1066008 Yoshifumi Sugito

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1932 K.Sollner 1) A.Katchalsky J.N.WeinsteinA.Chapiro 2)4) Fig. 1-1 5) 6) M M X X + A d C M + X M X + Fig. 1-1 1

4) 7) 8) 9) Fig. 1-2 Fig. 1-2 (Molau 10) ) 2

10cm10cm 11) 12) 13) SEM 3

(PVA) (PMMA ) 14) (MMA ) (DVB ) PVA Bragg PVA PVA MMA MMA PMMA PVA PMMA PVA SEM Fig. 1-3 PVA 7/3 (wt/wt) PMMA SEM PVA 15) 4 Fig. 1-4Depletion

Fig. 1-3 PMMA SEM 5

depletion depletion Fig. 1-4 depletion (PSSS ) (P4VP ) 15) SEM 20% (KCl) KCl (P4VP ) (MeI ) -P(SSS-AAm) (GA) P4VP 16) P4VP P4VP P4VP -P(SSS-AAm) GA MeOH 17) 20) 6

-P(SSS-AAm) P4VP -P(SSS-AAm) 21) MMA 4VP -P(SSS-AAm) GA P4VP PSSS PVA P4VP 4VP PVA PSSS SSS 22) 23) P4VP PSSS GA 24) Fig. 1-5 Fig. 1-5 7

P4VP PSSS -P(SSS-AAm) P4VP P4VP -P(SSS-AAm) PSSS GA 16) 18) 8

K.Sollner, Biochem.Z., 244, 370 (1932) O.Kedem and A.Katchalsky, Trans.Faraday Soc.,59, 1918 (1963) J.N.Weinstein, B.J.Bunow and S.R.Caplan, Desalination, 11, 341,(1972) A.Chapiro, Europ.Polym.J., 12, 773 (1976) J.N.Weinstein and S.R.Caplan, Science, 161,70, (1968) F.B.Leitz and W.A.McRae, Saline Water Conversion Report (1968) C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307, 8, 212 (1983), 20 330 (1982) G.E.Molau, Block Polymers (S.L.Aggarwal ed.) (1970) Plenum Press, New York K.Ishizu and T.Fukutomi, Charge Mosaic MembraneHandbook of Polymer Science and Technology, Marcel-Dekker (New York) 4, 541 (1989) 9

G.H.Ma and T.Fukutomi, Macromolecules., 25, 1870 (1992) G.H.Ma and T.Fukutomi,Trends in Polymer Science(Indian Reseach Council Ed.) (1993) T.Fukutomi, H.Ohmori andy.sugito, J. Polym. Sci., Polym.Chem.,34,2729,(1996) M.Takizawa,Y.Sugito, S.Doi, Y.Isono, M.Nakamura, S.Horiguchi and T.Fukutomi, Current Trend in Polymer Science, 6, 59 (2001),, 2,681,852,, 2,895,705,, 3,234,426 Y.Sugito, M.Takizawa, N.Oguma, M.Nakamura and T.Fukutomi, U.S.Patent 5,770,631,, 3,156,955,,, 3,016,406,,, 3,058,561,,, 3,012,153,,, 3,236,754 10

11 1) 2) 10nm 10m 3) 4) P4VP 4VP P4VP 4VP DVB

V 80 (NaCl ) P4VP P4VP Table 2-1 P4VP 4VP (g) DVB (g) V-50 (g) H 2 O (g) P4VP 20 2 0.4 1000 P4VP MeOH P4VP P4VP 1.2 (MeI) 12 P4VP MeI P4VP (P4VP-MeI HEMA t PSt PSSS PSt St HEMADVB KPS 80 8 NaCl PSt 12

PSt Table 2-2 Table 2-2 PSt St (g) HEMA (g) DVB (g) KPS (g) H 2 O(g) PSt 76.4 11.4 12.2 1.0 1000 PSt 98% 650g PSt 100g 50 24 80 ph PSSS DMF Coulter N-4 P4VP PSSS Table 2-3 P4VP SEM Fig. 2-1Fig. 2-2 PSSS SEM Fig. 2-3Fig. 2-4 Table 2-3 (nm) (nm) P4VP 348 81.0 P4VP-MeI 346 84.6 PSSS 350 80.3 P4VP PSSS 13

Fig. 2-1 P4VP SEM Intensity 100 300 1000 Size (nm) Fig. 2-2 P4VP (DMF ) 14

Fig. 2-3 PSSS SEM Intensity 100 300 1000 Size(nm) Fig. 2-4 PSSS (DMF ) 15

Table 2-4 Table 2-4 (meq/g) P4VP 8.6 PSSS 4.0. Table 2-5 PSSS P4VP P4VP PSt 16

Table 2-5 S P P4VP 1) 23.4 1) 14.3 12.9 12.0 11.5 12.1 11.2 10.2 9.5 9.3 9.1 8.9 8.8 8.2 DMF N,N- NMP N- H.Kawakuchi, F.Hoshino and Y.Ohtsuka, Makromol.Chem.Rapid Commun.,7,109(1986) F.Hoshino,M.Sakai,H.Kawauchi and Y.Ohtsuka, Polym.J.,19.383(1987) M.Takizawa,Y.Sugito, N.Oguma, M.Nakamura, S.Horiguchi and T.Fukutomi, J.Polym.Sci: Part A: Polym. Chem. 41,1251(2003) 17

Fig. 3-1 Fig. 3-2 18

Fig. 3-1 Fig. 3-2 19

P4VP PSSS P4VP PSSS 20

P4VP PSSS 20c 100c P4VP MeI 21

P4VP P4VP-MeI PSSS PSSS MeI 48 Fig. 3-3 29% DMF Table 3-1 O O O (CH 2 ) 6 O C O CH 2 O C NH m 6 CH 2 NH C O n Fig. 3-3 Table 3-1 P4VP PSSS DMF NMP P4VP PSSS DMF NMP P4VP PSSS 22

ph ph ph 1 P4VP PSSS DMFNMP 2) Table 3-1 23.4 14.3 12.9 12.0 11.5 DMF 12.1 NMP 11.2 10.2 9.5 9.3 9.1 8.9 8.8 8.2 23

DMF P4VP DVB 9.1wt%PSSS10mol% KCl Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig. 3-4 20 KCl KCl 60% SEM 50wt% 24

Fig. 3-4 P4VP4VP/ PSSS 1 / 1 ( mol ) (P4VP+PSSS) / 1 / 1 ( wt ) DMF / (MEK )4 / 1 ( wt ) MEK 18,00020,000 mpas No.3 6rpm Table 3-2 25

Table 3-2 (g) 13wt % P4VP ( DMF/MEK) 22.1 15wt % PSSS ( DMF/MEK) 44.8 29wt % ( DMF) 33.1 100 5 20 m Fig. 4-1 Cell (1wt%) (10wt%NaNO 3 ) 250g Cell 250g Fig. 3-5 NaNO 3 20m 26

Fig. 3-5 KCl Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig. 3-6 27

Fig. 3-6 80 P4VP P4VP-MeI PSSS DMF P4VP-MeI P4VP-MeI MeI MeI 48 28

KCl Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig. 3-7 KCl KCl ( NaCl ) Fig. 3-7 J KCl mol/m 2 h 29

Fig. 3-8 1 50 1 P4VP:9.1 wt% PSSS:10mol% 1 DMF 2P4VP / PSSS= 1 / 1(mol) 3 = 1 / 1 (wt) 1 20 2 1NaCl 24 Fig. 3-8 5cm 48 Table 3-3 01.0 30

Table 3-3 wt% 10 34 % 0 % 20 6 0 30 1215 0 40 2023 0 50 2325 0 60 2528 1.0 70 2628 1.0 AUTOGRAPH AG-500A() 25-597.0 kgf / cm 2 50mm/min 15mm15mm - 0.12 kg / cm (JIS L-1092A) (JIS L-1092B) WP-5K 25-100cm 2 60cm/min. 31

- 100cm 2 1kgf/cm 2 (98.1kPa) - Table 3-4 Table 3-4 * ) (kpa) (kpa) 7.8 33.6 11.3 35.2 * Fig. 3-8 TEM Fig. 3-9 P4VP PSSS DMF P4VP MeI 2) 3) 32

Fig. 3-9 TEM 33

20 TEM 3)-5) 6) ) Fig. 3-8 P4VP-MeI, 83 11-239,720 Y.Sugito, M.Takizawa, N.Oguma, S.Doi, M.Nakamura and T.Fukutomi, U.S.Patent 6,484,887 3,261,047 2000-072,898 2001-070,768 C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307 34

P4VP PSSS DMF 1) ( Fig. 3-8 ) (Fig. 4-1) Cell I KCl Cell II 25 19.6cm 2 Cell(250ml) KCl Cell(250ml) Fig. 4-1 35

ICP TOC Fig. 4-1 Cell I 250g Cell II 250g Js ; mol/m 2 h ; KCl / Fig. 4-1 Cell I KCl 250g Cell II 250g KCl KCl / (Jv) 60ml ( 25mm) Cell I KCl Cell II KCl KCl KCl KCl (Ps) Fig. 4-1 Cell I KCl Cell II Cell I KCl s KCl s KCl C - C 36

Fig. 4-1 0.1mol/l Table 4-1 KCl 2 3 1 2) 37

Table 4-1 Solute Molecular Flux10-1 Relative Flux Weight (mol/m 2 h) (KCl=1.00) HCl 36.5 5.60 1.30 KCl 74.6 4.30 1.00 NaCl 58.4 3.01 0.70 NaNO 3 84.9 3.30 0.77 NH 4 Cl 53.5 1.91 0.44 CaCl 2 111.0 1.99 0.46 MgCl 2 95.3 2.14 0.49 Na 2 SO 4 142.0 1.14 0.27 NaH 2 PO 4 119.9 0.97 0.23 Na 2 HPO 4 141.9 0.93 0.21 Ethylene glycol 62.1 0.99 0.23 Diethylene glycol 106.1 0.42 0.09 Triethylene glycol 150.2 0.19 0.04 Tetraethylene glycol 194.2 0.13 0.03 Glucose 180.2 0.13 0.03 Saccharose 342.3 0.08 0.02 0.1mol/l Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g 10 25 50 Fig. 4-2 KCl 25 KCl 1.0 10 0.8 50 1.4 38

Fig. 4-2 (Js) () Cell I 0.05mol/l KCl 250g Cell II 250g Fig. 4-3 J KCl 0.24 mol/hm 2 0.02 mol/hm 2 J 13 39

Fig. 4-3 25 Jv Cell I KCl Cell II KCl 0.0011.0 mol/l Cell I II Cell I Cell II Fig. 4-4 KCl Fig. 4-4 40

Ps Cell I KCl Cell II KCl 0.051.0mol/l J KCl Ps Fig. 4-5 Ps)KCl NaCl -- (0.025mol/l ) NaCl(2mol/l) 250g NaCl Fig. 4-6 Fig. 4-5 (KCl) 41

Fig. 4-6 (NaCl) Fig. 4-7 Fig. 4-7 42

(MW:610 4 1wt% )NaNO 3 (10wt%) Cell 1 250 8000g Fig. 4-8 Cell NaNO 3 Fig. 4-8 43

(1.0wt% )NaCl (0.3wt% ) 250g Cell 5 19.6 cm 2 Fig. 4-9 NaCl Fig. 4-9 0.025mol/l (MW:300 2mol/l NaCl 250g Cell 1 Fig. 4-10 NaCl 14.3 mol/m 2 h 44

Fig. 4-10 13 KCl KCl 45

KCl KCl KCl 20% K.Sollner, Biochem.Z., 244, 370 (1932) Jacob N.Israelachvili, M.Tasaka, T.Okano and T.Fujimoto, J. Membrane Sci., 19, 273 (1984) A.Yamauti, J.Tateyama, B.Etoh, M.Takizawa, Y.Sugito and S.Doi, J. Membrane Sci., 173, 275 (2000) 46

DMF Fig. 3-8 Fig. 5-1 47

1 P4VP :9.1 wt% PSSS 10 mol% 1 DMF 2P4VP/PSSS=1 / 1mol 3 =1 / 1 (wt) 1 1NaCl 24 Fig. 5-1 P4VP MeI P4VP MeOH MeI MeIMeOH DMF 48

Fig. 5-2 CH 2 CH CH CH CH 2 CH 2 CN m n p Fig.5-2 Table 5-1 Table 5-1 P4VP PSSS DMFNMP P4VP PSSS DMF DMF 49

Table 5-1 23.4 14.3 12.9 12.0 11.5 DMF 12.1 NMP 11.2 10.2 9.5 9.3 9.1 8.9 8.8 8.2 P4VP4VP / PSSS 1 / 1 ( mol ) (P4VP+PSSS) / 1 / 1 ( wt ) DMF / (MEK ) = 4 / 1 ( wt ) 18,00020,000mPasB No.3, 6rpm Table 5-2 50

Table 5-2 ( g ) 15wt% P4VP ( DMF/MEK) 18.0 20wt% PSSS ( DMF/MEK) 18wt% ( DMF/MEK) 31.5 50.0 DMF/MEK 0.5 100 2070 Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig.5-3 Table 5-3 20m SEM 30m 51

Fig. 5-3 1.9610-3 m 2 0.05mol/l KCl0.05mol/l 250g 250g 25 Table 5-3 (m) (mol/m 2 ) 20 30 0.95 25 40 0.89 23 50 0.85 26 60 0.78 22 70 0.64 26 52

P4VP MeOH MeI MeOH 48 P4VP MeI 0.520 1600cm -1 1640cm -1 Fig. 5-4 P4VP 10 MeI Fig. 5-4 P4VP 50cm 2 MeI P4VP 020 MeOH30ml 48 50ml 53

Fig. 5-1 1m50m TEM TEM Fig. 5-5 54

Fig. 5-5 TEM 55

Fig. 4-1 Cell 0.1mol/l 250g Cell 250g KCl Table 5-4 Table 5-4 0.1mol/l Solute Molecular Flux10-1 Relative Flux Weight (mol/m 2 h) (KCl=1.00) HCl 36.5 21.4 1.65 KCl 74.6 13.0 1.00 LiCl 42.4 9.36 0.72 NaCl 58.4 9.57 0.74 NaNO 3 84.9 9.06 0.70 NH 4 Cl 53.5 10.2 0.78 CaCl 2 111.0 5.36 0.41 MgCl 2 95.3 2.93 0.22 Na 2 SO 4 142.0 5.87 0.45 NaH 2 PO 4 119.9 4.59 0.35 Na 2 HPO 4 141.9 4.85 0.37 Ethylene glycol 62.1 2.43 0.19 Diethylene glycol 106.1 0.94 0.07 Triethylene glycol 150.2 0.44 0.03 Tetraethylene glycol 194.2 0.42 0.03 Glucose 180.2 0.55 0.04 Saccharose 342.3 0.33 0.02 56

() (Js) Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig. 5-6 J KCl =0.95mol/m 2 h J =0.04 mol/m 2 h 25 =13 Fig. 5-6 25 57

(J V ) Cell KCl Cell KCl 0.0011.0 mol/l Cell, Fig.5-7 1mol/l 0.010.5mol/l KCl Fig. 5-7 (Ps) (NaCl) Fig. 4-1 Cell NaCl Cell NaCl 0.053mol/l J NaCl (Ps) Fig. 5-8 NaCl 58

Fig. 5-8 (NaCl) 1cm 2 6V 30 (ma) Fig. 5-9 59

Fig. 5-9 Fig. 4-1 Cell 250g 250g Ps Fig. 5-10 LiCl NaClKCl Table 5-5 2) 3) Fig. 5-10 60

3) Table 5-5 (nm) (nm) (1) H 3 O + 0.28 3 Li + 0.068 0.38 5-6 Na + 0.095 0.36 4-5 K + 0.133 0.33 3-4 Ca 2+ 0.099 0.41 6 Mg 2+ 0.065 0.43 6 AUTOGRAPH AG-500A 25-420.5 kgf / cm 2 50mm/min 15mm15mm - 0.11 kg / cm (JIS L-1092A) (JIS L-1092B) WP-5K 25 Table 5-6 61

Table 5-6 (kpa) (kpa) *) 4.7 13.6 6.7 20.3 4) 4) Fig. 5-11 Fig. 5-12 10.5 % Fig. 5-13 NaCl NaCl Fig. 5-11 62

Fig. 5-12 63

Fig. 5-13 2566cm 2 8 kg J NaCl ( 1h)268g / m 2 h J NaCl ( 10h)= 175g / m 2 h Fig. 5-14 5) 64

Fig. 5-14 65

30m :1.54cm 2 50l C.I. 27755 M.W. 800 (7wt%) NaCl Na 2 SO 4 0.95wt% 45g 24 Fig. 5-15 Fig. 5-16 Fig. 5-15 ph ph:7.6 Fig. 5-16 HCl ph 3.0 NaCl Na 2 SO 4 ph HCl Na 2 SO 4 HCl Cl 2 SO 4 HCl Fig. 5-16 NaCl Cl 6) 7) Fig. 5-15 ph Fig. 5-16 (ph 3.0) 66

8)-10) 25 KCl 0.010.5mol/l NaCl 20wt% Symmetry structure (Asymmetry structure) 11) 67

M.Tasaka, N.Aoki, Y.Kondo and M.Nagasawa, J. Phys. Chem., 79, 1307 (1975),96 Jacob N.Israelachvili,, (1981) 15, No.3, 611 (1989), 3,167,013, 2001-259,386 2000-070,687 2000-309,654 2001-212,439 C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307 68

75mm75mm2.5 1m 2 (1m) Table 6-1 20 69

70

Na + K + Ca 2+ Mg 2+ NaCl 71

1) 96.5% 3.5% 2) 72

, 2001-259,386 4. 73

P4VP PSSS PSSS DMF P4VP PSSS 1 / 1 20wt% KCl (60wt% ) KCl 50wt% 74

KCl 20wt% 75

76

K.Sollner, Biochem.Z., 244, 370 (1932) O.Kedem and A.Katchalsky, Trans.Faraday Soc.,59, 1918 (1963) J.N.Weinstein, B.J.Bunow and S.R.Caplan, Desalination, 11, 341,(1972) A.Chapiro, Europ.Polym.J., 12, 773 (1976) J.N.Weinstein and S.R.Caplan, Science, 161,70, (1968) F.B.Leitz and W.A.McRae, Saline Water Conversion Report (1968) G.E.Molau, Block Polymers (S.L.Aggarwal ed.) (1970) Plenum Press, New York K.Ishizu and T.Fukutomi, Charge Mosaic MembraneHandbook of Polymer Science and Technology, Marcel-Dekker (New York) 4, 541 (1989) G.H.Ma and T.Fukutomi, Macromolecules., 25, 1870 (1992) G.H.Ma and T.Fukutomi,Trends in Polymer Science(Indian Reseach Council Ed.) (1993) T.Fukutomi, H.Ohmori and Y.Sugito, J. Polym. Sci., Polym.Chem.,34,2729,(1996) M.Takizawa,Y.Sugito, S.Doi, Y.Isono, M.Nakamura, S.Horiguchi and T.Fukutomi, Current Trend in Polymer Science, 6, 59 (2001) H.Kawakuchi, F.Hoshino and Y.Ohtsuka, Makromol.Chem.Rapid Commun.,7,109(1986) F.Hoshino,M.Sakai,H.Kawauchi and Y.Ohtsuka, Polym.J.,19.383(1987) M.Takizawa,Y.Sugito, N.Oguma, M.Nakamura, S.Horiguchi and T.Fukutomi, J.Polym.Sci: Part A: Polym. Chem. 41,1251(2003) K.Sollner, Biochem.Z., 244, 370 (1932) M.Tasaka, T.Okano,and T.Fujimoto, J. Membrane Sci., 19, 273 (1984) A.Yamauti, J.Tateyama, B.Etoh, M.Takizawa, Y.Sugito and S.Doi, J. Membrane Sci., 173, 275 (2000) M.Tasaka, N.Aoki, Y.Kondo and M.Nagasawa, J. Phys. Chem., 79, 1307 (1975) 77

, 8, 212 (1983), 20 330 (1982), 83 Jacob N.Israelachvili,,96, (1981) 15, No.3, 611 (1989) 4. Jacob N.Israelachvili,,, 2,681,852,, 2,895,705,,, 3,012,153,,, 3,016,406,,, 3,058,561,, 3,156,955, 3,167,013,, 3,234,426, 3,236,754 3,261,047 11-239,720 2000-070,687 2000-072,898 2000-309,654 2001-070,768 2001-212,439, 2001-259,386 78

C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307 Y.Sugito, M.Takizawa, N.Oguma, M.Nakamura and T.Fukutomi, U.S.Patent 5,770,631 Y.Sugito, M.Takizawa, N.Oguma, S.Doi, M.Nakamura and T.Fukutomi, U.S.Patent 6,484,887 79

80