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, Volume 7, Issue 2, pp 177–189 | Cite as

Comb-Like Polymethylsiloxanes. Synthesis, Structure and Properties

  • M. A. ObrezkovaEmail author
  • A. A. Kalinina
  • I. V. Pavlichenko
  • N. G. Vasilenko
  • M. V. Mironova
  • A. V. Semakov
  • V. G. Kulichikhin
  • M. I. Buzin
  • A. M. Muzafarov
Original Paper

Abstract

Comb-like polymethylsiloxanes consisting of a silsesquioxane backbone and dimethylsiloxane side chains were synthesized by means of the “grafting to” method using a linear polyfunctional matrix [SiMe(ONa)O]n and monofunctional oligomers (CH3)3Si[OSi(CH 3)2]nOCOCH3. The effects of architecture of the synthesized methylsiloxane polymers on their physicochemical properties, rheology, and behavior at the air–water interface were studied and compared with those for the linear analogue – polydimethylsiloxane.

Keywords

Polycondensation Polydimethylsiloxane Comb-like polymethylsiloxanes Polyfunctional matrix Intrinsic viscosity 

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References

  1. 1.
    Vlassopoulos D, Fytas G, Loppinet B, Isel F, Lutz P, Benoit H (2000) Polymacromonomers: structure and dynamics in nondilute solutions, melts, and mixtures. Macromol 33:5960–5969CrossRefGoogle Scholar
  2. 2.
    Djalali R, Hugenberg N, Fischer K, Schmidt M (1999) Amphipolar core-shell cylindrical brushes. Macromol Rapid Commun 20:444–449CrossRefGoogle Scholar
  3. 3.
    Börner HG, Beers K, Matyjaszewski K, Sheiko SS, Möller M (2001) Synthesis of molecular brushes with block copolymer side chains using atom transfer radical polymerization. Macromol 34:4375–4383CrossRefGoogle Scholar
  4. 4.
    Djalali R, Li S-Y, Schmidt M (2002) Amphipolar core −shell cylindrical brushes as templates for the formation of gold clusters and nanowires. Macromol 35:4282–4288CrossRefGoogle Scholar
  5. 5.
    Ying Z, Constantini N, Mierzwa M, Pakula T, Neugebauer D, Matyjaszewski K (2004) Super soft elastomers as ionic conductors. Polymer 45:6333–6339CrossRefGoogle Scholar
  6. 6.
    Retsos H, Gorodyska G, Kiriy A, Stamm M, Creton C (2005) Adhesion between chemically heterogeneous switchable polymeric brushes and an elastomeric adhesive. Langmuir 21:7722–7725CrossRefGoogle Scholar
  7. 7.
    Rathgeber S, Pakula T, Wilk A, Matyjaszewski K, Beers KL (2005) On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters. J Chem Phys 122:124904CrossRefGoogle Scholar
  8. 8.
    Pakula T, Zhang Y, Matyjaszewski K, Lee H-I, Boerner H, Qin S, Berry GC (2006) Molecular brushes as super-soft elastomers. Polymer 47:7198–7206CrossRefGoogle Scholar
  9. 9.
    Rathgeber S, Pakula T, Wilk A, Matyjaszewski K, Lee H-I, Beers KL (2006) Bottle-brush macromolecules in solution: Comparison between results obtained from scattering experiments and computer simulations. Polymer 47:7318–7327CrossRefGoogle Scholar
  10. 10.
    Gerle M, Fischer K, Roos S, Mueller AHE, Schmidt M, Sheiko SS, Prokhorova S, Moeller M (1999) Main chain conformation and anomalous elution behavior of cylindrical brushes as revealed by GPC/MALLS, light scattering, and SFM. Macromol 32:2629–2637CrossRefGoogle Scholar
  11. 11.
    Subbotin A, Saariaho M, Ikkala O, Ten Brinke G (2000) Elasticity of comb copolymer Cylindrical brushes. Macromol 33:3447–3452CrossRefGoogle Scholar
  12. 12.
    Fischer K, Schmidt M. (2001) Solvent-Induced Length Variation of Cylindrical Brushes. Macromol Rapid Commun 22:787–791CrossRefGoogle Scholar
  13. 13.
    Sheiko SS, Prokhorova S, Beers KL, Matyjaszewski K, Potemkin II, Khokhlov AR, Moeller M (2001) Single molecule rod −globule phase transition for brush molecules at a flat interface. Macromol 34:8354–8360CrossRefGoogle Scholar
  14. 14.
    Neugebauer D, Zhang Y, Pakula T, Sheiko SS, Matyjaszewski K (2003) Densely-grafted and double-grafted PEO brushes via ATRP. A route to soft elastomers. Macromol 36:6746–6765CrossRefGoogle Scholar
  15. 15.
    Potemkin II, Khokhlov AR, Prokhorova S, Sheiko SS, Moeller M, Beers K, Matyjaszewski K (2004) Spontaneous curvature of comblike polymers at a flat interface. Macromol 37:3918–3923CrossRefGoogle Scholar
  16. 16.
    Gallyamov MO, Tartsch B, Khokhlov AR, Sheiko SS, Boerner HG, Matyjaszewski K, Moeller M (2004) Reversible collapse of brushlike macromolecules in ethanol and water vapours as revealed by real-time scanning force microscopy. Chem-Eur G 10:4599–4605CrossRefGoogle Scholar
  17. 17.
    Xu H, Shirvaniants D, Beers K, Matyjaszewski K, Dobrynin AV, Rubinstein M, Sheiko SS (2005) Molecular Visualization of Conformation-Triggered Flow Instability. Phys Rev Lett 94:237801CrossRefGoogle Scholar
  18. 18.
    Zubarev AY, Odenbach S, Fleischer J (2002) Rheological properties of dense ferrofluids. Effect of chain-like aggregates. J Magn Magn Mater 252:241–243CrossRefGoogle Scholar
  19. 19.
    Vasilenko NG, Chernikova EA, Myakushev VD, Moeller M, Muzafarov AM (2003) Synthesis of polydimethylsiloxane polymacromonomers. Doklady Chem 388:1–5Google Scholar
  20. 20.
    Chernikova EA, Vasilenko NG, Myakushev VD, Muzafarov AM (2004) Synthesis of functional polymacromonomers with siloxane main chains. Polym Sci Ser A 46:682–691Google Scholar
  21. 21.
    Wang Q, Zhang H, Prakash GKS, Hogen-Esch TE, Olah GA (1996) Cationic ring-opening polymerization of cyclosiloxanes initiated by electron-deficient organosilicon reagents. Macromol 29:6691–6694CrossRefGoogle Scholar
  22. 22.
    Shinoda H, Matyjaszewski K, Okrasa L, Mierzwa M, Pakula T (2003) Structural control of poly(methyl methacrylate)-g-poly(dimethylsiloxane) copolymers using controlled radical polymerization: effect of the molecular structure on morphology and mechanical properties. Macromol 36:4772–4778CrossRefGoogle Scholar
  23. 23.
    Neugebauer D, Zhang Y, Pakula T, Matyjaszewski K (2005) PDMS−PEO densely grafted copolymers. Macromol 38:8687–8693CrossRefGoogle Scholar
  24. 24.
    Cai GP, Weber WP (2000) Synthesis of polymethyl (trimethylsiloxy)siloxane by anionic ring-opening polymerization of 1,3,5,-trimethyl-1,3,5-tris(trimethylsiloxy)cyclotrisiloxane. Macromol 33:6310–6314CrossRefGoogle Scholar
  25. 25.
    Obrezkova MA, Rogul’ GS, Vasilenko NG, Demchenko NV, Muzafarov AM (2008) Synthesis of linear poly(sodiumoxy) methylsilsesquioxanes and their functional and nonfunctional derivatives. Doklady Chem 419:349–353CrossRefGoogle Scholar
  26. 26.
    Obrezkova MA, Vasilenko NG, Myakushev VD, Muzafarov AM (2009) Hydrolytic polycondensation of sodiumoxymethyl (dialkoxy)silanes as a method for producing linear poly[(sodiumoxy)methylsilsesquioxane]. Polym Sci Ser B 51:457–464CrossRefGoogle Scholar
  27. 27.
    Blagodatskikh IV, Shchegolikhina OI, Pozdniakova YA, Molodtsova YA, Zhdanov AA (1994) Application of size exclusion chromatography to the structural study of polyorganometallosiloxanes. Russ Chem Bull 43:993–998CrossRefGoogle Scholar
  28. 28.
    Lu P, Paulasaari JK, Weber WP (1996) Reaction of dimethyldich lorosilane, phenylmethyldichlorosilane, or diphenyldichlorosilane with dimethyl sulfoxide. Evidence for silanone and cyclodisiloxane intermediates. Organometallics 15:4649–4652CrossRefGoogle Scholar
  29. 29.
    Chernyshev EA, Ivanov PV, Golubykh DN (2001) Intermediates of chemical assembling of oligoorganosiloxanes in hydrolysis of organochlorosilanes. Russ Chem Bull 50:1998–2009CrossRefGoogle Scholar
  30. 30.
    Schappacher M, Billaud C, Paulo C, Deffieux A (1999) Synthesis, dimensions and solution properties of linear and macrocyclicpoly(chloroethyl vinyl ether)-g-polystyrene comblike polymers. Macromol Chem Phys 200:2377–2386CrossRefGoogle Scholar
  31. 31.
    Vinogradov GV, AYa Malkin (1977) Rheology of polymer. Khimiya, MoscowGoogle Scholar
  32. 32.
    Mehta SC, Somasundaran P, Maldarelli C, Kulkarni R (2006) Effects of functional groups on syrface pressure-area isotherms of hydrophilic silicone polymers. Langmuir 22:9566– 9571CrossRefGoogle Scholar
  33. 33.
    Arslanov VV (1994) Polymer monolayers and Langmuir-Blodgett films. The influence of the chemical structure of the polymer and of external conditions on the formation and properties of organised planar assemblies. Russ Chem Rev 63:1–39CrossRefGoogle Scholar
  34. 34.
    Rabek JF (1983) Experimental methods in polymer chemistry in 2 parts. P. 2. MIR, MoscowGoogle Scholar
  35. 35.
    Gordon A, Ford R (1976) Satellite of chemist. MIR, MoscowGoogle Scholar
  36. 36.
    Armarego WLF, Perrin DD (2002) Purification of laboratory chamicals. Elsevier Science, OxfordGoogle Scholar
  37. 37.
    Rebrov EA, Muzafarov AM (2006) Monosodiumoxyorganoalkaxysilanes: synthesis and properties. Heteroatom Chem 17:514–541CrossRefGoogle Scholar
  38. 38.
    Brown PL, Hyde JF (1966) Linear chlorosoxanes US PatentGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • M. A. Obrezkova
    • 1
    Email author
  • A. A. Kalinina
    • 1
  • I. V. Pavlichenko
    • 1
  • N. G. Vasilenko
    • 1
  • M. V. Mironova
    • 2
  • A. V. Semakov
    • 2
  • V. G. Kulichikhin
    • 2
  • M. I. Buzin
    • 3
  • A. M. Muzafarov
    • 1
    • 3
  1. 1.N. S. Enikolopov Institute of Synthetic Polymeric Materials of the Russian Academy of SciencesMoscowRussia
  2. 2.A. V. Topchiev Institute of Petrochemical Synthesis of the Russian Academy of SciencesMoscowRussia
  3. 3.A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of SciencesMoscowRussia

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