論 文 ポリビニルピロリドン 水， アルカノール (n 1 4)， 1-メ …

1 Netsu Sokutei 36 3 130-139.. ( n 1 4) . 1- -2- .. 2009 3 16 2009 4 6 . Thermodynamic Study on the Polyvinylpyrrolidone Water, Alkanol (n 1 4), 1-Methyl-2-Pyrrolidone at K. Takuya Sugiura, Fumio Kimura, and Hideo Ogawa (Received March 16, 2009; Accepted April 6, 2009). Enthalpies of solution of polyvinylpyrrolidone (PVP, molecular weight average, Mw . 1 10 4) in water, alkanol (n 1 4) and 1-methyl-2-pyrrolidone (NMP) were measured at K using newly constructed calorimeter to investigate the solvation behavior of PVP in those solvents. Enthalpy of solution of PVP in water is exothermic. Enthalpies of solution of PVP in other solvents are smaller than uncertainty of calorimeter. Densities and sound velocities were also measured in same series of solution to calculate partial specific volumes at infinite dilution, V w,2 , partial specific isentropic compressions at infinite dilution, K s,w,2 , of PVP of different molecular weight. And viscosity was also measured to evaluate specific viscosity, SP, of these solutions.

2 V w,2 of PVPs in water is larger than V w,2 of PVPs in alkanols, and K s,w,2 . of PVPs in water is zero. For the alkanol solutions, V w,2 , K s,w,2 and SP of PVPs increase with increasing number of carbon atoms in the alkanol molecules. V w,2 in NMP shows the largest value among all systems investigated. Positive values of K s,w,2 mean that solvent molecule surrounding PVP are easily compressible, for NMP system. Keywords: polyvinylpyrrolidone; enthalpy of solution; partial specific volume;. partial specific isentropic compression; specific viscosity 1.. PVP PVP .. 1 2 1) . 1 . PVP N-C O PVP . 2009 The Japan Society of Calorimetry and Thermal Analysis. 130 3 . Netsu Sokutei 36 2009. (n 1 4) . 1- -2- . Table 1 Densities and sound velocities of used solvent in this study at K. d u Literature value of d 1). Solvent g cm 3 ms 1 g cm 3. NMP Methanol Ethanol 1-Propanol 1-Butanol 1) .. PVP . Schematic diagram of the constructed calorimetric . unit of the twin conduction type calorimeter PVP 1- -2- NMP.

3 For enthalpy of solution of polymer. n 1 4 . PVP. V/hour W/hour . V P-P 2.. W P-P . 19 cm 3 . Mw 1 10 4 . 4 10 4 . Mw 10 5 3 4,5) . NMP . 1- 1- 6,7) . 1- % . 4A 66 . GC-8A KCl . % 500 mol . 2) 5 kJ mol 1. Table 1 IUPAC 200 mol . kJ mol 1 8) Kilday 500 mol . 3) kJ mol 1 9) % % .. V/W . 3 . Netsu Sokutei 36 2009 131.. Table 2 Enthalpies of solution of polyvinylpyrrolidone ( Mw 1 10 4) in NMP, water and alkanols (n 1 4) at K. soln H / J g 1. Mass fraction Volume fraction solnH. mass- % vol- % J g 1. NMP. solvents average error Enthalpies of solution, soln H, for poly- vinylpyrrolidone (Mw 1 10 4 ) in water, Water alkanols (n 1 4) and 1-methyl-2-pyrrolidone at K. average . error . Methanol . PVP Mw 1 10 4 K .. average K. error 1 mass-% 3 . Ethanol . DMA-602M, Anton Paar .. average error cm . UVM-2, Cho-onpa kogyo Co. Ltd . 1-Propanol . 10 6. g cm 3 10 2 m s 1 . average 5 mass-% 5 . error AEL-200, Shimadzu Co. Ltd .. 1-Butanol TV-22, Toki sangyo Co.

4 Ltd . K . K . average 3.. error PVP Mw 1 10 4 1 g NMP . n 1 4 soln H. Table 2 PVP soln H . kJ g 1 . 132 3 . Netsu Sokutei 36 2009. (n 1 4) . 1- -2- . Table 3 Densities and sound velocities of poly- vinylpyrrolidone - NMP solutions at K. Concentration d u soln H / J g 1. mass- % g cm 3 m s 1. Mw 1 10 4. 2 Conceptual diagram of concentration dependency of enthalpy of solution, soln H, for poly- vinylpyrrolidone (Mw 1 10 4) in water and alkanols (n 1 4) at K. Hypothetical Mw 4 10 4. enthalpy level of liquid pure polyvinylpyrrolidone was assumed arbitrarily. : aqueous solutions, : methanol solutions, : ethanol solutions, : 1-propanol solutions, : 1-butanol solutions. Goldfarb . PVP Mw 10 4 soln H kJ g 1 10). Mw 10 5. kJ g 1 .. PVP PVP n 1 4 soln H .. 3 % dilH . PVP PVP J g 1 n 1. PVP 4 J g 1 . PVP . PVP PVP . dil H soln H . soln H 2 1 .. PVP PVP . PVP PVP . PVP . PVP soln H . dil H soln H . 1 2 1) PVP 1 g PVP . PVP 2 . 2 dilH PVP . 3 . Netsu Sokutei 36 2009 133.

5 Table 4 Densities and sound velocities of poly- Table 5 Densities and sound velocities of poly- vinylpyrrolidone - aqueous solutions at vinylpyrrolidone - methanol solutions at K. K. Concentration d u Concentration d u mass- % g cm 3 m s 1 mass- % g cm 3 m s 1. Mw 1 10 4 Mw 1 10 4. Mw 4 10 4 Mw 4 10 4. Mw 10 5 Mw 10 5. P V P . soln H dilH . Table 3 8 . soln H PVP 1 g V w,2 . PVP PVP 1 g . K s,w,2 . dilH . 1 g . 2 . PVP NMP . soln H PVP NMP 1 g V w,2 . V W1 kg . W i c .. 134 3 . Netsu Sokutei 36 2009. (n 1 4) . 1- -2- . Table 6 Densities and sound velocities of poly- Table 7 Densities and sound velocities of poly- vinylpyrrolidone - ethanol solutions at vinylpyrrolidone - 1-propanol solutions at K. K. Concentration d u Concentration d u mass- % g cm 3 m s 1 mass- % g cm 3 m s 1. Mw 1 10 4 Mw 1 10 4. Mw 4 10 4 Mw 4 10 4. Mw 10 5 Mw 10 5.. V SP,2 lim ( ) V. (1). c 0 W2. W 1 . ,P,W 1. s . 1. V ( ). V. P s . 1. du 2. (3). 1 kg V/W1 K s,w . W 2 /W 1.

6 V w,2 .. K s,w ( ). V. P s V s (4). 1 g K s,w,2 . V W,2 lim c 0 ( V/W 1. W 2/W 1 ) ,P,W 1.. (V/W 1). (2). K S,W,2 lim c 0 ( K S,W. W2. ) T,P,W 1. (5). (W 2/W 1). V w,2 K s,w,2 . s Laplace d u 1 kg K s,w /W 1 . 3 . Netsu Sokutei 36 2009 135.. Table 8 Densities and sound velocities of poly- vinylpyrrolidone - 1-butanol solutions at K. V w,2 / cm 3 g 1. Concentration d u mass- % g cm 3 m s 1. Mw 1 10 4. solvents Partial specific volumes at infinite dilution, Vw,2 , for polyvinylpyrrolidone in water, alkanols (n 1 4) and 1-methyl-2-pyrrolidone at K. : Mw 1 10 4, : Mw 4 10 4, : Mw Mw 4 10 4. 10 5. K s,w,2 / cm 3 GPa 1 g 1. Mw 10 5. solvents Partial specific compressions at infinite dilution, Ks,w,2 , for polyvinylpyrrolidone in water, alkanols W 2 /W 1 . (n 1 4) and 1-methyl-2-pyrrolidone at . K. : Mw 1 10 4, : Mw 4 10 4, : Mw K S,W,2 lim c 0 ( K S,W/W 1. W 2/W 1. ) T,P,W 1. 10 5. V w,2 . (K S,W/W 1).. (6) K s,w,2 . (W 2/W 1). K s,w,2 . Ks,w,2 (4) V.

7 W,2.. 0 .. K S,W,2 lim . m2 0 ( V w,2. P ) (. s . V w,2 . P ) s (7) PVP V w,2 K s,w,2 . V w,2 . V w,2 K s,w,2 K s,w,2 PVP . Table 9 . 136 3 . Netsu Sokutei 36 2009. (n 1 4) . 1- -2- . Table 9 Partial specific volumes at infinite dilution and partial specific compressions at infinite dilution of polyvinylpyrrolidone in the several solvent SP C 1 / cm 3 g 1. at K. Solvents V w,2 K s,w,2 . cm 3 g 1 cm 3 GPa 1 g 1. Mw 1 10 4. NMP Water Methanol Ethanol C / g cm 3. 1-Propanol Solution viscosity, SP/C, against concentration 1-Butanol of polyvinylpyrrolidone (Mw 1 104) at Mw 4 10 4 K. : 1-methyl-2-pyrrolidone solutions, : NMP aqueous solutions, : methanol solutions, : Water ethanol solutions, : 1-propanol solutions, : Methanol 1-butanol solutions. Ethanol 1-Propanol 1-Butanol Mw 10 5. SP C 1 / cm 3 g 1. NMP Water Methanol Ethanol 1-Propanol 1-Butanol C / g cm 3. PVP . Solution viscosity, SP/C, against concentration . of polyvinylpyrrolidone (Mw 4 104) at.

8 K. : 1-methyl-2-pyrrolidone solutions, : . aqueous solutions, : methanol solutions, : . ethanol solutions, : 1-propanol solutions, : 1-butanol solutions. V w,2 .. PVP V w,2 K s,w,2 . PVP V w,2 PVP . K s,w,2 NMP PVP . V w,2 K. s,w,2. V w,2 K s,w,2 NMP . Sadeghi 11,12) P V P V w , 2 . PVP NMP K s,w,2 PVP NMP. PVP . 3 . Netsu Sokutei 36 2009 137.. PVP .. SP C 1 / cm 3 g 1. PVP NMP .. PVP .. C / g cm 3.. Solution viscosity, SP/C, against concentration . of polyvinylpyrrolidone (Mw 10 5 ) at . K. : 1-methyl-2-pyrrolidone solutions, . : aqueous solutions, : methanol solutions, . : ethanol solutions, : 1-propanol solutions, 18- -2 . : 1-butanol solutions.. PVP . PVP NMP 1) H. Ogawa, Y. Baba, and A. Kagemoto, Makromol. PVP NMP Chem. 182, 2495 (1981). NMP PVP 2) J. A. Riddick, W. B. Bunger, and T. K. Sakano, Organic Solvents Physical Properties and Methods K s,w,2 . of Purification Fourth Edition, Wiley-Interscience . (1986). PVP . 3) 5 6 , , , 160.

9 SP /C . (2005).. 4) H. Ogawa, S. Murakami, T. Takigawa, and M. Ohba, Moattar Fluid Phase Equilib. 136, 279 (1997). 13) PVP NMP 5) 5 6 , , , 226. PVP (2005). 6) H. Ogawa and M. Kojima, J. Thermal Analysis 38, 1 PVP 1873 (1992). 7) , , , . PVP NMP , , 48 (1993). 8) E. F. G. Herington, Pure Appl. Chem. 40, 432(1974). PVP 9) M. V. Kilday, J. Research of the National Bureau of Standards 85, 467 (1980). 10) J. Goldfarb and S. Rodriguez, Die Makromolekulare . Chemie 116, 96 (1968). 4. 11) R. Sadeghi and F. Ziamajidi, J. Chem. Thermodyn. 39, 1118 (2007). PVP . 12) R. Sadeghi and M. T. Zafarani-Moatter, J. Chem. Thermodyn. 36, 665 (2004). 13) M. T. Zafarani-Moattar and Zh. Khoshsima, J. Chem. Thermodyn. 40, 1569 (2008). PVP . 138 3 . Netsu Sokutei 36 2009. (n 1 4) . 1- -2- . Takuya Sugiura . ,Graduate School of Advanced K 1- -2- NMP .. Science and Technology, Tokyo Denki PVP . Univ., TEL. 049-296-5424, FAX. 049- Mw 1 10 4 solnH 296-2960, e-mail: soln H kJ g 1 soln H.

10 3 P V P . NMP . PVP 1 g V w,2 Fumio Kimura PVP 1 g , Div. of Science, School of Science and K s,w,2 V w,2 . Engineering, Tokyo Denki Univ., TEL.. 049-296-6062, FAX. 049-296-2960, e- PVP K s,w,2 . mail: V w,2 .. K s,w,2 . PVP .. PVP NMP . PVP NMP Hideo Ogawa V w,2 , Div. of K s,w,2 Science, School of Science and Engineering, Tokyo Denki Univ., TEL. 049-296-5079, FAX. 049-296-2960, e- mail: .. 3 . Netsu Sokutei 36 2009 139.