Abstract
The formation of homopolymer and block copolymer brushes grafted from flat and nanoparticle surfaces via surface-initiated anionic and cationic polymerization methods is reviewed. Unique properties of these chain addition polymerization methods distinguish them from free-radical and living-radical methods, i.e., primarily the formation of charged reactive propagating centers. This involves the use of methods that preserve the reactivity of the charged species, where the monomer, solvent quality, and lack of terminating species allow for grafting to surfaces and for the formation of homopolymer and block copolymers. While these initiators are analogous to solution and bulk methods and adapted to surfaces, their mechanisms do not necessarily follow their counterparts. Several systems for surface-initiated polymerization (SIP) will be reviewed including early attempts at “grafting onto” and “grafting from” particles. For initiation, alkylsilane or alkylthiol anionic initiators are grafted onto planar and particle surfaces by self-assembled monolayer (SAM) techniques. For the cationic (carbocationic) polymerization methods, methods of tethering Lewis acids to surfaces have been reported. The grafted polymer chains can be investigated in situ using a number of surface-sensitive spectroscopic and microscopic techniques. They can also be analyzed ex situ when the polymer chains are removed from the substrate surface. Activation of the grafted initiator, control of polymerization conditions, and removal of excess activators are emphasized. Interesting differences in particle properties, morphology, thickness, grafting density, and polymerization conditions contrast anionic and cationic charged species from other SIP mechanisms. The problems and potential of these techniques will also be discussed. The formation of block copolymer sequences highlights a unique utility of living anionic and cationic polymerization techniques on surfaces.
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Abbreviations
- SIP:
-
Surface-initiated polymerization
- SAM:
-
Self-assembled monolayers
- MW:
-
Molecular weight
- R g :
-
Radius of gyration
- LASIP:
-
Living anionic surface-initiated polymerization
- ATRP:
-
Atom-transfer radical polymerization
- ROMP:
-
Ring-opening metathesis polymerization
- TEMPO:
-
2,2,6,6-tetramethyl-1-piperidyloxy
- RAFT:
-
Reversible addition fragmentation chain transfer
- NMR:
-
Nuclear magnetic resonance
- GPC:
-
Gel permeation chromatography
- XPS:
-
X-ray photoelectron spectroscopy
- AFM:
-
Atomic force microscopy
- TEM:
-
Transmission electron microscopy
- PS:
-
Polystyrene
- PBd:
-
Polybutadiene
- PI:
-
Polyisoprene
- DPE:
-
1,1-diphenylethylene
- THF:
-
Tetrahydrofuran
- QCM:
-
Quartz crystal microbalance
References
Advincula R, Ruehe J, Brittain W, Caster K (eds) (2004) Polymer Brushes. Wiley, Weinheim, p 483
Advincula R (2003) J Dispersion Sci Tech 24:361
Advincula R (2004) Polymer Brushes. In: Kroschwitz J (ed) Encyclopedia of Polymer Science and Technology. Wiley, New York
Halperin A, Tirrell M, Lodge TP (1992) Adv Polym Sci 100:31
Tadros T (1982) The Effect of Polymers on Dispersion Properties. Academic, London
Krishnamoorti R, Vaia R (2002) Polymer Nanocomposites. ACS Symposium Series 804. Oxford University Press, Cary, NC
Prücker O, Rühe J (1998) Langmuir 14:6893
Zhao B, Brittain W (2000) Prog Polym Sci 25:677
Prücker O, Rühe J (1998) Macromolecules 31:592
Jordan R, Ulman A (1998) J Am Chem Soc 120:243
Weck M, Jackiw J, Rossi R, Weiss P, Grubbs R (1999) J Am Chem Soc 121:4088
Ejaz M, Yamamoto S, Ohno K, Tsujii Y, Fukuda T (1998) Macromolecules 31:5934
Kong X, Kawai T, Abe J, Iyoda T (2001) Macromolecules 34:1837
Yamamoto S, Tsujii Y, Fukuda T (2000) Macromolecules 33:5995
von Werne T, Patten T (2001) J Am Chem Soc 123:7497
Jones D, Brown A, Huck W (2002) Langmuir 18:1265
Husseman M, Malmstrom E, McNamara M, Mate M, Mecereyes D, Genoit G, Hedrick J, Mansky P, Huang E, Russell T, Hawker C (1999) Macromolecules 32:1424
Zhou Q, Nakamura Y, Inaoka S, Park M, Wang Y, Mays J, Advincula R (2000) Poly Math Sci Eng Preprint (Am Chem Soc) 82:291
Baum M, Brittain WJ (2002) Macromolecules 35:610
Sedjo RA, Mirous BK, Brittain WJ (2000) Macromolecules 33:1492
Odian G (2004) Principles of Polymerization, 4th edn. Wiley, New York
Pitsikalis M, Pispas S, Mays J, Hadjichristidis N (1998) Adv Polym Sci 135:1
Zhou Q, Wang S, Fan X, Pispas S, Sakellariou G, Hadjichristides N, Mays J, Advincula R (2001) Polym Preprints 42:59
Quirk R, Mathers R (2001) Polym Bull 6:471
Ingall M, Honeyman C, Mercure J, Bianconi P, Kunz R (1999) J Am Chem Soc 121:3607
Jordan R, Ulman A, Kang J, Rafailovich M, Sokolov J (1999) J Am Chem Soc 121:1016
Zhou Q, Fan X, Xia C, Mays J, Advincula R (2001) Chem Mater 13:2465
Zhou Q, Wang S, Fan X, Advincula R, Mays J (2002) Langmuir 18:3324
Fan X, Zhou Q, Xia C, Cristofoli W, Mays J, Advincula R (2002) Langmuir 18:4511
Hsieh H (1965) J Polym Sci A3:163
Fetters LJ, Morton M (1974) Macromolecules 7:552
Bhattacharyya DN, Lee CL, Smid J, Szwarc M (1965) J Phys Chem 69:612
Wakefield BJ (1974) The Chemistry of Organolithium Compounds. Pergamon, Oxford
Papirer E, Nguyen VT (1972) J Polym Sci Polym Lett Ed 10(3):167
Horn J, Hoene R, Hamann K (1975) Macromol Chem Suppl 1:329
Donnet JB, Papirer E (1975) Colloques Internationaux du Centre National de la Recherche Scientifique 231:117
Tsubokawa N, Yoshihara T, Sone Y (1991) Colloid Polym Sci 269:324
Tsubokawa N, Funaki A, Hada Y, Sone Y (1982) J Polym Sci Polym Chem Ed 20(12):3297
Tsubokawa N, Funaki A, Sone Y (1983) J Appl Polym Sci 28(7):2381
Tsubokawa N, Kobayashi K, Sone Y (1987) Polym J 19(10):1147
Tsubokawa N, Hamada H, Sone Y (1989) Polym-Plast Technol Eng 28(2):201
Tsubokawa N, Kogure A, Sone Y (1990) J Polym Sci Part A Polym Chem 28(7):1923–1933
Tsubokawa N, Hamada H, Fujiki K (1994) Polymer 35(5):1084
Tsubokawa N, Hamada H, Sone Y (1990) J Macromol Sci Chem A27(6):779
Tsubokawa N, Yoshihara T, Sone Y (1991) Colloid Polym Sci 269(4):324
Tsubokawa N, Yoshihara T, Sone Y (1992) J Polym Sci Part A Polym Chem 30(4):561
Raghavendran VK, Drzal LT (2002) Composite Interfaces 9(1):1
Schomaker E, Zwarteveen AJ, Challa G, Capka M (1988) Polym Commun 29:158
Husemann M, Morrison M, Benoit D, Frommer J, Mate M, Hinsberg W, Hedrick J, Hawker C (2000) J Am Chem Soc 122:1844
Milner ST (1991) Science 252:905
Milner ST, Witten TA, Cates ME (1988) Macromolecules 21:2610
Minko S, Gafijchuk G, Sidorenko A, Voronov S (1999) Macromolecules 32:4525
Alexander S (1977) J Phys 38:977
Rockford L, Mochrie S, Russell T (2001) Macromolecules 34:1487
Russell T, Thurn-Albrecht T, Tuominen M, Huang E, Hawker C (2000) Macromolecular Symp 159:77
Rockford L, Liu Y, Mansky P, Russell T, Yoon M, Mochrie S (1999) J Phys Rev Lett 82:2602
Zhulina EB, Balazs AC (1996) Macromolecules 29:6338
Fasolka M, Banerjee P, Mayes A, Pickett G, Balazs A (2000) Macromolecules 33:5702
Pereira G, Williams D (1999) Macromolecules 32:758
Ulman A (1991) An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembled Monolayers. Academic, Boston
Oosterling M, Sein A, Schouten A (1992) Polymer 33(20):4394
Morton M, Fetters L (1975) J Rubber Chem Technol 48:359
Quirk RP, Mathers RT (2001) Polym Mater Sci Eng 84:873
Quirk RP, Mathers RT (2001) Polym Mater Sci Eng 85:198
Zhou Q, Nakamura Y, Inaoka S, Park M, Wang Y, Mays J, Advincula R (2000) Polym Mater Sci Eng 82:290
Advincula R, Zhou Q, Mays J (2001) Polym Mater Sci Eng 84:875
Zhou Q, Fan X, Xia C, Mays J, Advincula R (2001) Polym Mater Sci Eng 84:835
Quirk RP, Yoo T, Lee Y, Kim J, Lee B (2000) Adv Polym Sci 153:67
Zhou Q, Nakamura Y, Inaoka S, Park M, Wang Y, Mays J, Advincula R (2002) In: Polymer Nanocomposites, Krishnamoorti R, Vaia R (eds) ACS Symposium Series 804. Oxford University Press, Cary, NC
Glasse MD (1983) Prog Polym Sci 9:133
Quirk R, Mathers R, Cregger T, Foster M (2002) Macromolecules 35:9964
Advincula R, Zhou Q, Park MK, Wang S, Mays J, Sakellariou G, Pispas S, Hadjichristidis N (2002) Langmuir 18:8672
Förster S, Krämer E (1999) Macromolecules 32:2783
Hadjichristidis N, Iatrou H, Pispas S, Pitsikalis M (2000) J Polym Sci A Polym Chem 38:3211
Wirth M, Fairbank R, Fatunmbi H (1997) Science 275:44
Fadeev AY, McCarthy TJ (1999) Langmuir 15:3759
Prucker O, Ruhe J (1998) Langmuir 14:6893
Szwarc M (1956) Nature 178:1168
Wittmer J, Cates M, Jhoner A, Turner M (1996) Europhys Lett 33:397
Knoll W (1998) Annu Rev Phys Chem 49:569
Buzdugan E, Ghioca P, Badea E, Serban S, Stribeck N (1997) Eur Polym J 33:1713
Galuska A (1999) Surf Interface Anal 27:889
Iwata H, Hirata I, Ikada Y (1997) Langmuir 13:3063
Zhao B, Brittain WJ (2000) Macromolecules 33:342
Zhao B, Brittain WJ (2000) Macromolecules 33:8813
Zhao B, Brittain WJ, Zhou W, Cheng SZD (2000) J Am Chem Soc 122:2407
Sidorenko A, Minko S, Schenk-Meuser K, Duschner H, Stamm M (1999) Langmuir 15:8349
Tsubokawa N, Takeda N, Iwasa T (1981) Polym J 13(12):1093
Tsubokawa N (1980) J Polym Sci Polym Lett Ed 18(6):461
Tsubokawa N, Maruyama H, Sone Y (1988) J Macromol Sci Chem A25(2):171
Tsubokawa N, Yoshihara T (1991) Polym J 23(3):177
Tsubokawa N, Maruyama H, Sone Y (1986) Polym Bull 15(3):209
Tsubokawa N, Takeda N, Kanamaru A (1980) J Polym Sci Polym Lett Ed 18(9):625
Tsubokawa N, Handa S (1993) J Macromol Sci Pure Appl Chem A30(4):277
Tsubokawa N, Yoshihara T (1993) Polym Bull 30(4):421
Tsubokawa N, Yoshihara T (1993) J Macromol Sci Pure Appl Chem A30(8):517
Tsubokawa N, Kogure A (1993) Polym J 25(1):83
Tsubokawa N, Saitoh K, Shirai Y (1995) Polym Bull 35(4):399
Tsubokawa N, Kimoto T, Endo T (1994) Polym Bull 33(2):187
Tsubokawa N, Oyanagi K, Yoshikawa S (2000) J Macromol Sci Pure Appl Chem A37(6):529–548
Yoshikawa S, Nishizaka R, Oyanagi K, Tsubokawa N (1995) J Polym Sci Part A Polym Chem 33(13):2251
Hoehne S, Seifert A, Friedrich M, Holze R, Spange S (2004) Macromol Chem Phys 205(12):1667
Hoehne S, Spange S (2003) Macromol Chem Phys 204(5/6):841
Spange S, Eismann U, Hoehne S, Langhammer E (1998) Macromolecular Symposia (6th Dresden Polymer Discussion Surface Modification, 1997) 126:223
Jordan R, West N, Ulman A, Chou YM, Nuyken O (2001) Macromolecules 34(6):1606
Kim IJ, Faust RJ (2003) Macromol Sci Pure A40(10):991
Kim IJ, Angelopoulos A, Faust R (2001) Polym Preprints 42(2):481
Wang WP, Pan CY (2004) Polymer 45(12):3987
Jordan R, Ulman A (1998) J Am Chem Soc 120(2):243
Leonard-Stibbe E, Lecayon G, Deniau G, Viel P, Defranceschi M, Legeay G, Delhalle J (1994) J Polym Sci Part A Polym Chem 32(8):1551
MacDonald S, Hult A, Allen R, Wilson CG (1985) Proceedings of the International Conference on Organic Coatings, Science and Technology, New Paltz, NY, p 203
MacDonald S, Hult A, Wilson CG (1985) Macromolecules 18(10):1804
MacDonald S, Hult A, Allen R, Wilson CG (1985) Polym Mater Sci Eng 52:339
Zhao B, Brittain WJ (2000) Macromolecules 33(2):342
Acknowledgments
I would like to acknowledge my collaborators in this research area: QingYe Zhou, Mi-Kyoung Park, Shuangxi Wang, Jimmy Mays, George Sakellariou, Stergios Pispas, and Nikos Hadjichristidis. I would like to acknowledge the Advincula research group and especially Derek Patton for help in preparing updated references. I would also like to acknowledge technical support from Molecular Imaging (Agilent technologies), Optrel GmBH, and Maxtec Inc.
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Advincula, R. Polymer Brushes by Anionic and Cationic Surface-Initiated Polymerization (SIP). In: Jordan, R. (eds) Surface-Initiated Polymerization I. Advances in Polymer Science, vol 197. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_066
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