Skip to main content
SpringerLink
Log in

The influence of structural modification and composition of glycidyl carbamate resins on their viscosity and coating performance

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

Abstract

The synthesis, characterization, and coatings performance of a series of glycidyl carbamate (GC) resins synthesized from a hexamethylene diisocyanate biuret resin, glycidol, and alcohols were explored. The partial replacement of glycidol with alcohols was explored as a way to reduce the viscosity of multifunctional GC resins. Six modified GC resins were obtained by replacing one-third of the glycidol with alcohols and ether alcohols. The modified GC resins were characterized using FTIR and 13C NMR. The alcohol-modified GC resins had significantly lower viscosity than that of the control GC resin. The effect of amount of alcohol modifier on resin viscosity was also studied by making a series of resins with different levels of modifier. Both amine-cured and self-crosslinked coatings were prepared from the resins. Coating properties such as hardness, impact strength, methyl ethyl ketone double rubs, flexibility, and adhesion were studied. Differential scanning calorimetry and thermogravimetric analysis were also used to study the thermal properties of the coatings. The resin structures and their coating performance showed an excellent correlation. The coating performance was found to be governed by the type of modifier, structural compositions of the modifier in the resins, type of amine crosslinkers, and techniques of crosslinking used.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14

Similar content being viewed by others

Abbreviations

13C NMR:

Carbon-13 Nuclear magnetic resonance spectroscopy

1BuOH:

1-Butanol

2EHA:

2-Ethyl hexanol

A-2353:

Ancamide 2353

BGC:

Biuret glycidyl carbamate

BGC-1BuOH:

Glycidyl carbamate resin modified with 1-butanol

DB:

Diethylene glycol butyl ether

DBTDL:

Dibutyltindilaurate

DMA:

Dynamic mechanical analysis

DSC:

Differential scanning calorimetry

E′:

Storage modulus

EB:

Ethylene glycol butyl ether

EEP:

Ethyl 3-ethoxy propionate

EP:

Ethylene glycol propyl ether

FTIR:

Fourier transform infrared

GC:

Glycidyl carbamate

GPC:

Gel permeation chromatography

HDB:

Hexamethylene diisocyanate biuret resin

HDT:

Hexamethylene diisocyanurate trimer resin

IGC:

Isocyanurate glycidyl carbamate

IsoBuOH:

Isobutanol

MEK:

Methyl ethyl ketone

PACM:

Para-aminocyclohexyl methane

R :

Gas constant (8.3 J/K/mol)

SC:

Self-crosslinked

T :

Absolute temperature (K)

TBA:

Tertiary butyl acetate

T g :

Glass transition temperature

TGA:

Thermogravimetric analysis

THF:

Tetrahydrofuran

υ e :

Crosslink density (mol/L)

VOC:

Volatile organic compound(s)

References

  1. Wicks, ZW, Jr, Jones, FN, Pappas, SP, Wicks, DA, Organic Coatings: Science and Technology, 3rd ed. Wiley, NJ, 2007

    Google Scholar 

  2. Chattopadhyay, DK, Raju, KVSN, “Structural Engineering of Polyurethane Coatings for High Performance Applications.” Prog. Polym. Sci., 32 (3) 352–418 (2007)

    Article  CAS  Google Scholar 

  3. Tarlas, HD, “Amine Cured Epoxy Resin Coatings for Resistance to Atmospheric Corrosion.” Mater. Prot., 9 (5) 37–42 (1970)

    CAS  Google Scholar 

  4. Edwards, PA, Erickson, J, Webster, DC, “Synthesis and Self-crosslinking of Glycidyl Carbamate Functional Oligomers.” Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 44 (1) 54–55 (2003)

    CAS  Google Scholar 

  5. Crivello, JV, Liu, S, “Photoinitiated Cationic Polymerization of Epoxy Alcohol Monomers.” J. Polym. Sci. A: Polym. Chem., 38 (3) 389–401 (2000)

    Article  CAS  ADS  Google Scholar 

  6. Royappa, AT, Vogt, ML, Sharma, V, “Composition and Long-Term Stability of Polyglycidol Prepared by Cationic Ring-Opening Polymerization.” J. Appl. Polym. Sci., 91 (2) 1344–1351 (2004)

    Article  CAS  Google Scholar 

  7. Edwards, PA, Erickson, J, Webster, DC, “Synthesis and Characterization of Glycidyl Carbamate Functional Oligomers.” Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 44 (1) 144–145 (2003)

    CAS  Google Scholar 

  8. Edwards, PA, Striemer, G, Webster, DC, “Novel Polyurethane Technology Through Glycidyl Carbamate Chemistry.” J. Coat. Technol. Res., 2 (7) 517–527 (2005)

    CAS  Google Scholar 

  9. de Meijer, M, “Review on the Durability of Exterior Wood Coatings with Reduced VOC-Content.” Prog. Org. Coat., 43 (4) 217–225 (2001)

    Article  Google Scholar 

  10. Geurink, PJA, Scherer, T, Buter, R, Steenbergen, A, Henderiks, H, “A Complete New Design for Waterborne 2-Pack PUR Coatings with Robust Application Properties.” Prog. Org. Coat., 55 (2) 119–127 (2006)

    Article  CAS  Google Scholar 

  11. Tanabe, H, Ohsugi, H, “A New Resin System for Super High Solids Coating.” Prog. Org. Coat., 32 (1–4) 197–203 (1997)

    Article  CAS  Google Scholar 

  12. Mishra, AK, Chattopadhyay, DK, Sreedhar, B, Raju, KVSN, “FT-IR and XPS Studies of Polyurethane-Urea-Imide Coatings.” Prog. Org. Coat., 55 (3) 231–243 (2006)

    Article  CAS  Google Scholar 

  13. Carrasco, F, Pagès, P, Lacorte, T, Briceño, K, “Fourier Transform IR and Differential Scanning Calorimetry Study of Curing of Trifunctional Amino-Epoxy Resin.” J. Appl. Polym. Sci., 98 (4) 1524–1535 (2005)

    Article  CAS  Google Scholar 

  14. Sperling, LH, Introduction to Physical Polymer Science, 4th ed. Wiley, NJ, 2006

    Google Scholar 

  15. Edwards, PA, Striemer, G, Webster, DC, “Synthesis, Characterization and Self-crosslinking of Glycidyl Carbamate Functional Resins.” Prog. Org. Coat., 57 (2) 128–139 (2006)

    Article  CAS  Google Scholar 

  16. Nair, KP, Breedveld, V, Weck, M, “Complementary Hydrogen-Bonded Thermoreversible Polymer Networks with Tunable Properties.” Macromolecules, 41 (10) 3429–3438 (2008)

    Article  CAS  ADS  Google Scholar 

  17. Hilger, C, Draeger, M, Stadler, R, “Molecular Origin of Supramolecular Self-assembling in Statistical Copolymers.” Macromolecules, 25 (9) 2498–2501 (1992)

    Article  CAS  ADS  Google Scholar 

  18. De Lucca Freitas, LL, Stadler, R, “Thermoplastic Elastomers by Hydrogen Bonding. 3. Interrelations Between Molecular Parameters and Rheological Properties.” Macromolecules, 20 (10) 2478–2485 (1987)

    Article  ADS  Google Scholar 

  19. Hill, LW, “Structure/Property Relationships of Thermoset Coatings.” J. Coat. Technol., 64 (808) 29–42 (1992)

    CAS  Google Scholar 

  20. Scanlan, JC, Webster, DC, Crain, AL, “Correlation Between Network Mechanical Properties and Physical Properties in Polyester-Urethane Coatings.” ACS Symp. Ser. on Film Formation in Waterborne Coatings, vol. 648, pp. 222–234

  21. Hill, LW, “Determination of Crosslink Density in Thermoset Coatings.” Polym. Mater. Sci. Eng., 77 387–388 (1997)

    CAS  Google Scholar 

  22. Koleske, JV, Paint and Coating Testing Manual, 14th ed. ASTM publication, Philadelphia, PA, 1995

    Google Scholar 

  23. Masatsugu, O, Noriyuki, K, Tatsuo, K, “Effects of Crosslinking on Physical Properties of Phenol-Formaldehyde Novolac Cured Epoxy Resins.” J. Appl. Polym. Sci., 48 (4) 583–601 (1993)

    Article  Google Scholar 

  24. Kong, X, Yue, J, Narine, SS, “Physical Properties of Canola Oil Based Polyurethane Networks.” Biomacromolecules, 8 (11) 3584–3589 (2007)

    Article  CAS  PubMed  Google Scholar 

  25. Narine, SS, Kong, X, Bouzidi, L, Sporns, P, “Physical Properties of Polyurethanes Produced From Polyols From Seed Oils: I. Elastomers.” J. Am. Oil Chem. Soc., 84 (1) 55–63 (2007)

    Article  CAS  Google Scholar 

  26. Petrovic, ZS, Zhang, W, Javni, I, “Structure and Properties of Polyurethanes Prepared from Triglyceride Polyols by Ozonolysis.” Biomacromolecules, 6 (2) 713–719 (2005)

    Article  CAS  PubMed  Google Scholar 

  27. Sorathia, UA, Yeager, WL, Dapp, TL, “Interpenetrating Polymer Network Acoustic Damping Material.” US Patent 5,225,498, 1993

  28. Rodriguez, MT, Garcia, SJ, Cabello, R, Suay, JJ, Gracenea, JJ, “Effect of Plasticizer on the Thermal, Mechanical, and Anticorrosion Properties of an Epoxy Primer.” J. Coat. Technol. Res., 2 (7) 557–564 (2005)

    CAS  Google Scholar 

  29. Hill, LW, Lee, S-B, “Effect of Melamine-Formaldehyde Structure on Cure Response of Thermoset Coatings.” J. Coat. Technol., 71 (897) 127–133 (1999)

    Article  CAS  Google Scholar 

  30. Dusek, K, Duscaronková-Smrcková, M, Fedderly, JJ, Lee, GF, Lee, JD, Hartmann, B, “Polyurethane Networks with Controlled Architecture of Dangling Chains.” Macromol. Chem. Phys., 203 (13) 1936–1948 (2002)

    Article  CAS  Google Scholar 

  31. Skaja, A, Fernando, D, Croll, S, “Mechanical Property Changes and Degradation During Accelerated Weathering of Polyester-Urethane Coatings.” J. Coat. Technol. Res., 3 (1) 41–51 (2006)

    CAS  Google Scholar 

  32. Higginbottom, HP, Bowers, GR, Ferrell, PE, “Cure of Secondary Carbamate Groups by Melamine-Formaldehyde Resins.” J. Coat. Technol., 71 (894) 49–60 (1999)

    Article  CAS  Google Scholar 

  33. Hill, LW, “Calculation of Crosslink Density in Short Chain Networks.” Prog. Org. Coat., 31 (3) 235–243 (1997)

    Article  CAS  Google Scholar 

  34. Schwalm, R, “Crosslinking Effect on Mechanical Properties of UV Curable Coatings.” PPCJ, Polym. Paint Colour J., 189 (4421) 18–20, 22 (1999)

    CAS  Google Scholar 

Download references

Acknowledgments

This material is based upon work supported by the Naval Sea Systems Command under Contract No. N00024-050-C-4139.

Author information

Authors and Affiliations

  1. Department of Coatings and Polymeric Materials, 2760, North Dakota State University, P.O. Box 6050, Fargo, ND, 58108, USA

    Umesh D. Harkal, Aaron J. Muehlberg, Jung Li & Dean C. Webster

  2. Luna Innovations Incorporated, 706 Forest Street; Suite A, Charlottesville, VA, 22903, USA

    James T. Garrett

Authors
  1. Umesh D. Harkal
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Aaron J. Muehlberg
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jung Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. James T. Garrett
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dean C. Webster
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Dean C. Webster.

Additional information

Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the Naval Sea Systems Command.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Harkal, U.D., Muehlberg, A.J., Li, J. et al. The influence of structural modification and composition of glycidyl carbamate resins on their viscosity and coating performance. J Coat Technol Res 7, 531–546 (2010). https://doi.org/10.1007/s11998-010-9262-5

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-010-9262-5

Keywords

Search

Navigation