh et al [12] determined the kinetic parameters for the anionic copolymerization of styrene/butadiene initiated with an alkyllithium compound in the presence of a high concentration of polar modifier, tetramethylethylenediamine, in a hydrocarbon solvent. Rate crossover copolymerization constants were determined for a SSBR with a styrene content of 25 (wt%/wt%).…”

Section: Reactor Simulation Modelmentioning

confidence: 99%

Modeling of batch production of high vinyl styrene/butadiene copolymers for high performance tires

Rodríguez-Guadarrama¹

2020

J of Applied Polymer Sci

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Mathematical modeling of batch production of high vinyl random styrene/butadiene copolymers in an industrial batch reactor was accomplished. Mass and energy balance equations were solved to model the nonisothermal anionic copolymerization of styrene/butadiene performed in an industrial batch reactor. The simulation model allows to predict the variation of the individual and global monomer conversion(s), temperature, pressure, and volume level of reactor with the time. Simulation model was used to determine the optimal polymerization conditions to maximize the production of a high vinyl random styrene/butadiene copolymer used in the manufacture of high performance tires.

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Estimation of Kinetic Parameters for the Polar‐Modified Anionic Solution Copolymerization of 1,3‐Butadiene and Styrene

Cited by 13 publications

References 13 publications

Determination of the Compositional Profile for Tapered Copolymers of Ethylene Oxide and 1,2-Butylene Oxide by In-situ-NMR

Determination of the Compositional Profile for Tapered Copolymers of Ethylene Oxide and 1,2-Butylene Oxide by In-situ-NMR

Synthesis of random or tapered solution styrene–butadiene copolymers in the presence of sodium dodecylbenzene sulfonate as a polar modifier

Modeling of batch production of high vinyl styrene/butadiene copolymers for high performance tires

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