Natural rubber modification by vinyl monomers grafting: a review


  • Supat Moolsin Department of Chemistry, Faculty of Science, Rangsit University, Patumthani, 12000, Thailand
  • Nikki K. Robishaw Faculty of Science, Ohio State University, Ohio, 44906, USA


natural rubber, vinyl monomers, core-shell, graft copolymerization, free radical polymerization


This review article provides information on chemical modification of natural rubber (NR) by grafting with hydrophilic or hydrophobic vinyl monomers, involving a free radical polymerization on the backbone of the rubber.  Graft copolymer can be generated from a latex, solvent, or monomer medium using a variety of initiation systems.  Key processing parameters consist of monomer to rubber ratio, type of initiator, initiator concentration, reaction temperature and time.  Characterization techniques such as Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and transmission electron microscopy (TEM) are presented.  The properties of the graft product such as grafting efficiency, conversion, molecular weight, thermal property, mechanical properties, oil resistance, water absorption, and phase morphology are discussed.  The review also includes the applications of the presented graft copolymers.


Afifi, H., & El-Wakil, A. A. (2008). Study of the effect of natural rubber-graft-maleic anhydride (NR-g-MA) on the compatibility of NR-NBR blends using the ultrasonic technique. Polymer-Plastics Technology and Engineering, 47(10), 1032-1039. DOI: 10.1080/0360 2550802355271

Angnanon, S., Prasassarakich, P., & Hinchiranan, N. (2011). Styrene/acrylonitrile graft natural rubber as compatibilizer in rubber blends. Polymer-Plastics Technology and Engineering, 50(11), 1170-1178. DOI: 10.1080/03602559.20 11.574667

Arayapranee, W., Prasassarakich, P., & Rempel, G. L. (2002). Synthesis of graft copoly mers from natural rubber using cumene hydroperoxide redox initiator. Journal of Applied Polymer Science, 83(14), 2993-3001. DOI: 10.1002/app.2328

Arayapranee, W., & Rempel, G. L. (2004). Factorial experimental design for grafting of vinyl monomers onto natural rubber latex. Journal of Applied Polymer Science, 93(1), 455-463. DOI: 10.100 2/app.20450

Arayapranee, W., & Rempel, G. L. (2008a). Morphology and mechanical properties of natural rubber and styrene-grafted natural rubber latex compounds. Journal of Applied Polymer Science, 109(3), 1395-1402. DOI: 10.1002/ app.28217

Arayapranee, W., & Rempel, G. L. (2008b). Preparation of a natural rubber core/poly mer shell in a nanomatrix by graft copoly merization. Journal of Applied Polymer Science, 110(4), 2475-2482. DOI:10.10 02/app. 28765

Asletha, R., Kumaran, M. G., & Thomas, S. (1998). Thermal behavior of natural rubber/polystyrene blends: thermogravi metric and differential scanning calorime tric analysis. Polymer Degradation and Stability, 61(3), 431-439. DOI: 10.1016/S 0141-3910(97)00 229-2

Budchar, P., Ruksakulpiwat, C., & Khansawai, P. (2008). Graft copolymerization of methyl methacrylate onto natural rubber prepared by emulsion polymerizations. KKU Research Journal, 13(6), 663-668.

Charmondusit, K., Kiatkamjornwong, S., & Prasassarakich, P. (1998). Grafting of methyl methacrylate and styrene onto natural rubber. The Journal of Scientific Research Chulalongkorn University, 23(2), 167-181.

Chuayjuljit, S., Moolsin, S., & Potiyaraj, P. (2005). Use of natural rubber-g-polystyrene as a compatibilizer in casting natural rubber/ polystyrene blend films. Journal of Applied Polymer Science, 95(4), 826-831. DOI: 10.1002/app.21246

Chuayjuljit, S., Siridamrong, P., & Pimpan, V. (2004). Grafting of natural rubber for preparation of natural rubber/unsaturated polyester resin miscible blends. Journal of Applied Polymer Science, 94(4), 1496-1503. DOI: 10.10 02/app.21064

Dafader, N. C., Haque, M. E., Akhtar, F., & Ahmad, M. U. (2006). Study on grafting of different types of acrylic monomers onto natural rubber by g-rays. Radiation Physics and Chemistry, 75(1), 168-172. DOI: 10.1016/j.radphyschem.2005.04.002

Derouet, D., Tran, Q. N., & Thuc, H. H. (2009). Synthesis of polymer-grafted natural rubber by radical photopolymerization of vinyl monomers initiated from the rubber chains. Journal of Applied Polymer Science, 114(4), 2149-2160. DOI: 10.10 02/app.30266

Enyiegbulam, M. E., & Aloka, I. U. (1992). Graft characteristics and solution properties of natural rubber-g-methyl methacrylate copolymer in MEK/toluene. Journal of Applied Polymer Science, 44(10), 1841-1845. DOI: 10.1002/app.1992.070441018

George, B. (2006). Graft copolymerization of methyl methacrylate on to natural rubber: effect of polymerization conditions on particle morphology. Journal of Elastomers and Plastics, 38(4), 319-331. DOI: 10.1177/009524430 6067129

George, V., Britto, I. J., & Sebastain, M. S. (2003). Studies on radiation grafting of methyl methacrylate onto natural rubber for improving modulus of latex film. Radiation Physics and Chemistry, 66(5), 367-372. DOI: 10.101 6/S0969-806X(02)00390-0

Hossain, K. M. Z., & Chowdhury, A. M. S. (2010). Grafting of n-butyl acrylate with natural rubber latex film by gamma radiation: a reaction mechanism. Daffodil International University journal of science and technology, 5(1), 81-88.

Hourston, D. J., & Romaine, J. (1989). Modification of natural rubber latex—I. Natural rubber-polystyrene composite latices synthesized using an amine-activated hydroperoxide. European Polymer Journal, 25(7), 695-700. DOI: 10.1016/0014-305 7(89)90031-1

Hu, G. H., & Cartier, H. (1999). Styrene-assisted melt free radical grafting of glycidyl methacrylate onto an ethylene and propylene rubber. Journal of Applied Polymer Science, 71(1), 125-133. DOI:10.1002/(SICI)1097-4628(199901 03)71:1<125::AID-APP15>3.0.CO;2-S

Juntuek, P., Ruksakulpiwat, C., Chumsamrong, P. & Ruksakulpiwat, Y. (2011). Glycidyl methacrylate grafted natural rubber: synthesis, characterization, and mechanical property. Journal of Applied Polymer Science, 122(5), 3152-3159. DOI: 10.1002/ app.34324

Kangwansupamonkon, W., Fellows, C. M., Lamb, D. J., Gilbert, R. G., & Kiatkamjornwong, S. (2004). Kinetics of surface grafting on polyisoprene latexes by reaction calorimetry. Polymer, 45(17), 5775-5784. DOI: 10.1016/j.polymer.2004.06.042

Kangwansupamonkon, W., Gillbert, R. G., & Kiatkamjornwong, S. (2005). Modification of natural rubber by grafting with hydrophilic vinyl monomers. Macromolecular Chemistry and Physics, 206, 2450-2460. DOI: 10.1002/macp.20 0500255

Kawahara, S., Kawazura, T., Sawada, T., & Isono, Y. (2003). Preparation and characterization of natural rubber dispersed in nano-matrix. Polymer, 44(16), 4527-4531. DOI: 10.1016/S0032-3861(03)00415-4

Kochthongrasamee, T., Prasassarakich, P., & Kiatkamjornwong, S. (2006). Effect of redox initiator on graft copolymerization of methyl methacrylate onto natural rubber. Journal of Applied Polymer Science, 101(4), 2587-2601. DOI: 10.10 02/app.23997

Kohjiya, S., & Ikeda, Y. (2014). Chemistry, manufacture and applications of natural rubber. Cambridge, UK: Woodhead Publishing Limited.

Kreua-ongarjnukool, N., Pittayavinai, P., & Tuampoemsab, S. (2012). Grafted deproteinized natural rubber as an impact modifier in styrene-methyl methacrylate copolymer sheet. Journal of Chemical Engineering, 6, 698-707.

Lamb, D. J., Anstey, J. F., Fellows, C. M., Monteiro, M. J., & Gilbert, R. G. (2001). Modification of natural and artificial polymer colloids by “topology-controlled” emulsion polymerization. Biomacromolecules, 2(2), 518-525. DOI: 10.1021/bm005654e

Lee, D., Subramaniam, N., Fellows, C. M., & Gilbert, R. B. (2002). Structure-property relationships in modified natural rubber latexes grafted with methyl methacrylate and vinyl neo-decanoate. Journal of Polymer Science Part A: Polymer Chemistry, 40(7), 809-822. DOI: 10.100 2/pola.10165

Monteiro, M. J., Subramaniam, N., Taylor, J. R., Pham, B. T. T., Tonge, M. P., & Gilbert, R. G. (2001). Retardative chain transfer in free radical free-radical polymerisations of vinyl neo-decanoate in low molecular weight polyisoprene and toluene. Polymer, 42(6), 2403-2411.DOI: 10.10 16/S0032 3861(00)00647-9

Moolsin, S. (2014). Cure characteristics, thermal and mechanical properties of natural rubber/synthetic rubber blends with and without compatibilizer. Rangsit Journal of Arts and Sciences, 4(2), 105-116.

Nakason, C., Kaesaman, A., Rungvichaniwat, A., Eardord, K. & Kiatkamjornwong, S. (2003). Rheological and curing behavior of reactive blending. II. Natural rubber-g-poly(methyl methacrylate)- cassava starch. Journal of Applied Polymer Science, 89(6), 1453-1463. DOI: 10.100 2/app.12191

Nakason, C., Kaesaman, A., & Supasanthitikul, P. (2004). The grafting of maleic anhydride onto natural rubber. Polymer Testing, 23(1), 35-41. DOI: 10.1016/S0142-9418 (03) 00059-X

Nakason, C., Kaesaman, A., & Yimwan, N. (2003). Preparation of graft copolymers from deproteinized and high ammonia concentrated natural rubber lattices with methyl methacrylate. Journal of Applied Polymer Science, 87(1), 68-75. DOI:1 0.1002/app.11671

Nakason, C., Pechurai, W., Sahakaro, K. & Kaesaman, A. (2006). Rheological, thermal, and curing properties of natural rubber-g-poly(methyl methacrylate. Journal of Applied Polymer Science, 99(4), 1600-1614. DOI: 10.1002/app.22 518

Nampitch, T., & Buakaew, P. (2006). The effect of curing parameters on the mechanical properties of styrene-NR elastomers containing natural rubber-graft-polystyrene. Kasetsart Journal (Natural Science), 40, 7-16.

Neoh, S. B., & Hashim, A. S. (2004). Highly grafted polystyrene-modified natural rubber as toughener for polystyrene. Journal of Applied Polymer Science, 93(4), 1660-1665. DOI: 10.1002/app.20 576

Okieimen, F. E., & Urhoghide, I. N. (1996). Studies on miscibility of poly(vinyl chloride) with natural rubber-graft-polyacrylonitrile and natural rubber-graft-poly(methyl methacrylate). Journal of Applied Polymer Science, 59(11), 1803-1808. DOI: 10.1002/ (SICI)1097-4628 (19960314)59:11 <1803::AID-APP17> 3.0.CO;2-U

Okieimen, F. E., & Urhoghide, I. N. (2002). Graft copolymerization of acrylonitrile and methyl methacrylate monomer mixtures on crumb natural rubber. Journal of Applied Polymer Science, 84(10), 1872-1877. DOI: 10.1002/ app.10474

Oliveira, P. C., Guimaraes, A., Cavaille, J., Chazeau, L., Gilbert, R. G., & Santos, A. M. (2005a). Poly(dimethylaminoethyl methacrylate) grafted natural rubber from seeded emulsion polymerization. Polymer, 46(4), 1105-1111. DOI: 10.10 16/ j.polymer.2004.11.048

Oliveira, P. C., Oliveira, A. M., Garcia, A., Souza Barboza, J. C., Carbalho Zavaglia, C. A., & Santos, A. M. (2005b). Modification of natural rubber: A study by 1H NMR to assess the degree of graftization of polyDMAEMA or polyMMA onto rubber particles under latex form in the presence of a redox couple initiator. European Polymer Journal, 41(8) 1883-1892. DOI: 0.1016/j.europoly mj.2005.02.030

Oommen, Z., Groeninckx, G., & Thomas, S. (2000). Dynamic mechanical and thermal properties of physically compatibilized natural rubber/poly(methyl methacrylate) blends by the addition of natural rubber-graft-poly(methyl methacrylate). Journal of Polymer Science Part B: Polymer Physics, 38(4), 525-536.

Oommen, Z., Nair, M. R. G., & Thomas, S. (1996). Compatibilizing effect of natural rubber-g-poly(methyl methacrylate) in heterogeneous natural rubber/ poly(methacrylate) blends. Polymer Engineering and Science, 36(1), 151-160.

Paul, D. R., & Newman, S. (1978). Polymer blends. New York, USA: Academic Press, Inc.

Perera, M. C. S. (1999). Structure and dynamic of MG rubber studied by dynamic mechanical analysis and solid-state NMR. Journal of Polymer Science Part B: Polymer Physics, 37(11), 1141-1153.

Perera, M. C. S., & Rowen, C. C. (2000). Radiation degradation of MG rubber studied by dynamic mechanical analysis and solid state NMR. Polymer, 41(1), 323-334. DOI: 10.1016/S0032-3861(99) 00087-7

Prasassarakich, P., Sintoorahat, P., & Wongwisetsirikul, N. (2001). Enhanced graft copolymerization of styrene and acrylonitrile onto natural rubber. Journal of Chemical Engineering of Japan, 34(2), 249-253.DOI: 52/jcej.34.249

Pukkate, N., Kitai, T., Yamamoto, Y., Kawazura, T., Sakdapipanich, J., & Kawahara, S. (2007). Nano-matrix structure formed by graft-copolymerization of styrene onto natural rubber. European Polymer Journal, 43(8), 3208-3214. DOI: 10.10 16/j.eurpolymj.2007. 04.037

Pukkate, N., Yamamoto, Y. & Kawahara, S. (2008). Mechanism of graft copolymeri zation of styrene onto deproteinized natural rubber. Colloid and Polymer Science, 286(4), 411-416. DOI: 10.10 07/s00396-007-1787-5

Qudsieh, I. Y. M., Fakhrul-Razi, A., Muyibi, S. A., Ahmad, M. B., Rahman, M. Z., & Wan Yunus, W. M. Z. (2004). Preparation and characterization of poly(methyl methacrylate) grafted sago starch using potassium persulfate as redox initiator. Journal of Applied Polymer Science, 94(5), 1891-1897. DOI: 10.1002/app.20 883

Schneider, M., Pith, T., & Lambla, M. (1996). Preparation and morphological characterization of two- and three-component natural rubber-based latex particles. Journal of Applied Polymer Science, 62(2), 273-290.

Schneider, M., Pith, T., & Lambla, M. (1997). Toughening of polystyrene by natural rubber-based composite particles: part I impact reinforcement by PMMA and PS grafted core-shell particles. Journal of Materials Science, 32(23), 6331-6342.

Shellenberg, J., & Hamann, B. (1992). On the graft polymerization of styrene and acrylonitrile onto polybutadiene in the presence of vinyl acetate. I. preparation of graft polymers. Journal of Applied Polymer Science, 45(8), 1425-1430. DOI:10.1002/app.1992. 070450811

Songprateepkul, S., & Chumsamrong, P. (2010). Studies of natural rubber grafted with acrylic monomers. Advances in Materials Research, 123, 1263-1266. DOI: 10.4028/

Subramaniam, N., Monteiro, M. J., Taylor, J. R., Simpson-Gomes, A., & Gilbert, R. G. (2000). Nevel graft copolymers from mechanistically-designed seeded emulsion polymerization. Macromolecu lar Symposium, 152(1), 43-53.

Suksawad, P., Yamamoto, Y., & Kawahara, S. (2011). Preparation of thermoplastic elastomer from natural rubber grafted with polystyrene. European Polymer Journal, 47(3), 330-337. DOI:10.1016/ j.eurpolymj. 2010.11.018

Suriyachai, P., Kiatkamjornwong, S., & Prasassarakich, P. (2004). Natural rubber- g-glycidyl methacrylate/styrene as a compatibilizer in natural rubber/PMMA blends. Rubber Chemistry and Technology, 77(5), 914-930. DOI: http://

The Thai Rubber Association (2014). Thai rubber statistics: Thailand NR Production in 1999-2014. Retrived from [24 September 2014]

Thamrongananskul, N., Boonjawat, J., Sonsuk, M., & Swasdison, S. (2007). Grafting of natural rubber copolymer with ethylmethacrylate by g-irradiation for using as denture base soft lining material. Journal of Oral Tissue Engineering, 4(3), 161-165. DOI: jarde.4.161

Thiraphattaraphun, L., Kiatkamjornwong, S., Prasassarakich, P., & Damronglerd, S. (2001). Natural rubber-g-methylmetha crylate/poly(methyl methacrylate) blends. Journal of Applied Polymer Science, 81(2), 428-439. DOI: 10.1002/app.1455

Tho, N. V., Kadir, M. O. A., & Hashim, A. S. (2002). A comparative study of styrene polymerization in deproteinized and undeproteinized natural rubber latex. Rubber Chemistry and Technology, 75(1), 111-118. DOI: 5254/1.3547663

Wade, L. G. (2011). Organic chemistry, 8th ed. New Jersey, USA: Prentice-Hall, Inc.

Zeng, Z., Wang, L., Cai, T., & Zeng, X. (2004). Synthesis of high rubber styrene-EPDM-acrylonitrile graft copolymer and its toughening effect on SAN. Journal of Applied Polymer Science, 94(2), 416-423. DOI: 10.1002/ app.20579

Zhang, S., Cao, L., Shao, F., Chen, L., Jiao, J., & Gao, W. (2008). Grafting of methyl methacrylate onto natural rubber in supercritical carbon dioxide. Polymers for Advanced Technologies, 19(1), 54-59. DOI: 10.1002/pat.971




How to Cite

Supat Moolsin, & Nikki K. Robishaw. (2023). Natural rubber modification by vinyl monomers grafting: a review. Journal of Current Science and Technology, 5(1), 99–116. Retrieved from



Review Article