Polímeros: Ciência e Tecnologia
Polímeros: Ciência e Tecnologia
Original Article

Evaluation of lignin as stabilizer in vulcanized natural rubber formulations

Gelsa Adriana Carpenedo; Nayrim Brizuela Guerra; Marcelo Giovanela; Marco Aurelio De Paoli; Janaina da Silva Crespo

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In this study we evaluated the use of eucalyptus lignin as a stabilizer in combination with other stabilizers in a vulcanized elastomeric based on natural rubber. The stabilizers tested were 6PPD (N-1,3-dimethyl-butyl-N'-phenyl-p-phenylenediamine), TMQ (oligomerized 2,2,4-trimethylquinoline), paraffin wax and eucalyptus lignin. At predetermined time intervals, samples were taken from aging conditions and the mechanical properties and additive content were determined. The sample with a combination of wax and lignin in the same formulation showed the greatest resistance to oxidative degradation. In samples with only one stabilizer, the migration test indicated greater diffusion of lignin to the surface. Samples exposed to thermo-oxidative aging showed greater loss in the mechanical properties of tear strength and 6PPD consumption. In the accelerated aging with ozone, all showed a behavior more resistant to aging. We concluded that lignin can be used as a substitute for synthetic stabilizers, without impairing the performance of natural rubber compounds.




accelerated aging, lignin, natural rubber, paraffin wax


1 Guerra, N. B., Pegorin, G. S., Boratto, M. H., Barros, N. R., Graeff, C. F. O., & Herculano, R. D. (2021). Biomedical applications of natural rubber latex from the rubber tree Hevea brasiliensis. Materials Science and Engineering C, 126, 112126. http://dx.doi.org/10.1016/j.msec.2021.112126. PMid:34082943.

2 Zhao, X., Hu, H., Zhang, D., Zhang, Z., Peng, S., & Sun, Y. (2019). Curing behaviors, mechanical properties, dynamic mechanical analysis and morphologies of natural rubber vulcanizates containing reclaimed rubber. E-Polymers, 19(1), 482-488. http://dx.doi.org/10.1515/epoly-2019-0051.

3 Manaila, E., Stelescu, M. D., & Craciun, G. (2018). Degradation studies realized on natural rubber and plasticized potato starch based eco-composites obtained by peroxide cross-linking. International Journal of Molecular Sciences, 19(10), 2862. http://dx.doi.org/10.3390/ijms19102862. PMid:30241399.

4 Galiani, P. D., Malmonge, J. A., Soares, B. G., & Mattoso, L. H. C. (2013). Studies on thermal-oxidative degradation behaviours of raw natural rubber: PRI and thermogravimetry analysis. Plastics, Rubber and Composites, 42(8), 334-339. http://dx.doi.org/10.1179/1743289811Y.0000000046.

5 Radhakrishnan, C. K., Alex, R., & Unnikrishnan, G. (2006). Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends. Polymer Degradation & Stability, 91(4), 902-910. http://dx.doi.org/10.1016/j.polymdegradstab.2005.06.013.

6 Fainleib, A., Pires, R. V., Lucas, E. F., & Soares, B. G. (2013). Degradation of non-vulcanized natural rubber: renewable resource for fine chemicals used in polymer synthesis. Polímeros, 23(4), 441-450. http://dx.doi.org/10.4322/polimeros.2013.070.

7 Chatterjee, A. K. (2003). Applications in organic synthesis. In R. B. Grubbs (Ed.), Handbook of Metathesis (pp. 2246-2295). Weinheim: Wiley-VCH.

8 Carpenedo, G. A., Demori, R., Carli, L. N., Giovanela, M., Paoli, M. A. D., & Crespo, J. S. (2020). Evaluation of stabilizing additives content in the mechanical properties of elastomeric compositions subject to environmental and accelerated aging. Materials Research, 23(5), e20201039. http://dx.doi.org/10.1590/1980-5373-mr-2020-0139.

9 Barana, D., Ali, S. D., Salanti, A., Orlandi, M., Castellani, L., Hanel, T., & Zoia, L. (2016). Influence of Lignin Features on Thermal Stability and Mechanical Properties of Natural Rubber Compounds. ACS Sustainable Chemistry & Engineering, 4(10), 5258-5267. http://dx.doi.org/10.1021/acssuschemeng.6b00774.

10 Giese, U., Hahn, H., & Thust, S. (2017). Degradation and stabilization of elastomers. Nippon Gomu Kyokaishi, 91(7), 227-231. http://dx.doi.org/10.2324/gomu.91.227.

11 Sabaa, M. W., Madkour, T. M., & Yassin, A. A. (1998). Polymerization products of p-benzoquinone as bound antioxidants for SBR. Part II: the antioxidizing efficiency. Polymer Degradation & Stability, 22(3), 205-222. http://dx.doi.org/10.1016/0141-3910(88)90011-0.

12 De Paoli, M. A. (2009). Degradação e estabilização de polímeros. São Paulo: Artliber.

13 Roy, K., Debnath, S. C., & Potiyaraj, P. (2020). A review on recent trends and future prospects of lignin based green rubber composites. Journal of Polymers and the Environment, 28(2), 367-387. http://dx.doi.org/10.1007/s10924-019-01626-5.

14 Li, G.-Y., & Koenig, J. L. (2005). A review of rubber oxidation. Rubber Chemistry and Technology, 78(3), 355-390. http://dx.doi.org/10.5254/1.3547889.

15 Furlan, L. T., Rodrigues, M. A., & De Paoli, M.-A. (1985). Sugar cane bagasse lignin as stabilizer for rubbers: part III—Styrene/butadiene rubber and natural rubber. Polymer Degradation & Stability, 13(4), 337-350. http://dx.doi.org/10.1016/0141-3910(85)90082-5.

16 Sharj-Sharifi, M., Taghvaei-Ganjali, S., & Motiee, F. (2020). The effect of protecting waxes on staining antidegradant performance in tyre sidewall formulation. Journal of Rubber Research, 23(2), 111-124. http://dx.doi.org/10.1007/s42464-020-00042-y.

17 Sulekha, P. B., Joseph, R., & Prathapan, S. (2001). Synthesis and characterization of chlorinated paraffin wax-bound paraphenylenediamine antioxidant and its application in natural rubber. Journal of Applied Polymer Science, 81(9), 2183-2189. http://dx.doi.org/10.1002/app.1654.

18 Sarkar, P., & Bhowmick, A. K. (2018). Sustainable rubbers and rubber additives. Journal of Applied Polymer Science, 135(24), 45701-45712. http://dx.doi.org/10.1002/app.45701.

19 Arabit, J., & Pajarito, B. B. (2015). Effect of ingredient loading on surface migration of additives in a surfactant-loaded natural rubber vulcanizate. Advanced Materials Research, 1125, 64-68. http://dx.doi.org/10.4028/www.scientific.net/AMR.1125.64.

20 Yehia, A. A., Khalifa, W. D., & Ghanem, N. A. (1971). Compounding and testing of weather resistant rubber-I antioxidant effects on the accelerated light-ageing of rubbers of different network structures. European Polymer Journal, 7(5), 549-557. http://dx.doi.org/10.1016/0014-3057(71)90086-3.

21 American Society for Testing and Materials - ASTM. (2019). ASTM D3895-19: standard test method for oxidative: induction time of polyolefins by differential scanning calorimetry. West Conshohocken: ASTM.

22 American Society for Testing and Materials - ASTM. (2007). ASTM D624-00R07: standard test method for tear strength of conventional vulcanized rubber and thermoplastic elastomers. West Conshohocken: ASTM.

23 American Society for Testing and Materials - ASTM. (2006). ASTM D412-06: standard test methods for vulcanized rubber and thermoplastic elastomers: tension. West Conshohocken: ASTM.

24 American Society for Testing and Materials - ASTM. (2010). ASTM D572-04R10: standard test method for rubber-deterioration by heat and oxygen. West Conshohocken: ASTM.

25 American Society for Testing and Materials - ASTM. (2006). ASTM G154-06: standard practice for operating fluorescent light apparatus for UV exposure of nonmetallic materials. West Conshohocken: ASTM.

26 American Society for Testing and Materials - ASTM. (2007). ASTM D1149-07: standard test method for rubber deterioration: surface ozone cracking in a chamber. West Conshohocken: ASTM.

27 American Society for Testing and Materials - ASTM. (1996). ASTM D3156-96: standard practice for rubber: chromatographic analysis of antidegradants (antioxidants, antiozonants and stabilizers). West Conshohocken: ASTM.

28 Parra, D. F., Freire, M. T. A., & De Paoli, M.-A. (2000). Diffusion of amine stabilizers in vulcanized natural rubber compositions used in tires. Journal of Applied Polymer Science, 75(5), 670-676. http://dx.doi.org/10.1002/(SICI)1097-4628(20000131)75:5<670::AID-APP9>3.0.CO;2-K.

29 Cataldo, F. (2000). On the ozone protection of polymers having non-conjugated unsaturation. Polymer Degradation & Stability, 72(2), 287-296. http://dx.doi.org/10.1016/S0141-3910(01)00017-9.

30 Khinnavar, R. S., & Aminabhavi, T. M. (1991). Diffusion and sorption of organic liquids through polymer membranes. I. Polyurethane versus n-alkanes. Journal of Applied Polymer Science, 42(8), 2321-2328. http://dx.doi.org/10.1002/app.1991.070420823.

31 Wei, H., Zhou, J., Zheng, J., & Huang, G. (2015). Antioxidation efficiency and reinforcement performance of precipitated-silica-based immobile antioxidants obtained by a sol method in natural rubber composites. RSC Advances, 5(112), 92344-92353. http://dx.doi.org/10.1039/C5RA15435A.

32 Yu, P., He, H., Jia, Y., Tian, S., Chen, J., Jia, D., & Luo, Y. (2016). A comprehensive study on lignin as a green alternative of silica in natural rubber composites. Polymer Testing, 54, 176-185. http://dx.doi.org/10.1016/j.polymertesting.2016.07.014.

33 Barbosa, R., Nunes, A. T., & Ambrósio, J. D. (2017). Devulcanization of Natural Rubber in Composites with Distinct Crosslink Densities by Twin-Screw Extruder. Materials Research, 20(Suppl. 2), 77-83. http://dx.doi.org/10.1590/1980-5373-mr-2016-0956.

34 Jiang, C., He, H., Yao, X., Yu, P., Zhou, L., & Jia, D. (2015). In situ dispersion and compatibilization of lignin/epoxidized natural rubber composites: reactivity, morphology and property. Journal of Applied Polymer Science, 132(23), 42044. http://dx.doi.org/10.1002/app.42044.

35 Ahagon, A., Kida, M., & Kaidou, H. (1990). Aging of tire parts during service. I. Types of aging in heavy-duty tires. Rubber Chemistry and Technology, 63(5), 683-697. http://dx.doi.org/10.5254/1.3538282.

36 Escócio, V. A., Martins, A. F., Visconte, L. L. Y., & Nunes, R. C. R. (2004). Effect of ageing on mechanical and dynamic mechanical properties of natural rubber compositions with mica. Polímeros: Ciência e Tecnologia, 14(1), 13-16.

37 Oliani, W. L., Parra, D. F., & Lugão, A. B. (2010). UV stability of HMS-PP (high melt strength polypropylene) obtained by radiation process. Radiation Physics and Chemistry, 79(3), 383-387. http://dx.doi.org/10.1016/j.radphyschem.2009.08.037.

38 Oßwald, K., Reincke, K., Döhler, S., Heuert, U., Langer, B., & Grellmann, W. (2010). Aspects of the ageing of elastomeric materials. International Polymer Science and Technology, 44(12), 1-10. http://dx.doi.org/10.1177/0307174X1704401201.

39 Mathew, N. M., & De, S. K. (1983). Thermo-oxidative ageing and its effect on the network structure and fracture mode of natural rubber vulcanizates. Polymer, 24(8), 1042-1054. http://dx.doi.org/10.1016/0032-3861(83)90158-1.

40 Cataldo, F., Faucette, B., Huang, S., & Ebenezer, W. (2015). On the early reaction stages of ozone with N,N′-substituted p-phenylenediamines (6PPD, 77PD) and N,N′,N″-substituted-1,3,5-triazine “Durazone®”: an electron spin resonance (ESR) and electronic absorption spectroscopy study. Polymer Degradation & Stability, 111, 223-231. http://dx.doi.org/10.1016/j.polymdegradstab.2014.11.011.

41 Douminge, L., Feaugas, X., Bernard, J., & Mallarino, S. (2013). Extrinsic fluorescence as a sensitive method for studying photo-degradation of high density polyethylene correlated with mechanical stresses. Current Applied Physics, 13(8), 1751-1757. http://dx.doi.org/10.1016/j.cap.2013.06.027.

42 Varghese, S., Kuriakose, B., & Thomas, S. (1994). Short sisal fibre reinforced natural rubber composites: high-energy radiation, thermal and ozone degradation. Polymer Degradation & Stability, 44(1), 55-61. http://dx.doi.org/10.1016/0141-3910(94)90032-9.

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