1389 1 mat Bub Ree, BO 184906 Epoxidised Natural Rubber IR. GELLING* Epoxidised natural rubber (ENR) is now an established commercial polymer which is produced by the chemical modification of natural rubber. Two grades are available with epoxide contents of 25 and 50 mole%. They have a unique set of properties offering high Strength, due 10 their abuity to undergo strain crystalisatian, along with increased glass transition temperatures and solubility parameters. These properties are reflected in vulcanisates with increased oil resistance, enhanced adhesive properties. a high degree of damping and reduced gas permeation. Specific interactions, via. epoxide groups, result in a thigh degree of reinforcement with silica filers without the need for coupling agents. Functional group interactions also result in ENR forming compatile blends with a range of chlorine-containing polymers. Reactions between the epoxide groups in ENR and reactive -rroups on other polhmers result in ‘self-vulcanisine’ blends. Practical formulations and a ‘mumber of applications, including tyres, are outlined. AAs long ago as 1922, natural rubber (NR) PREPARATION AND STRUCTURE vas reatied" with a peronyatid aa although the structure of the product was not The chemistry of epoxidation of unsaturated elucidated epoxidation must have occurred. low molecular weight compounds is well Since then, 2 number of conflicting reports established" and it is known that have been published on the preparauon and Secondary ring-opening reactions of the properties of epoxidised natural rubber initially formed epoxide group can occur (ENR). A variety of reaction conditions were employed and the products, variously A systematic study*” of the epoxidation described as hard thermoplastic” to soft of NR latex with peroxyacetic solution rubbery polymers. The epoxidation of revealed that high total acid concentra- NR and other unsaturated polymers was tions and elevated temperatures favoured stated to increase, solvent resistance and the formation of secondary rins-opened improve wear resistance and mechanical products. Two distinct types of ring- properties". However, other publications opened products were obtained depending have reported a reduction in tensile strength principally on the level of epoxidation, At properties!” A number af eparidiced Ina Invele af radifiration, the majority a latices have also been studied? epoxide groups are isolated and the main ring-opened products are those expected In the early to mid-1970's, there was from simple epoxide chemistry" (Scheme 1), renewed interest in the cliemival iwlifcation The final yroduct is nonually the eas diol, Of NR to produce other polymeric materiais but dehydration of the tertiary alcohol as a result of the oil crises. Epoxidation was can occur. As the level of modification is an attractive route because of the simple increased and hence, the number of adjacent Acavtion procedure, the reaction can be epoxide groups, a five-membered eyelic ether carried out in the latex phase, and the becomes the major product™. This arises relatively low cost of reagents involved, from the attack of a ring-opened epoxide on ‘Malaysian Rubber Producer’ Research Assocation, Brickendonbury, Hertord, SGI3 BNL, United Kingdom 184LR, Gelling: Epoxidised Natural Rubber 0 Ps — : A. NR ENR meow fe 7 7 Jaltm. . From. é R seneme Epoxidaton of NR with a peronyecid and secondary rng-opeing of isolated epoxide groups the adjacent epoxide group with the reaction proceeding along the rubber backbone until stopped by a non-epoxide group or steric Considerations (Scheme 2). The various Ting-opened structures were characterised by @ combination of IR and 'H NMR spectroscopy and hy model chemistry” Epoxidation products that contain ring- opened structures are generally insoluble and this can be attributed to the formation ‘father erotslinks ar ilsteated in Scheme 3 such products are observed in the acid catalysed ring-opening of model epoxides. i Q nae oO a 7 aa a ol ie AAO Ring-opened structures as reported above were also observed by Ng and Gant in the epoxidation of NR latex with hydroen peroxide and formic acid. In the light of the established ring- ‘opening chemistry that can occur during the epoxidation of NR, itis easy to understand the variety of products that were reported in the earlier literature on this topic. Epoxidation of NR to 100 mole% under conditions which favour ring-opening cs x Scheme 2 Ring-opening of adjacent epoxide groups to yield five-membered © 185 ethersJournal of Natural Rubber Research, Volume 6(3), 1991 ‘ Dain Pr Scheme 3 Crosslinking of ENR via ring-opened epoxide groups yields a hard thermoplastic material G, Scheme 2), termed furanised NR. This material resembles polystyrene in many of its properties”. Under carefully controlled conditions, NR latex can he eporidised to aver 75 mole% without the formation” of secondary ting-opened structures. Both preformed peroxyacetic acid" or the inetitu generation of peronyformie acid from hydrogen peroxide and formic acid can be employed (Scheme 4). The latter is the preferred route for commercial productiou, as uuly lydiuyeu petuaide is consumed, Peroxyacctic acid epoxidation of NR is 4 second-order reaction with an overall activation energy of 52.6 KJ/mol”, The major factor in controlling the in-situ epoxidation rate is the formation of the peroxyformic acid from hydrogen peroxide and formic acid® A more detailed study has shown that the double-bond concentration changes in the hydrocarbon phase also affect reaction rates ‘Almougn reacuon conaitions nave pen established which yield ENR free from secondary reaction products, 'd NMR specira of these materiais (Figure 1) do not reveal any information on the structure of products. Latex epoxidations are two-phase systems and dls heterogeneity could vomrol ue structure of the products. NR latex particles vary in size from 0.02 yum to over 2.0 pm, if the rate of epoxidation is greater than the rate of dilfusion of the preoxycarboxyhic acid into the particle then a heterogeneously epoxidised product would be expected. At HO. + HCOOH === HCOOOH + H.0 cH HeoooH + Sp ’ ae 5 Pee + HCOOH ne ‘The in-citu epoxidation af NB. employing hydrogen peroxide and formic acid 186LR. Gelling: Epoxidised Natural Rubber s 4 7 = (CH) = ppm. Figure 1. HNMR spectrum of 50 mole% epoxidised natural rubber. an epoxidation level of 50 mole% in the extreme case, the outer shell of the latex sd to 100% while the terior would be unmoditied. ine mathematics of diffusion of a substance through a medium with which it can simultaneously react are well established". Calculations" based on approximate diffusion coefficients and epoxidation rates indicate that diffusion is not the controlling factor, This is suoported by size partitioning of NR latex followed by epoxidatio no differences in rate or epoxidation level ‘were observed’, Further confirmation is ahtsined from DCNMB. If it ie ascumed that the epoxidation of unsaturated units is random, then the mole per cont of the variously positioned epoxide groups can be saloulatsd for any level of spoxidation (Figure 2), The epoxide group sequences of both ENB. 20:(20 mole epoxidized NR) and ENR 50 (50 mole% epoxidised) have been measured by °C NMR and the observed sequences match those calculated for 2 totally random epoxidation’. The °C NMR spectrum of ENR 20 is recorded in Figure 3, slong with the peak assignments. ‘An ozonolysis study of ENR also sub- stantiates a random epoxidation process”. Quantitative analvsis of epoxide orou utilises tetraethylammonium bromide", hydrochloric or hydrobromic acids, but these reagents when applied to ENR give significantly lnwer epavide values than NMR.or IR techniques”. Where there are two or more adjacent epoxide groups, one reagent molecule initiates ring-opening of he epoxide ooquvnae / Sabewne 2). Chomioal titrimetric methods of this type thus measure the isolated epoxide groups plus the number of blocks containing two or more epoxide units, and are thus more a measure of the epoxide distribution than the total epoxide content Bponidation reactions arc sterco-apecific"® and thus ENR is a cis I,4-polyisoprene with epoxide groups randomly situated along the polymer backbone.S , Epoxide unit Sow OAL 0, Oetin unt & doo 2 =m & 0 ET ee ee er es) Total epoxidation (mole%) Figure 2. Calculated distribution of epoxide groups for a random epoxidation process. 2 12 100. l a re 914 wet PAA 1920 217 6 us 12416 1 154)° 7) 120 80 60 40 20 ppm, Figure = 4C NMP spectrum of 20 moleté oponidised nanural rubber.LR, Gelling: Bpoxidised Natural Rubber PROPERTIES. Raw Rubber ENR with epoxide levels of 1-75 mole% can readily be prepared and a systematic change in properties is observed with ihe epoxidation level.” Currently, ‘two levels. 25 mole% and 50 mole% ENR are produced commercially by Kumpulan Guthrie Berhad in Malaysia and marketed as Epoxyprene 25 and Bpoxyprene 50. Density increases with the extent of spoxidation while ‘refractive indices decrease (Figure 4). For every mole per cent increase in the epoxidation level, the glass tcansition temperature (T,) increases by 093°C. Tz mensuromonts, sisted toa libration curve derived from NMR data, can be used to routinely determine epoxide 1.520 Refractive index 1.300 25 Epoxide (2%) Figure 4. Variation of refractive index and density of ENR with extent of epoxidation, 189 levels, as any inhomogeneity due to the presence of ring-opened products is readily observed in a broadening of the transition’, ihe change in 1, Of EINK 1s clearly retlected in their physical properties which are described in subsequent sections. ‘The compatibility of « rubber with othor polymers or liquids, e.g. its oil resistance, can be related to its solubility parameter. As the level of epoxidation of ENR increases so does the solubility parameter* (Tuble 1), each 1 mole% epoxidation raises the solubility, parameter by approximately 0.031 Im)" Even at low levels of epoxidation, ENR is significantly more resistant to low temperature crystallisation than NR", e.g. tn tj, i increased from 2.5 to 3.65 on epoxidation to $ mole%. At 50 mole% epoxide (ENR 50) no crystallisation I —— Refractive index = Density, Density (mg/im*) 50Journal of Natural Rubber Research, Volume 6(3), 1991 ‘TABLE |, SOLUBILITY PARAMETERS OF ENR “T Solubitiy ENR ameter rot epic) am ° 167 2% a « 182 n 186 ‘occurred when the product was stored at O°C for three months. Increases in the viscosity of NR occur after production due to storage hardening, Which hgs. been tengrted to be due, t0 aldehyde or epoxide” groups on the NR molecule reacting with non-rubber proteins form a small number of crosslinks in the fuhher ENR does nat storage harden and Subramaniam” has shown that the epoxide group is not responsible for the storage hardening of NR. Compounding and Valeanisation Epoxyprene 25 and Epoxyprene 50 have Monney viteasities in the eungr 70 te. 10 units but’ break down more readily than NR of comparable viscosity” and thus require litle if any premastication. Generally, their processing. characteristic are similar to those of NR, although problems can be encountered with low Viscosity ENR, in that compounds ean stick to processing’ equipment. One suggested solution is to add low levels of sulphur at the start of the mix eycle™ but it is more appropriate to include @ process aid in Ue fecutuladon, eg. SuuRtUl AGO oF un equivalent material at 3~ 5 p.p.he., which eflestively overcomes this problem END. can be vulesnised by any of the standard sulphur. peroxide or Novor formulations normally employed to cross- link unsaturated polymers”. Dibasic carboxylic acids can also be used" Although acceptable cure characteristics are oblained from a conventional high 190 sulphur formulation (Tables 2 and 3), this system ig not recommended for ENR because the vuleanisates have poor ageing characteristics. To optimise the ageing resistance of ENR, it is essential that the Wuleauiseus aie asi. Suuuger Dascs ale more effective but can result in a loss of processing safety”. Calcium stearate is an effective antidegradant which does not Feduce processing saiety. Kecommendea semi-EV and EV formulations for ENR and their cure characteristics are recorded in Tables 2 and 3 respectively. Vuleanisates Practically all chemical modifications ENR sesull ia @ seduction its basic strength properties. This is due to the disruption of the stereo-regularity of the NR backbone ‘and hence, inhibition of strain crystallisation, Because of the slereo-specifeiyy uf we epoxidation reaction and spacial position of the epoxide oxygen atom, ENR under- goes strain crystallisation”. ‘It is only at Epoude levels in excess of 20 mole% tat a marked reduction in the level of crystallinity is observed Table 4), suggesting that the NR. unit cell, four isoprene units. can accept (WO epoxide groups without ‘undue disruption, The high tensile (Table 4) and tear strengths (Figure 5) of unfilled ENR vulcanisates™ reflect their ability 10 strain crystalise. ‘The properties of ENR vulcanisstes are dominated by their ability to strain crystal- lise and the changes in 7, and soluDinty parameter that occur on epoxidation, ‘The increase in T, and hence, increase in aiublewt tempeidiuie nysteresis can be related to a number of changes in property that occur on epoxidation of NR. Damping increases and thus, Fepound resience decreases 1 rable 5). The temperature/hysteresis profiles of number of epoxidised NR are recorded in Figure 6. Air permeability decreases (Table 5)", peel ‘adhesion increases as does ‘wet traction™®, The latter is dealt with in more detail in the section under applications. TheLR, Gelling: Epoxidised Natural Rubber TABLE 2, FORMULATIONS FOR ENR Compound | 1 Conventional ine oxide Sica acid 5 Anuoxidant® . Parafinie was 3 Sande > cast a ast : T™T™Ht : Formation 2 3 Semicev Bv Vacies Varies Varies Varies i 5 Ls 1s 3 : 25 Ls 1s a °N(13-imethylbuty)-N-pheny-p-phenylenediansine ‘poly-2.2 4-imetby-12- 3 | Adhesion The strength of adhesion of rubbers to substrates depends on a number of factors. The eneray required to peel 2 rubber olf 4 substrate is related to the thermodynamic work and hysteretic energy loss of the rubber compound, Particularly ‘hich adhesion is observed. between ENR. and chlorinated polymers (Table 7)*, this is due to specific interactions e.g. hydrogen Trending or dipale. interactions between the epoxide groups and the chlorinated polymer. The adhesive strength of ENR fo NBR increases with the extent of cponidation, while the reverse it obeerved with NR (Table 7) where the difference in solubility parameter increases with the extent of the epoxidation EV Moo 0 3 Calcium stearate (p.p.r.) Figure 7. Air aged properties. three days at 100°C. of bidek ana > p,p.h.r. process oil: senn-EV Forms R50 vulcanisates (50 p.p.hr, N-330 on 2 and EV Formulation 3 in Vable 2)LR. Gelling: Epoxidised Natural Rubber ‘TAGLE 7. CURED ADHESION OF ENR TO Ply composition ER/ENR 25 NRIENR 50 NRiPvE RPC ENR 25)P0C ENR SUPVE NRINBR ENR 25)NBR ENR 25CR ENR S0:CR Adhesive sicength (Nim) Rubber fulure Bond failure A blend of NR/ENR 50 (50:50) applied ‘The adhesive strength to other substrates, nylon”, brass coated stee!® and. glass" 3 increased by epoxidation, Compared. 0 NR a three-fold increase was observed in the adhesive veel, strength of ENR 25 to brass-coated steel and a factor of ten in that of ENR 50 to nylon. In both results, the increase in visco-elasticiy will be a conirihitory factor A number of adhesive systems have been developed, which are based on ENR, these will be dealt with in the section on applications. Blends For polyiner_ blends to be uty com patible, the Gibbs free energy of mixing ust be negative. The entropies of mixing of polymers are small because of their high Inoiecular weights and thus the majonty of miscible blends occur because of specific interactions eg. hydrogen bonding, berween 97 the two materials. Ng" and Haidzie® have otudied blonds of NR with ENR. and ENR. blends with a range of epoxide contents. Even when the difference in epoxide level between the blend components was villy 10 uwie%% tworphase syateuns wee still obtained. The properties of blends are largely determined by the phase morphology" and this is particularly marked with regard 10 ait permeability. Blends of ENR with cis 14 polybutadiene (BR) and styrene butadiene copolymer! (SBR) are also two-phase systems and m the former case, optimum properties are reported’ to occur at s blend ratio of 60/40 ENR SO/BR. Although blends of ENR 50 and a medium acrylonitrile NBR only exhibit one glass transition temperature, due to the proximity of the component values, phase contrast optical microscopy, clearly shows the presence of tivo phases ‘The epoxide group in ENR can act as a proton acceptor and the possibility of specitic interactions vetween ENR and chlorine containing polymers initiated a number of blend studies. Of the ENR blend systems studied, those with PVC have received by far the greatest attention. Subsequent 10 a report? on the high’ adhesion between ENR. 50 and PVC, Margariis et ai" showed that these materials are miscible across the complete composition range as determined by phase feanteast micrographs and elise transition measurements. The S shape of the blend glass transition/composition curve supports the existence of hydrogen bonding between she two polymers ea a similar dependence” ‘vas observed in other miscible blends where hydrogen bonding was independently established. Only partial miscibility was observed between 25 mole% epoxidised NR and PVC. Workers from the Indian Institute of Technology have published data on both rigid and plasticised” PVC/ENR blends confirming the single-phase natureJournal of Natural Rubber Research, Volume 6(3), 1991 of the PVC/ENR 50 materials. Mechanical propertica, over @ range of compositions, Were reported and the failure mechanism studied by scanning electron microscopy*”. Values of tensile and tear strengths (Table 6) wete lower and ie elongation ut break higher than the additive values of the components. Nasir et al have also published studies in this area. The effect of Innung conditions and blend compositions ‘on tensile and tear strengths were reported for both unvulcanised and sulphur cross- linked blends. The dynamic vulcanisation of PYCVENR biends has also been reported" The melt viscosity of plasticised PVC increases with the increase of ENR, 50 content of the blend, but with rigid PVC/ ENR blends, an improvement in process- ability was observed". ‘The addition of PVC Ww ENR siguifi cantly improves ozone resistance. Flame resistance is also increased", Rigid and plasticised PVC/ENR 50. blends with 2 mimmum ot 33% and >>ve ENK respectively have limiting oxygen index (LO!) values in excess of 21, the criteria for self-extinguishing or flame-resistant matenals. ENR also acts as antidegradant for PVC limiting the evolution of hydrogen chloride, the first step in its degradation®. ‘Chlorinated potyeinyiene“, chtorosut- phonated polyethylene, " chlorinated polypropylene”, poly (vinylidene chloride alkyl acrylate) copolymer” and chloroprene” blends with ENR have also been studied. Blends of two chlorinated polyethylenes (CPE), 25% and 48% chlorine vontent, with ENR 25 and ENR 50 were evaluated. Of the four blend systems, only the ENR 50) CPE 25 system was incompatible. The rest were miscible (ENR 50/CPE 48) or miscible af certain compositions. The addition af lav levels of ENR 50 to CPE 48 increases the modulus and elongation at break but this ‘wend is reversed on increasing the ENR sontent. Chloroprenc/LMR 50. blends are miscible across the complete composition range. To-date, no information has been published on the mechanical or rheological roperies of dese blends. At high temperatures, carboxylic acids react with the oxirane’ group in ENR. Blends of ENR $0 with carboxylated NBR undergo crosslinking without the addition of curatives. Such materials have been termed ‘self-vulcanising blends"™”. Physicil properuies of gum vuleanisatey ate poor, but the addition of @ reinforcing filler’ increases mechanical properties to acceptable values (Table 9). No crosslinking was observed with ENK i> and carboxy- lated NBR. Based on calorimetric and dynamic glass transition data, these biends are reported to be one-phase systems”. Blends of carboxylated NBR and pol chloroprene are also ‘self’ vulcanisable’ but are a two-phase immiscible system”. It TABLE §. PHYSICAL PROPERTIES OF ENR/PVC BLENDS ‘Blend composition (0H ENR 30) Hardaess hore 5 » Proper ‘Tensile strength Elongation at break ( a0 ca) 2.02) 255 (510) 109) 0 320 (720) 0 str 198LR. Gelling: Epoxidised Natural Rubber ‘TABLE 9, PHYSICAL PROPERTIES OF ‘SELF-VULCANISING’ ENR BLENDS Hardness hore Ab ENR Sojearborylated NBR 1091100 0 100/50 2 sooo 38 ENR S0iHypalon | 00/100 6 Propersy Min TS EB (MPa) MPa) B36 mM ns ug 30 8 na ist 68 7 we 618 190 2 1s Contains 45 ppt. of N220 carbon black hhas_been reported that the addition of ENR 50 to this system results in a tertiary miveible blend’ The chlorosulphony! groups in chlorosul- phonated polyethylene react with ENR and blending, also. vields a selif-vulcanisine system!"*"""The broad. glass transition observed with this blend is probably indicative of the occurrence of extensive cparide ring opening ‘Thermoplastic Elastomers Thermoplastic elastomers (TPE) are a rapidly expanding class of materials. One sroup of materials is based on 2 dynamically vulcanised elastomer and_a thermoplastic, Commonly palyprapylene® TPE. haved. on ENR, covering a range of hardnesses have ‘been produced”. Tensile and tear properties are typical of dynamically vulcanised blends of clastomers and polypropylene, while exhibiting excellent oil resistant and ait ageing properties (Tables 10 and 11). ENR have len eon added to NR polyethylene and NR/polypropylene-based ‘TPE as compatibilising agents" Thermoplastic clastomers _have in produced by blending ENR. aj styrene-acryionitrile (SAN) copolymer" Tensile, and tear strength and abrasion resistance increased with content of SAN While tha omuarea won ohearved with egard to impact resistance and elongation at break. ‘The compatibility of ENR with hydroxy! containing polymeric resins has also been investigated, Compatibility was. greatest When the resin contained acidic hydrogens, due to hydrogen-bonding interactions”. APPLICATIONS. ‘The increases in glase transition tempera ture and solubility parameter that occur ‘on epoxidation, plus the ability of ENR to undergo strain crystallisation, suggest a wide range of potential applications, some of which are discussed below. In addition the epoxide groups in ENR have been studied as sites for a novel crosslinking reacon™, as a means of Mmtroducing rubber bound antioxidants'** and as intermediates for further chemical modification”, Adhesives, Adhesive compositions based on epoxi- ised natural rubber have been developed for the bonding of vulcamsed rubbers ot polarity and rubber compounds 199Journal of Natural Rubber Research, Volume 6(3), 1991 Hardaess (Shore A) vr oe ‘reunite sreugils (MPa) | 03 as 6 Eine et) “0 ce Tarek je fe compton 219008) * oe eee mea oe ‘TARLE I] PERCENTAGE RETENTION OF PROPERTIES ON AGEING A 65 HARD TPENE, Aenit Hoa oa a |e ae Ain Property \ Taalasc | tes basic 168 WBS ——_____,__Pvesr —_, eee M100 36 a 130 18 | %6 104 2 to steel. The adhesive and sealant resistance and wear need to be contidered properties of ENR have also been utilised in ‘The hysteresis temperature profile of the area of epory resin technology” and to ENR 25 is such that both safety from high develop glazing sealing systems" Wet traction and good fuel economy from i low tolling. resiatance can be obtained”, Low molecular weight epoxidised natural Generally, high wet traction values. are rubbers have been produced as part of achieved at the expense of fuel economy. UNIDO-sponsored research programme, The relative rolling resistance and wet the main uve of these materisls b considered —_queylon propeaties Uf ENR 23 cumpaced to be adhesives®, those of NR and of SBR are recorded in Figure 8. The partial replacement of the ‘carbon black filler by silica further enhances The fuel economy. 1 his substitution 1s easy with The tyre is by far the largest single market ENR. because ‘of the high reinforcement for rubber and is also the largest potential Obtained without the need to resort to. arbre END coupling agents. Tyre wear properties, of ENR 25 black and biack/silica (35/15) filled The high wet traction properties of compounds are comparable with an NR ENR® ‘make them attractive for tyre tread stock. Improvement in wear a treads but other nraneries sich a roline ahiained hy lending with BR. rubberLR. Gelling: Sponidised Natural Rubber @ ENE 25 silica | : 0 390 @ ENR 25 35 blackitS silica @ ENR 25 black eee uo 120 Rolling resistance rating. Figure d. Put uf ruling reaivcance uiad wee enaetion propertics of ENR 25 compared to similar NR and OESBR tre compounds. Although this cesult in a slight reduction in wet traction, tyre treads based on ENR 25 blended with 20 ppl. BR have rolling resistances similar to that of NR and wet gnip and. wear properties comparable to those of OESBR". Blends of ENR 30 and NR have aiso been evaluated with particular ‘emphasis placed on. the safety aepecte AF motorcycle tyres ENR SO has been investigated as a replacement for butyl rubbers in tyre inner liners and tubes. Tyres with ENR 50) NR (60/40) inner liners have _ been manufactured in Malaysia and during an extensive test programme compared favourably with a standard chlorobuty!/NR liner compound", Other publications” confirm the air retention properties of ENR- bbaved inner liners but concider the higher rate of water vapour permeation, compared to a chlorobutyl, to be 2 disadvantage. General Rubber Goods ENR have found commercial applications in a wide range of areas, e.g, their hysteresis propetties aie utilised in both. mechanical and acoustic damping devices and in speciality shoe soles to give high wet grip. ENR are used in the construction of composite conveyor elts vecause of their adhesive properties and the combination of high strength and low resilience of ENR- based conveyor belts are advantageous under severe service conditions, Now that ENR are established commer- cial rubbers. marketed as Epoxvprene 25 and Epoxyprene 50, their use in applications and market volume are expected to increase rapidly. Date of receipt: June 1991 Date of acceptance: August 1991Journal of Natural Rubber Research, Volume 6(3), 1991 REFERENCES (1922) Uber Kautschak. Ber Dtsch. Chom, Ges. 55, MS. BRITISH PATENT 369 716 (1932) Improve. Corrosion Products of Rubbers BLOOMFIELD. GP. AND FARMER, EH. (93) The Oxsstion of Rubber with Aaueous Soe. Chem. dnd, $3, 1217. NG, SC. AND GAN, LJ. (1981) Reactions of Natural Rubber with Performe Acid. Eur Polym ste i003 GELLING, LR. AND SMITH, 1.F. (979) Controlled Viscosity by Natural Rubber Modification. Proc. It. Rabb, Cont. Venice. NETH. 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