Bulk Polymerization Kinetics of Hydroxy Terminated Polybutadiene and Toluene Diisocyanate with Infrared Spectroscopy

Heri Budi Wibowo; Widhi Cahyo; Ratih Sanggra

doi:10.22146/ijc.24807

Bulk Polymerization Kinetics of Hydroxy Terminated Polybutadiene and Toluene Diisocyanate with Infrared Spectroscopy

https://doi.org/10.22146/ijc.24807

Heri Budi Wibowo^(1*), Widhi Cahyo⁽²⁾, Ratih Sanggra⁽³⁾

(1) Indonesian National Institute of Aeronautics and Space - LAPAN, Jl. Pemuda Persil No. 1, Jakarta 13220, Indonesia
(2) Indonesian National Institute of Aeronautics and Space - LAPAN, Jl. Pemuda Persil No. 1, Jakarta 13220, Indonesia
(3) Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No. 2 Kampus UGM, Yogyakarta 55281, Indonesia
(*) Corresponding Author

Abstract

A study on bulk polymerization kinetics of HTPB (Hydroxy Terminated Polybutadiene) and TDI (Toluene Diisocyanate) with infrared (IR) spectroscopy has been conducted. The investigations included the molar ratio of 2,4-TDI to 2,6-TDI isomers, the initial molar ratio of isocyanate group to a hydroxyl group, and the reaction temperature. The polymerization rate constant was calculated based on the decrease rate of TDI. Kinetics model had been evaluated through the following reaction steps: (1) 2,4-urethane production, (2) 2,6-urethane production, (3) the reaction between 2,4-urethane and the isocyanate group of 2,4-TDI, (4) the reaction between 2,4-urethane and the isocyanate group of 2,4-TDI, (5) the reaction between 2,6-urethane and isocyanate group of 2,4-TDI, and (6) the reaction between 2,6-urethane and the isocyanate group of 2,6-TDI. Those reaction steps were assumed to be the first order reaction with the reaction rate constants k₁, k₂, k₃, k₄, k₅, and k₆, respectively. The reaction rate constants obtained at molar ratio of 2,4-TDI to 2,6-TDI of 80:20, isocyanate group to hydroxyl group (R_NCO/OH) initial molar ratio of 1:1, and reaction temperature of 40 °C were 6.2 × 10^-5, 5.8 × 10^-5, 3.1 × 10^-5, 2.8 × 10^-5, and 2.5 × 10^-5 L.mole^-1.min^-1 for k₁, k₂, k₃, k₄, k₅, and k₆, respectively, with the activation energy of 1152, 952, 1001, 656, and 1001 kJ/mole for reaction (1)–(6), respectively. The results show that the polymerization reaction rate-determining step was the reaction of 2,6-urethane and isocyanate group of 2,6-TDI (reaction (6)).

Keywords

bulk polymerization; kinetics; hydroxy terminated polybutadiene; toluene diisocyanate

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DOI: https://doi.org/10.22146/ijc.24807