Abstract
This article is a review of the research on environmentally responsive polymer gels done by Stevin H. Gehrke's research group at the University of Cincinnati. This group has studied a wide variety of responsive gels, including crosslinked cellulose ethers, poly(N-isopropylacrylamide), and radiation-crosslinked poly(vinyl methyl ether). Equilibrium swelling has been studied both experimentally and theoretically, with the general goal of learning how to control the nature of the volume transition. Conditions under which transition-inducing stimuli affect the rate of volume change have been identified and a diffusion analysis is shown to be broadly useful for correlating the kinetics. Polymer scaling theory provides a qualitative basis for understanding how polymer composition and stimulus interval influence the magnitude of the network diffusion coefficient. The response rate of gels can be several orders of magnitude greater than this if they are microporous and can absorb and expel solvent by a convective process. Diffusion coefficients of solutes in gels decline as the gel shrinks, in generally good agreement with free volume theories. Hydrophobic interactions between gels and drugs are often quite strong, especially in deswollen gels. The ability of these gels to dewater coal slurries has also been established.
Preview
Unable to display preview. Download preview PDF.
Abbreviations
- APS:
-
ammonium persulfate
- C:
-
mass of crosslinking monomer per 100 g of monomers
- CMC:
-
carboxymethylcellulose
- D:
-
diffusion coefficient
- Do :
-
diffusion coefficient in free solution
- DSC:
-
differential scanning calorimetry
- DVS:
-
divinyl sulfone
- f:
-
friction factor between network and solvent
- G:
-
shear modulus of gel
- GRAS:
-
generally recognized as safe
- HPC:
-
hydroxypropylcellulose
- HPMC-E:
-
hydroxypropylmethylcellulose, Type E
- HPMC-K:
-
hydroxypropylmethylcellulose, Type K
- k:
-
mass transfer coefficient
- K:
-
bulk modulus of gel
- K:
-
partition coefficient
- Ko/w :
-
octanol/water partition coefficient
- LCST:
-
lower critical solution temperatures
- L0 :
-
initial sample thickness
- Lt/L∞ :
-
normalized change in characteristic sample dimension
- MC:
-
methylcellulose
- Mt/M∞ :
-
normalized approach to equilibrium mass
- N:
-
number of polymer structural units in an effective chain segment
- NIPAAm:
-
N-isopropylacrylamide
- P*g :
-
polymer cohesive energy density
- PNIPAAm:
-
poly(N-isopropylacrylamide)
- P*s :
-
solvent cohesive energy density
- PVME:
-
poly(vinyl methyl ether)
- Q:
-
equilibrium swelling degree of gel
- SDS:
-
sodium dodecyl sulfate
- SMB:
-
sodium metabisulfite
- T:
-
mass of monomers (in grams) added to 100 ml of water
- T:
-
temperature
- t:
-
time
- TEAC:
-
tetraethylammonium chloride
- TEMED:
-
N,N,N′,N′-tetramethylethylenediamine
- Te :
-
equilibrium temperature
- Ti :
-
initial temperature
- Ts :
-
spinodal temperature
- Tt/T∞ :
-
normalized approach to equilibrium temperature
- v:
-
velocity
- Zsg :
-
correction for deviation from a geometric mean mixing rule
- φ:
-
polymer volume fraction
- η:
-
solvent viscosity
- Ξ:
-
correlation length
9 References
Gehrke SH, Lee PI (1990) In: Tyle P (ed) Specialized drug delivery systems: manufacturing and production technology. Marcel Dekker, New York, p 333
Tanaka T (1981) Sci Am 244: 124
Peppas NA, Barr-Howell BD (1986) In: Peppas NA (ed) Hydrogels in medicine and pharmacy, vol I fundamentals. CRC Press, Boca Raton, FL, p 27
Freitas RFS, Cussler EL (1987) Chem Eng Sci 42: 97
Gehrke SH, Cussler EL (1989) Chem Eng Sci 44: 559
Tanaka T, Nishio I, Sun S, Ueno-Nishio S (1982) Science 218: 467
Tanaka T (1978) Phys Rev Lett 40: 820
Suzuki A, Tanaka T (1990) Nature 346: 345
Mamada A, Tanaka T, Kungwatchakun D, Irie M (1990) Macromolecules 23: 1517
Lee KK, Cussler EL, Marchetti M, McHugh MA (1990) Chem Eng Sci 45: 766
Ohmine I, Tanaka T (1982) J Chem Phys 11: 5725
Huang X, Unno H, Akehata T, Hirasa O (1988) J Chem Eng Jpn 21: 10
Horbett TA, Kost J, Ratner BD (1984) In: Shalaby SW, Hoffman AS, Ratner BD, Horbett TA (eds) Polymers as biomaterials. Plenum, New York, p 193
Sussmann MV, Katchalsky A (1970) Science 167: 45
Tatara Y (1978) Polym J 10: 563
Lyu LH, Gehrke SH (1989) AIChE Annual Meeting, Paper 98j, San Francisco, CA
Katchalsky A (1949) Experientia 5: 319
Katchalsky A, Sussmann MV, Oplatka A, Steinberg I (1967) US Patent No. 3,321,908
Dusek, K, Patterson D (1968) J Polym Sci A-2 6: 521
Research Institute for Polymers and Textiles Bulletin (1989) Ibaraki, Japan p 12
Taylor LD, Cerankowski LD (1975) J Polym Sci, Polym Chem Edn 13: 2551
Hirokawa Y, Tanaka T (1984) J Chem Phys 81: 6379
Katayama S, Hirokawa Y, Tanaka T (1984) Macromolecules 17: 2641
Bae YH, Okano T, Kim SW (1989) J Controlled Release 9: 271
Okano T, Bae YH, Jacobs H, Kim SW (1990) J Controlled Release 11: 255
Mukae K, Bae YH, Okano T, Kim SW (1990) Polym J 22: 250
Hoffman AS, Afrassiabi A, Dong LC (1986) J Controlled Release 4: 213
Hoffman AS (1987) J Controlled Release 6: 297
Cussler EL, Stokar MR, Varberg JE (1984) AIChE J 30: 578
Gehrke SH, Andrews GP, Cussler EL (1986) Chem Eng Sci 41: 2153
Trank SJ, Cussler EL (1987) Chem Eng Sci 42: 381
Siegel RA, Firestone BA (1988) Macromolecules 21: 3254
Firestone BA, Siegel RA (1988) Polym Commun 29: 204
Beltran S, Hooper HH, Blanch HW, Prausnitz JM (1990) J Chem Phys 92: 2061
Hooper HH, Baker JP, Blanch HW, Prausnitz JM (1990) Macromolecules 23: 1096
Yoshio N, Hirohito N, Matsuhiko M (1986) J Chem Eng Jpn 19: 274
Amiya T, Tanaka T (1987) Macromolecules 20: 1162
Harsh DC, Gehrke SH (1990) In: Brannon-Peppas L, Harland R (eds) Absorbent polymer technology. Elsevier, Amsterdam, p 103
Huang X, Unno H, Akehata T, Hirasa O (1987) J Chem Eng Jpn 20: 123
Peppas NA (1987) In: Hydrogels in medicine and pharmacy, vol. 2 polymers. CRC Press, Boca Raton FL, p 1
Urry DW, Harris D, Long MM, Prasad KU (1986) J Peptide Protein Res 28: 649
Klier J, Scranton AB, Peppas NA (1990) Macromolecules 23: 4944
Scranton AB, Klier J, Peppas NA (1991) J Polym Sci, Polym Phys Ed 29: 211
Scranton AB, Klier J, Aronson CL (1992) In: Harland RS, Prud'homme, RK (eds) Polyelectrolyte gels, ACS symposium series 480. American Chemical Society, Washington, DC
Gehrke SH, Palasis M, Akhtar MK (1992) Polymer Int 28: 29
Kabra BG, Akhtar MK, Gehrke SH (1992) Polymer 33: 990
Ilavsky M (1981) Polymer 22: 1687
Ilavsky M (1982) Macromolecules 15: 782
Prange MM, Hooper HH, Prausnitz JM (1989) AIChE J 35: 803
Marchetti M, Prager S, Cussler EL (1990) Macromolecules 23: 1760
Marchetti M, Prager S, Cussler EL (1990) Macromolecules 23: 3445
Harsh D, Gehrke SH (1991) J Controlled Release 17: 175
Harsh D, Gehrke SH (1993) In: El-Nokaly M, Piatt D, Charpentier B (eds) Polymeric delivery systems. ACS symposium series 520. American Chemical Society, Washington, DC, p 105
Otake K, Inomata H, Konno M, Saito S (1990) Macromolecules 23: 283
Tanaka T, Sun ST, Hirokawa Y, Katayama S, Kucera J, Hirose Y, Amiya T (1987) Nature 325: 796
Matsuo ES, Tanaka T (1988) J Chem Phys 89: 1695
Grimshaw PE, Grodzinsky AJ, Yarmush ML, Yarmush DM (1990) Chem Eng Sci 45: 2917
Chou LY, Blanch HW, Prausnitz JM (1992) J Appl Poly Sci 45: 1411
Gehrke SH, Lyu LH, Yang MC (1989) Polym Prepr 30: 482
Tanaka T, Fillmore DJ (1979) J Chem Phys 70: 1214
Gehrke SH, Akhtar MK (1990) In: 33rd IUPAC international symposium on macromolecules. July 8–13, Montreal, Canada
Tanaka T, Sato E, Hirokawa Y, Hirotsu S, Peetermans J (1985) Phys Rev Lett 55: 2455
Li Y, Tanaka T (1990) J Chem Phys 92: 1365
Li Y, Tanaka T (1991) In: De Rossi D, Kajiwara K, Osada Y, Yamauchi A (eds) Polymer gels: Fundamentals and biomedical applications. Plenum Press, New York, p 41
Kabra B, Gehrke S (1991) Polym Commun 32: 322
Tatara Y, Mori M (1972) Trans Jpn Soc Mech Eng 38: 2807
Chiarelli P, Umezawa K, De Rossi D (1991) In: De Rossi D, Kajiwara K, Osada Y, Yamauchi A (eds) Polymer gels: Fundamentals and biomedical applications. Plenum, New York, p 195
Leung BK, Robinson J (1990) J Membr Sci 52: 1
Feil H, Bae YH, Feijen J, Kim SW (1991) J Membr Sci 64: 283
Palasis M, Gehrke SH (1992) J Controlled Release 18: 1
De Rossi D, Kajiwara K, Osada Y, Yamauchi A (eds) (1991) Polymer gels: Fundamentals and biomedical applications. Plenum, New York
Urry DW, Harris RD, Prasad KU (1988) J Am Chem Soc 110: 3303
Suzuki M (1989) Kobunshi Ronbunshu 46: 603
Tatara Y (1987) Adv Robotics 2: 69
Bishop JE (1990) In: The Wall Street Journal, August 13, p B1
De Rossi DE, Galletti PM, Dario P, Richardson PD (1983) ASAIO J 6: 1
De Rossi DE, Parrini P, Chiarelli P, Buzzigoli G (1985) Trans Am Soc Artif Intern Organs 31: 60
De Rossi DE, Chiarelli P, Buzzigoli G, Domenici C, Lazzeri L (1986) Trans Am Soc Artif Intern Organs 32: 157
Chiarelli P, De Rossi D (1988) Progr Colloid Polym Sci 78: 4
Stinson S (1990) Chem Eng News, January 8, p 30
Shiga T, Hirose Y, Okada A, Kurauchi T (1990) Polym Prepr 30: 310
Sheppard NF, Lee HL, Madrid Y, Melcher JR, Langer RS (1988) Annual AIChE Meeting, paper 120i, Washington DC
Osada Y, Umezawa K, Yamauchi A (1988) Makromol Chem 189: 597
Umezawa K, Osada Y (1987) Chem Lett 1795
Gillmore VE (1989) Popular Sci 235: 24
Wald ML (1992) In: The New York Times, August 16, p F9
Tanaka T (1992) In: Harland RS, Prud'homme RK (eds) Polyelectrolyte gels, ACS symposium series 480. American Chemical Society, Washington, DC, p 1
Urry DW (1990) Polymeric Materials Eng Sci 63: 329
Cornejo-Bravo JM, Siegel RA (1990) Proc Intern Symp Contr Rel Bioact Mat 17: 174
Grimshaw PE, Grodzinsky AJ, Yarmush ML, Yarmush DM (1989) Chem Eng Sci 44: 827
Grodzinsky AJ, Grimshaw PE, Yarmush ML (1990) Proc Intern Symp Contr Rel Bioact Mat 17: 108
Afrassiabi A, Hoffman AS, Cadwell LA (1987) J Membr Sci 33: 191
Dong LC, Hoffman AS (1992) J Controlled Release 19: 171
Dong LC, Hoffman AS (1990) J Controlled Release 13: 21
Mukae K, Bae YH, Okano T, Kim SW (1990) Polym. J 22: 206
Bae YH, Okano T, Kim SW (1989) J Controlled Release 9: 271
Bae YH, Okano T, Kim SW (1991) Pharm Res 8: 531
Bae YH, Okano T, Kim SW (1991) Pharm Res 8: 624
Kwon IC, Bae YH, Kim SW (1991) Nature 28: 291
Kwon IC, Bae YH, Okano T, Kim SW (1991) J Controlled Release 17: 149
Horbett TA, Ratner BD, Kost J, Singh M (1984) In: Anderson JM, Kim SW (eds) Recent advances in drug delivery systems. Plenum, New York, p 209
Horbett TA, Ratner BD (1988) Proceedings Pharm Tech Conference '88. East Rutherford, NJ, p 356
Kost J, Horbett TA, Ratner BD (1985) J Biomed Mater Res 19: 1117
Albin GW, Horbett TA, Miller SR, Ricker NL (1987) J Controlled Release 6: 267
Osada Y, Takeuchi Y (1981) J Polym Sci, Poly Lett Ed 19: 303
Osada Y, Takeuchi Y (1983) Polym J 15: 279
Osada Y, Hasebe M (1985) Chem Lett 12: 85
Huang X, Akehata T, Unno H, Hirasa O (1989) Biotech Bioeng 34: 102
Hirasa O, Ito, S, Yamauchi A, Fujishige S, Ichijo H (1991) In: DeRossi D, Kajiwara K, Osada Y, Yamauchi A (eds) Polymer gels: Fundamentals and biomedical applications. Plenum Press, New York, p 241
Dong LC, Hoffman AS (1986) J Controlled Release 4: 223
Gehrke SH (1986) Kinetics of gel volume change and its interaction with solutes. Thesis, University of Minnesota, Minneapolis, MN
Kabra BG, Gehrke SH, Hwang ST, Ritschel W (1991) J Appl Polym Sci 42: 2409
Gehrke SH (1992) to appear in: Lee PI (ed) Fundamental aspects of polymers in pharmaceutics. Elsevier, Amsterdam
Gehrke SH, Johnson JF, Robeson J, Vaid N (1991) Biotech Prog 7: 355
Gehrke SH, Lyu, LH, Barnthouse K (1992) submitted
Lyu LH (1990) Dewatering fine coal slurries by gel extraction. Thesis, University of Cincinnati, Cincinnati, OH
Gehrke SH, Lyu LH (1990) Final project report: Dewatering fine coal slurries by gel extraction. Ohio Coal Development Office, Columbus, Ohio
Gehrke SH, Yang MC, Kabra BG, Lyu LH, Akhtar MK (1989) Proceed Intern Symp Control Rel Bioact Mater 16: 209
Gehrke SH, Akhtar MK (1992) submitted
Akhtar MK, Gehrke SH (1992) submitted
Akhtar MK (1990) Volume change kinetics in near critical gels. Thesis, University of Cincinnati, Cincinnati OH
Palasis M, Gehrke SH (1990) Proceed Intern Symp Contr Rel Bioact Mater 17: 385
Palasis M (expected, 1993) Permeability of responsive polymer gels. Thesis, University of Cincinnati, Cincinnati OH
Harsh DC, Gehrke SH (1989) Proceed Intern Symp Contr Rel Bioact Mater 16: 383
Harsh DC (1992) Controlling swelling characteristics of novel cellulose ether gels. Thesis, University of Cincinnati, Cincinnati OH
Kabra BG (expected, 1993) Relationships between synthesis, structure, and swelling properties of responsive polymer gels. Thesis, University of Cincinnati, Cincinnati OH
Gehrke SH, Agrawal G, Yang MC (1992) In: Harland RS, Prud'homme, RK (eds) Polyelectrolyte gels, ACS symposium series 480. American Chemical Society, Washington, DC, p 211
Hrouz J, Ilavsky M, Ulbrich K, Kopecek J (1981) Eur Polym J 17: 361
Ilavsky M, Hrouz J, Ulbrich K (1982) Polym Bull 7: 107
Hirotsu S, Hirokawa Y, Tanaka T (1987) J Chem Phys 87: 1392
Trank SJ, Johnson DW, Cussler EL (1989) Food Tech. 43: 78
Dualeh AJ, Steiner CA (1992) In: Harland RS, Prud'homme, RK (eds) Polyelectrolyte gels, ACS symposium series 480. American Chemical Society, Washington, DC, p 42
Doelker E (1990) In: Brannon-Peppas L, Harland RS (eds) Absorbent polymer technology. Elsevier, Amsterdam, p 125
Doelker E (1986) In: Peppas NA (ed) Hydrogels in medicine and pharmacy, vol. II polymers. CRC Press, Boca Raton, FL, p 115
Butler RW, Klug ED (1980) In: Davidson RL (ed) Handbook of water-soluble gums and resins. McGraw-Hill, New York, p 1
Brannon-Peppas L (1990) In: Brannon-Peppas L, Harland RS (eds) Absorbent polymer technology. Elsevier, Amsterdam, p 67
Brannon-Peppas L, Peppas NA (1988) Polym Bull 20: 285
Sanchez IC, Lacombe RH (1976) J Phys Chem 80: 2352
Lacombe RH, Sanchez IC (1976) J Phys Chem 80: 2568
Sanchez IC, Lacombe RH (1978) Macromolecules 11: 1145
Sanchez IC, Balazs AC (1989) Macromolecules 22: 2325
Welty JR, Wicks CE, Wilson RE (1984) Fundamentals of momentum, heat, and mass transfer, 3rd edn. John Wiley, New York
Perry RH, Green D (1984) Chemical engineering handbook, 6th edn. McGraw-Hill, New York
Carslaw AS, Jaeger JC (1959) The conduction of heat in solids, 2nd edn. Oxford Clarendon Press, Oxford
Helfferich F (1965) J Phys Chem 69: 1178
Helfferich F (1962) Ion Exchange. McGraw-Hill, New York
Dana PR, Wheelock TD (1974) Ind Eng Chem Fund 13: 20
Levenspiel O (1972) Chemical Reaction Engineering, 2nd edn. John Wiley, New York
Crank J (1975) The mathematics of diffusion, 2nd edn. Oxford University Press, London
Meares P (1968) In: Crank J, Park G (eds) Diffusion in polymers. Academic, London, p 373
Tanaka T, Hocker LO, Benedek GB (1973) J Chem Phys 59: 5151
de Gennes. PG (1979) Scaling concepts in polymer physics. Cornell Unoversity Press, Ithaca, New York
Billovits GF, Durning CJ (1989) Chem Eng Commum 82: 21
Peters A, Schosseler F, Candau SJ (1989) In: Glass J (ed) Polymer in aqueous media: performance through association. Advances in chemistry series 223. American Chemical Society, Washington, DC, p 45
Chatterjee PK, Nguyen HV (1985) In: Chatterjee PK (ed) Absorbency. Textile science and technology, vol. 7. Elsevier Science Publishers, Amsterdam, p 29
Williams JM, Wrobleski DA (1989) Langmuir 4: 656
Barby D, Haq Z (1982) European Patent 0,060,138
Williams JM, Wilkerson KR (1990) Polymer 31: 2162
Yasuda, H, Peterlin A, Colton CK, Smith KA, Merrill EW (1969) Die Makromol Chem 126: 177
Schnitzer JE (1988) Biophys J 54: 1065
Peppas NA, Reinhart (1983) J Membr Sci 15: 275
Lustig SR, Peppas NA (1988) J Appl Polym Sci 36: 735
Dearden JC, Tomlinson E (1971) J Pharm Pharmac 73: 735
Hansch C, Anderson S (1967) J Org Chem 32: 2583
Ruckenstein E, Lesins V (1988) In: Mizrahi A (ed) Downstream processes: equipment and techniques. Alan R. Liss, New York, p 246
Luck WA (1980) In: Rowland SP (ed) Water in polymers, ACS symposium series 127. American Chemical Society, Washington DC, p 43
Scopes RK (1987) Protein purification: principles and practice, 2nd edn. Springer, Berlin Heidelberg New York
Hashman T, Palasis M (1988) unpublished research
Author information
Authors and Affiliations
Editor information
Rights and permissions
Copyright information
© 1993 Springer-Verlag
About this chapter
Cite this chapter
Gehrke, S.H. (1993). Synthesis, equilibrium swelling, kinetics, permeability and applications of environmentally responsive gels. In: Dušek, K. (eds) Responsive Gels: Volume Transitions II. Advances in Polymer Science, vol 110. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0021130
Download citation
DOI: https://doi.org/10.1007/BFb0021130
Received:
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-56970-1
Online ISBN: 978-3-540-47836-2
eBook Packages: Springer Book Archive