Preparation of Semi-IPN Type Antifouling UF Membranes and Their Application TAKADA Tetsuo, SUGANUMA Toshikazu and KUROKI Katsuhito A novel hydrophilic ultrafiltration(uf) membrane having a semi-ipn(interpenetrating polymer network) structure of a linear polymer and hydrophilic cross-linked polymer was prepared. The adsorption of Bovine Serum Albumin(BSA) significantly decreased with the increase in the hydrophilic groups introduced into the membranes. A polyethylene glycol(peg) introduced membrane showed good performance during blood filtration compared with the commercial polysulfon(psf) UF membrane, and almost no decrease in flux occurred during a 6-hr. filtration. The PEG-introduced membrane also showed good filtration performance and antifouling during the filtration of oil-polluted drainage. 1 (MF) (UF) 1,2 MF UF 3,4 IPN UF 5-7 (PSf) DIC Technical Review No.6 / 2000 Fig. 1 Schematic diagram of formation of semi-ipn porous structure. 33
(PEG) UF 2 2.1 N,N IPN(Fig.1) 2.2 ESCA-850 (depth-profiling) Fig.2 UF filter consisting of an antifouling UF membrane and housings having spiral channels. 2.3 47a 20ml 50mg/dl ph7.024 2.4 3000ml 1000ppm Fig. 3 Change in pore size of membranes with the content of crosslinking monomer. a is the air-side(membrane surface), b is the substrate-side; a1,b1, 10wt%; a2,b2, 20wt%; a3,b3, 26wt%; a4,b4, 33wt%. 34 DIC Technical Review No.6 / 2000
10 100ppm 2.5 Fig.2 17.5f (Ht) 30-35% T.P. 5-6g/dl ( ) 200ml/min200mmHg 49kPa QF 30 (BSA) Fig.5 Change of element composition of surface with introduction of hydrophilic groups into the membranes. PA stands for the polyamide; PSf, for the polysulfone; Am, for the amide group. 2.6 Na + K + 348 (Chiron Diagnostics Co.) (UN) B( ) 3 3.1 Fig.3 IPN Fig.6 Contact angle of surface of semi-ipn UF membranes. Fig.4 The element composition of the surface of semi- IPN type hydrophilic UF membranes. d stands for the depth from the front surface of the membranes. The values in parentheses are segregation rates. 3.2 ESCA Fig.4 DIC Technical Review No.6 / 2000 35
Fig. 7 Change of BSA adsorptivities with introduction of the hydrophilic groups into the membranes. PA stands for polyamide; PEG, for polyethylene glycol; PSf, for polysulfone; Am, for amide group; CA, for cellulose acetate. Fig.5 (Fig.6) Fig. 8 Heat resistance of UF membranes having semi- IPN structures of polysulfone and crosslinked polymer. CA stands for cellulose acetate; PSf, for polysulfone; BPE-4, for bisphenol A ethoxylate diacrylate; TMPT, for trimethylolpropane triacrylate; HDDA, for hexanediol diacrylate; 310HP, for tripropyleneglycol diacrylate; A-400, for polyethylene glycol diacrylate; UA, for 3 functional urethane acrylate. Heat treatment condition is 120 steam for 20min. 3.3 (BSA) Fig.7 3.4 Fig.8 Ft/Fo Fig. 9 Change of flux with time during the filtration of 6 hours with bovine whole blood. The filtration condition is 200 mmhg, 200ml/min. PA-PEG stands for the PEG-containing polyamide UF membrane; the values in parentheses are the content of PEGcontaining monomer; commercail PSf memb., for the commercial UF membrane with molecular weight cut off of 50000. (CA) (PSf) 36 DIC Technical Review No.6 / 2000
Fig. 10 Change of ion concentration in permeate with time during the filtration of 6 hours. 3.5 Fig.9 PEG 20% QF (0.3ml/min) QF UF QF Na + K + Fig.10 10 99.9% Fig. 12 Picture of hemodialysis monitoring system. 3.6 6-8 Na + K + (UN) UF UF Na + K + UN Fig. 11 Schematic diagram of hemodialysis monitoring system. DIC Technical Review No.6 / 2000 Fig. 13 Change of ions, UN concentration with time during the filtration of 6 hours.,, are the values in blood;,, are the values in permeate. 37
(Fig.11,12) UF 0.3ml/min UF (Fig.11, 12) 6 (Na + K + UN) Fig.13 Na + K + UN 99.9 6 (TMP) UF Fig. 14 Changes of flux with the filtration time of fuel oil dispersed sea water for different UF and MF membranes. CN(0.2 m) stands for the cellulose nitrate MF membrane with pore size of 0.2 m; PA- PEG, for the semi-ipn antifouling UF membrane of polyamide/crosslinked polymer containing PEG(mole-cule weight cutoff, 20,000); CA, for the cellulose acetate UF membrane with molecular weight cutoff of 20,000 and 10,000 respectively; PSf (50k), for the polysulfone UF membrane with molecular weight cutoff of 50,000. 3.7 11) Fig.7 UF PEG IPN UF Fig.14 0.2 m MF (CN, 0.2 m) 30 6 1266 10-8 k/g-sec-kpa UF 3 PEG IPN UF (PA-PEG) 20,000 Fig. 15 Photographs of MF and UF membranes after filtration of fuel oil dispersed sea water. a, CN (0.2 m); b, PSf (50k); c, PA-PEG; d, CA (20k). UF (CA, 20k) PA-PEG CA 6 146 10-8 122 10-8 39 10-8 k/g-sec-kpa MF (CN,0.2 m) MF 38 DIC Technical Review No.6 / 2000
Fig.16 SEM of MF and UF membranes before(b) and after(a) filtration of fuel oil dispersed sea water. UF (PSf, 50k) (Fig.15) MF (CN, 0.2 m) p. 2 2 4-6 (SEM) (Fig.16) UF PA-PEG CA(20k) UF SEM (Fig.16) UF Fig.16 PA-PEG (Fig.14) SEM 4 IPN UF PEG PEG (0.3ml/min) 6 Na + K + PEG '99 1) H. Reihanian, C.R. Robertson and A.S. Michaels, J. Membrane Sci., 16, 237(1983). 2) 14(1) 64(1989). 3) 26(2) 418(1997). 4) 43 97 50(1997). 5) H.S. Chang, Y. Watanabe, T. Suganuma, M. Miyajima, DIC Technical Review No.6 / 2000 39
and T. Anazawa, RadTech'97, 832(1997). 6) 45 98 52(1998). 7) 35(1997). 8) 29(3) 205(1996). 9) 43(3) 2 05(1985). 10) 27(4) S-16(1998). 11) 35(1996). TAKADA Tetsuo SUGANUMA Toshikazu KUROKI Katsuhito 40 DIC Technical Review No.6 / 2000