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Pergamon

SOO79-6700(97)00052-X

frog. Pohm. Ser.. Vol. 23, h6Sm706, IYYX Copyright 0 1998 Elsevier Science Ltd Printed m Great Britain. All rights reterved. 0079%6700/9x $19.00

THERMOPLASTIC

NATURAL

RUBBER

BLENDS

A. IBRAHIM and M. DAHLAN Chemistry Department, Univeniti Kebungsaan Maluysiu, 43600 Bangi, Selangor. Mulaysiu

CONTENTS
I. 2. 3. 4. 5. 6. 7. 8.

Introduction Natural rubber - polypropylene blends Liquid natural rubber Natural rubber - liquid natural rubber-polypropylene Natural rubber - polyethylene blends Epoxidised natural rubber Thermoplastic epoxidised natural rubber References

blends

665 667 671 674 677 694 696 703

1.

INTRODUCTION

Polymer blends are a popular form of new thermoplastic engineering materials and constitute a rapidly changing field. Their growth rate is very significant and exceeds more than 10% which is a few times that of the plastics industry on the whole. The most outstanding is performance engineering or speciality blends and more than 600 new grades of these blends appear on the market annually. The phenomenal growth is due to the material being very commercializable, its convenience of being prepared by reactive processing and the flexibility of three phase blends for the purpose of reinforcing or the preparation of foamed blends. Improving blend morphology by utilizing reactive blending techniques is possible with the advancement of multifunctional copolymers and trans-reaction catalysts. Technically the preparation does not involve sophisticated machinery and it is a straight forward process. Thermoplastic elastomer (TPE) is a blend of rubber and thermoplastic and most probably the fastest growing sector in the polymer market. -j The main advantages of these materials are that the thermoplastic machinery for processing does not require factory compounding or vulcanization and the scrap and rejects can be reprocessed. In rubber modified thermoplastics, the role of rubber is to improve the impact strength and ductility of the plastic as in toughened polystyrene and polypropylene.4-7 The stiffness of the rubber is increased with the incorporation of plastic into the rubber matrix. Usually TPE and rubber modified thermoplastics are of multi-phase polymer systems consisting of hard and soft domains which can either be copolymers or mechanical blends. The microphase separation into domains of an appropriate molecular architecture leads to materials possessing unique and technologically useful physical properties. The influence of molecular architecture on the physical properties of blends 665

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A. IBRAHIM

and M. DAHLAN

has stirred a lot of interest in rubber-thermoplastic blending. Most olefinic TPEs are made by blending ethylene-propylene rubber (EPR) or ethylene-propylene-diene monomer rubber (EPDM) with polypropylene (PP). -O The rubber phase is partially cross-linked and thereby produces a morphology involving microphase separation responsible for the unique properties of the material. A number of patents exist on thermoplastic oletin elastomers (TPOE) made by physical blending of EPDM and PP. The blending of natural rubber (NR) with synthetic rubbers to produce materials with desired technical specifications is a widely practised technology in the rubber industry. ,* Two or more rubbers are blended with the aim of obtaining an improvement in overall properties, better processing and lower compounding costs. Most products in the rubber industry are likely to be based on blends in all or part of their construction. Typical examples of such products in large-scale production are tyres. Table 1 shows typical blends of NR with synthetic rubber used in different parts of a tyre. The blends are tailor made to meet the requirements for individual parts of the tyre. A thermoplastic material known as a thermoplastic natural rubber (TPNR) is produced on blending thermoplastic with NR. 13.14 The development of TPNR was principally based on the criteria set by EPDM blends with thermoplastics. Analogous to olefinic TPE, NR has also developed along a similar direction with polyolefins being the most suitable thermoplastic. The research into the preparation and evaluation of TPNR was initiated in the early 1960s at the Malaysian Rubber Producers Research Association (MRPRA) in London. The compatibility of the NR-thermoplastic pair was studied from the aspect of processing and additives. Generally the mutual solubilities of the polymers determine the dynamic mechanical properties while the phase size, cohesive strength of the rubber phase and the adhesion between phases influence the impact properties. Cross-linking or interfacial reaction promoters can be added into the blend. Therefore, the physical properties of a blend primarily depend on three main parameters: blend composition, processing conditions and crosslinking or curing agent added. Dry mixing of NR with any compatible thermoplastic is done at a temperature above the melting point of the plastic as it is already above that of NR. For the NR/PP and NRIPE systems, the recommended temperatures are about 180 and 15OC, respectively. Varying the mixing temperatures near the melting points of the thermoplastic will yield TPNR materials exhibiting different physical properties. The mixing rate and duration of mixing
Table 1. Typical NR blends used in car, truck and earthmover tyres

Type
Tread Car Light truck Large truck Earthmover Radial Radial Cross-ply 75125 OESBR/ SBR 33133134 NR/ OESBR/OEBR 70/30 NIUIR or NIUBR NR Casing 70130 NR/SBR NR X0/20 NR/IR NR

Part
Sidewall 50150 NR/BR 50150 NR/BR 40160 NRI OESBR NR Liner 70130 CIIWNR X0/20 NR/IR 70/30 CIIIRDBR 20/30 ClIIR/NR

BR: butadiene rubber; SBR: styrene-butadiene rubber; IR: isoprene rubber; OEBR: oil extended BR; OESBR: oil extended SBR; CIIIR: chlorobutyl rubber (copolymer isobutylene-isoprene).

THERMOPLASTIC

NATURAL

RUBBER BLENDS

667

also influence the properties of the blend produced. The tailor made TPNR will then have to be identified with the composition, temperature, mixing rate and processing time. Normally the quality of the material is judged from the physical and mechanical properties exhibited. The homogeneity of the blend is determined by the ability of the component to mix which is known by the processing parameters. Dynamically, optimum mixing is feasible when the viscosities of the components are comparable. It is difficult to mix any two fluids if the difference in their viscosities is large. The dependence of viscosity on temperature and the phase distribution on the rate and duration of mixing will help to explain the morphology of the blend obtained. In many rubber or plastic blends, the homogeneity is assessed from the position of the glass transition temperature, Tg, of the blend where a compatibilised blend will show a single Tg within the two Tgs of the components. 16.17A Tg outside of the two component Tgs strongly indicates a plasticising effect of the added component. However, in NR-polyolefin blends, the glass transition temperatures of NR(-67C) and polyolefin (- - 60C) are close together; the separation is less than 10C. and as such the movement of Tg in the blends will not be very indicative of the phase distribution. Scanning electron microscopy (SEM) remains the best option for the morphological studies. 6,8X9 NR polyolefin blends, the rubber phase is extracted out with suitable In solvents like toluene before the SEM examination is carried out to facilitate a better phase contrast micrograph. TPNR is normally prepared in the laboratory via mixing in a Banbury mixer or Brabender Plasticorder attached with a mixer or a twin screw compounder. The equipment allows the processing characteristics of the blend to be studied in detail. This allows for the optimization of the process as it can be easily evaluated and adopted. On a larger scale, mixing of NR with the polyolefins can be carried out in an internal mixer or compounder. Pelletization and other related industrial procedures are similar to any other thermoplastic processing.

2.NATURALRUBBER-POLYPROPYLENEBLENDS Natural rubber-polypropylene blend is the most widely studied system and it is synonymous with TPNR. A major portion of research has been done at the Malaysian Rubber Producers Research Association (MRPRA) in London which initiated these studies about 25 years ago with the aim of producing various rubber products for new applications. -* PP is considered to be the best choice for blending with NR due to its high softening temperature of about 150C and low glass transition temperature of about - 60C for the blend, giving rise to a very versatile thermoplastic applicable over a wide range of temperatures.. NR/PP thermoplastic blend compositions can be varied to give materials of different mechanical properties ranging from a soft elastomer to a semirigid plastic. The soft grade TPNR is produced by blends with compositions richer in rubber while the harder grades can contain up to about 30% NR. The flexural modulus of the blend is determined by NR and the grade of PP, with the homopolymer PP producing higher stiffness while the copolymer PP contributes to a greater ductility and impact strength at low temperatures. Tailoring a TPNR to meet the requirements of certain mechanical and physical specifications can be done by optimising the blend composition and selecting a suitable thermoplastic. The compatibility of NR and PP can be realised from the microstructures of the individual polymers, i.e.

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A. IBRAHIM and M. DAHLAN

NR:

CH, -C=

CH-CH2

and

PI?

CH,-CH-CH,-CHz

I Cfk

I CH3

At the molecular level, NR and PP are incompatible which will give rise to a two-phase blend but their solubility parameters are fairly similar and thus a stable dispersion of NR particles in a PP matrix or vice versa is possible.24325 Commercial grade PP, which is normally used in the preparation of TPNR, is made up of not only the -CHj groups as branches on the polymer backbone but also groups such as propane, butane, etc.26 These side chains and branches are likely to cause an increase in the level of incompatibility with the NR in a TPNR blend. The processing temperature is between 175 and 185C and higher temperatures are undesirable due to the possibility of oxidation of NR which becomes significant at 200C and increases with temperature. The effect on the physical properties of TPNR is minimal but oxidation will increase the odour and may affect the ageing of the blend. To overcome incompatibility and produce a homogenised blend, the mixing of the two polymers during blending requires an agent that can induce interactions within the phases, between phases or at the interface.27 In natural rubber processing, the normal and most effective cross-linking reagent is either elemental sulfur or sulfur donating compounds where highly cross-linked systems in the NR phase and the are desired. 28 However, in TPNR blends, partial cross-linking formation of graft copolymers for interfacial adhesion between the NR and PP phases are required. These reactions occur during blending and are induced by the compatibilizer added. This process is categorised as reactive blending or dynamic vulcanization. Analogous to natural rubber vulcanization but with only partial cross-linking within the NR phase, the curing reaction in TPNR can be effected by low concentrations of elemental sulfur or sulfur donor efficient vulcanisation (EV) systems such as thiuram disulfides or dithiobismorpholine (DTM), dimaleimides, di-isocyanate derivatives and tetramethylthiuram disulfide (TMTD). K*~-~The effects of TMTD in the presence of zinc oxide, stearic acid and 3-mercaptobenzothiazole (MBT) on the degree of cross-linking in TPNR was studied in relation to the physical properties exhibited. An improvement in the physical properties observed was related to an increase in the cross-linking density. However, surface blooming and odour resulting from residual chemicals in the TPNR were observed. Dynamic curing of NR/PP blends by a mixture containing equal amounts of TMTD, DTM and N-cyclohexylbenzothiazole-2-sulphenamide (CBS) was also investigated and it was found that the mechanical and physical properties were optimised at about 2 phr of each component. Addition of free sulfur caused the properties to degrade. The sulfur releasing compounds are also unsuitable to coexist with UV inhibitors (hindered amines) which are widely used in the stabilization of PP. Morphological studies by SEM showed that cross-linking the elastomeric phase caused a change in the flow behavior of the materials which accounted for the increase in tear resistance of the sulfur-cured TPNR in comparison to the uncured system. 33 Organic peroxides have been described as good cross-linking agents in NR/PP blends and

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NATURAL

RUBBER

BLENDS

669

0.5
WA 2tp.p.h.p.b

1.0

10
I.5

Fig. 1. Effect of HVA-2 on tensile properties (die C) of an 80:20 NR/PP blend. * dicumyl peroxide (DCP) was one of the first reagents used for dynamic vulcanization of TpNR. 720.33 A marked improvement in hardness, modulus, strength and elasticity of TPNR was observed with the addition of DCP into the blends especially for softer grades of TPNR with NR compositions of more than 65%. 1sV34 Although the surface texture of TPNR is not as smooth and shiny as other thermoplastics like polystyrene, the material flows very well without any tackiness during injection moulding or extension processes. However, surface

50-

loo

-m

-60

-40

0.5 WA-2 (p P.h.P.)

10

Fig. 2. Effect of HVA-2 on tension set and gel content of an 80:20 NR/PP blend. Ix

670

A. IBRAHIM and M. DAHLAN

blooming on exposure to sunlight or heat ageing is a problem with samples compatibilised by peroxides. This was rationalised as due to the induced oxidation of NR and PP by the peroxide. The effect was not inhibited by normal antioxidants or photostabilisers or UV inhibitors added into the blend. DCP cured TPNR also had a disagreeable odour from the acetophenone formed. Dimaleimides are well-known to initiate cross-linking in elastomers including NR in the presence of small quantities of peroxides, dibenzothiazol-2-yl disulphide (MBTS) or high energy radiation. The cross-links formed are heat stable.36 It is thus promising to use these compounds as agents for dynamic vulcanization of TPNR. One such material, m-phenylene bismaleimide, commercially known as HVA-2, was found to be an effective cross-linking agent in the presence of a radical activator like an organic peroxide or MBTS. The effect on the physical properties of TPNR by HVA-2 is shown in Figs 1 and 2. * The performance of TPNR is considerably improved by the addition of about 7.5 phr HVA-2 into the blend containing 50-60% NR and the value surpasses that of the EPDM-PP blend.2 Increasing the concentration of HVA-2 causes the tensile and tear strengths, and the gel content which is a measure of the cross-link density to increase and the tension set to decrease. Most probably, a maximum in tensile properties will be obtained at around IO phr HVA-2. Dynamic vulcanization of TPNR with HVA-2 has been noted to be the best curing system thus far and it has been applied on a commercial scale in the production of NR/PP thermoplastics under the trade name of DVNR. Alkyl phenol-formaldehyde resins have also been tried in the dynamic vulcanization of NR/PP blends. 3X363-40 One phenolic resin, SP 1045, when added in the order of 15 phr, was found to improve the physical properties of TPNR. In addition, ZnO in the range of 5 phr had to be mixed with PP before compounding with NR for the enhancement of the physical and mechanical properties (in particular the impact strength).4 The inclusion of Novar 924, a diurethane cross-linking reagent, at a level of 10 phr was also reported to cause significant dynamic vulcanization in the NIUPP blends so as to produce TPNR having respectable mechanical properties4* In summary, organic peroxides, low sulfur and sulfur E.V. systems, dimaleimides diisocyanate derivatives and phenolformaldehyde resins are suitable curing reagents as all afford heat stable cross-links in NR. Copolymers and ionomers have been widely used as compatibilising agents in polymer blends due to the functionality of the different parts of the molecule which can physically and/ or chemically interact with the different components of the blend.4-46 These surface interactions help to bind the different phases together or to increase the adhesion of component particles in the matrix of the other component. A modified polymer with various functional groups attached will behave like a copolymer where the different functional groups act as interaction points leading to a chemical or physical interaction between the incompatible components of the blend. The use of low molecular weight rubber or liquid rubber to compatibilise the different phases of rubber-modified thermosetting polymers such as epoxies was discussed by A. J. Kinloch. Choudhury and Bhowmick48 showed that the adhesion between the NR and PP increased with the addition of either EPDM or chlorinated polyethylene (CPE) to the rubber. Consequently the improvement in the tensile strength of NR/PP blends on adding EPDM or CPE in the mix was attributed to these effects. In our laboratory, the role of liquid natural rubber (LNR) in NR/PP blends was investigated from the aspect of physical and mechanical properties exhibited and morphology of phase distribution. Liquid natural rubber is a

THERMOPLASTIC

NATURAL RUBBER

BLENDS

671

chemically modified NR generated via oxidative degradation of NR. Such groups like OH and C=O are formed during the degradation of NR and these groups form the active sites in LNR. Being of similar polymers, NR and LNR are miscible and thus chemical and physical interactions are possible when LNR disperses into the NR phase. PP and LNR are immiscible and hence the only interaction expected is through physical and/or chemical interactions through the active sites of LNR.

3.

LIQUID

NATURAL

RUBBER

LNR has been defined in a UNIDO report4 as dry natural rubber or natural rubber precursors which can be poured or pumped (having viscosities below 1500 poises at temperatures below 100C) without the assistance of an external medium such as a solvent. It is also defined as a form of natural rubber with a similar microstructure of shorter polymeric chains with molecular weights (Mw) lower than 10. Liquid rubbers including liquid natural rubber can be classified into three main categories:50 1. First generation: LNR with no reactive groups leading to poor physical properties. 2. Second generation: LNR with reactive groups but poor physical properties. 3. Third generation: LNR with low molecular weight, reactive groups and good physical properties. When the idea of liquid natural rubber was first proposed, the objective was to reduce the internal viscosity of the rubber. This facilitates the incorporation of other processing aids and reduces the energy required for their incorporation. Today this original idea has been widely broadened i.e. to turn natural rubber into specialty chemicals and/or chemical feedstocks. There are several methods of obtaining LNR reported in the literature.5i The nature of the LNR is much determined by the technique chosen to produce it. The first production of LNR, prepared by a high temperature mechanochemical peptisation method, was reported in 1923 in the USA.52 It was used mainly in the field of adhesives. Other methods developed thus far involve various combinations of thermal, mechanical, chemical and radiation treatments. However, these products often fail to satisfy industrial requirements. Considering the fact that the economic advantages would be substantial to natural rubber producing countries, in 198 1 following a symposium held in May of the same year in Phuket, Thailand, the United Nations Industrial Development Organization (UNIDO) sponsored a study on the pilot plant production of liquid natural rubber in the Ivory Coast, West Africa. 52 The aims of the project were to select the best technique available leading to the commercial production of LNR and, at the same time, to evaluate the materials industrial applications based on properties and economics. The technology chosen was based on the technique developed and patented by Institute Francais du Caoutchouc, France. The process made use of an oxydo-reducing system of oxygen-phenylhydrazine to depolymerise natural rubber in a latex form as shown by its depolymerization mechanism in Fig. 3. The process was able to reduce the molecular weight, Mw, down to a range near 8000-25 000, depending on the concentrations of the reagents used. Other patents by the same group54 reported the use of another redox couple, i.e. p-methylbenzene sulphinic acid and hydrogen peroxide, while heating at 100C for 7 h to depolymerize natural rubber in solution. Mori and Fujii5 prepared LNR also in solution by making use of phenylhydrazine, FeCl* and oxygen. In Sri Lanka, attempts were made to produce

612

A. IBRAHIM and M. DAHLAN

2 #NH-NH2

+ 302 --)

j#-NH-i+fd+2HOd+No

+2H#)

J.,

HO CH

HO- CH

Fig. 3. Proposed mechanism

of NR depolymerization.

LNR by photosensitised oxidation using solar radiation in the presence of nitrobenzene. x, Since all of the techniques mentioned employ toxic chemicals, little impact has been made in the industrial sector. Regarding more recent developments, in 1985, the Malaysian Rubber Producers Research Association (MRPRA) patented a technique for producing LNR based on a redox reaction involving the use of a reducing agent i.e. sodium chlorite or sodium nitrite and an oxidising agent i.e. hydrogen peroxide or its organic derivatives. 58 The method reported is well suited for use with natural rubber in a latex form, including epoxidised natural rubber latex. It is capable of reducing molecular weight levels over a wide range. Ravindran et al. 5yxioemployed a photochemical technique based on the use of hydrogen peroxide and UV light to produce hydroxyl terminated liquid natural rubber in solution. The

THERMOPLASTIC NATURAL RUBBER BLENDS

673

product was later used for the preparation of thermoset polyurethanes from hydroxylterminated natural rubbers6 Gan et ~1.~~used a mixture of sodium hypochlorite and hydrogen peroxide to reduce the molecular weight of natural rubber in latex form. In the initial step, they believed that the formation of hydroperoxides was the result of an oxygenation reaction by singlet oxygen generated in the system. Subsequent decomposition of these peroxides gave rise to a reduction in the molecular weight of the polymer. Production of LNR by a combination of mechanical and thermal energies aided by a peptiser, activated pentachlorothiophenol, has also been reported. 63 The depolymerization process wa? attempted at various temperatures in the range of 220-260C. Though the degradation was found to be rapid at higher temperatures, the process at lower temperatures was preferred. In our study, we observed a slight degradation of natural rubber upon exposing its solution to visible light.64 However, the degradation increased significantly in the presence of carbonyl-containing photosensitizers such as benzophenone, xanthone and flavone-in that order of effectiveness. Their abilities to affect degradation depended on their efficiency to promote hydrogen abstraction. XX In another study, benzoylferrocene with an active carbony1 group was found to be more effective than ferrocene in inducing rubber photolysis.h7 Formation of new groups such as -OH, C=O and C-O of epoxide resulting from the oxidation of rubber has been reported. The differences in NMR spectra for freshly-degraded samples and samples taken 5 days later are provided in Table 2. The presence of -0OH and -0OR groups in the freshly-degraded sample indicates the involvement of hydroperoxides in the intermediate stage before decomposing into more stable products like hydroxyl, epoxy and carbonyl. These groups, though small in quantity, are very important in determining the reactivity of LNR as we observed later.6m7 Unlike liquid natural rubber, only a few studies were reported in the literature on the subject of liquid epoxidised natural rubber (LENR). There are two approaches available to prepare LENR, i.e. epoxidation of liquid natural rubber or depolymerization of solid ENR in solution. 72,73 The former is a more popular approach. 74-76Chemical degradation of ENR into liquid form is also possible via cleavage of glycol derived from the rubber epoxide., Table 2. The assignment of NMR peaks (ppm) for LNR in C6D,68
Fresh sample I .40 broad 5 day sample Assigment -C&-C- c \/
0

1.40 broad

1.72 2.20 2.70 broad

1.61 I .62 1.78 2.20 2.60 broad

-CH, truns CHI-CH= -CLI, -CXCH-CH0

4.30 broad 5.30

3.80 broad 5.30

-0-OH,-CH,-OOR -CH=

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A. IBRAHIM and M. DAHLAN

However the technique is not practical on a large scale. Furthermore the chemical used, Pb(OAc)4 might pollute the environment. Since the methods so far discovered have yet to fulfill the industrial requirements for LNR production, investigations regarding this subject are still active. Gelling has suggested that three criteria have to be met before chemical modification of natural rubber (including the depolymerization process) can be considered to be technologically and commercially viable: I. Reagents cannot cause unintended chemical changes in the rubber molecules. 2. Catalysts used cannot be disturbed by non-rubbers. 3. Process must be cheap but efficient.

4.

NATURAL

RUBBER-LIQUID NATURAL POLYPROPYLENEBLENDS

RUBBER-

NR/PP blends were prepared in our laboratory

by mixing in a Brabender

Plasticorder

and

--_--

- strain ot bra - strea at break


I 60 70

T
20

50

40

50

Rotor

speed

Crpm)

Fig. 4. Effect of mixing rate (rotor speed) on the stress and strain of NRlPP blends processed at different temperatures.

THERMOPLASTIC

NATURAL RUBBER

BLENDS

615

LNR was added into the blend as a compatibiliser. Generally the TPNR obtained was pale yellow in colour and exhibited physical and mechanical properties associated with many thermoplastics. The physical properties of the material depends on the processing conditions and composition of the blends.69.70 Fig. 4 shows the dependence of tensile properties on the processing temperature and rate of mixing which is proportional to the rotor speed. The variation in mechanical properties based on the composition of NR, PP and LNR is shown in Table 3. Dynamic mechanical analysis of the sample shows a single glass transition temperature at around - 60C and typical plots are depicted in Fig. 5(a) and (b). The tensile properties of the blend are determined by the homogeneity of mixing, i.e. the properties are better with higher homogeneity. As noted in Fig. 4, the stress and strain at break are optimised at a processing temperature of 150C and a rotor speed of 50 r.p.m. These indicate a maximum homogeneity is attained at these processing conditions which implies the relative viscosities of the melted NR and PP are comparable at this temperature. At higher rotor speed, the mixing leads to agglomeration of similar species which causes phase separation. Fig. 6 shows the variation in torque during the mixing of NlUPP blends at a processing temperature of 180C. Without LNR the rise in mixing torque is associated with the normal melting of PP and curing of the blend. However, in the presence of LNR a secondary torque peaks at around 6 min after the introduction of PP. The increase in torque depends on the amount of LNR added and it reaches a maximum at around 15-25% LNR depending on the composition of NR in the blend. The torque increase is higher with more LNR. Apparently the level of curing is higher with more LNR and thereby the blend is more difficult to stir. These two aspects of study thus strongly suggest an important role of LNR in the NR/PP thermoplastic blends. As discussed earlier, the strength of the material arises from partial cross-linking in the NR phase and surface interactions between the NR and PP phases which increases the adhesion between the respective phases. These effects which can be described as a curing process do not occur immediately on addition of LNR into the blend but soon after and during the mixing as shown by the rise in the processing torque. The LNR is able to
Table 3. The mechanical % of NR* properties % LNR 5
IO

of NRIPP blends at various compositions Stress at break (MPa) 7.7 8.2 8.5 8.6 2.3 4.3 4.1 4.2 12.2 12.9 13.2 13.5

of LNR.

Strain at break (%>) 400 650 610 460 350 870 780 800 300 580 450 350

50

13 17 67 5
10

13 17 33 5 10 13 17 *Total composition of NR including LNR.

676

A. IBRAHIM

and

M. DAHLAN

I.OOE+O

(4

____----

/I

I
_-

/-

__

- -- - _ E
_----

_E

_ TCJ

Fig. 5. (a) DMTA traces of an NR/PP blend. (b) DMTA traces of an NWPP blend with

10% LNR.

function as such in these blends due the presence of active groups on the polyisoprene chain. As reported by Gelling and Mente,79 the role of LNR in influencing the physical properties of the vulcanizate depends on the chain length of the polyisoprene. With molecular weights around 6000, the LNR acts as bulk viscosity modifiers and this role decreases with increasing molecular weight. Covulcanization of LNR into the rubber network is optimum at molecular

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-.-.-._._

e---w-

0% LNR 10% LNR IS% LNR

0
0

4
Time tmin)

Fig. 6. Variation of torque with mixing time of 70:30NR/PP blends with different compositions of LNR. weights around 30 000 and yields a vulcanizate with high hardness and modulus. In the NR/ PP blend, the role of LNR as a dynamic vulcanization agent is thus shown, SEM studies on the toluene extracted samples showed a honeycomb structure of the blend. A cocontinuous structure of the morphology is thus indicated and this structure is more refined with increasing amounts of LNR added. An improved morphology associated with the increase in LNR is in agreement with the changes in physical properties observed and confirms the compatibilising role of LNR in NR/PP blends.

5.

NATURAL

RUBBER-POLYETHYLENE

BLENDS

Polyethylene (PE), with a microstructure consisting of repeating units of CH2 is more likely to be compatible with NR in a blend. However, little work has been done on this system in comparison to the NR/PP system, due most probably to the lower softening point of the material, i.e. at about 100C.80 The versatility of this material and hence applications will be less and as such less attractive for studying. Nevertheless it is interesting to look at the degree of interaction between NR and a straight chain PE polymer in comparison with the substituted chain of the PP polymer. PE is softer and more ductile than PP and thus a totally different type of thermoplastic will be produced on blending with NR. The blending of synthetic rubbers like Santoprene 64 and 80 and EPDM with HDPE has

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A. IBRAHIM and M. DAHLAN

been reported. ~ One of the many objectives given for the study was to improve the impact strength and related physical properties of the thermoplastics. Commercially availabe PE is classified into three grades i.e. high density PE (HDPE), low density PE (LDPE) and linear low density PE (LLDPE). Among these PEs, many reports focus on blends of NR/HDPE whose properties are closer to those of NR/PP. In the NR/HDPE blends, dicumyl peroxide (DCP) was widely used as the dynamic vulcanizing agent. De et al. reported the effects of DCP and carbon black on the rheology of NlUHDPE blends with NR compositions varying from 30-70%. The viscosity of the blends increased with the addition of DCP and this was rationalised as due to the development of cross-links between the particles which hindered the particulate movement in the process of deformation. Lu Feijie observed an improvement in the tensile properties of NR/HDPE blends on the addition of DCP. Apparently the cross-links formed affect the orientation of NR molecules but caused little effects on the crystallization behavior of HDPE. The effects of ethylenepropylene diene monomer (EPDM) rubber, chlorinated polyethylene (CPE) and chlorosulfonated polyethylene (CSPE) on the physical properties of NR:PE blends were reported by Choudhury and Bhowmick. 84These materials were found to increase the interaction between the NR and PE phases in uncured systems and in DCP cured systems. SEM studies have indicated that the size of the dispersed particles is reduced by the addition of the third component (CPE, EPDM or CSPE) into the blend and the particle distribution is more uniform. The reasons cited for the increased interphase interactions are the structural similarities between CPE, EPDM, CSPE and PE, and the amorphous nature of the polymers which is similar to NR. The adhesion between the components was also found to increase with the addition of the third component. The EPDM gave the most significant effect due to the higher interaction between the polymer with PE and NR. A greater surface interaction yields a better adhesion between the phases. These interactions help to promote better morphology in the blend and hence contribute to the overall improvement in its physical properties. Choudhury and Bhowmick27 also reported a study on the compatibilization of NRpolyolefin blends by phase modification. Chemical modification was done on the thermoplastic phase, i.e. PE, with the aim of introducing appropriate functional groups which could improve the interfacial interaction. The modified polymer was added as an intercopolymer into the blend during mixing. The modifications were in the form of chlorinated PE (CPE), maleic anhydride modified PE (PEm), and sulfonated EPDM (S-EPDM). In the study, NR/PE blends containing PEm or CPE exhibited improved tensile strengths and moduli. Better interaction between the two phases is suspected to be due to the presence of modified PE. Addition of CPE and PEm or EPDM and PEm or S-EPDM and PEm into any blend also results in a very significant improvement in the stress and strain properties of the material. The tensile strength and elongation of NR/ENR/PEm/PE system increase by about 35 and 25%, respectively, over the NR/ENR/PE system. The interaction between ENR and PEm was quoted as a plausible explanation for the increase in tensile properties. However, the addition of DCP into NlUPE/PEm blends causes a deterioration in tensile strength which was ascribed to the occurrence of dynamic vulcanization in the system. In their recent report, Choudhury and BhowmickRS reported an investigation of the strength of thermoplastic NRIPE blends in the present of different types of compatibilisers and curing agents. The results are as shown in Table 4. They observed that blends containing ZnO, stearic acid, S and CBS showed the highest stress and strain with values about twice those of

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Table 4. The formulation of the blends and their physical propertiesx5 Formulation of blends NR
CPE ENR PE

A 70
30

B 70 -

D 70 20 27 3 -

E 70 27 3 0.5 -

PEm
DCP

0.5 -

30 5 1 2.5 0.8

ZnO Stearic acid S CBS Physical properties Modulus E (MPa) Tensile strength (MPa) Tearing energy for trouser specimen (kJm_)

30 6.4 17.0

54 15.5 120.0

42 8.4 12.0

35 5.2 19.8

30 5.3 15.0

blends with PE or without CPE as compatibiliser and with DCP as the dynamic vulcanising agent. The lowest stress and strain were exhibited by blends containing ENR and PEm, or PEm and DCP. If the tensile properties can be taken as a measure of the interaction parameters between the phases, then the sulfur vulcanizing system has proved to be the most effective in promoting interphase interaction. With high cross-linking, the NR phase will increase in cohesive strength and allow the rubber particles to undergo greater deformation before cohesive failure. The modulus also increases with cross-linking and hence the stress across the interface for a given extent of deformation of rubber particles increases. The sulfur and cross-linking activators such as ZnO and stearic acid have been shown to promote more extensive cross-linking in NR than peroxides. The effectiveness of the sulfur and EV system as dynamic curing agents is again shown by the tearing energy obtained where the value for the blend containing ZnO, stearic acid. S and CBS is several times more than other blends. From SEM studies on the mode of tearing the authors rationalised the different values of tearing energy as due to the different rates of tear propagation which follow different mechanisms. Thermal and SEM analyses on NR vulcanizates filled with HDPE were reported by Kurian et al. xc The glass transition temperature of NR vulcanizates cured at 150C under 45 kg/cm pressure was found to be - 62C and was independent of the thermoplastic content. The melting temperature reported was 128C and presumed to be that of HDPE. The endoterm peak was also found to be a function of HDPE only which suggested that the crystallinity of HDPE was not affected. These observations seem to indicate strongly that there is little interaction between the NR and HDPE phases under these conditions of mixing and moulding. It also implies that the respective polymers are of very low compatibilities. The tensile strength of the vulcanizate was also reported to be unaffected by HDPE until about 30 phr loading but decreased significantly on further addition. The 300% modulus increased proportionately but the elongation at break decreased with an increase in HDPE loading. Apparently the elastomeric characteristics of the material seem to decrease slowly with the introduction of the hard plastic phases into the rubber matrix. The progressive

680

A. IBRAHIM and M. DAHLAN

change in these features was further shown in an SEM analysis of the fractured surface of the vulcanizate. A rubbery and ductile nature of the fracture ends was observed for samples with low HDPE contents. With high HDPE loadings the material lost its rubbery properties and phase separation became more probable as indicated by the uneven surface of the fracture ends. The size of HDPE particles in the NR matrix was also observed to be bigger when more than 30 phr HDPE was loaded into the system which explained the drop in tensile properties. Generally, adhesion will be low when the particles (HDPE in the NR matrix) get bigger. These will easily debond and induce crack precipitating failure. LNR was also used to compatibilise NR/HDPE blends in our laboratory.7 Various compositions of NlUHDPE blends containing LNR were prepared. Blendings were done in a Brabender Plasticorder at temperatures of 140- 160C and rotor speeds or rates of mixing of 60-40 r.p.m respectively for about 15 min. Typical stress-strain curves as a function of LNR composition and HDPE/NR compositions are as shown in Figs 7 and 8, respectively. The stress and strain increase steadily with LNR composition up to about 20% LNR. Increasing the percentage of LNR to 22% causes the strain to decrease and on further increases, the stress also decreases. The optimum LNR composition for the 60/40 NR/HDPE blend is about 20% LNR and apparently further addition of LNR does result in the dilution of the NR phase leading to a softening of the material.

6 27%
LNR

20%

LNR

13% LNR

200

400 Strain

600 t%)

600

1000

Fig. 7. Stress-strain

curve for 70:30 NR/HDPE blends with varying LNR compositions.

THERMOPLASTIC NATURAL RUBBER BLENDS

681
strain

Maximum stress (MM

Maximum P/d

IO

1400

cr,
1200

Strain

1000

6 600

600

400

200

0
% HWE

20

30

40

50

60

70

60

50

% NR

Fig. 8. Maximum stress and strain for various compositions

of NR/HDPE blends with 10%

LNR.

The relationship between LNR composition with the degree of cross-linking, as approximated by swelling analysis, is shown in Table 5. The maximum cross-linking density is observed at 27% LNR which corresponds to a sample with the maximum stress. The hardness of the material as shown by shore A measurements, seems to increase up to about 20% LNR and remains steady there on. All of the mechanical properties measured are thus related to the cross-links formed in the system. An increase in the cross-linking density within the NR phase and interfacial NR/HDPE interactions occur with the addition of LNR. The LNR is believed to function both as a curing agent and a plasticiser in the blend. The curing role of LNR is more prominent at lower concentrations but when the relative concentrations of LNR are higher, the plasticising effect of LNR predominates. After the optimum concentration of about 20%, the dissolved LNR in the NR phase does not promote interaction but merely increases the ratio of the short polyisoprene polymer over the normal NR polymer resulting in

682

A. IBRAHIM and M. DAHLAN

Table 5. The influence of LNR on the degree of cross-linking HDPE blend % LNR Density p (g/ml) Cross-linking density (mol/g)

and physical properties

of a 60/40 NR/

Maximum stress (MPa)

Maximum strain (%)

Hardness

(shore A) 89 90 93 94 94

0 7 13 20 27

0.88 0.91 0.93 0.94 0.93

2.1 2.8 3.1 3.7 4.6

x x x x x

1o-5 lo- loms lo-


lo-

3.6 4.2 5.5 6.5


7.0

500 600 650 700 7.50

an overall viscosity drop for the NR phase due to the plasticization of the latter by the former and thereby affects the mixing process giving rise to a lower homogeneity blend. The thermal properties of NR/HDPE blends compatibilised with LNR were examined by TGA, DSC and DMTA. A typical DMTA trace is shown in Fig. 9. The thermogram indicates the blend is stable up to about 130C. A single glass-transistion temperature (Tg) and melting point (Tm) were also typical features of the blend. A Tg of - 55C for the 60140 NR/HDPE blend and - 46C for the 70/30 NR/HDPE blend show that the Tg is between that of NR, about - 60C the 0 transition of HDPE which is in the 0 to - 60C range. At about 130C (see Fig. 9) the blend exhibits a sharp drop in E and E which corresponds to the melting point of the crystalline phase. These observations strongly suggest that a homogeneous phase distribution has occurred in the blend induced by LNR. The Tg of the blend also decreases with the LNR composition and the decrease is from - 56C for 0% LNR to - 59C for 20% LNR. This corresponds to an increase in cross-links and the plasticization process when more LNR is added to the blend as observed in other types of blends.

II

IO

E
,
E
_

.c
c

z
,

3
w I

7 -I 6

-I

-Ill P 3

,I00

-2

-so

SO

loo

15c

1mlprrorurr t-c>
Fig. 9. DMTA traces for 60:40 NR/HDPE blends with 10 % LNR.

THERMOPLASTIC

NATURAL

RUBBER

BLENDS

683

Stress at break. (MPa)

--------

27%

LNR

-.-.
--mu----

-._.

20%

LNR

13% LNR 7% LNR 0% LNR

----_-_-~

, 0

I 2

I 4

I 6 Ageing time (days)

1 6

I IO

Fig. 10. Stress at break for 60:40 NR/HDPE blends with different compositions of LNR after ageing. Fig. 10 shows the retention of tensile strength for the 60/40 NR/HDPE blends with different compositions of LNR after thermal ageing at 70C. The degradation is very severe for the first 4 days and levels-off later on. The severity increases with the amount of LNR added. After 7 days the tensile strength drops to about 60% for the blend containing 27% LNR in comparison to about 75% for blend without LNR. Similar observation were also recorded for strain measurements. The oxidative degradation of NR and HDPE during thermal ageing is obvious when white spots are observed on samples after 10 days of exposure. Elliott et al. * reported a similar observation with NR/PP blends on ageing where oxidation of both NR and PP were indicated. The oxidation was inhibited by the incorporation of antioxidants common for NR into the blend. The heat of fusion was observed to be almost a linear function of blend composition. NR and HDPE are known to be incompatible and thus with the addition of LNR, the compatibility of the polymeric system is slightly improved. The homogeneity of the phase distribution in the blend is further substantiated by the smoothness of phase-contrast scanning electron micrographs for these blends. The effects of LNR on the morphology of the blend is shown by SEM micrographs for toluene extracted samples as provided in Fig. 11. A cocontinuous structure is clearly shown and the honeycomb structure becomes more refined with increases in LNR composition. At 0% LNR, the particles are bigger and irregular in size and distribution. The 27% LNR sample shows the holes left by NR are smaller and are homogeneously dispersed within the matrix.

684

A. IBRAHIM and M. DAHLAN

(a)

(b)

(cl

Fig. 11. SEM (1500 x magnification) of cryogenically fractured end and toluene extracted samples of 60:40 NR/HDPE blends with (a) 0% LNR, (b) 13% LNR and (c) 27% LNR.

(a)

(b)

Fig. 12. SEM (1500 x magnification) for the fractured end of 60:40 NR/HDPE blends with (a) 0% LNR, (b) 27% LNR after 10 days of ageing at 70C.

THERMOPLASTIC NATURAL RUBBER BLENDS

685

The NR particle size decreases from more than 10 pm to about 2-5 pm at 27% LNR content. The morphological study thus corresponds to observations from swelling studies where an increase in homogeneity is associated with an increase in NR/HDPE particle interactions caused by LNR. The physical properties of the material are also in accordance with the morphological characteristics shown. Fig. 12 shows the fracture surfaces for samples of 60140 NR/HDPE, containing 0 and 27% LNR after 10 days ageing at 70C. In the 0% LNR material, the smooth fracture surface consists of large hollow cavities of different shapes with fibrils. The rupture surface becomes more refined with increasing amounts of LNR. At 27% LNR content, the HDPE domain becomes smaller and more fibrils are observed. Without LNR, where the domains are bigger, fracture is brittle as compared to the sample with 27% LNR. The brittle nature of the aged sample is typical in NR. Fibrils representing ductile failure are more likely when the interactions between the components are more pronounced. Reports on the blending of NR/LDPE are limited and we may assume that there is no significant interest in this system. The lack of research on the subject is probably due to the fact that the blend does not exhibit good physical properties. Our work on this subject has not produced any interesting results thus far. A study on the subject was reported by Qin et al. a on the mechanical properties, structure and morphology of NIULDPE blends prepared by different processing methods. Curing of the blends was done dynamically and statically with a sulfur vulcanizing system consisting of S, ZnO and stearic acid. The overall mechanical strength of the unvulcanized blends increased with the composition of LDPE but the elongation at break was lowest at about 50% NR composition. This is consistent with changes in the morphology of the blend from a finer dispersion with better adhesion between the phases when either NR or LDPE predominates to relatively bigger particles at compositions consisting of comparable amounts of NR and LDPE. The tensile strengths and elongations at break decrease with a decrease in the NR content of the blends for the statically vulcanised systems. However, the 300% modulus and strength increase with an increase in LDPE composition. These properties are believed to be a function of the nature of LDPE and are probably not due to the morphological changes of the blends. For the dynamically vulcanized blends, the properties related to the plastic component such as 300% modulus and hardness were found to increase with LDPE but the tensile strength and elongation at break depended on composition and processing.87 These tensile properties recorded maximum values for samples with NR contents at about 60%. Fig. 13 shows that at high NR concentrations, the tensile strength of statically cured materials is better than dynamically cured systems. It becomes comparable at intermediate compositions. However, the overall properties are better than the unvulcanised blends but are poorer than statically vulcanised blends. Dynamic vulcanization of the NR/LDPE system involved processing the sample through cycles of extrusion-vulcanization until a satisfactory mix was obtained. It was reported that by processing the blend at 160C a cocontinuous morphology was obtained as shown by SEM after 2-3 passes. Extended processing produced blends with lower mechanical properties which was explained as due to the breaking down of the NR network during processing. As a result the morphology will change from a continuous phase to discrete particles of NR dispersed homogeneously in the LDPE matrix. As such, the mechanical properties of blends with higher NR contents were more sensitive to the number of passes or cycles of extrusion.

686

A. IBRAHIMand M. DAHLAN

TENSILE + z -a_*_ -

STRENQTH Unvukmlr~d Statlwlly Dymmkol) rulcahd vuloanlr.d

24

- 1200

ELONOATION Al

SRLAK rulconlrad rukenlz*d

20

k
_*_

UnVutconl~~d Stotlmlly Dplmlcolly

- 1000

800

Fig. 13. Tensile strength and elongation at break for NR/LLDPE blends as a function of blend composition.

On the other hand, properties which mainly depended on the plastic component such as tensile strength, 300% modulus, hardness and permanent set were found to increase with the LDPE content and were less sensitive to processing methods. As in the blending of NFULDPE, the only report on NFULLDPE is also from Qin et al. * A diblock copolymer, hydrogenerated polybutadiene-b-polyisoprene (HPB-b-PI or PE-h-PI), was used to compatibilize NR/LLDPE blends. The copolymer consisting of polyethylene and polyisoprene structures capable of dissolving and interacting with the plastic and rubber domains, respectively, due to similar structures. The compatibility was estimated from the mechanical properties, morphology and transition state behaviour exhibited by the blends. The domain size of the interface changed significantly on addition of PE-b-PI as shown by SEM and TEM micrographs of fractured surfaces. The interface between the NR and LLDPE

THERMOPLASTIC NATURAL RUBBER BLENDS

687

phases changed from a clear to a diffused structure which implied an increase in the interaction and adhesion between the two phases. The copolymer was believed to act as an emulsifier in reducing the interfacial tension and the emulsification was better with higher molecular weight copolymers. The longer the chain of the compatibilising polymer, the greater will be the interaction within the domain and hence between the domains. A similar observation was reported by Gelling and Mente 79 in their investigation on the role of LNR as co-vulcanisable processing aids. LNR with molecular weights around 6000 were found to act as bulk viscosity modifiers. These became less effective as processing aids with increases in molecular weight. Covulcanization into the rubber network is said to be possible with the low molecular weight, 2500-30000 range. But further increases in molecular weight have a minimal effect on vulcanizate properties. Dynamic mechanical behaviour of the blend is unchanged from the compatibilising interaction. The thermal parameters, Tm, Tc, Tg and crystallinity Xc, were not affected by the composition of the copolymer. The rationale is that in the blend, the segments in the copolymer are either similar to PE or NR and as such the various domains in the blend will be physically either pure LLDPE or NR. The crystallizing behaviour of the polymers thus will not be affected significantly by the diffusion of these compatiblisers into the domains. The increase in the interfacial interaction between the NR and LLDPE with the incorporation of PE-b-P1 into the blend results in the material exhibiting improved mechanical properties. The stress and strain of the blend increase with increasing composition of the compatibiliser and reach their maxima at about 5% PE-b-PI; see Table 6. Besides composition, the molecular weight of PE-&PI also affects the mechanical properties. Improvements in the morphology of the blend were more effective with higher molecular weight copolymers and hence the tensile properties will follow a similar trend. In our work, LNR was used as a compatibiliser for NR/LLDPE blending. Usually the TPNR obtained exhibits good thermoplastic properties, except the surface was less shiny or had a matt finish. The material did not show any crazing effects after being folded or other forms of stress. Though blends of NR/LLDPE are compatible, further improvements with respect to miscibility can be achieved by incorporating LNR into the blend. The properties (physical and mechanical) will be enhanced with an improvement of the blend morphology. A typical torque-time curve for the processing of NR/LNR/LLDPE blend is shown in Fig. 14. It consists of three torque maxima; at the beginning, after the third minute and after the sixth minute. The first and second peaks correspond to the shearing torque before the melting of

Table 6. Mechanical properties, stress and strain, of NRILLDPEIPE-b-PI NR/LLDPE/PE-b-PI 01i0010 50/50/o 491501I 4715013 45/50/5 4 I15019 371501I 3 37/50/13 Tensile strength (kg cm-) 240 84 99 112 132 II3 II0 96

blendx

Elongation at break (%I 13x7 97s 965 981 II90 1089 II88 935

A. IBRAHIM and M. DAHLAN

_-.-._

O%LNR
10% LNR IS% LNR

_---

I 6

I 9

I 12

IS

Time

(mid

Fig. 14. Variation of torque with mixing time for 70:30 NR/LLDPE blends with different compositions of LNR.

NR and LLDPE, respectively. The third curing torque which is broad and occurs over a longer period of time is ascribed to the slow curing of the material leading to an increase in the viscosity of the blend. In the absence of LNR, this peak does not appear which confirms the crucial role of LNR in causing the curing or fusion of the material. In comparison with other NR-polyolefin systems, the order of peak height, the fusion due
Table 7. Physical properties Blend ratio 50:50 of NR/LLDPE blends with the composition Stress break (MPa) 7.3 9.0 10.6 11.4 11.5 5.0 6.0 7.6 9.8 10.6 ratios of SO:50 and 60:40 Hardness (shore A) 87 x9 90 90 90 61 63 65 67 70

Composition of LNR (%) 0 5 10 15 20 0 5 10 15 20

Strain at break (%) 900

1000
1020 970 910 900 1160 1250 1260 1100

60:40

THERMOPLASTIC

NATURAL RUBBER

BLENDS

689

to LNR, is NR/LLDPE

> NIUPP > NR/HDPE > NR/LDPE. Apparently the extent of the secondary curing reaction in the NR phase and the interfacial interaction are most extensive in the NR/LLDPE system. Table 7 shows a typical stress and strain at break for NR/LLDPE blends of compositions 50:50 and 60:40 with varying concentrations of LNR. Plots of stress and strain at break against LNR concentrations are depicted in Fig. 15. The stress increases with LNR concentration and reaches a maximum value of about 11 MPa at an LNR concentration around 20% for both the 50:50 and 60:40 samples. On the other hand, the maximum strains of 1000 and 1300% occur at the LNR concentrations of 10 and 13% for the 50:50 and 60:40 blends, respectively. It is obvious that the best mix of the NR/LLDPE thermoplastic (optimization of stress and strain) occur at LNR concentrations of about 13 and 15% for the 50:50 and 60:40 blends, respectively. The hardness of the NR/LLDPE blends as a function of LNR concentrations is shown in

Strerr
MPa II

at break

Strain at break x 1300

10

I200

900

+ - Stress
* - Strain 700

600

5 LNR

IO

IS (Y.1

20

Composition

Fig. 15. Tensile properties

of NR/LLDPE blends at various compositions

of LNR.

690

A. IBRAHIM

and M. DAHLAN

IO LNR compositlcm P/o)

15

20

Fig. 16. Hardness of NRILLDPE blends with various compositions of LNR. Fig. 16. For the 5050 blend, the addition of LNR into the blend causes an increase of hardness from 87 to 90 in Shore A values and the increment is obtained after about 10% incorporation of LNR. The effect of LNR is more pronounced in the 60:40 sample where the hardness increases from 62 to about 70 in the shore A values. Apparently the LNR interacts more effectively with the NR phase in the blend and thus an increase in the NR composition will result in a more significant effect of LNR. As the NR is softer than the plastic, any composition richer in NR will produce a softer elastomeric material. The stress and strain at break of NR/LLDPE blends are comparable to those for the NR/PP blend but are slightly higher than in NR/HDPE blend. However, a strain of 1300% for the 60:40 NIULLDPE blend seems to be the highest recorded value for any TPNR system. These observations suggest that the NR/LNR/LLDPE combination is the most compatible in comparison to other NR-thermoplastic mixes like NR/LNR/PP and NR/LNR/HDPE. Further comparison reveals that PE is more compatible with NR than PP and among the PEs, LLDPE is the most compatible. The improved interfacial interaction most probably arises from the high degree of molecular interaction between the component polymers in the blend. From a molecular structural aspect, the basic polymeric chains of the two polymers are similar except the presence of -CH3, as a side group on the PP chain. The presence of this methyl group and other side chains or copolymers in commercial PP are probably the cause of a slight incompatiblity between NR and PP. In the PE group, the difference between the individual polymer is from the chain length and branchings. Commercially available HDPE carries groups such as -CH?, -C2HS, -CAHg, etc., as side-chains or branches which can hinder interactions between NR and HDPE. HDPE also has a longer chain length than LLDPE and thus reorganisation of the polymer during blending and subsequent interaction with the NR chain become less effective.

THERMOPLASTIC

NATURAL

RUBBER

BLENDS

691

II

950

750

6 120 130 140 Temperoturr 160 (*Cl 160 170

Fig. 17. Tensile properties of 50:50 NFULLDPE blends processed at different temperatures with a rotor speed of 45 r.p.m. Fig. 17 shows the variations in tensile properties, stress and strain at break with different processing temperatures. The stress seems to decrease with temperature and reaches a maximum at around 130C while the strain climbs to a maximum at about 145C and decreases thereafter. The optimum physical properties of the blend are obtained at a processing temperature of about 140C with a stirring rate or rotor speed of 55 r.p.m. Fig. 18 shows the influence of the rate of stirring on the stress and strain of TPNR. As depicted on the plot, the stress and strain increase with the rate of stirring and maximise at the rotor speed of 55 r.p.m. A drop in the physical properties of TPNR is observed with further increases in the rate of stirring. The increase in the tensile properties and hardness with the addition of LNR can be rationalised as due to an increase in interfacial interactions or bonding formations in the blend. Further increases in LNR composition after the optimum value produces limited effects on polymer interactions but also results in an overall increase in NR composition leading to the formation of a softer blend which exhibits lower tensile properties. In the NW LNR/LLDPE system, the optimum composition of LNR is about 13 and 15% for the 50:50 and 60:40 NRILLDPE blends, respectively. The blend which contains more NR is obviously able to absorb more LNR before a saturation level is reached. The mixing temperature is found to optimise near the melting point of LLDPE, i.e. 135C. At this temperature the LLDPE is in a semisolid state of high viscosity and the stirring action will thus produce the maximum mixing effect with the other components. However, at higher

692

A. IBRAHIM

and M. DAHLAN

IOQO

990

2 960 x
0 : P

970

-5 t

960

-.-.-.-

stress Strain

I
25 35

I
45 Rotor speed (rpm)

I
55 65

950

Fig. 18. Effect of mixing rate (rotor speed) on the tensile properties of 50:50 NIULLDPE

blends processed at 140C. temperatures, the liquid LLDPE will be at lower viscosities and thus stirring will result in less effective mixing and agglomeration of the components. Too high a processing temperature also causes the material (especially the NR) to degrade from oxidation. At temperatures lower than 135C the LLDPE is either not melted or is partially melted and thus mixing with NR will not be possible. Varying the rate of stirring also produces a similar effect as in changing the temperature. The homogeneity of the blend will be optimum at a certain stirring rate for a particular temperature. The level of mixing increases directly with the rate of stirring before the optimum rate is reached. At a temperature much higher than the melting point of LLDPE, agglomeration of like particles is highly probable during high speed mixing. As a result, phase separation will set in giving rise to an inferior TPNR. A well mixed blend is thus possible at high temperatures with low rates of mixing or vice versa. It is obvious that at the processing temperatures of 140 and 155C the optimum mixing rates are 55 and 30 r.p.m., respectively. SEM micrographs of toluene extracted 5050 NR/LLDPE blends are shown in Fig. 19. The honeycomb structure of the micrograph consists of white and dark spots. The dark spots correspond to the empty hole left behind by the NR after dissolving in toluene. The white spots represent the insoluble LLDPE and cross-linked NR, physically or chemically, attached to the LLDPE particles. It is apparent that the dark spots decrease in size from Fig. 19(a) (0%

THERMOPLASTIC NATURAL RUBBER BLENDS

693

(a)
Fig. 19. SEM (1000 x

(b)

(c)

magnification) obtained from cryogenically fractured ends of toluene extracted 50:50 NRILLDPE blends with (a) 0% LNR, (b) 10% LNR and (c) 27% LNR.

LNR) to (c) (20% LNR), and the uniformity of the distribution is higher in Fig. 19(c) (20% LNR) than in (a) (0% LNR) and (b) (10% LNR). From the distribution of the white or the dark spots, these data indicate that the dispersity of particles is improved with the addition of LNR. The DMTA traces of the blend show a single Tg for the system as shown in Fig. 20. In all the

1
0.5

QO

-0.5

1
_I p

B -,.o

z
-1.5

--._.--_-

OY.lNR W. LNR 2oY.LNR

-2c

40

-50

0 Temp.r.atr.

50

100

Is0

PC)

Fig. 20. DMTA traces of 60:40 NRnLDPE blends with different compositions of LNR.

694

A. IBRAHIM

and M. DAHLAN

measurements, the Tgs observed fall within the Tgs of NR and LLDPE and only a slight variation is observed with the various compositions of LNR. The crystallizing behaviour of the components, NR and LLDPE, does not seem to be affected significantly by LNR. The role of LNR in the interaction process is not totally clear but it is believed to be associated with the active functional groups present in the LNR. As discussed in our earlier report, 68 the active groups present include -OH, -0OH and -OR. These groups are likely to induce physical and chemical interactions with the LLDPE and NR polymer chains. With LNR and NR having a similar microstructure, the diffusion of LNR into the NR phase is more probable. Thus, the LNR in the blend functions both as a cross-linking agent within the NR phase and also as an interfacial binder between the NR and LLDPE phases. As such the blend becomes more homogenous in the presence of LNR.

6.

EPOXIDISED

NATURAL

RUBBER

Natural rubber consists of a long chain with an unsaturated double bond at every five carbon atoms. 9o The unsaturated double bond is the functional group of the rubber molecule which can be reacted to form a new copolymer or branching. There are a number of processes which have been used commercially for the production of chlorinated, hydrochlorinated, cyclised, methylmethacrylate grafted, and epoxidised (ENR) natural rubbers. The commercial production of ENR was started in the late 80s by a Malaysian company called Kumpulan Guthrie Berhad. The research work had been carried out by the Malaysian Rubber Producers Research Association (MRPRA), Tun Abdul Razak Laboratory, U.K. with the cooperation of the Rubber Research Institute of Malaysia (RRIM) since the 1970s. The production involves natural rubber field latex which under controlled conditions is converted to an epoxidised form by the in situ generation of peroxyformic acid from hydrogen peroxide and formic acid, prior to coagulation and dyring.92 The advantage of this process is that only hydrogen peroxide is consumed. The commercial production route of epoxidised natural rubber can be represented as follows: 93

Hz02 + HCOOH

HCOOOH

+ Hz0

CH,
\ HCOOOH+ / C=CH \ -+

CH,

\I\ C-CH+HCOOH / \

Two commercial grades of ENR are currently produced under the trade name Epoxyprene, i.e. Epoxyprene 25 and Epoxyprene 50. The numbers denote the mole percentage level of epoxidation produced. Epoxyprene 50 shows a typical Mooney viscosity (ML 1 + 4 at 100C) of about 80 units, a gel content of 30-40% and an alkaline aqueous extract of about pH 1O.94 The storage stability of the products has been reported to be fairly good and consistent. However, on extended aging, Epoxyprene-50 undergoes some significant changes which

THERMOPLASTIC

NATURAL

RUBBER BLENDS

695

-60

-60

20 Epoxy

40 content, (mole

60 %I

60

Fig. 21. Effect of epoxidation on the glass transition temperature, Tg, of ENR.

are reflected in an increase in the carbonyl absorption in its infrared spectra. This increase in carbonyl absorption is attributed to oxidation of the rubber through chain scission.95 Roy et a1.,96 working on laboratory-prepared ENR, concluded that during thermal ageing of ENR, carbonyl, alcohol, tetrahydrofuran and ether cross-links were formed presumably due to traces of acid present in the rubber. Addition of a phenolic antioxidant such as 2,4dinitrophenyl hydrazine (DPH) ensures adequate storage stability of ENR. Increasing the level of epoxidation changes certain physical properties of ENR. These changes are attributed to an increase in its polarity and glass transition temperature (Tg).97 Its Tg has a direct relationship with the level of epoxidation of ENR as depicted in Fig. 2 1. 98The Tg increases by approximately 1C for every 1 mol% epoxidation.99 The ability of ENR to undergo strain crystallization and the increase in their Tgs are two factors that are responsible for their high tensile strengths as shown in Table 8.O The ability to crystallize is retained even by ENR with a 95% mol level of epoxidation.

Table 8. Properties of gum vulcanisates of natural rubber (NR) and ENR O Rubber NR ENR-25 ENR-50 ENR-70 ENR-95 Tensile strength (MPa) 25.8 24.1 30.9 28.4 21.9 Elongation at break (%) 760 789 762 622 587 % Crystallinity (40% elongation)
11

11 IO 4 2

696

A. IBRAHIM and M. DAHLAN

Table 9. Adhesion of ENR compounds Components PVUNR PVCIENR-25 PVUENR-50 PVUNR: ENR-25: ENR-50 blend 50:25:25

to PVChy7 strength, N/mm (IS0 36) 0.4 2.4 9.8 10.6

Adhesion

Formulation contains other components including 30 parts phr of N220 black. Standard polyester reinforced PVC conveyor carcass.

7. THERMOPLASTIC

EPOXIDISED

NATURAL

RUBBER

ENR is acknowledged to possess excellent properties like oil resistance, gas impermeability, good wet grip and high damping characteristics. It has been reported that the compatibility of ENR with other polymers increases with an increasing polarity of ENR. Gelling9 reported the presence of a high level of vulcanised adhesion between ENR-50 and PVC as shown in Table 9 and this property has been utilised to prepare strong PVUENR thermoplastic blends. lo2 Studies lo3.04 show that stabilised or plasticised PVC and ENR are miscible at any ratio indicating various conceivable properties of the blends are possible. They are miscible both at the uncross-linked stage 1053106 the cross-linked stage. lo7 Their compatibility is reflected in and their single glass transition temperature which lies between that of PVC and ENR. *,09 Ramesh and De 04 indicated that unstabilised or unplasticised PVC and ENR form self cross-linkable blends during high temperature mouldings. Such a blend however was reported to be immiscible. lo The immiscibility has been explained in terms of the furanization of ENR which occurred during blending in the absence of a PVC stabilizer or plasticizer. Fig. 22 illustrates the possible mechanism of cross-linking between PVC and ENR. HCl from the PVC chain formed during high temperature moulding causes an increase in the allyllic chlorine groups in PVC. HCl then will react with the epoxy groups of ENR, causing the formation of chlorohydrin groups that can perform as further reactive sites. In case of the immiscible blends, the immiscibility is probably due to physicochemcial changes, i.e. phase separation. Several factors can contribute to phase separation such as the reduction in

- CH2- CHI Reactive site in PVC + 0 / ; Blend network structure Reactive site in ENR Fig. 22. Possible mechanism of cross-linking between PVC and ENR. L * CH, Cl 1k-L CH2 CH-

I
0 H

THERMOPLASTIC NATURAL RUBBER BLENDS

697

Table 10. The effects of PVC content on the physical strength of PVUENR-50 PVC content (%) Tensile strength (MPa) Tear strength (MPa)

blends (

Tensile strength after 70C aging for 7 days

(MM 10 20 30 40 50 6.1 6.0 7.3 10.5 15.9 10.2 10.2 12.7 22.3 60.0 4.5 4.5 6.5 10.5 16.3

C -Cl groups in PVC and the opening up of epoxy groups in ENR. lo These two factors cause a decrease in intermolecular interactions which in turn provide for phase separation. Therefore, the blend network consists of furanized and cross-linked ENR, together with the crosslinked PVUENR. To produce PVC/ENR thermoplastics with optimum properties, several procedures need to be followed. Nasir et al. 1o3,2 reported suitable mixing conditions for PVC-dominant and ENR-dominant blends. Both blends require different mixing procedures as is evident from the Brabender mixing data, dynamic mechnical analysis and morphological studies. They observed that by utilizing the correlation between mixing temperature and rotor speed, good PVUENR blends can easily be produced. In other words, the rheological properties of PVC/ ENR blends are governed by their blending conditions. Tables 10 and 1 I summarize their tindings on the effects of composition and blending temperature on physical properties of the stabilised PVUENR-50 blends. An increase in physical properties is mainly attributed to the hard domains of the thermoplastics phases of the blends, i.e. PVC. I3 From Table 10, it is evident that increasing PVC content imparts better ageing characteristics to the blend. However, it has been reported I4 that the PVC-dominant blends do not seem capable of retaining tensile strength. At certain ageing temperatures, the blend becomes more glass-like, i.e. stiffer and brittle and consequently loses most of its mechanical properties. Table 11 shows that samples processed at 170C exhibit the best physical properties as expected since it is closer to the melting point of PVC. Coran and Pate1 concluded that this behavior results from dynamic cross-linking within the blend. Further data has been obtained from morphological studies. I4 At low mixing temperatures, agglomeration of PVC particles and the incomplete dissociation of PVC grains were both observed. However, at higher mixing temperatures ( > 18OC), due to improved melting
Table I I. The effect of blending temperature Physical properties 120 Tensile strength (MPa) Elongation at break (%a) Modulus 100 Tensile strength after 70C 7 days aging (MPa) Hardness (Wallace) 14.0 300 11.6 15.9 86.5 on the physical properties of 50% PVUENR-50 Blending temperature 150 15.9 470 13.6 17.6 87.0 (C) 170 20.7 200 17.8 23.0 99.0 180 18.5 350 12.8 9.5 97.0 blends

698

A. IBRAHIM and M. DAHLAN

and fusion of PVC, individual primary particles and distinct interfaces were not observed. This indicates that better mixing between PVC and ENR takes place with increasing mixing temperatures. Kallitsis et al. reported the miscibility behavior of blends between chlorinated polypropylene and chlorinated polyethylene* with ENR. Dynamic mechanical analysis and DSC studies indicated that both systems were miscible. Their miscibility was attributed to specific interactions involving the chlorine atom and the epoxy group of ENR. Thus, the higher the epoxidation level and the chlorine content, the easier for the blends to be miscible. The behavior is very similar to that described in an earlier report concerning blends between PVC and ENR.19 Another example of two or even more dissimilar polymers that can form self-crosslinkable blends via their reactive functional groups involves ENR and chlorosulfonated polyethylene (CSM).20-23 ENR and CSM cross-link during blending at high temperatures without any curatives. It was found12 that the extent of crosslinking depends on several factors such as time and temperature of blending, level of expoxidation of ENR and composition of the blend. The miscibility of the blend is dependent on the blend composition. 12*It has been reported that CSM and ENR-25 (25 mol% of epoxy content) produce homogeneous blends at all blend compositions. 24 In the case of ENR-50 (50 mol% of epoxy content), the blend shows miscibility when the ENR proportion in the blend is much higher than CSM. Fig. 23 illustrates the stress-strain behaviour of ENR and CSM blends at various blend compositions. 12 ENR-dominant blends show viscoelastic deformation of a very soft rubber
12

240

360

480

600

720

Fig. 23. Stress-strain

behaviour

of ENR-75/hypalon, hypalon blends.

ENR-SO/hypalon

and ENR-25/

THERMOPLASTIC

NATURAL

RUBBER BLENDS

699

and break at high strain. The 50/50 blend of ENR-CSM gives the highest tensile and tear strength but minimum elongation. In an earlier report24 they observed moderately high modulus and tensile strength for the blend, i.e. 6.18 MPa at 100% strain and 10.03 MPa, respectively. It was suggested that CSM reacts with epoxy groups in ENR through its sulfonyl chloride (-S02Cl) functionality as compared to other chlorinated rubbers through ally1 chloride moeities. 22 Upon cross-linking, sulfur dioxide and hydrogen chloride are released. These two gases induce a series of chemical changes in the blend such as ring opening reactions, furanization and c&tram isomerization of the double bonds. These secondary reactions are responsible for the miscibility behavior of the blend between CSM and ENR. lz2 However, there are some differences in opinion regarding the role of sulfonyl chloride groups. Some reports 20,2,24proposed the formation of sulfonate ester linkages. A later report by Roychoudhury et al. 122employing an FTIR spectroscopic technique and proton as well as carbon-13 NMR spectroscopy ruled out the formation of this type of linkage by the following reaction:

-CH,-CH,

-CHI SOzCl

-C

CH-

CHz-CH2

CH-

-7

-FCH3 Cl

Instead, they proposed that CSM first reacts with ENR to form a sulfonate ester intermediate which subsequently eliminates SO2 to give ether cross-links as suggested by the following equations:
CH, \/ -CH2-CH2-CHSO&I + 0 \ C-CH-

CH2 - CH2 - CHI

SO2
I P -C-CHI I CHz Cl -

-so2

CH, - CHz -

CHI 0

I -C-CHI I CH, Cl

700

A. IBRAHIM and M. DAHLAN

Fig. 24. The structure of phenoxy resin. Z

The compatibility behaviour of ENR with hydroxyl-containing resins such as phenolic resins (Novolac and Resole resins), cured epoxy resins and the poly(hydroxy ether) of bisphenol A (phenoxy) was also studied. lz5 Fig. 24 shows the structure of phenoxy resin which is related to the other materials studied. They found that ENR was compatible with Novolac, semi-compatible with Resole and phenoxy resins but was incompatible with cured epoxy resin (CER). The compatibility is attributed to the formation of hydrogen bonding between the hydrogen of the phenolic hydroxyl and the oxygen of the epoxy ring. In the case of Resole and phenoxy resins, the interactions are weaker whereas in the case of CER, no effective interactions can take place since CER cannot provide acidic hydrogens due to the competing action of the curing agent. In short it can be interpreted that the compabilility behavior of these blends is due to the acidic character of the hydroxyl groups of the resins. * However, from morphological studies of the blends (especially for the ENR-phenoxy blends), distinct phase boundaries are evident. The boundaries are more diffuse in the

Teneile strength

I
0

IO 20 30 40 So Weight percentage ot SAN in SAN-ENR

60 blends

70

Fig. 25. Effect of blend ratio on the tensile stregth and elongation at break of SAN-ENR blends.

THERMOPLASTIC

NATURAL

RUBBER

BLENDS

701

I 60

10

20

30

40

60

70

Weight

percentage

SAN in SAN-EM?

bbndr

Fig. 26. Effect of blend ratio on the tear strength and impact resistance blends.

of SAN-ENR

ENR-_50-Novolac blend where a finer state of dispersion is achieved. With this, they I25 conclude that ENR with a high level of epoxidation is compatible but not miscible at the molecular level with Novolac resins. When methyl01 groups are also present, such as in Resole, the compatibility is reduced. A study on an ENR-styrene-acrylonitrile copolimer (SAN) blend showed that the proces126 sing characteristics, mechanical properties and failure mode were all additive in nature.
Table 12. % Die swell values for ENR and EAA-g-l$JR rates Shear rate (s-l) ENR 90 9x 306 503 699 109 105 99 102 110 94 106 108 106 130 91 102 101 107 90 59 63 68 70 at various extrusion temperatures and shear

Temperature

(C) EAA-g-ENR 110 56 59 61 61 130 56 58 58 61

702

A. IBRAHIM and M. DAHLAN

Increasing the proportion of SAN in the blend improves mechanical properties such as tensile strength, tear strength, modulus and abrasion resistance whereas elongation at break and impact resistance decrease with an increase in the SAN ratio, as shown by Figs 2.5 and 26. The increase in tensile and tear strength is more prominent when the SAN content is more than 50%. On the other hand, elongation at break and impact resistance show inverse behavior after this composition. The two distinct behaviours are due to the formation of a continuous plastic phase which causes the brittleness of the matrix26 to increase when the ratio of SAN is increased. As evident from the morphological studies by scanning electron microscopy (SEM), the fracture of the tensile failure surface is brittle in nature with multidirectional cracks in different planes. The phase separation is also evident at this point. Tear fractographs further confirm the existence of phase separation. As the rubber content in the blend increases, the brittle nature decreases making the fracture surface smoother. In other words, the mode of sample failures changes from brittle fracture to ductile failure with elongated continuous dimple structure.

H c\H3/\ c-c / CH, /H \ / H, ,


CH,;: CH2

H s+/ ,O\ /H
7 CHz-

CH, II C-C-H / HzC

OH

(1) CHz-

(2)

C-C-0-ti-CH I I CHz CW

Fig. 27. The proposed mechanism for the formation of EAA-g-ENR like polymer. X

THERMOPLASTIC

NATURAL

RUBBER BLENDS

703

In other developments, it has been reported that the mill and extrusion processing characteristiscs of ENR are poor resulting in highly rough extrudate surfaces. 127To improve this property, ENR was blended with a small amount of a thermoplastic material with a reactive site such as ethylene-acrylic acid copolymer (EAA) to form a graft polymer like EAA-gENR. I** As a result, die swell and flow characteristics of the ENR showed a significant improvement as is evident in Table 12. From IR spectroscopic analysis, the schematic mechanism of the reaction was proposed with the formation of the allylic group in the first step followed by an ester type linkage in the second step. This mechanism is illustrated in Fig. 27.

8.

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