On the Pyrolysis of Polymers I. Thermogravimetric Analysis of Polymers

高分子物質의 熱分解에 關한 硏究 (第1報) 熱天秤에 依한 硏究

  • Published : 19630600

Abstract

The weight decrease curves of 18 kinds of polymers have been measured by thermobalance at the same condition where temperature is increased $1^{\circ}C$ per minutes under nitrogen or air atmosphere. The curves are further differentiated to obtain rate curve of weight decrease. Those curve offer a method to compare relative thermal stability, effects of oxygen or modes of thermal degradation of polymers qualitatively. The curves could be classified into following four types: Polystyrene, polymethylmethacrylate and acetal polymer belong to the first type. Those polymers depolymerize mainly into corresponding monomers, weight decrease curves are steepy up to perfect vaporization of polymers and rate curves show a relatively sharp peak. (Type I) Polyvinyl chloride represents the second type. This polymer decomposes with splitting off of hydrogen chloride. The thermogravimetric curve rises rapidly at first, then level off at the moderate weight decrease and gradually rises. Polyvinyl acetate also belongs to this class. (Type II) The modification of the second type is represented by polyester. The curve at the early stage is less steep, the leveling off at the next stage is less clear and the final rising of the curve is steeper than the normal second type. Polyamide, polyurethane, and polycarbonate belong to this type. (Type II') The thermal decomposition of the third type polymers is more complex than that of others. Various irregular chain scissions including side chain splitting and depolymerization to monomers occur simultaneously. The weight of the polymer decreases gradually and the rate curve does not show sharp peaks. Polyvinyl alcohol and diene polymers belong to this type. (Type III) Generally, polycondensation polymers are more stable toward heat than addition polymers and polymers having aromatic nucleus show good thermal stability. Polymers having tertiary carbon atoms such as polystyrene or polypropylene and acetal resin start decomposition under airatmosphere at the temprature below $50^{\circ}C$ or more of the temperature where the polymers start decomposition under nitrogen atmosphere.

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