ESS ww fs Non-Rubbers and Their Effects on Natural Rubber Properties By Dr Eng Aik Hwee, Ansell Introduction Natural rubber latex from Hevea brasiliensis origin contains about 30-40% of rubber hydrocarbon and 5% non-rubbers. The rubber and non rubbers contents may vary according to clonal origin, soil and climate conditions, season, type of fertilizers used, and tapping frequency. While the rubber hydrocarbon in the rubber particles is dispersed in the aqueous medium, the non-rubbers could be dissolved or suspended in the aqueous serum or adsorbed on the surface of rubber particles, ‘A large proportion of these non-rubbers are removed during latex centrifugation and processing of the latex into dry rubber or latex products. Most of the non-rubbers in the dry rubber and rubber products are trapped, tenaciously held, or co- precipitated due to their poor solubility in the aqueous medium or strong entanglement with the rubber molecule. When chemically bonded to the rubber molecules, these non-rubbers are known as abnormal groups. A typical composition of fresh latex is shown in Table 1 Table 1: Composition of fresh latex Component Percentage, w/w Rubber hydrocarbon 360 Proteins, amino acids & | 1.7 nitrogenous compounds Upids 16 Ash 0s Inositols & carbohydrates | 1.6 Water 586 pom Non-rubbers could affect the physical and chemical properties of the latex, dry rubber and rubber products, Here are some examples. The mechanical stability of the latex increases with storage time. This is due to the presence of non-rubbers which is @ unique property of natural rubber latex because the stability of synthetic latices would normally deteriorate with storage time. Natural rubber is also known to have a higher green strength value than the synthetic polyisoprene, which could help to maintain the shape of dry rubber compound before curing.’* In addition, due to the ability of natural rubber to reseal,"° natural rubber glove has been reported to show no leak in the water tight test after puncturing with a 0.25mm_ needle. The barrier properties of 80-90% vinyl and nitrile gloves, on the other hand, were found to be compromised when punctured with the same needle. The leak was also significantly lower than those of vinyl and nitrile gloves when a larger diameter needle was used. However, when purified natural rubber was used, ‘the amount of water that leaked through the hole was found to increase significantly, indicating that non-rubbers play @ significant role in controlling the aperture of the tear slit. The presence of high volatile fatty acids in natural rubber has been found to significantly reduce the compressive strength of the rubber modified concrete."2 The non rubbers have been reported to reduce the tack properties of natural rubber. In addition, the non-rubbers that are insoluble in rubber solvents, have been found to be responsible for the higher modulus, faster scorch time, heat build up, and higher hot tear strength of compounded natural rubber. These materials were thought to act as a reinforcing filler and cure activator The naturally occurring network, formed by interactions of proteins and phospholipids with the terminal units of isoprene cchains, was reported to be mainly responsible for the superior stress-strain behavior and the strain- induced crystallization of NR in both unvulcanized and vulcanized states.” Upids Lipids, which consist of non-polar lipids and neutral lipids, are the largest group of by weight. Polar lipids ‘are further sub-divided into phospholipids and glycolipids. The amount of lipids isolated from NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIESdifferent clones can vary from 1.3 ~ 3.5%w/w ‘Typically, a whole natural rubber latex contains 54% neutral lipids, 33% glycolipids, and 14% Phospholipids."* The lipids are mainly adsorbed on the surface of large rubber particles, such as those in the cream fraction, The small rubber particles, such as those in the serum, on the other hand, have a very low level of adsorbed lipids.%* High temperature treatment of rubber such as smoking, has been found to increase the amount of lipid extract significantly but decrease the free fatty acid content." 21 Neutral ids The procedure for extracting neutral or non-polar lipids has been published.* The major component Of these lipids is triglycerides, followed by esters, phenolic compounds (tocotrienols), and sterols, Free tocotrienols could be found in both latex 18 and dry rubber.” There are four types tocotrienols namely; a, Br, 8 y-tocotrienols.:* ® Tocotrienols together with other phenolic compounds from the Uunsaponifiable fraction are the most important natural antioxidant, preventing the autoxidation of the raw rubber The other minor components are free fatty acids, fatty alcohols, monoglycerides, diglycerides, and carotenoid pigments. The major components of free fatty acids are stearic, oleic and linoleic acids. These fatty acids could form soaps with cations such as ammonium and contribute to the colloidal stability of the latex, The free fatty acids and unsaturated methyl fatty esters have been reported to accelerate the oxidation and chain scission of deproteinized natural rubber. Free fatty acids such as stearic and linolenic are activators of sulphur vuleanization, giving better heat build-up properties to natural rubber, * and also function as a crystallization nuclei 2° with bonded fatty acids being the more effective than those of unbonded ones.>: Polyunsaturated fatty acids such as linolenic acid, can also function as a plasticizer to natural rubber. However, they do not contribute to the stretch induced crystallization of the rubber, a property that enhances the physical strength of natural rubber>* 2.2 Glycolipids NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIES Br QUARTER 2014 Giycolipids are a class of polar lipids and can vary from 0.3 ~ 1.0% in natural rubber. The four main components of glycolipids are digalactosyi diglyceride (DGDG), steryl glucosides (SG), esterified steryl glucosides _(ESG), and monogalactosyl diacylglycerals (MGD6), The sterols are mainly stigmasterol, b-sitosterol and DS-avenasterol. The distribution of covalently bonded long chain fatty acids (acyl components) is, very similar to that of free fatty acids, suggesting that these free fatty acids could be originated from the hydrolysis breakdown of the bonded fatty acids 2.3 Phospholipids Like glycolipids, phospholipids are polar lipids and normally below 0.6% w/w. The major components are phosphatidyl choline (PC) and lysophosphatidyl choline (LPC) while the minor components are phosphatidyl ethanolamine (PE), phosphatidyl inositol (PI), lysophosphatidyl inositol (LPI), and ‘metal phosphatidates (MP) or phosphatidic acid (PA). % The isolated fatty acids from the phospholipids are mainly palmitic, stearic, oleic and linoleic acids. Fatty acids containing phospholipids have been postulated to be chemically bonded to the rubber molecule at the a-terminal end and are the branching point of the rubber.” Phospholipids can undergo hydrolysis and produce phosphate which form precipitates with magnesium ion. The removal of magnesium jon from the latex increases the stability of ammoniated latex during storage. Of phosphatidyl choline, phosphatidyl ethanolamine and phosphatidic acid, phosphatidyl ethanolamine has been found to be the most effective antioxidant.»* 3. Proteins, Amino Acids and Other Nitrogenous Compounds 3.1 Proteins The protein content of natural rubber can be estimated by the semi-micro Kjeldahl method using the formula: nitrogen content x 6.25. In centrifuged field latex, half of the proteins is in the serum, one quarter on the surface of rubber particles and another quarter in the bottom fraction.” The serum phase of natural rubber latex has been shown to contain proteins different from those of rubber particles in terms of their molecular weights."2 QUARTER 2054 aeglobulin, the largest component of proteins, has a low sulphur content of about 0.06% and an isoelectrical pH of 4.5, which is similar to that of rubber particles,«.«) while hevein has a high sulphur content of 5%, with an isceletrical pH range of 4.7- 4.9. Hevein Is a single polypeptide containing 43 ‘amino acids with glutamic acid as the terminal group" Hevein has been reported to have antifungal properties.“ Other natural rubber proteins are microfibrils, basic proteins such as hevamines A and 8, **” some high isoelectrical pH proteins “** and various types of enzymes.” The most important enzyme is, of course, the rubber transferase, which is responsible for the biosynthesis of natural rubber Recently the enzymes have also been found in the bottom fraction, °° The molecular weights of proteins in the high ammonia latex concentrate hhave also been isolated and characterized.» The rubber proteins could influence the latex and dry rubber properties significantly. When adsorbed ‘on the surface of rubber particles, they provide negative charges to the particles, contributing to the colloidal stability of the latex.tss Proteins has been reported to contribute to about 14% of the total negative charges on the latex particles,* and that they cover 84% of the surface area of the rubber particles while phospholipids 16%." Like lipids, most of the adsorbed proteins are found in the rubber particles in cream fraction while the rubber particles in the skim latex have a very low level of adsorbed proteins. Natural rubber proteins, have also been reported to act as an antioxidant, giving a better tensile retention to the rubber. *” Glutathione, a tripeptide with a gamma peptide linkage between the amine group of cysteine and the carboxy! group of the glutamate ide-chain, isa well-known antixidant.2%° The cysteine on the glutathione molecule provides a reactive site for radical attack.” Proteins can promote storage hardening of natural rubber, * which has been shown to contribute to the Plasticity Retention Index (PRI) value of natural rubber, a measurement of aging resistance of natural rubber Here, PRI is defined as:PRI = (PYPyao) x 100%, where P, is the initial plasticity and Pru is the plasticity of the rubber after heating for 30 minutes at 1400 in an air oven."* ‘ MAR GM? \ hewsletior myn Proteins could also function as free radical scavengers and retard the chemical modification of natural rubber via radical processes. Therefore, in the absence of proteins, a more uniform crosslink distribution along the rubber molecules can be obtained in the peroxide crosslinking reaction," more grafting points per chain was found in the grafting reaction," and a high speed _ of degradation to form liquid rubber was observed in the degradation experiment." Natural rubber proteins also increase the moisture absorption,”””’ and dynamic properties such as high modulus,” creep and stress relaxation,76 improve silica dispersion and work as cross-linking sites and reinforcing fillers in the rubbery matrix. "”” Certain water soluble proteins from natural rubber can also cause Type | hypersensitivity (Igé mediated allergy) to certain sensitive individuals. Of the 13 allergenic proteins, Hev b 1, 3, 5, and 6.02 have been shown to contribute significantly to the ‘total allergenicity of the proteins. The sum of these four allergens has been found to be significantly correlated with the validated human IgE-based ELISA-inhibition test." The four allergenic proteins can be quantified using a commercial test kit, known as FIT-kit and the test method has been adopted in the ASTM test method, i.e, ASTM D7427. The other two test methods are ASTM 05712 for total extractable proteins, based on the modified Lowry, and ASTM 06499 for the antigenic proteins, 3.2 Amino acids Free amino acids constitute about 0.1% of the latex lof which 80% are in the serum fraction.*" A large proportion of amino acids, around 80%, Is located in the cytoplasmic serum of the latex. The major components are glutamic acid, alanine, ‘and aspartic acid while the minor ones are glycine, phenylalanine, tryptophan, leucine, _ Isoleucine, lysine, cystine. ** In addition, some trace amount of valine, arginine, proline, serine and threonine are also present. Cystine, alanine, asparagine, and phenylalanine have been found to exhibit high anti-aging properties. In addition, several amino acids such as histidine, cystein, glutamic acid, and glutamine, have also been reported to show antioxidant activities via NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIES oachain breaking donor reactions.**** Amino acids have also been reported to promote storage hardening of natural rubber® Alanine, asparagine and cysteine have been reported to be a good antiozonant for the sulphur vulcanized natural rubber. 3.3 Other Nitrogenous Compounds Other nitrogenous compounds in the latex include amines and the corresponding derivatives, such a5 choline, methylamine, tetramethylenediamine, Pentamethylenediamine, ethanolamine, and trigonelline.*” These amine compounds, such as choline, @ quaternary saturated amine, have been Feported to be an accelerator, and antioxidant for the raw rubber® 4 Inositols and Carbohydrates Quebrachitol (2-0- methyl Linositol) is the largest single non-rubber compound present in the latex, Constitutes about 1% of fresh natural rubber latex. 't has a peak melting temperature of 188-189°C Due to its unique and chiral structure, it could be Used to simplify the synthesis of many drugs such 5 antifungal (E}-B-methoxyacrylate,.* Valienamine,>* Conduritol> The main glucid or saccharid in the latex is sucrose, |n addition, a small quantity of glucose, galactose, fructose, raffinose and two pentoses has also been reported." Glucose could reduce the viscosity of Unvulcanized NR and cause of discoloration to vulcanization products. The, reaction between glucose and accelerators in the sulphur vulcanization system, could lead to the reduction of accelerator/sulfur ratio and this affects the cure characteristics, crosslink density, tensile and dynamic properties of sulphur vuleanizates. This was not observed in the peroxide curing system, * Improper preservation can lead to bacteria attack on carbohydrates, which generates volatile fatty acids (VFA). The succinic to malic acid ratio could be used to gauge the quality of latex. For a well-preserved latex, the values for succinic to malic acid ratio are Rormally below 0.6 while a poorly-preserved latex has the values of above 0.6. * VFA number could also affect the physical properties of the rubber films with a low VFA number correlated to a better physical property of the film either un-vulcanized or vuleanized, vice versa." NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIES SAsh The mineral content varies according to the clonal crigin of the latex, soil conditions, weather, and type of fertilizer used." The magnesium level in the latex increases significantly during wintering period due to translocation of magnesium from drying leaves.%® A high magnesium level can cause instability tothe latex." In addition, it can also lead to an increase in the Volatile fatty acids and formation of crystals on the surface of latex. Phosphorous compounds Particularly phosphates, on the other hand, are known to give a good stability property to the latex. The ratio of phosphate to magnesium is important in determining the stability of the latex." The phosphate can form an insoluble precipitate with the magnesium ions. During storage in ammonia, the hydrolysis of phospholipids further releases more phosphates to reduce the magnesium content and leading to an increase in the latex stability Heavy metals such as copper, manganese, and iron are the known pro-oxidants to natural rubber, with copper having the highest pro-oxidant activities ‘among the three." Only free copper can act as a catalyst in the rubber oxidation process." When in the latex, copper might form complex with proteins and amino acids, making it inactive as a pro-oxidant, However, when the complexes are attacked by ‘micro-organisms, free copper is released and this Probably explains the general susceptibility of auto. coagulated rubber to thermal oxidative degradation when compared to the normal acid coagulated rubber Multivalent metal ions have been postulated to involve in the ionic crosslinking of natural rubber! Although the addition of these metal ions did not lead to the hardening of the rubber," probably due to the excessive amount used. © ‘A microanalysis on the gel fraction of natural rubber by transmission electron microscopy associated to electron energy-loss spectroscopy revealed that the calcium:carbon (Ca/C) and calciumioxygen (Ca/0) ratios are relatively higher in the gel than in the soluble fraction, indicating the strong evidence in favor of ionic crosslinking, probably by COO-Ca’+ - 00 bridges.”ro QUARTER 2018 ‘The study also found that the nitrogen:carbon (N/C) ratio is almost the same in both sol and gel fractions suggesting that, protein content seems to have a limited effect in gel formation. This seems to contradict the conclusion from an early study using deproteinization, saponification, and centrifugation methods to obtain the purified rubber, which are rather non-specific."8* 6. Volatile Matters. Moisture is the main component in the volatile matters. There are small quantities of other volatile ‘acids such as formic, acetic, and propionic in the latex.120 The moisture retention of natural rubber is enhanced by the presence of hydrophilic impurities ‘mainly inorganic salts and to some extent proteins.” 'A moisture content can promote mold growth and ‘cause an undesirable odour to the dry rubber.” Mal-odour compounds may also be generated from ‘microbial / enaymatic degradations (fermentation), thermal degradation, and redox reactions during processing of natural rubber. There are four classes of mal-odour compounds, namely (1) Low polarity compounds; (2) Moderate polarity compounds; (3) High polarity compounds; (4) Nitrogen & sulfur containing compounds. Acids of low molecular weight such as acetic acid, propionic acid, butanoic acid and valeric acid constitute 50% of the odorant compounds." 7. References 1. SF Chen, and CS. Ng, Rubb. Chem Technol., 1984, 57, 243. 2, H.Hasma, J. Nat: Rubb. Res., 1991, 6, 105. 3. S. Kawahara, ¥, Ison, J. T. Sakdapipanich, ¥. Tanaka and A. H. Eng, Rubber Chem. Technol., 2002, 75, 739, 4, VIL Folt, Rubb. Chem. Tecnol., 1974, 44, 12. 5. KW, Scott, G.S. Trick, RH. Mayor, WIM. Mayor, and, RIM. Pierson, Rubb. Chem. Technol., 1976, 42, 175. 6. DP, Mukherjee, Rubb, Chem Technol, 1974, 47, 1234. 7. VA. Grechanovskii, LS, Ivanona, and 17. Poddubnyl, Rubb, Chem Technol., 1973, 46, 1234. 8. LF Ramos De Valle, and M. Montelongo, Rubb. Chem. Technol, 1978, 51, 863 9, WSE. Fernando, and M.CS. Perera, Kautsch, Gummi. Kunstst., 1987, 40, 1149, 10. 1 12, 3B. 4 15. 16, w. 18. 19, 20. 21 22 23 24, 25, 26. 21, 28, 29, 30. 31 32, 33 Hi. Hasma, A.B, Othman, and MS. Fauzi, J. Rub Res,, 2003, 6, 231. H. Hasma, A.B, Othman, and M.N. Shaffe, J. Rubb. Res,, 2006, 9, 133. 8 Muhammad, M, Ismail, M.A.R, Bhutta, and Z Abdul-Majid, Constr. Build, Mater., 2012, 27, 241. M. 0. David, . Nipithakul, M. Nardin, J. Schultz, and . Suchiva, J. Appl. Polym. Sci., 2000, 78, 1486. LF. Fan, $.Q, Liao, €.0, Li, XX. Liao, M.W. Guo, Adv. Mat. Res., 2013, 668, 57 E.G. Gregg and 1.H. Macey, Rub. Chem. Technol. 1973, 46, 47, PY. Wang, ¥2. Wang, B.L. Zhang, H.H Huang, J. Appl. Polym. Sci., 2012, 126, 1183 5, Amnuaypornsri, 1. Sakdapipanich, S. Toki, B.S. Hsiao, N. Ichikawa, and ¥. Tanaka, Rubb. Chem. Technol., 2008, 81, 753. H. Hasma, and A. Subramaniam, J. Rubb. Res., 1996, 1,30. AH. Eng, J. Tangpakdee, S. Kawahara, and ¥. Tanaka, J. Nat, Rubb. Res., 1997, 12, 11, MM. Rippel, LT. Lee, CAP. Leite, and F. Galembeck, J. Colloid interface Sci,, 2003, 268, 330, S. Rodphukdeekul, S. Liengprayoon, V. Santisopasri, K. Sriroth, F, Bonfils, €, Dubreuca, and L. Vaysse, Kasetsart J. Not. Sci, 2008, 42, 306, 5. Liengprayoon, Rubb. Conf. Bangkok, 2007. M. Morimoto, Proc. Int. Rubb, Conf. 1985 Kuala Lumpur, 1985, 2, 61. H, Hasma, and A.B. Othman, J. Nat. Rubb. Res., 1990, 6, 105, AR. Arnold, and P. Evans, J. Nat. Rubb. Res., 1991, 6, 75. 5. Nait, Proc. Rubbercon’87, PRI London, 1987, P 2A/a. AN, Gent, LJ. Trans., 1954, 30, 139 DR, Burfield, Polymer, 1984, 25, 1823. ¥. Tanaka, N. Nishiyama, €. Eljri, and S. Kawahara, Polym. Prepr. Jpn, 1993, 42, 4324, PJ. Dunphy, K4. White, J.f. Penock, and R.A Morton, Nature, 1965, 207, 521. '. Kawahara, T. Kakubo, JT. Sakdapipanich, ¥.lsono, and ¥, Tanaka, Polymer, 2000, 41, 7483. . Kawahara and ¥. Tanaka, J. Polym. Sci. Polym. Phys. Ed., 1995, 33, 753, D. Visitnonthachal, Rubb. Conf, Bangkok, 2007. NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIES34. S. Kohjiya, M. Tosaka, M. Furutani, ¥. Ikeda, S. Toki, B.S. Hsiao, Polymer, 2007, 48, 3801, 35. S. Liengprayoon, K. Sriroth, E. Dubreucg, and L Vaysse, Phytochem., 2001, 72, 1902. 36. S. Liengprayoon, Rubb. Conf. Bangkok, 2007. 37. ¥. Tanaka, and L. Tarachiwin, Rubb. Chem. Technol, 2009, 82, 284. 38. 1.5. Bhatia, N. Kaur, PS. Sukhija, J. Sei. Food Agric., 1978, 29, 747 39. SJ. Tata, J. Rubb. Res. Inst. Malaya, 1980, 28, 77. 40. J. Sansatsadeekul, J. Sakdapipanich, and P. Rojruthai, J. Biosci. Bioengin., 2011, 111, 628. 41. BL Archer, BG. Audley, G.P. Sweeney, and .C. Hong, J. Rubb. Res, Inst. Malaya, 1969, 21, 560. 42, S.J. Tata, Proc. Int. Rubb. Conf. 1975 Kuala Lumpur, 1976, 2, 441. 43, BLL. Archer, Biochem. 1.1960, 75, 236. 44, K. Walujono, R.A. Scholma, JJ. Beintema, A, Mariono, AM. Hahn, Proc. Int. Rubb. Conf. 1975 Kuala Lumpur, 1976, 2, 518. 45, J. Beintema, J, Rubb. Res, 2010, 13, 265. 46. WF, Parijs. J. Broekaert, IJ. Goldstein, and Wy. Peumans, Planta, 1991, 183, 258. 47. B.L.Acher, Phytochemistry. 1976, 15, 297. 48. BL. Archer, D. Barnard, E.G. Cockbain, PB. Dickenson, and A.!, McMullen, The Chemistry and Physics of Rubber and Rubber-like Substances, ed. L Bateman, Maclaren & Son Ltd, London, 1963, p. 41. 49, S.J. Tata, and GJ. Molt, J, Rubb. Res, Inst. Malaya, 1964, 18, 97, 50. J, d’Auzac, and J.L. Jacob, Physiology of Rubber Tree Latex: The Lacticiferous Cell and Latex ~ A Model of Gytoplasm, ed. J. e’auzac, J... Jacob, and H. Chrestin, CRC Press, Florida, 1989, p. 59. SL. J. Tangpakdee, ¥. Tanaka, K. Ogura, T, Koyama, R. Wititsuwannakul and D. Wititsuwannakul, Phytochemistry, 1997, 45, 269 52. J, Tangpakdee, Y. Tanaka, K. Ogura, T. Koyama, R, Wititsuwannakul and N. Chareonthiphakorn, Phytochemistry, 1997, 45, 275. 53. H. Hasma, J. Nat Rubb. Res., 1992, 7, 102. 54. G. Verhaar, Rubb. Chem. Technol, 1958, 32, 1627. 55. C.C. Ho, Colloid Polym. Sci., 1989, 267, 643. 56. K. Nawamawat, JT. Sakdapipanich, C.C. Ho, ¥. Ma, 4. Song, and J.G. Vancso, Colloid Surface A., 2011, 390, 157, 87, 58, 59, 60. 61, 62, 63, 64, 65. 66. 67. 68. 69. 70. 7. R. B. 74, 75. 76 7 K. Nawamawat, 1. Sakdapipanich and C.C. Ho, ‘Macromolecular Symposia, 2010, 288, 95. |. Aimi lzyana and M.N. Zairossani, MUM Eng. J, 2011, 12, 61. AR. Ndhlala, M. Moyo and JV. Staden, Molecules, 2010, 15, 6905. M4. Gregory and AS. Tan, Proc. Int. Rubb. Conf 1975 Kuala Lumpur, 1976, 4, 28. DR. Burfield, Development of Plastics and Rubber Product industries, ed. J.C. Rajaro, Rubber Research, Institute of Malaysia, 1989, p. 204, M.D. Mortis, J, Nat. Rubb. Res., 1991, 6, 96. Rubber Research Institute of Malaysia, SMR Bull No. 7, 1973. P. Tangboriboonrat, D. Polpanich, T. Suteewong, K. Sanguansap, U. Paiphansiri, C. Lerthititrakul, Colloid Polym. Sci,, 2003, 282, 177. Y, Fukushima, S. Kawahara and ¥. Tanaka, J. Rubb, Res,, 1998, 1, 154, NV. Tho, M.O.A. Kadir, and A.S. Hashim, Rubb. Chem. Technol, 2002, 75, 111. P. Wongthonga, C. Nakasonb, Q. Panc, GL Rempeld, 5. Kiatkamjornwong, Eur. Polym. J, 2013, 49, 4035. J. Tangpakdee, M. Mizukoshi, A. Endo and ¥, Tanaka, Rubb. Chem. Technol, 1998, 71, 795. J.T. Sakdapipanich, T. Kowitteerawut, S. Kawahara, and ¥, Tanaka, J: Rubb. Res., 2001, 4, 1. ©. Chaikumpollert, ¥. Yamamoto, K. Suchiva, and S. Kawahara, Colloid Polym. Sci., 2012, 290, 331. A. Stevenson, Rubber in Offshore Engineering, ed. AA Stevenson, Adam Hilger, Bristol, 1984, Chapter 2. DAR. Burfield, AH. Eng, and PST. Loi, Brit. Polym. J., 1989, 21, 77. KL Chong, and M. Porter, Int. Polym. Latex. Conf., 1978 London, 1980, Prepr. 16 K.L Chong, and M. Porter, Int. Conf. Structure ~ Properties Relations of Rubber, Kharagpur, 1980, Prepri ‘AN, Chapman, and M. Porter, Natural Rubber Science and Technology, ed. A.D. Robert, Oxford University Press, 1988, Chapter 12. SS. Sarkawia, b, WK. _Dierkesa, Noordermeer, Eur. Polym. J, 2013, 49, 3199. T. Karino , ¥. Ikeda , ¥. Yasuda , S. Kohjiya and M. Shibayama, Biomacromolecules, 2007, 8 (2), PP 693-699 JNM. NON-RUBBERS AND THEIR EFFECTS ON NATURAL RUBBER PROPERTIES