Artículo

La versión final de este artículo es de uso interno de la institución.
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

One of the most popular cured rubbers used in industrial applications is polybutadiene rubber (BR) and frequently its network structure, in the cured state, is studied by means of swelling in a solvent. Normally, toluene is used as solvent in this test. In order to estimate the crosslink density from the equilibrium volume fraction of rubber in the swollen state, the correct evaluation of the Flory-Huggins interaction parameter χ is necessary. This work covers the swelling behaviour of two types of cured BR in toluene. The rubbers used have sulphur and accelerator in their composition and were vulcanized at 433 K at different times in order to obtain several network structures and crosslink densities. The crosslink densities were evaluated from uniaxial stress-strain data measured at room temperature and analysed in the frame of the conformational tube model. Using this information and the swelling measurements in the frame of the Flory-Rehner relationship, a relationship between χ and vr, the polymer volume fraction at equilibrium (maximum) degree of swelling was established for the cured BR/toluene system. It was found that χ is not a constant but depends on the crosslink density of the sample. © 2009 Elsevier Ltd. All rights reserved.

Registro:

Documento: Artículo
Título:Evaluation of the polymer-solvent interaction parameter χ for the system cured polybutadiene rubber and toluene
Autor:Marzocca, A.J.; Rodríguez Garraza, A.L.; Mansilla, M.A.
Filiación:Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, LPMPyMC, Pabellón 1, Ciudad Universitaria Buenos Aires C1428EGA, Argentina
Palabras clave:Crosslinking; Flory-Huggins interaction parameter; Polybutadiene rubber; Swelling; Toluene; Cross-link densities; Degree of swelling; Flory-Huggins interaction parameter; Network structures; Polybutadiene rubber; Polybutadiene rubbers; Polymer volume fraction; Polymer-solvent interactions; Room temperature; Swelling behaviour; Swelling measurements; Tube model; Uniaxial stress; Curing; Industrial applications; Polybutadienes; Rubber; Rubber applications; Solvents; Sulfur; Swelling; Titration; Toluene; Organic solvents
Año:2010
Volumen:29
Número:1
Página de inicio:119
Página de fin:126
DOI: http://dx.doi.org/10.1016/j.polymertesting.2009.09.013
Título revista:Polymer Testing
Título revista abreviado:Polym Test
ISSN:01429418
CODEN:POTED
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01429418_v29_n1_p119_Marzocca

Referencias:

  • Kuzma, L.J., (1987) Rubber Technology, p. 235. , Morton M. (Ed), Van Nostrand Reinhold, New York
  • Flory, P.J., Rehner, J., Statistical mechanics of cross-linked polymer networks I. Rubberlike elasticity (1943) J. Chem. Phys., 11, p. 512
  • Flory, P.J., Rehner, J., Statistical mechanics of cross-linked polymer networks II. Swelling (1943) J. Chem. Phys., 11, p. 521
  • Bahar, I., Erbil, H.Y., Baysal, B.M., Erman, B., Determination of polymer-solvent interaction parameter from swelling of networks. The system poly(2-hydroxyethyl methacrylate)-diethylene glycol (1987) Macromolecules, 20, p. 1353
  • Bahar, I., Erman, B., Osmotic compressibility and mechanical moduli of swollen polymeric networks (1987) Macromolecules, 20, p. 1696
  • Horta, A., Pastoriza, M.A., The interaction parameter of crosslinked networks and star polymers (2005) Eur. Polym. J., 41, p. 2793
  • McKenna, G.B., Flynn, K.M., Chen, Y., Mechanical and swelling of crosslinked natural rubber: consequences of the Flory-Rehner hypothesis (1988) Polym. Commun., 29, p. 272
  • Mc.Kenna, G.B., Flynn, K.M., Chen, Y., Swelling in crosslinked natural rubber: experimental evidence of the crosslink density dependence of χ (1990) Polymer, 31, p. 1937
  • Hergenrother, W.L., Hilton, A.S., Use of χ as a function of volume fraction of rubber to determine crosslink density by swelling (2003) Rubber Chem. Technol., 76, p. 832
  • Marzocca, A.J., Evaluation of the polymer-solvent interaction parameter χ for the system cured styrene butadiene rubber and toluene (2007) Eur. Polym. J., 43, p. 2682
  • Hergenrother, W.L., Characterization of networks from the peroxide cure of polybutadiene (1972) J. Appl. Polym. Sci., 16, p. 2611
  • Parker, W.O., Ferrando, A., Ferri, D., Canepari, V., Cross-link density of a dispersed rubber measured by 129Xe chemical shift (2007) Macromolecules, 40, p. 5787
  • Guo, F., Andreasen, J.W., Vigild, M.E., Ndoni, S., Influence of 1,2-PB matrix cross-linking on structure and properties of selectively etched 1,2-PB- b-PDMS block copolymers (2007) Macromolecules, 40, p. 3669
  • Saeki, S., Holste, J.C., Bonner, D.C., Vapor-liquid equilibria for polybutadiene and polyisoprene solutions (1982) J. Polym. Sci. Polym. Phys., 20, p. 793
  • Brotzman, R.W., Flory, P.J., Elastic behavior of cis-1,4-polybutadiene (1987) Macromolecules, 20, p. 351
  • Jessup, R.S., Thermodynamic properties of the systems polybutadiene - benzene and polyisobutene - benzene (1958) J. Res. Natl. Bur. Stand., 60, p. 47
  • Gregg, E.C., Katrenick, S.E., Chemical structure in cis-1,4-polybutadiene vulcanizates. Model compound approach (1970) Rubber Chem. Technol., 43, p. 549
  • Krauss, G., Quantitative characterization of polybutadiene networks (1963) J. Appl. Polym. Sci., 7, p. 1257
  • Short, J.N., Thornton, V., Krauss, G., Effect of the cis-trans ratio on the physical properties of 1,4 polybutadienes (1957) Rubber Chem. Technol., 30, p. 1118
  • Gavrilov, V.M., Shvarts, A.G., Dependence of the polymer-solvent interaction parameter of vulcanizates based on cis-1,4-poly(butadiene) on the type and concentration of vulcanizing agent (1974) Rubber Chem. Technol., 47, p. 303
  • Heinrich, G., Straube, E., Helmis, G., Rubber elasticity of polymer networks: theories (1988) Adv. Polym. Sci., 85, p. 33
  • Matzen, D., Straube, E., Mechanical properties of SBR-networks: I. Determination of crosslink densities by stress-strain measurements (1992) Colloid Polym. Sci., 270, p. 1
  • Heinrich, G., Vilgis, T.A., Contribution of entanglements to the mechanical properties of carbon black filled polymer networks (1993) Macromolecules, 26, p. 1109
  • Marzocca, A.J., Estimation by mechanical analysis of the molecular parameters of SBR vulcanizates at different cure conditions (1995) J. Appl. Polym. Sci., 58, p. 1839
  • Marzocca, A.J., Cerveny, S., Raimondo, R.B., Analysis of variation of molecular parameters of NR during vulcanization in the frame of conformational tube model (1997) J. Appl. Polym. Sci., 66, p. 1085
  • Cerveny, S., Marzocca, A.J., Analysis of variation of molecular parameters of natural rubber during vulcanization in conformational tube model. II influence of sulfur/accelerator ratio (1999) J. Appl. Polym. Sci., 74, p. 2747
  • Marzocca, A.J., Cerveny, S., Mendez, J.M., Some considerations concerning the dynamic mechanical properties of cured styrene-butadiene rubber/polybutadiene blends (2000) Polym. Int., 49, p. 216
  • Marzocca, A.J., Goyanes, S., An analysis of the influence of the accelerator/sulfur ratio in the cure reaction and the uniaxial stress-strain behavior of SBR (2004) J. Appl. Polym. Sci., 91, p. 2601
  • Kaliske, M., Heinrich, G., An extended tube-model for rubber elasticity: statistical-mechanical theory and finite element implementation (1999) Rubber Chem. Technol., 72, p. 602
  • Wu, S.J., Chain structure and entanglement (1989) J. Polym. Sci. B Polym. Phys., 27, p. 723
  • Ferry, J.D., (1980) Viscoelastic Properties of Polymers, , John Wiley & Sons, New York p. 267
  • Valentine, R.H., Ferry, J.D., Homma, T., Ninomiya, K., Viscoelastic properties of polybutadienes - linear and lightly crosslinked near the gel point (1968) J. Polym. Sci. Part-2: Polym. Phys., 6, p. 479
  • Aharoni, S.M., Correlations between chaín parameters and the plateau modulus of polymers (1986) Macromolecules, 19, p. 426
  • Seber, G.A.F., Wild, C.J., (2003) Nonlinear Regression, , John Wiley & Sons Inc, Hoboken, NJ
  • (1997) CRC Handbook of Chemistry and Physics, pp. 3-55. , Lide D.R. (Ed), CRC Press, New York
  • Scott, R.L., Magat, M., The thermodynamics of high-polymer solutions: I. The free energy of mixing of solvents and polymers of heterogeneous distribution (1945) J. Chem. Phys., 13, p. 172
  • (1975) Polymer Handbook. second ed, pp. IV-341-IV-354. , Brandrup J., and Immergut R.H. (Eds), J. Wiley & Sons, New York
  • Small, P.A., Some factors affecting the solubility of polymers (1953) J. Appl. Chem., 3, p. 71
  • Sheehan, C.J., Bisio, L., Polymer/solvent interaction parameters (1966) Rubber Chem. Technol., 39, p. 149
  • Queslel, J.P., Mark, J.E., Structure of randomly cross-linked networks. A theoretical relationship between the molecular weight between crosslinks and the cycle rank, and its comparison with experiment (1985) J. Chem. Phys., 82, pp. 3449-3452

Citas:

---------- APA ----------
Marzocca, A.J., Rodríguez Garraza, A.L. & Mansilla, M.A. (2010) . Evaluation of the polymer-solvent interaction parameter χ for the system cured polybutadiene rubber and toluene. Polymer Testing, 29(1), 119-126.
http://dx.doi.org/10.1016/j.polymertesting.2009.09.013
---------- CHICAGO ----------
Marzocca, A.J., Rodríguez Garraza, A.L., Mansilla, M.A. "Evaluation of the polymer-solvent interaction parameter χ for the system cured polybutadiene rubber and toluene" . Polymer Testing 29, no. 1 (2010) : 119-126.
http://dx.doi.org/10.1016/j.polymertesting.2009.09.013
---------- MLA ----------
Marzocca, A.J., Rodríguez Garraza, A.L., Mansilla, M.A. "Evaluation of the polymer-solvent interaction parameter χ for the system cured polybutadiene rubber and toluene" . Polymer Testing, vol. 29, no. 1, 2010, pp. 119-126.
http://dx.doi.org/10.1016/j.polymertesting.2009.09.013
---------- VANCOUVER ----------
Marzocca, A.J., Rodríguez Garraza, A.L., Mansilla, M.A. Evaluation of the polymer-solvent interaction parameter χ for the system cured polybutadiene rubber and toluene. Polym Test. 2010;29(1):119-126.
http://dx.doi.org/10.1016/j.polymertesting.2009.09.013