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1 Yoshifumi Sugito
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6 1932 K.Sollner 1) A.Katchalsky J.N.WeinsteinA.Chapiro 2)4) Fig ) 6) M M X X + A d C M + X M X + Fig
7 4) 7) 8) 9) Fig. 1-2 Fig. 1-2 (Molau 10) ) 2
8 10cm10cm 11) 12) 13) SEM 3
9 (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
10 Fig. 1-3 PMMA SEM 5
11 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
12 -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
13 P4VP PSSS -P(SSS-AAm) P4VP P4VP -P(SSS-AAm) PSSS GA 16) 18) 8
14 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), (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
15 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
16 11 1) 2) 10nm 10m 3) 4) P4VP 4VP P4VP 4VP DVB
17 V 80 (NaCl ) P4VP P4VP Table 2-1 P4VP 4VP (g) DVB (g) V-50 (g) H 2 O (g) P4VP 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
18 PSt Table 2-2 Table 2-2 PSt St (g) HEMA (g) DVB (g) KPS (g) H 2 O(g) PSt PSt 98% 650g PSt 100g 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 P4VP-MeI PSSS P4VP PSSS 13
19 Fig. 2-1 P4VP SEM Intensity Size (nm) Fig. 2-2 P4VP (DMF ) 14
20 Fig. 2-3 PSSS SEM Intensity Size(nm) Fig. 2-4 PSSS (DMF ) 15
21 Table 2-4 Table 2-4 (meq/g) P4VP 8.6 PSSS 4.0. Table 2-5 PSSS P4VP P4VP PSt 16
22 Table 2-5 S P P4VP 1) ) 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
23 Fig. 3-1 Fig
24 Fig. 3-1 Fig
25 P4VP PSSS P4VP PSSS 20
26 P4VP PSSS 20c 100c P4VP MeI 21
27 P4VP P4VP-MeI PSSS PSSS MeI 48 Fig % 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
28 ph ph ph 1 P4VP PSSS DMFNMP 2) Table DMF 12.1 NMP
29 DMF P4VP DVB 9.1wt%PSSS10mol% KCl Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig KCl KCl 60% SEM 50wt% 24
30 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
31 Table 3-2 (g) 13wt % P4VP ( DMF/MEK) wt % PSSS ( DMF/MEK) wt % ( DMF) m Fig. 4-1 Cell (1wt%) (10wt%NaNO 3 ) 250g Cell 250g Fig. 3-5 NaNO 3 20m 26
32 Fig. 3-5 KCl Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig
33 Fig P4VP P4VP-MeI PSSS DMF P4VP-MeI P4VP-MeI MeI MeI 48 28
34 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
35 Fig P4VP:9.1 wt% PSSS:10mol% 1 DMF 2P4VP / PSSS= 1 / 1(mol) 3 = 1 / 1 (wt) NaCl 24 Fig cm 48 Table
36 Table 3-3 wt% % 0 % AUTOGRAPH AG-500A() kgf / cm 2 50mm/min 15mm15mm kg / cm (JIS L-1092A) (JIS L-1092B) WP-5K cm 2 60cm/min. 31
37 - 100cm 2 1kgf/cm 2 (98.1kPa) - Table 3-4 Table 3-4 * ) (kpa) (kpa) * Fig. 3-8 TEM Fig. 3-9 P4VP PSSS DMF P4VP MeI 2) 3) 32
38 Fig. 3-9 TEM 33
39 20 TEM 3)-5) 6) ) Fig. 3-8 P4VP-MeI, ,720 Y.Sugito, M.Takizawa, N.Oguma, S.Doi, M.Nakamura and T.Fukutomi, U.S.Patent 6,484,887 3,261, , ,768 C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307 34
40 P4VP PSSS DMF 1) ( Fig. 3-8 ) (Fig. 4-1) Cell I KCl Cell II cm 2 Cell(250ml) KCl Cell(250ml) Fig
41 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
42 Fig mol/l Table 4-1 KCl ) 37
43 Table 4-1 Solute Molecular Flux10-1 Relative Flux Weight (mol/m 2 h) (KCl=1.00) HCl KCl NaCl NaNO NH 4 Cl CaCl MgCl Na 2 SO NaH 2 PO Na 2 HPO Ethylene glycol Diethylene glycol Triethylene glycol Tetraethylene glycol Glucose Saccharose mol/l Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig. 4-2 KCl 25 KCl
44 Fig. 4-2 (Js) () Cell I 0.05mol/l KCl 250g Cell II 250g Fig. 4-3 J KCl 0.24 mol/hm mol/hm 2 J 13 39
45 Fig Jv Cell I KCl Cell II KCl mol/l Cell I II Cell I Cell II Fig. 4-4 KCl Fig
46 Ps Cell I KCl Cell II KCl mol/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
47 Fig. 4-6 (NaCl) Fig. 4-7 Fig
48 (MW: wt% )NaNO 3 (10wt%) Cell g Fig. 4-8 Cell NaNO 3 Fig
49 (1.0wt% )NaCl (0.3wt% ) 250g Cell cm 2 Fig. 4-9 NaCl Fig mol/l (MW:300 2mol/l NaCl 250g Cell 1 Fig NaCl 14.3 mol/m 2 h 44
50 Fig KCl KCl 45
51 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
52 DMF Fig. 3-8 Fig
53 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
54 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
55 Table DMF 12.1 NMP P4VP4VP / PSSS 1 / 1 ( mol ) (P4VP+PSSS) / 1 / 1 ( wt ) DMF / (MEK ) = 4 / 1 ( wt ) 18,00020,000mPasB No.3, 6rpm Table
56 Table 5-2 ( g ) 15wt% P4VP ( DMF/MEK) wt% PSSS ( DMF/MEK) 18wt% ( DMF/MEK) DMF/MEK Fig. 4-1 Cell 0.05mol/l KCl 250g Cell 250g Fig.5-3 Table m SEM 30m 51
57 Fig m mol/l KCl0.05mol/l 250g 250g 25 Table 5-3 (m) (mol/m 2 )
58 P4VP MeOH MeI MeOH 48 P4VP MeI cm cm -1 Fig. 5-4 P4VP 10 MeI Fig. 5-4 P4VP 50cm 2 MeI P4VP 020 MeOH30ml 48 50ml 53
59 Fig m50m TEM TEM Fig
60 Fig. 5-5 TEM 55
61 Fig. 4-1 Cell 0.1mol/l 250g Cell 250g KCl Table 5-4 Table mol/l Solute Molecular Flux10-1 Relative Flux Weight (mol/m 2 h) (KCl=1.00) HCl KCl LiCl NaCl NaNO NH 4 Cl CaCl MgCl Na 2 SO NaH 2 PO Na 2 HPO Ethylene glycol Diethylene glycol Triethylene glycol Tetraethylene glycol Glucose Saccharose
62 () (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
63 (J V ) Cell KCl Cell KCl mol/l Cell, Fig.5-7 1mol/l mol/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
64 Fig. 5-8 (NaCl) 1cm 2 6V 30 (ma) Fig
65 Fig. 5-9 Fig. 4-1 Cell 250g 250g Ps Fig LiCl NaClKCl Table 5-5 2) 3) Fig
66 3) Table 5-5 (nm) (nm) (1) H 3 O Li Na K Ca Mg AUTOGRAPH AG-500A kgf / cm 2 50mm/min 15mm15mm kg / cm (JIS L-1092A) (JIS L-1092B) WP-5K 25 Table
67 Table 5-6 (kpa) (kpa) *) ) 4) Fig Fig % Fig NaCl NaCl Fig
68 Fig
69 Fig cm 2 8 kg J NaCl ( 1h)268g / m 2 h J NaCl ( 10h)= 175g / m 2 h Fig ) 64
70 Fig
71 30m :1.54cm 2 50l C.I M.W. 800 (7wt%) NaCl Na 2 SO wt% 45g 24 Fig Fig Fig ph ph:7.6 Fig HCl ph 3.0 NaCl Na 2 SO 4 ph HCl Na 2 SO 4 HCl Cl 2 SO 4 HCl Fig NaCl Cl 6) 7) Fig ph Fig (ph 3.0) 66
72 8)-10) 25 KCl mol/l NaCl 20wt% Symmetry structure (Asymmetry structure) 11) 67
73 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, , , , ,439 C.Linder, M.Nemas and M.Perry, U.S.Patent 5,304,307 68
74 75mm75mm2.5 1m 2 (1m) Table
75 70
76 Na + K + Ca 2+ Mg 2+ NaCl 71
77 1) 96.5% 3.5% 2) 72
78 , ,
79 P4VP PSSS PSSS DMF P4VP PSSS 1 / 1 20wt% KCl (60wt% ) KCl 50wt% 74
80 KCl 20wt% 75
81 76
82 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
83 , 8, 212 (1983), (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, , , , , , ,439, ,386 78
84 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
85 80
後期化学_01_濃度
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