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Paper No. T11-2.4, pp. 1-6

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PSU-UNS International Conference on Engineering and Environment - ICEE-2005, Novi Sad 19-21 May, 2005
University of Novi Sad, Faculty of Technical Sciences Trg D. Obradovia 6, 21000 Novi Sad, Serbia & Montenegro

THE INFLUENCE OF REACTION CONDITIONS ON THE PROPERTIES OF GRAFTED NATURAL RUBBER WITH ACRYLONITRILE
Charun Bunyakan*, Jarun Phumnok
*Prince of Songkla University, Faculty of Engineering, Hat Yai, Songkhla, Thailand Songkhla Rajabhat University, Faculty of Sciences, Songkhla, Thailand Email: charun.b@psu.ac.th, Fax: 66-7421-2896
Abstract: The graft copolymerization of acrylonitrile onto natural rubber was successfully prepared by emulsion polymerization process using cumene hydroperoxide and tetraethylene pentamine as an initiator. The influences of initial monomer concentration, initial initiator concentration and reaction temperature on particle size, particle size distribution, 300% modulus and swelling properties of grafted NR with AN have been investigated.. The results indicated that the particle and the particle size distribution of grafted latex were increased and broader, respectively, with increasing of monomer, initiator and reaction temperature. As increased in the monomer concentration, the 300% modulus of grafted NR was decreased in constart with the swelling property which was improved singificantly with increasing monomer concentration. The influence of changing in temperature and initiator concentration on both 300% modulus and swelling property was much less that that of changing in monomer concentration In conclusion, to improve the oil resistant, the NR/AN mole ratio, initial inititor concentration and reaction temperature of 90/10, 0.009 mol/L and 50oC, respectively, are reccommended for using in producing of grafted NR with AN by emulsion polymerization. These optimum values, however, may be limited by reactor characteristic (reactor size, heat and mass transfer in reactor) used in this investigation. Further verification in pilot scale rector is then recommended and being investigated in our laboratory. Key Words: Natural Rubber, Resistance, Latex Property Acrylonitrile, Oil non-polar solvent resistant resulting in a limitation of NR usage. Although, the blending of NR with some polymer can improve the oil resistance, the polymer blends are immiscible and incompatible which may cause in loosening of good physical properties. The better way to improve properties of polymer is graft copolymerization with selected monomer. Graft copolymer contains long sequence of one monomer (often refers as backbone polymer) with one or more branches (grafts) of a long sequence of a second monomer. The graft copolymer properties will be determined by graft monomer and backbone polymer ratio. The addition of a graft copolymer reduces the interfacial tension, persists a finer dispersion, provides a measure of stability against gross segregation resulting in improved interfacial adhesion thus makes the immiscible polymer pairs more compatible than blending polymer. Phumnok and Bunyakan [1] reported that the oil resistance property of natural rubber can be improved by graft copolymerization of acrylonitrile (AN) onto natural rubber. However, the properties of grafted polymer are strongly depend on reaction conditions [2,3]. An understanding of the reaction conditions on grafting properties and properties of grafted polymer is crucial particularly for optimizing the reaction conditions. Thus, this work was aimed to investigate the influence of the reaction conditions including the reaction temperatue, the monomer mole ratio and the initiator concentration on latex property, oil resistance and tensile properties of grafted natural rubber with acrylonitrile by emulsion polymerization process. 2. MATERIAL AND METHODS 1. INTRODUCTION Natural rubber (NR) is one of the most important agriculture products of Thailand. It has good tensile strength, elongation, and abrasion resistance. Therefore, it was employed to produce many rubber and mechanical goods such as tires, tubes, and gloves. One major problem of NR is that it has very poor petroleum oil or 2.1 Graft NR preparation The graft copolymerization of AN onto NR was carried out in reactor system as showed in Figure 1. From this figure, the 5-liter reactor was equipped with agitator, condenser, thermocouple, and temperature control device.

2.4 Oil and non-polar solvent resistance The oil and non polar solvent resistance were determined in term of swelling percentage of standard specimen. The specimens (20mmx20mmx0.1mm) of both NR and graft NR were prepared and placed in separated seeding disk. The commercial diesel oil and toluene was selected to use as solvent in this testing. A 30-ml of solvent was then added in to the disk and left for 24 hours. The volume of specimen was measured at 12 and 24 hours. The swelling percentage was calculated according to equation (1)
Swelling = Volume after immers Volume before immerse x100 Volume before immerse

(1)

3. RESULT AND DISCUSSION Figure 1. Experimental setup for study graft copolymerization of AN onto NR by emulsion copolymerization process. The monomer tank was 500-ml flask with magnetic stirrer and connected to reactor via feeding pump. NR latex containing 60.5 % dried rubber content from Chana Concentrated Latex Co. Ltd. Songkhla, Thailand was used as received. AN monomer was washed with 10wt.% aqueous sodium hydroxide solution and distilled. Initially, 2348 g of a NR latex mixture contained 1836 g of NR, 12 g of tetraethylene pentamine and 500 g of deionized water was charged into the reactor. The 421g of AN monomer mixture contained 96 g of AN monomer, 10 g of cumene hydroperoxide, 36 g of potassium laureate and 279 g of deionized water was then continuously fed at 5 ml/min into reactor via feeding pump. The reactions were taking placed under nitrogen atmosphere. The stirring speed of 150 rpm was used for all runs. The NR: AN mole ratios of 95/5, 93/7, 90/10 and 85/15 were used in this investigation while the reaction temperature and initiator concentration were varied from 30-55 oC and 0-0.031 mol/L, respectively. The total reaction time was 3 hours. In the first and a half-hour, the reaction took place in the reactor that can be described as a semi-batch reactor where AN was continuously fed into NR placed in the main reactor. AN was completely supplied to main reactor within 1 hour then the reactor performed as a batch reactor. The reaction was then allowed to take place for another 1 hour to ensure that all of monomer are converted and grafted onto NR backbone. The grafted copolymer latex was withdrawn to analyze its properties. 2.2 Particle size and Particle size distribution The particle size and the particle size distribution of grafted latex particle were determined by using Hydro 2000MU particle size analyzer. 2.3 Tensile properties The polymer sheet was prepared by drying of the graft latex. The specimen was cut and tested by following ASTM D412. 3.1 Latex properties: Particle size and particles size distribution 3.1.1 Effect of monomer mole ratio Figure 2 and Figure 3 show the particle size and the particle size distribution of grafted NR latex for various monomer mole ratios. It clearly shown from these figures that the surface weight mean diameter of the grafted NR latex increased significantly with increasing of AN monomer and the broader particle size distribution of grafted NR latex was also observed with increasing monomer concentration. These results are similar to those reported by other investigators who investigate the aliphatic polyester-grafted starch composites by in situ ring opening polymerization [4] and the seed emulsion polymerization of methyl methacrylate (MMA) using aqueous polyurethane (PU) dispersion [5]. 3.1.2 Effect of initiator concentration Figure 4 and Figure 5 show the particle size and the particle size distribution of grafted NR latex for various initiator concentrations. As shown in Figure 3, the surface weight mean diameter was progressively increased with increasing initiator concentration up to 1.6x10-2 mol/L then slightly increased and decreased thereafter. From Figure 4, the initiator concentration at 1.6 x 10-2 mol/L gave the broadest size distribution. After this concentration, the size distribution became narrower. This may be due to the fact that the free radical is increased with increasing initiator concentration, as a consequent of, the mean diameter is increased with increasing initiator concentration up to 1.6x10-2 mol/L and the particle size distribution is broadest at this concentration. At initiator concentration higher than 1.6x10-2 mol/L, we speculate that there are side reactions such as homopolymerization, chain transfer reaction and termination of oligomer free radical with initiator free radical took place as evident by increasing initiator concentration resulting in smaller particle size of grafted latex and also narrower in size distribution as compared to lower initiator concentration.

0.9

1.2
Mean diameter (micrometer)
NR 95/5 93/7 90/10

Mean diameter (um.)

0.85 0.8 0.75 0.7 0.65

1 0.8 0.6 0.4 0.2 0 0 0.009 0.016 0.022 [I] mol/L 0.031

Figure 2. Particle size of grafted NR latex (m) for various AN mole ratios at T = 50 oC and [I]0 = 0.009 mol/L
18 16 14 12 10 8 6 4 2 0 100.00

Figure 4. Particle size of grafted NR latex for various initiator concentration at T = 50 oC and [M]0 = 0.52 mol/L

Volume (%)

16 14 Volume (%)
NR

12 10 8 6 4 2 0 0.01 0.10 1.00 Particle size (um) 10.00 100.00

[I]=0.032 mol/L

0.01

1.00 10.00 Particle size (um ) NR/AN=95/5 NR/AN=93/7 NR/AN=90/10 NR

0.10

Figure 3. Particle size distribution of grafted NR latex for various NR/AN mole ratios at T = 50 oC and [I]0 = 0.009 mol/L 3.1.3 Effect of reaction temperature Figure 6 and Figure 7 show the particle size and the particle size distribution of grafted NR latex for various reaction temperatures. From Figure 6, the surface weight mean diameter was increased with increasing reaction temperature. This result may be attributed to the fact that the decomposition rate of redox initiator increased with increasing reaction temperature. Thus, the higher temperature the more free radical sites on the particle surface could be produced consequently the particle size of grafted NR at high temperature was lager than that at lower temperature. From Figure 7, The particle size distribution of graft copolymer latex at 550C is broader than at 500C and the large particles (> 45 m) was 19.08 volume percentage at 550C. The graft copolymer latex is a colloid and its stability decreased when the reaction temperature increased. Thus, the flocculation of unstability particles could be took place at high temperature resulting in the larger particle and broader particle size distribution.

[I]=0.009 mol/L

[I]=0.016 mol/L

[I]=0.021 mol/L

Figure 5.. Particle size distribution of grafted NR latex for various initiator concentration at T = 50 oC and [M]0 = 0.52 mol/L
1.2

Mean diameter (um.)

1 0.8 0.6 0.4 0.2 0 NR 50 55 Reaction temperature (C)

Figure 6. Particle size of grafted NR latex at various reaction temperature ([I]0= 0.009 mol/L and [M]0 = 0.52 mol/L)

16 14 12 10 8 6 4 2 0.01 0.10 0 1.00 10.00 100.00 1000. 10000. Particle size (um) 00 00 t=50 C t=55 C NR

3.3.2 Effect of initiator concentration The influence of initiator concentration on 300% modulus is depicted in Figure 9.
Volume (%)

300%Modulus (N/sq.mm)

0.5 0.4 0.3 0.2 0.1 0 NR 0.009 0.016 0.0022 [I] mol/L 0.031

Figure 7. Particle size distribution at various reaction temperatures ([I]0= 0.009 mol/L and [M]0 = 0.52 mol/L) 3.2 Tensile properties of grafted polymer: 300% modulus 3.2.1 Effect of monomer concentration. Figure 8. illustrates the effect of monomer mole ratios on 300% modulus.
300%Modulus (N/sq.mm)
0.6 0.5 0.4 0.3 0.2 0.1 0 NR 95/5 92/8 90/10 NR/AN mole ratio

Figure 9. Effect of initiator concentration on 300% modulus at T = 50 oC and [MI]0 = 0.52 mol/L From Figure 9, it can be seen that the 300% modulus of grafted NR was approximately unchanged with increasing initiator concentration. However, it was greater than that of NR at all initiator concentration used in this investigation. 3.2.3 Effect of reaction temperature Figure 10. illustrates the effect of reaction temperature on 300% modulus. It shown from this figure that the 300% modulus of grafted NR is unchanged with reaction temperature. This results implies that the initiator free radicals were decomposed completely at 50oC and all monomers were complety consumed at this temperature. As a result, there is no significant effect of reaction temperature, at 50oC or higher, on 300% modulus.

Figure 8. Effect of NR/AN mole ratio on 300% modulus at T = 50 oC and[I]0 = 0.009 mol/L . As shown in Figure 8, the 300% modulus of PAN-gNR at any investigated monomer mole ratios was higher than that of NR. However, the failure of both grafted NR and NR did not occurred even it was continuously test to high extension. The high strength of grafted NR was due to the present of polyacrylonitrile while the high extension is provided by natural rubber. Therefore, both elongation and modulus of grafted NR are high as compared to NR as evidence in Figure 8. For varied monomer mole ratios, the experimental results show that the 300% modulus was decreased when the monomer mole ratio increased. These may be caused by part of polyacrylonitrile homopolymer contaminate in rubber sheet, which decreased the homogeneity of rubber sheet and thus lower 300% modulus. The decreasing elastic modulus, yield stress, tensile strength and elongation at break with increasing monomer mole ratios has also been found in grafting of poly butyl acylate onto low density polyethylene [6].

300%Modulus (N/sq.mm)

0.5 0.4 0.3 0.2 0.1 0 NR 50 Reaction temperature (C) 55

Figure 10. Effect of reaction temperature on 300% modulus. ([M]0= 0.52 mol/L, [I]0=0.009mol/L) 3.3 Oil resistance properties: % swelling 3.3.1 Effect of monomer concentration The % swelling in diesel oil of grafted NR at various monomer mole ratios are compared with that of NR as shown in Figure 11.

3000 2500 Swelling,% 2000 1500 1000 500 0 100:0 95:5 92:8 NR:AN ratio 90:10

13. The % swelling at 550C is slightly lower than that at 500C. To avoid the incresing in viscosity during emulsion polymerization as evidenced by increasing in particle size and particle size distribution detailed in previous section, thus the reaction temperatue of 50oC should be applied for synthesis of grafted NR with AN by emulsion polmerization process.
3000 2500
Swelling, %

2000 1500 1000 500 0 NR 50 Reaction temperature, C

0

Figure 11. % swelling in diesel oil of grafted NR for various NR/AN ratios (T=50oC and [I]0=0.009 mol/L) As shown in Figure 11, The % swelling of grafted NR with AN in diesel oil was significant lower than that of NR and it decreased with increasing monomer concentration. These results were the consequence of the PAN grafting content on NR was increased with increasing monomer mole ratio. 3.3.2 Effect of initiator concentration The effect of the initiator concentration on swelling properties of grafted NR in diesel oil is illustrated in Figure 12.
3000 2500 Swelling, % 2000 1500 1000 500 0 NR 0.009 0.016 [I], mol/L 0.022 0.031

55

Figure 13. % swelling in diesel oil of grafted NR for various reaction temperatures (NR/AN = 90/10 and [I]0=0.009 mol/L) 4. CONCLUSION The graft copolymerization of acrylonitrile onto natural rubber was successfully prepared by emulsion polymerization process using cumene hydroperoxide and tetraethylene pentamine as an initiator. The influences of initial monomer concentration, initial initiator concentration and reaction temperature on particle size, particle size distribution, 300% modulus and swelling properties of grafted NR with AN have been investigated.. The conclusions from this work are as follow: 1. The particle size of grafted latex were increased with increasing monomer, initiator and temperature. 2. The particle size distribution of grafted latex were broader with increasing monomer, initiator and temperature 3. The 300% modulus of grafted NR were decreased with increasing monomer while both reaction temperature and initiator concentration has approximately no effect on 300% modulus of grafted NR. 4. The swelling properties of grafted NR in disel oil was significantly improved as compared to NR. The increasing in AN concentration was found to improve oil resistance significantly while the increasing in initiator concentraion and reaction temperatue can only slightly improve oil resistant of grafted NR as compared to that obtained by varing in monomer concentration. In conclusion, to improve the oil resistant, the NR/AN mole ratio, initial initiator concentration and reaction temperature of 90/10, 0.009 mol/L and 50oC, respectively, are recommended for using in producing of grafted NR with AN by emulsion polymerization. These optimum values, however, may be limited by reactor characteristic (reactor size, heat and mass transfer in reactor) used in this investigation. Further verification in

Figure 12. % swelling in diesel oil of grafted NR for various initiator concentrations (T =50 oC and NR/AN=90/10) From Figure 12 the % swelling was increased slightly with increasing [I]. This may be attributed to the fact that the initiator dosage is limited by surface on the natural rubber. The overabundance initiator free radicals will be created the side reactions that are chain transfer, termination and homopolymerization. These reactions will be competed with graft copolymerization lead to low graft content of PAN. As a result, the slightly higher in % swelling of grafted NR was observed at higher initiator concentration. Thus, the initiator concentration of 0.009 mol/L should be used for copolymerization of AN onto NR since it gave the lowest %swelling and much lower than that of non grafted NR as evidence in Figue 12. 3.3.3 Effect of reaction temperature The % swelling in diesel oil of grafted NR at reaction temperature of 50 and 55 oC are shown in Figure

pilot scale rector is then recommended and being investigated in our laboratory. 5. ACKNOLEDGEMENT The authors are grateful to the Graduate School Prince of Songkla University for financial support to the student. Other supports from Department of Chemical Engineering Faculty of Engineering Prince of Songkla University are gratefully acknowledged. 6. REFERENCES [1] J. Phumnok, C. Bunyakan, C. Tongurai, Graft Copolymerization of Acrylonitrile onto Natural Rubber by Emulsion Process, The 12th National Conference on Chemical Engineering and Applied Chemistry, Bangkok (TH), Nov.2002, pp. 263-267. [2] C. Nakason, A. Kaesman, N. Yimwan, N. Preparation Graft Copolymers of Deprotenised Natural Rubber Latex and High Ammonia Concentrated Natural Rubber Latices with Methyl Methacrylate, Songkhlanakarin J. Sci. Technol, Vol. 22, 2000, pp. 467-476

[3] F. Sundari, S. Kadariah, Radiation Grafting of Methy Methacrylate Monomer on Natural Rubber Latex, J. Appl. Polym. Sci., Vol. 29, 1984, pp. 15151521. [4] D. Rutot, P. Degee, R. Narayan, P. Dubois, Aliphatic Polyester-Grafted Starch Composites by in situ Ring Opening Polymerization, Composite Interfaces., Vol. 7, 2000, pp. 215-225 [5] I.H. Kim, J. Shin, I. Cheong, J.I. Kim, J.H. Kim, Seeded Emulsion Polymerization of Methyl Methacrylate using Aqueous Polyurethane Dispersion: Effect of Hard Segment on Grafting Efficiency, Colloids Surf. A: Physicochem. Eng. Aspects, Vol. 207, 2002, pp. 169-176 [6] P. Ghosh, B. Chattopadhyay, A. Sen Modification of Low Density Polyethylene (LDPE) by Graft Copolymerization with Some Acrylic Monomers, Polym., Vol. 39, 1998, pp. 193-201 [7] Y. Shirai, K. Kawatsura, N. Tsubokawa Graft Copolymerization of Vinyl Monomers from Initiating Group Introduced onto Olymethylsiloxane-Coated Titanium Dioxide Modified with Alcoholic Hydroxyl Groups ProJ., Vol. 35, 1999, pp. 2207-2213.