4 4.1. 4.1.1.,,, /,,. [Wagick, 1990]. 1890 Maigrot Sabates [Maigrot et al. 1890].. 1903 Morse Pierce [Morse et al. 1903] 1920,. Bethe Toropoff [Bethe et al. 1914] (permagaate- impregated paper ad gelatie),. 1940. 1940 --. (multi-cell cofiguratio). diviylbezee. 1940 Ioic Ic. Juda [Juda et al. 1950] McRae, Rohm ad Hass o. Wiger, /.,,. 1980
. (Microfiltratio), (Ultrafiltratio), (Reverse osmosis), (Gas separatio), (pervaporatio). 1995 20 US $ [http://www.tifac.org.i/ews/memb.htm]. 40 % 50 US $, 12-15 %. 1. 50 %... 1. :. : () (1995) 4.1.2. (1),,,, Iterpolymer,. [Schröer, 1987].
M M R - Mt + R - Mt + Schematic of polymerizatio of moomers carryig io-exchage groups M M R - Mt + Schematic of itroductio of io-exchage groups ito polymers [Schröer, 1987]. M M 1 M 2 + m R - Mt + m M 2 R - Mt + Schematic of copolymerizatio of moomers cotaiig io-exchage groups with other moomers M 1 M 2 m + R- Mt + M 1 M 2 m R - Mt + Schmatic of itroductio of io-exchage groups ito radom copolymers [Ishizu et al, 1990],,. IAM IAM IAM M M M M IAM IAM iert polymer (e.g. PTE) is swolle with io-exchage moomer γ irradiatio M M M M IAM IAM IAM Schematic of graft polymerizatio of io-exchage moomers oto a iert polymer
Y Y Y M M M M Y Y Y iert polymer (e.g. PTE) swolle with moomer Y γ irradiatio M M M M Y Y Y uctioalizatio of Y with ioexchage groups M M M M Y Y Y R - Mt + R - Mt + R - Mt + Schematic of graft polymerizatio of moomer Y oto iert polymer, the fuctioalizatio of Y with io-exchage groups (IEP) (IEM)[Helfferich, 1959] host.. collodium host, (. ( )). Swellig With H 2 Impregatio Swolle etwork of host polymer + Dryig Solute of ioexchage polymer (polyelectrolyte) i H 2 Impregatio reactio for productio of io-exchage membraes Iterpolymer [Helfferich, 1959]. (. acrylitrile-viylchloride ) (, (), quarterized polymer (viylimida zole)).. N,N-dimethyl acetamide dimethyl sulfoxide. [Helfferich, 1959]
[Suryaaraya et al, 1963; Joshi et al, 1978]....,. (2),,,.. p-styree sulfoic acid, [Wiley et al, 1956]. [Eiseberg et at, 1982]. H H 2 Radical-iitiated solutio polymerizatio H Me=Na, K S 3 Me S 3 Me Radical polymerizatio of p-styree sulfoic acid, Na salt
H H 2 H H 2 Radical copolymerizatio + BP 60 o H H 2 poly(styree-co-diviylbezee) (crossliked) H H 2 Sulfoatio + H 2 S 4 ambiet T S 3 H partially sulfiated poly(styree-co-diviylbezee) H H 2 S 3 H S 3 H S 3 H Radical copolymerizatio of styree with diviylbezee ad subsequet sulfoatio of the crossliked copolymer (owove fabric) diviylbezee..., diviylbezee (). diviylbezee
. [riedlader, 1968]. ( ) [Schröer, 1987],,,. ( ). (/ acetyl sulfate) ethylee-propylee-diee terpolymers(thioic, producer Uiroyal). H 3 H 3 H 3 H 2 H 2 H 2 H H 2 H 2 H 2 H H 2 H 2 H 2 H H 2 S 4 NaH 3 or other base (H 3 ) 2 HH 3 H 3 H 3 S 3 H S 3 Na ( ) [Zschocke et al, 1985] ( ) [Guiver, 1987].. DuPot tetracluoroethylee trifluoroethylee- perfluoroether sulfoic acid [Hitzer, 1987] poly(perflorosulfoic acid) Nafio (maufacturer : DuPot) [oolly et at, 1966 : Grot, 1973].,, ioomer polymer-exchage membrae (PEM) PEM [Kerres et al, 1996-1998], chloralkali,.
+S 3 S rearragemet 3 + S reactio via rearragemet S 3 + x Radical copolymerizatio perfluoriated solvet peroxide or azo radical iitiators S 3 x The copolymer is extruded ; fially the sulfoyl fluoride group is hydrolyzed Nafio maufacturig process m tetrafluoroethee hexafluoro-4-trifluoroviyloxy-butaoic acid methyl ester perfluorocarboxylic acid ioomers [oue et al, 1980 : Asawa, 1981]. chloralkali.
H 3 + 3 Radical copolymerizatio H 2 NH 4 S 2 8 Na 2 HP 4 x12h 2 H 15 8 NH 4 H 3 3 The copolymer is extruded ; fially the methoxycarboyl group is hydrolyzed to yield the free carboxylic acid Maufacturig process for a perfluorocarboxylic acid ioomer m [Ishigaki et al, 1978], /.. host host... Perfluoriated host Nafio [Murphy et al, 1943 ; McRae et al, 1960 ; Sata et at, 1976]. PEM [Scherer, 1990]. (irradiatio) ethylee/ tetrafluor -oethylee copolymer film,,-trifluorostyree, [Scherer, 1990]. H 2 H 2 H 2 poly(tetrafluoroethee-co-ethee) γ radiatio radical formatio H 2 H H 2 radical graft polymerizatio H 2 H H 2 Sulfoatio H 2 H α,β,β trifluorostyree H 2 S 3 H S 3 H poly(tetrafluoroethee-coethee-graftα,β,β-trifluorostyree slufoic acid) Graft copolymer catio exchage membrae productio poly(tetrafluoroethee-coethee-graftα,β,β-trifluorostyree)
. (,, PV, ) [Helfferich, 1959]. 50-75 %..,... (3). 3 4,, -alkyledidihalogeide, 3 4,. backboe tertiary moo- difuctioal amie. Difuctioal amie. Udel bromomethylatio [Warshawsky et al, 1990]. H 3 H 3 H 3 H 3 Bromomethylatio H 3 (H 2 ) 7 --H 2 -Br Bromomethyl-oxtylether H 3 H 3 H 3 H 3 H 2 Br Amiatio INR 3 (R=Alkyl / Aryl) H 3 H 3 H 3 H 3 H 2 NR + 3 Br - Bromomethylatio ad subsequet amiaito of polysulfoe Udel
3 N 4 poly(viylpyridie) ( poly(4-viylpyridie), poly(2-viylpyridie)). poly(4-viylpyridie) poly(4-viylbezyl-chloride).. 4-viylpyridie radom poly(4-viyl pyridie-co-styree) [Reier et al, 1988]. chloromethylated polystyree H 2 l H 2 l H 2 l + N N N poly(4-viylpyridie) Amiatio H 2 H 2 H 2 l l l N N N crossliked quarterary polyammoium salt Akylatio of poly(4-viylpyridie) with poly(4-viylbezylchloride),-alkyledidihalogeide diamie, -alkyledidihalogeide [2.2.2]-diazabicyclooctae(DAB)
[Matsui et al, 1986; Dietrich et al, 1970; Bauer et al, 1980; Almarzoqi et al, 1986]. 4-viyl-bezee sulfoate [Schröer, 1987].. N N + Br x Br Br N N Br x Sythesis of a mai-chai-aio-exchage polymer 3 4. Poly(tetrafluoroethee) (PTE) -ray(o 60 ), PTE [aepa et al, 1973] 4-viylpyridie 4. lemio poly(perfluorocarboxylic acid) [Kitamura et al, 1986 : ukuda et al, 1987]. Tokuyama o. Ltd..,. R Sl 2 R NHR2 ' R H l NR 2 ' NaBH 4 R'-I R NR 4 ' + I - R NR 3 ' Scheme for direct modificatio of lemio poly(perfluorocarboxylic acid)
/ (Table 2). /. 2.
4.1.3...,. (1) (Specific Io Permselective Membraes) 70... [Yamae et al. 1962]... [da et al. 1961].. Tokuyama Soda o. (Neosepta MS) (Neosepta AS). MS sodium magesium 1.2 0.1, AS chloride sulfate 0.5 0.01 [Sata et al. 1984].. Yamae sodium 12 [Yamae et al. 1965].
(). Tokuyama Soda o. Neosepta AM [Urao et al. 1984]. Sata crow ethers 18-crow-6 15-crow-5 [Sata et al. 2000]. [ldai et al. 1992, Sata et al. 1995], [Sata et al. 1998].. - - - - (photoresposive) (photoirradiatio) - (thermally resposive).. (2) (atifoulig).... (degree of cross-likig).
Guderatsch poly-(4-viylpyridie) methyliodide dibromoalkae [Guderatsch et al. 1989].. Tokuyama Soda o. 4. (3) (fluorocarbo-type) chlor-alkali. Du Pot [Goolly et al. 1966]. perfluoroviylether tetrafluoroethylee (TE) TE sulfur trioxide. hexafluoropropylee oxide sulfoyl fluoride sulfoyl fluoride viyl ether TE. -S 2 -S 3Na -S 2 -H.. Du Pot Asahi hmical Ic., Tokuyama Soda o., Dow hemical Ic.. Du Pot Ic. Nafio Asahi hemical Ic. lemio luorocarbo, 50 % [Powers, 2000]. (4) (Alkalie Stable) polymer backobe perfluoriatio. Matsui [Matsui et al. 1986]. 1-bezyl-1-4-azo
-bicyclo[2.2.2]-octae hydroxide [Bauer et al. 1988]. (5) (bipolar membrae).. ph,,.. (6) (hybrid membrae).,. ioomer. (90-180 ) [Moica et al. 2001]. (7) (charged mosaic composite membrae) poly(4-viylpyridie-isopree-styree-isopree-4-viyl pyridie) poly(4-methylstyree-isopree-styree-isopree-4-methylstyree) petablock... poly(isopree-4-methylstyree) diblock copolymer poly(isopree-styree-isopree) triblock copolymer, [Behui et al. 2001]. gel (4VP/DVB) gel
(SSNa/DVB) [Yamauchi et al]..
Substrate Plasma Iducig Activated Substrate Graftig moomer Polymerizatio
4.1.4.