Effect of enthalpy of polar modifiers interaction with n-butyllithium on the reaction enthalpy,kinetics and chain microstructure during anionic polymerization of 1,3-butadiene |
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| Affiliation: | 1. Synthos S.A., Research and Development Department, ul. Chemików 1, 32-600 Oświęcim, Poland;2. Institute of Chemistry, Department of Materials Chemistry and Technology, Silesian University, ul. Szkolna 9, 40-006 Katowice, Poland;1. International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala 686560, India;2. School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala 686560, India;3. Department of Physics, Birla Institute of Technology & Science, Pilani, Hyderabad 500078, India;4. Normandie Univ, UNIROUEN Normandie, INSA Rouen, CNRS, Groupe de Physique des Matériaux, 76000 Rouen, France;5. Department of Soil, Plant and Food Sciences, University of Bari “Aldo Moro”, Via Amendola 165/A, 70126 Bari, Italy;6. School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala 686560, India;1. LabMAT, Department of Civil and Environmental Engineering, University of Bío-Bío, 4051381 Concepción, Chile;2. Department of Mechanical Engineering, University of the Basque Country, 48013 Bilbao, Spain;1. Lab of Advanced Elastomer, South China University of Technology, Guangzhou, 510640, China;2. The Key Laboratory of Polymer Processing Engineering, Ministry of Education, China (South China University of Technology), Guangzhou, 510640, China;3. College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China;4. State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, 610065, China |
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| Abstract: | The influence of interaction enthalpy (ΔHMOD/BuLi) of μ, σ, σ+μ and σ-μ complexing polar modifiers with n-butyllithium on the 1,3-butadiene anionic polymerization enthalpy (ΔHBD), polymerization reaction rate (kp) and polybutadiene microstructure was studied. It has been found that enthalpy of interaction depends on complex type, molar ratio of polar modifier to n-butyllithium (MOD/BuLi) and temperature. For the first time it has been proven that with increasing ΔHMOD/BuLi the content of 1,2 butadiene (vinyl) units in the chain increases individually for each complex type but the value of ΔHBD decreases similarly for all complexes containing σ-donor groups, exhibiting linear nature. Since ΔHMOD/BuLi controls the content of butadiene isomeric structures in the chain its value was compared with polymerization reaction rate, ranging from ∼46 to ∼5500 moL/L·min, and discussed on mechanistic level. |
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| Keywords: | Anionic polymerization 1,3-Butadiene Polar modifier Interaction enthalpy Polymerization enthalpy Kinetics Reaction rate Microstructure |
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