Skip to main content
Log in

Statistical thermodynamic properties of a new self-condensing vinyl polymerization system

  • Articles
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

A new self-condensing vinyl polymerization system consisting of AB f *-type inimers is studied by the principle of statistical mechanics. To obtain the relevant average properties of the system, a differential equation satisfied by the polymeric moment of interest is given, and as a result the zeroth, first, second, and third polymeric moments together with the size distribution function of hyperbranched polymers (HBPs) are explicitly presented. As an application of the method of statistical mechanics, several thermodynamic quantities such as the equilibrium free energy, law of mass action, isothermal compressibility, internal energy, and the specific heat associated with the polymerization are all derived. Furthermore, the scaling behavior of asymptotic size distribution function is discussed, by which a reasonable interpretation of the polydispersity index near the end of polymerization can be made. Also, the expressions of some structural parameters such as the numbers of inimers, terminal units, chain units, branched units, and the degree of branching (DB) are calculated. It is found that a high functionality is helpful to improve the DB of the resultant HBPs. These results show that the functionality f has a significant effect on the thermodynamic quantities and structural properties of HBPs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Gao C, Yan D. Hyperbranched polymers: from synthesis to applications. Prog Polym Sci, 2004, 29: 183–275

    Article  CAS  Google Scholar 

  2. Voit BI, Lederer A. Hyperbranched and highly branched polymer architectures synthetic strategies and major characterization aspects. Chem Rev, 2009, 109: 5924–5973

    Article  CAS  Google Scholar 

  3. Gao C, Yan D, Frey H. Promising Dendritic Materials: an Introduction to Hyperbranched Polymers. Hyperbranched Polymers. Hoboken: John Wiley & Sons, Inc., 2011 1–26

    Chapter  Google Scholar 

  4. Boogh L, Pettersson B, Månson JAE. Dendritic hyperbranched polymers as tougheners for epoxy resins. Polymer, 1999, 40: 2249–2261

    Article  CAS  Google Scholar 

  5. Zhao M, Liu Y, Crooks RM, Bergbreiter DE. Preparation of highly impermeable hyperbranched polymer thin-film coatings using dendrimers first as building blocks and then as in situ thermosetting agents. J Am Chem Soc, 1999, 121: 923–930

    Article  CAS  Google Scholar 

  6. Crooks RM, Zhao M, Sun L, Chechik V, Yeung LK. Dendrimerencapsulated metal nanoparticles: synthesis, characterization, and applications to catalysis. Acc Chem Res, 2001, 34: 181–190

    Article  CAS  Google Scholar 

  7. Zhu C, Liu L, Yang Q, Lv F, Wang S. Water-soluble conjugated polymers for imaging, diagnosis, and therapy. Chem Rev, 2012, 112: 4687–4735

    Article  CAS  Google Scholar 

  8. Flory PJ. Molecular size distribution in three dimensional polymers. VI. Branched polymers containing A-R-B f-1 type units. J Am Chem Soc, 1952, 74: 2718–2723

    Article  CAS  Google Scholar 

  9. Fréchet JMJ, Henmi M, Gitsov I, Aoshima S, Leduc MR, Grubbs RB. Self-condensing vinyl polymerization: an approach to dendritic materials. Science, 1995, 269: 1080–1083

    Article  Google Scholar 

  10. Hawker CJ, Fréchet JMJ, Grubbs RB, Dao J. Preparation of hyperbranched and star polymers by a “living”, self-condensing free radical polymerization. J Am Chem Soc, 1995, 117: 10763–10764

    Article  CAS  Google Scholar 

  11. Matyjaszewski K, Gaynor SG, Kulfan A, Podwika M. Preparation of hyperbranched polyacrylates by atom transfer radical polymerization. 1 Acrylic AB* monomers in “living” radical polymerizations. Macromolecules, 1997, 30: 5192–5194

    Article  CAS  Google Scholar 

  12. Simon PFW, Radke W, Müller AHE. Hyperbranched methacrylates by self-condensing group transfer polymerization. Macromol Rapid Commun, 1997, 18: 865–873

    Article  CAS  Google Scholar 

  13. Liu M, Vladimirov N, Fréchet JMJ. A new approach to hyperbranched polymers by ring-opening polymerization of an AB monomer: 4-(2-hydroxyethyl)-ε-caprolactone. Macromolecules, 1999, 32: 6881–6884

    Article  CAS  Google Scholar 

  14. Bai LB, Zheng RR, Li WL, Wu YG, Ba XW, Wang HJ. A synthetic approach for water soluble hyperbranched poly(N,N-ethylidenebis (N-2-chloroacetyl acrylamide)) with high degree of branching via atom transfer radical polymerization/self-condensing vinyl polymerization. Chin J Polym Sci, 2013, 31: 1038–1045

    Article  CAS  Google Scholar 

  15. Müller AHE, Yan D, Wulkow M. Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization. 1 Molecular weight distribution. Macromolecules, 1997, 30: 7015–7023

    Article  Google Scholar 

  16. Zhou Z, Yan D. Distribution function of hyperbranched polymers formed by AB2 type polycondensation with substitution effect. Polymer, 2006, 47: 1473–1479

    Article  CAS  Google Scholar 

  17. Zhou Z, Jia Z, Yan D. Kinetic analysis of AB2 polycondensation in the presence of multifunctional cores with various reactivities. Polymer, 2012, 53: 3386–3391

    Article  CAS  Google Scholar 

  18. Zhou Z, Yan D. A general model for the kinetics of self-condensing vinyl polymerization. Macromolecules, 2008, 41: 4429–4434

    Article  CAS  Google Scholar 

  19. He X, Liang H, Pan C. Monte Carlo simulation of hyperbranched copolymerizations in the presence of a multifunctional initiator. Macromol Theory Simul, 2001, 10: 196–203

    Article  CAS  Google Scholar 

  20. He X, Tang J. Kinetics of self-condensing vinyl hyperbranched polymerization in three-dimensional space. J Polym Sci Pol Chem, 2008, 46: 4486–4494

    Article  CAS  Google Scholar 

  21. Wang L, He X. Conformation of nonideal hyperbranched polymer in ABn (n=2, 4) type polymerization. J Polym Sci Pol Phys, 2010, 48: 610–616

    Article  CAS  Google Scholar 

  22. Cheng KC, Chuang TH, Chang JS, Guo W, Su WF. Effect of feed rate on structure of hyperbranched polymers formed by self-condensing vinyl polymerization in semibatch reactor. Macromolecules, 2005, 38: 8252–8257

    Article  CAS  Google Scholar 

  23. Cheng KC, Su YY, Chuang TH, Guo W, Su WF. Kinetic model of hyperbranched polymers formed by self-condensing vinyl or selfcondensing ring-opening polymerization of AB monomers activated by stimuli with different reactivities. Macromolecules, 2010, 43: 8965–8970

    Article  CAS  Google Scholar 

  24. Hong X, Gu F, Wang H, Ba XW. Statistical theory for self-condensing vinyl polymerization system with any initial distribution. Sci Sinica Chim, 2013, 43: 1505–1511

    Article  CAS  Google Scholar 

  25. Zhao ZF, Wang HJ, Ba XW. A statistical theory for self-condensing vinyl polymerization. J Chem Phys, 2009, 131: 074101

    Article  Google Scholar 

  26. (Gu F, Wang H, Zhao Z. Statistical and thermodynamic properties of binary self-condensing vinyl polymerization. Sci China Ser B, 2011, 54: 438–445

    Article  CAS  Google Scholar 

  27. Zhao ZF, Wang HJ, Ba XW. Statistical properties for the selfcondensing vinyl polymerization in presence of multifunctional core initiators. Polymer, 2011, 52: 854–865

    Article  CAS  Google Scholar 

  28. Zhao ZF, Li YF, Yao N, Wang HJ, Ba XW. Statistical mechanics approach to a general hyperbranched polymer system consisting of ABg monomers and Cf cores. Polymer, 2014, 55: 686–697

    Article  CAS  Google Scholar 

  29. Hawker CJ, Lee R, Fréchet JMJ. One-step synthesis of hyperbranched dendritic polyesters. J Am Chem Soc, 1991, 113: 4583–4588

    Article  CAS  Google Scholar 

  30. Yan D, Müller AHE, Matyjaszewski K. Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization. 2 Degree of branching. Macromolecules, 1997, 30: 7024–7033

    Article  CAS  Google Scholar 

  31. Hölter D, Burgath A, Frey H. Degree of branching in hyperbranched polymers. Acta Polym, 1997, 48: 30–35

    Article  Google Scholar 

  32. Lach C, Frey H. Enhancing the degree of branching of hyperbranched polymers by postsynthetic modification. Macromolecules, 1998, 31: 2381–2383

    Article  CAS  Google Scholar 

  33. Litvinenko GI, Müller AHE. Molecular weight averages and degree of branching in selfcondensing vinyl copolymerization in the presence of multifunctional initiators. Macromolecules, 2002, 35: 4577–4583

    Article  CAS  Google Scholar 

  34. Schüll C, Frey H. Grafting of hyperbranched polymers: from unusual complex polymer topologies to multivalent surface functionalization. Polymer, 2013, 54: 5443–5455

    Article  Google Scholar 

  35. Schüll C, Rabbel H, Schmid F, Frey H. Polydispersity and molecular weight distribution of hyperbranched graft copolymers via “hypergrafting” of ABm monomers from polydisperse macroinitiator cores: theory meets synthesis. Macromolecules, 2013, 46: 5823–5830

    Article  Google Scholar 

  36. Rubinstein M, Colby RH. Polymer Physics. Oxford: Oxford University, 2003

    Google Scholar 

  37. Strobl GR. The Physics of Polymers: Concepts for Understanding their Structures and Behavior. Beeeerkin: Springer, 2007

    Google Scholar 

  38. Sawada H. Thermodynamics of Polymerization. New York: Marcel Dekker, 1976

    Google Scholar 

  39. Stauffer D, Coniglio A, Adam M. Gelation and Critical Phenomena. Berlin: Springer, 1982 103–158

    Google Scholar 

  40. Stanley HE. Introduction to Phase Transitions and Critical Phenomena. Oxford: Oxford University, 1987

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Zuofei Zhao or Haijun Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, Z., Li, Y., Yao, N. et al. Statistical thermodynamic properties of a new self-condensing vinyl polymerization system. Sci. China Chem. 58, 1478–1488 (2015). https://doi.org/10.1007/s11426-015-5378-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-015-5378-x

Keywords

Navigation