Theoretical descriptions of ABn (n ≥ 2) hyperbranched polymerization systems have been known for some time [1], but in them, cyclization is a factor that is generally and largely ignored. However, it is now understood that cyclization is prevalent in polymerizations of this type, and that it can often affect to a significant extent both polydispersity and molecular weights of the polymer products. Since research in hyperbranched polymers has increased dramatically in recent years [2–4], a number of experimental and theoretical studies have focused on the presence and effects of cyclization in these systems (see, for example [5–10] and references cited therein). In essence, intramolecular cyclization of an oligomer in an ABn polymerization results in the consumption of the focal A group (see Section 15.3), which converts the oligomer into a Bx core. Although the newly formed core can continue to grow through the reaction of other A groups with the B groups, this growth is limited, especially if other A groups in the polymerization system are also consumed through similar intramolecular cyclization reactions. Thus, for the control and optimization of the resulting polymer molecular weight, it is necessary to understand these issues and the methods that can be used to avoid excessive amounts of cyclization
This chapter describes cyclization in organosilicon hyperbranched polymer synthesis, and techniques that have been used to minimize its occurrence. The focus is primarily on ABn (n ≥ 2) systems, although many of the principles apply to the similar A2 + B3 bimolecular systems that are now gaining more research attention (see Chapter 16) [11]
Keywords
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Flory PJ (1953) Principles of Polymer Chemistry. Chapter 9, Cornell University Press, Ithaca, NY
Yates CR and Hayes W (2004) Eur Polym J 40:1257
Gao C and Yan D (2004) Prog Polym Sci 29:183
Voit B (2005) J Polym Sci Part A Polym Chem 43:2679
Burgath A, Sunder A, and Frey H (2000) Macromol Chem Phys 201:782
Dusek K, Somvarsky J, Smrckova M, Simonsick Jr. WJ, and Wilczek L (1999) Polym Bull 42:489
Gooden JK, Gross ML, Mueller A, Stefanescu AD, and Wooley KL (1998) J Am Chem Soc 120:10180
Drohmann C and Möller M (2000) Polym Preprints 41:140
Cameron C, Fawcett AH, Hetherington CR, Mee RAW, and McBride FV (1998) J Chem Phys 108:8235
Fadeev MA, Rebrov AV, Ozerina LA, Gorbatsevich OB, and Ozerin AN (1999) Polym Sci Ser A 41:189
Dvornic PR, Hu J, Meier DJ, and Nowak RM (2004) Polym Preprints 45:585
Yoon K and Son DY (1999) Org Lett 1:423
Tamao K, Nakagawa Y, and Ito Y (1990) J Org Chem 55:3438
Tamao K, Nakagawa Y, and Ito Y (1993) Organometallics 12:2297
Zhang G-B, Fan X-D, Kong J, Liu Y-Y, Wang M-C, and Qi Z-C (2007) Macromol Chem Phys 208:541
Mathias LJ and Carothers TW (1991) J Am Chem Soc 113:4043
Carothers TW and Mathias LJ (1993) Polym Preprints 34(2):538
Rubinsztajn S (1994) J Inorg Organomet Polym 4:61
Miravet JF and Fréchet JMJ (1998) Macromolecules 31:3461
Gong C, Miravet J, and Fréchet JMJ (1999) J Polym Sci Part A Polym Chem 37:3193
Herzig C and Deubzer B (1998) Polym Preprints 39(1):477
Whitmarsh CK and Interrante LV (1991) Organometallics 10:1336
Brondani DJ, Corriu RJP, El Ayoubi S, Moreau JJE, and Man MWC (1993) Tetrahedron Lett 34:2111
Fry BE, Guo A, and Neckers DC (1997) J Organomet Chem 538:151
Wang X, Yuan Y, Graiver D, and Cabasso I (2007) Macromolecules 40:3939
Jaumann M, Rebrov EA, Kazakova VV, Muzafarov AM, Goedel WA, and Moller M (2003) Macromol Chem Phys 204:1014
Oishi M, Minakawa M, Imae I, and Kawakami Y (2002) Macromolecules 35:4938
Drohmann C, Möller M, Gorbatsevich OB, and Muzafarov AM (2000) J Polym Sci Part A Polym Chem 38:741
Xiao Y, Wong RA, and Son DY (2000) Macromolecules 33:7232
Yao J and Son DY (1999) J Polym Sci Part A Polym Chem 37:3778
Rubinsztajn S and Stein J (1995) J Inorg Organomet Polym 5:43
Yoon K and Son DY (1999) Macromolecules 32:5210
Rim C and Son DY (2003) Macromolecules 36:5580
Yao J and Son DY (1999) Organometallics 18:1736
Hanselmann R, Hölter D, and Frey H (1998) Macromolecules 31:3790
Son DY and Xiao Y (2001) Polym Mat Sci Eng 84:301
Marcos AG, Pusel TM, Thomann R, Pakula T, Okrasa L, Geppert S, Gronski W, and Frey H (2006) Macromolecules 39:971
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2009 Springer Science + Business Media B.V.
About this chapter
Cite this chapter
Son, D.Y. (2009). Cyclization Issues in Silicon-Containing Hyperbranched Polymers. In: Dvornic, P.R., Owen, M.J. (eds) Silicon-Containing Dendritic Polymers. Advances in Silicon Science, vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8174-3_15
Download citation
DOI: https://doi.org/10.1007/978-1-4020-8174-3_15
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-8173-6
Online ISBN: 978-1-4020-8174-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)