Skip to main content

Advertisement

Log in

A new approach to graft siloxanes to alkyds

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

The effect of oil length of alkyds and substitution of siloxane backbone has been studied for alkyd–siloxane hybrids. A series of nine alkyd–siloxane hybrids were synthesized by either varying the oil length of the alkyd or the siloxane backbone substitution. Three linseed oil-based alkyds with either a long, medium, or short oil length were grafted with three hydride-terminated siloxanes substituted with methyl, cyclopentyl, or cyclohexyl groups. A hydrocoupling reaction was used to couple the telechelic siloxane with the hydroxyl functionality of the alkyds using Wilkinson’s catalyst. The reaction was monitored by the disappearance of siloxane hydride signal using Fourier transform infrared. Characterization of siloxane–alkyd hybrids was performed using 1H-NMR, 13C-NMR, and gel permeation chromatography. The hybrids were formulated with a Co, Zr, and Ca drier package and auto-oxidatively cured without using any solvent. The tensile, viscoelastic, and coating properties were evaluated for the cured films. The crosslink density, flexibility, and reverse impact resistance were found to increase as a function of oil length. Tensile modulus, elongation-to-break, glass transition temperature, drying time, and fracture toughness decreased with increase in oil length. For the alkyd–siloxane hybrids, the mechanical and rheological properties were dependant on the size of the substituents. The larger-sized cyclopentyl and cyclohexyl groups resulted in better mechanical and rheological properties than the methyl-containing siloxanes.

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.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Gooch, JW, Bufkin, GB, Wildman, GC, “Coating Binders from Vegetable Oil Material.” US Patent 4419139, 1983, 6 pp

  2. Soucek, MD, “Inorganic/Organic Hybrid Coatings.” In: Kickelbick, G (ed.) Hybrid Materials-Synthesis, Characterization and Applications, Wiley-VCH, Weinheim (2007)

    Google Scholar 

  3. Bentley, J, “Composition, Manufacture and Use of Paint.” In: Caddy, B. (ed.) Forensic Examination of Glass and Paint: Analysis and Interpretation, p. 138. CRC Press, NY (2001)

    Google Scholar 

  4. Piekarski, G, Kippe, D, Kurz, D, Hundmeyer, A, Maier, S, “Low-Pressure Polyethylenes.” US Patent 3991259, 1975, 28 pp

    Google Scholar 

  5. Hofland, A (1994) “Water-Borne Coatings for Decorative and Protective Coatings: A Comparative Survey.’’ Surf. Coat. Int. 77 (7) 270–272

    CAS  Google Scholar 

  6. Kraft, WM (1962) “Alkyds-Past, Present, and Future?“ J. Am. Oil Chem. Soc., 39 (11) 501–502

    Article  CAS  Google Scholar 

  7. Fenzell, WA (1982) “Low VOC Silicone Alkyd Copolymers for Maintenance Paint Applications.” J. Water Borne Coat., 5 (3) 3–6

    Google Scholar 

  8. Brady, SA, Johnson, JC, Lyons, JD, “Reactive Silicone Resin Intermediates. Effects of Silicone Content on Typical Coatings.”Paints Varnish Prod., 48 (1) 25–31 (1958)

    CAS  Google Scholar 

  9. Emblem, HG, Marsden, C, Stockwell, GE, “Silicon-Modified Plastics.” Plastics (London), 12 (137) 525– 527 (1948)

    CAS  Google Scholar 

  10. Smith, AL, Brown, LH, Tyler, LJ, Hunter, MJ (1957) “Thermal stability of resins.” J. Ind. Eng. Chem. 49 1903–1906

    Article  CAS  Google Scholar 

  11. McLean, WM, “Coating Compositions from Silicone-Alkyd Resins and Epoxy Resins.” US Patent 2687398, 1954

  12. Rose, K, “Silicones-Properties and Uses.” Mater. Methods, 41 (2) 109–124 (1955)

    CAS  Google Scholar 

  13. Stebleton, LF, Hedlund, RC, “Silicones in the Paint Industry.” Paint. Ind. Mag., 69(10) 14–16 (1954)

    CAS  Google Scholar 

  14. Hedlund, RC (1959) “Silicone in Industrial Finishes.” Prod. Finish. (Cincinnati), 23 (9) 146–58

    CAS  Google Scholar 

  15. Karim, AFA, Golding, B, Morgan, RA (1960) “Silicone-Alkyd Copolymers and their Application to High-Temperature Surface Coatings.” J. Chem. Eng. Data., 5 (1) 117–125

    Article  Google Scholar 

  16. Dullius, J, Ruecker, C, Oliveira, V, Ligabue, R, Einloft, S (2006) “Chemical Recycling of Post-Consumer PET: Alkyd Resins Synthesis.” Prog. Org. Coat., 57 (2) 123–127

    Article  CAS  Google Scholar 

  17. Kogel, JE, Industrial Minerals & Rocks: Commodities, Markets, and Uses, p. 1308. SME, Littleton, CO (2006)

  18. Wicks, Jr, ZW, Jones, FN, Pappas, SP, “Organic Coating: Science & Technology, Volume II: Applications, Properties and Performance” Wiley, NY (1994)

    Google Scholar 

  19. Bunnell, RH, Hatcher, DB, “Siloxane-Modified Alkyd Resins.” US Patent 2624720, 1953

  20. Hunter, MJ, Rauner, LA, “Condensation of an Organosilane with a Polyhydric Alcohol and Thereafter with a Polycarboxylic Acid.” US Patent 2584351, 1952

  21. Alagar, M, Kumar, AA, Mahesh, KPO, Dinakaran, K (2000) “Studies on Thermal and Morphological Characteristics of E-Glass/Kevlar 49 Reinforced Siliconized Epoxy Composites.” Eur. Polym. J., 36 (11) 2449–2454

    Article  CAS  Google Scholar 

  22. Beetsma, J (1998) “Alkyd emulsion paints: properties, challenges and solutions.” Pigm. Resin Technol., 27(1) 12–19

    Article  CAS  Google Scholar 

  23. Bukingham, AM, Estes, TN, Gee, MB, Selley, DB, Smith, JM, “Water Repellent Compositions and Using the Same on Wood, Sandstone or Mortar.” US Patent 5695551, 1997, 10 pp

  24. Nagy, J, Hencsei, P, Ambrus, L, Bihatsi, L, Fabulya, EP, “Preparation, Investigation and Application of Modified Silicone Resin Based Varnish Paints.” FATIPEC Congress, 14, pp. 257–261 (1978)

  25. Heilen, W, Silicone Resins and Their Combinations, p. 28. Vincentz Network GmbH & Co, Hannover (2005)

  26. Zhang, R, Mark, JE, Pinhas, AR (2000) “Dehydrocoupling Polymerization of Bis-Silanes and Disilanols to Poly(silphenylenesiloxane) as Catalyzed by Rhodium Complexes.” Macromolecules, 33 (10) 3508–3510

    Article  CAS  ADS  Google Scholar 

  27. Chakraborty, R, Soucek, MD (2008) ”Synthesis of Amine and Epoxide Telechelic Siloxanes.” Macromol. Chem. Phys., 209(6) 604–614

    Article  CAS  Google Scholar 

  28. Patton, TC, “Alkyd Resin Technology”, Wiley, NY (1962)

    Google Scholar 

  29. Graessley, WW (ed.), Advances in Polymer Science: The Entanglement Concept in Polymer Rheology, Vol. 16, p. 179. Springer, NY (1974)

  30. Ballard, RL, Sailer, RA, Larson, B, Soucek, MD (2001) “Fracture Toughness of Inorganic–Organic Hybrid Coatings.” J. Coat. Technol., 73 (913) 107–114

    Article  CAS  Google Scholar 

  31. Sailer, RA, Soucek, MD (1998) “Oxidizing Alkyd Ceramers.“ Prog. Org. Coat., 33 (1) 36– 43

    Article  CAS  Google Scholar 

  32. Sailer, RA, Wegner, JR, Hurtt, J, Janson, JE, Soucek, MD (1998) “Linseed and Sunflower Oil Alkyd Ceramers.” Prog. Org. Coat., 33 (2) 117–125

    Article  CAS  Google Scholar 

  33. Clark, TJ, Lee, K, Manners, I (2006) “Transition-Metal-Catalyzed Dehydrocoupling: A Convenient Route To Bonds Between Main-Group Elements.” Chem. Eur. J., 12 (34) 8634–8648

    Article  CAS  Google Scholar 

  34. Kim, C, Kwark, K (2002) “Dehydrocoupling and Diels-Alder Reactions on Siloxane Polymers. “J. Polym. Sci. A: Polym. Chem., 40 (22) 4013–4019

    Article  CAS  Google Scholar 

  35. Hofer, R, Daute, P, Grutzmacher, R, Westfechtel, A (1997) “Oleochemical Polyols—A New Raw Material Source for Polyurethane Coatings and Floorings.” J. Coat. Technol., 69 (869) 65–72

    Article  CAS  Google Scholar 

  36. Dworak, DP, Soucek, MD (2007) “Synthesis, Characterization, and Evaluation of Amine-Terminated Cycloaliphatic-Substituted Polysiloxanes.” Macromol. Chem. Phys., 208(23) 2502–2509

    Article  CAS  Google Scholar 

  37. Gauthier, LA, LeGrow, GE, “Nonprecondensed Silicone-Alkyd Resins.” US Patent 4377676, 1983, 32 pp

    Google Scholar 

  38. Ronald, M, “Alkyd Modified Siloxane Coating Compositions.” CA Patent 504830, 1954

  39. Jones, RG, Chojnowski, J, Ando, W, “Silicon-Containing Polymers: The Science and Technology of Their Synthesis and Applications”, Springer, NY (2000)

    Google Scholar 

  40. Tugtepe, M, Orbay, M, “Investigation of the Heat Resistance and Thermal Oxidative Degradation of Alkyd Resins Modified by Organosilicon Compounds or an Intermediate Polysiloxane by DTA and TG.” Chim. Acta Turcica., 6 (2) 109–141 (1978)

    CAS  Google Scholar 

  41. Easton T, Poultney, S (2007) “Waterborne Silicone-Organic Hybrid Coatings for Exterior Applications.” J. Coat. Technol. Res., 4 (2) 187–190

    Article  CAS  Google Scholar 

  42. Dworak, DP, Soucek, MD, “Synthesis of Cycloaliphatic Substituted Silane Monomers and Polysiloxanes for Photocuring.” Macromolecules, 37 (28) 9402–9417 (2004)

    Article  CAS  ADS  Google Scholar 

  43. Flick, EW, “Prepaint Specialties and Surface Tolerant Coatings.”, William Andrew Inc., NY (1991)

    Google Scholar 

  44. Parr, LM, “Rheological and Performance Characteristics of Water Reducible Silicone Alkyds.” Org. Coat. Plast. Chem., 43 148–153 (1980)

    CAS  Google Scholar 

  45. Noll, W, “Silicate Bond from the Standpoint of the Electron Theory.” Angew. Chem., 75 123–130 (1963)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mark D. Soucek.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chakraborty, R., Thatte, M. & Soucek, M.D. A new approach to graft siloxanes to alkyds. J Coat Technol Res 6, 471–481 (2009). https://doi.org/10.1007/s11998-008-9155-z

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-008-9155-z

Keywords

Navigation