A Kinetic and Rheometric Investigation of Hexamethylol Melamine Derivative on the Cure of Natural Rubber Compounds

BIDYUT BARAN KONAR Science and Technology, Calcutta University, Calcutta-700 009, India


of Polymer


Hexamethylol melamine (HMM) was characterized by Fourier transform infrared (FTIR) spectroscopy. The optimum dose of HMM in the presence of a sulfur accelerator in a
natural rubber (NR)-filled formation black-filled indicate that compound HMM was determined. The cure rate and kinetics of crosslink
rate of vulcanization


the first-order properties

in an NR NR carbon

compound. The results reveal good mechanical

of an HMM-based

@ 1997 .John Wiley & Sons, Inc.


NH, Oc\ HOH,C TNH, Melamme HOH,C Hexamethylol Melimme IHMM I \ T

i H,”H /~H@H / ~–~\N/Yc

Resins are used as compounding ingredients for elastomers to improve the properties of the vulcanizate. Some resins are used as curing agents for the resin-cure vulcanization of elastomers. Tawney et al.l showed that with the methylol resin system the rate of vulcanization is considerably slower than in the sulfur system but it imparts a greater stability toward prolonged vulcanization. It also showed marked improvement in the rate and state of cure through the catalyzing action of metallic halides. Subsequently, a number of works have been reported for the catalytic activation of the methylol resin cure with polychloroprene rubber, chlorosulfonated polyethylene, chlorinated waxes, and halogenated butyl rubbersz and on the mechanism of the reactions.s-~ Recently, Sato8 prepared HMM by reacting melamine with formaldehyde and studied the reaction kinetics. The present communication reports a critical study on the role of hexamethylol melamine (HMM) in rubber vulcanization. Melaminelike urea reacts with formaldehyde under neutral or slightly alkaline condition to yield HMM}’l(’ The material has no definite melting point and is very stable and is resinified through methylene and ether Iinkagesg:

/c\N/c\ H,N


) ‘~-CH,/c\x II ,CH,— C—N \N/ \CH,— 1.

—CH, —CH,

-N-cli 1’ /~\ \



T? N—C C—N—CH,—N/ %N/ / ~ ~ se,,”



—O— CH, —N Rem

There is only reportl 1on HMM which deals only with the good cure, mechanical properties, and wire adhesion of rubber. The present work is a critical study of HMM on the kinetic and rheometric properties for crosslink formation and the physical properties of the vulcanizate in a natural rubber (NR) compound formulation.

EXPERIMENTAL Hexamethylol Melamine (HMM) Synthesis12-14

Journal @ 1S97

of Applied


John Wiley & Sons, Inc.

Science, Vol. 63, 233-237 (1997) (XT 0021 -8995/97/020233-05

A three-necked round-bottom flask was fitted with a stirrer and reflux condenser. To formaldehyde (360 g, 37% w/w formalize), which was neutralized with a sodium carbonate solution, was added melamine (63 g). The mixture was heated at 70°C for 2 h. It

90 1.00 55.90 1. The recipes differed only in the dose of HMM.60 5. w 3 % + 50 . S-II with the optimum dose.75 1.00 2. obtained from the Kerala Rubber Board. then cooled and made alkaline (PH 9) with 10VOaqueous NaOH. and S-III for a higher dose of HMM. o Ii 1 .I without HMM. according to the procedure given in ASTM D3185-88. 0 2 4 6 6 10 ) 12 CURE TIME (rein was then cooled. The NR-loaded formulations (Table I) were evaluated to determine the optimum concentration of the HMM in the vulcanization reaction under stan - dard conditions. BSM (Accicure BSM).02~ I I OLC)LOl:. I i 54 ) cm-l Figure 1 FTIR spectra of HMM.60 2.25. Rheometric curve of HMM-filled NR com- The NR (HMM 1. and Antioxidant (Accinox HFN) (all.50 0. Standard Chemicals).00 55. stearic acid (Rubo Chem Industries).75 — — 100. and the solution acidified with an oxalic acid solution (5Y0). (460 mm) platens using an electrically heated press maintained at 150”C.00 2.00 0.00 55. The cure rate index and cure kinetics were determined from the rheographs of the respective compounds.00 0. o .50 0. The optimum cure time and other cure characteristics for various mixes at 1500C were evaluated using a Monsanto rheometer (R-1OO) according to ASTM Standard D 2084-88. India).- m —---n 1 RMAI Zinc oxide Stearic acid Carbon black (N 330) HGN BSM MBTS Hexamine HMM 100..I.50 100.75 1. MBTS (Accicure MBTS). and carbon Black (N 330. It was heated again at 70”C for 1 h. The alkaline solution was distilled under reduced pressure at 50”C to yield HMM. three samples were chosen for investigation: S.- —-—- . Compounding and Testing Figure 2 pounds.50 0.00 5. sulfur (98%. 34 2 DOSE (PPHR) OF HMM Figure 3 Optimum dose of HMM in presence of BSMMBTS in standard NR compound. India) used had a Mooney viscosity ML 1 + 4 ( 100” C) of 72. Ltd. (460 mm) X 18 in. After determining the optimum concentration. India). All compounds were prepared on a laboratorysize two-roll mixing mill (30 X 15 cm) at a friction ratio of 1: 1.. Tensile properties were determined according to ASTM Standard D 412-87 with dumbbell specimens in an Instron Universal Tensile tester machine 4301 I 1 I t I 40 < < - 24 - i I 8 t -21.00 2. The other compounding ingredients were as follows: zinc oxide (98% purity). . LC.90 1.234 KONAR Table I Mix Formulation for NR Compound S-I S-II S-III n Ingredients K . the resulting viscous mass was dissolved in methanol. Phillips Carbon Black Ltd. The resulting solid was washed with water and dried.00 5. The test specimen vulcanization was carried out in 18 in.00 5.00 0.00 A . 45 kg/cm2 pressure.

it may be inferred that HMM has an accelerating effect on NR vulcanization with the sulfur–accelerator system.88 1.64 741 7. – R.6 8. thus enhancing the rate of reaction.28 1.3235 11.6 4.1 is assigned to the characteristic hydroxyl groups formed due to the reaction.16 1.85 t 2.57 1.2 6.70 1. 3).0 6.0 2.5 phr in the NR-filled compound (Fig. beyond which the curve criteria show a sharp change.) at a pulling rate of 500 mm per min at room temperature (30°C).CURE OF NATURAL RUBBER COMPOUNDS 235 Table II Curing Kinetics of HMM for NR Compounds as Studied by Monsanto Rheometer at 150°C s-I t 4. The rheographs (Fig.4 2.8 27. Hardness was measured according to ASTM D 2240-86. – R.00 0.41 1.0 s-III log (Ra – 1.4 log (R.75 807 10.87 72 cure time Cure rate index First-order Physical Tensile strength (MPa) First modulus Elongation Energy Hardness q (MPa) at break (Shore at test end (J) A. 2) clearly indicates that HMM improves the reactivity order sharply compared to the sulfur–accelerator system.2391 13.4 s-II log (R.54 1.8 24.4 5.8 3.4 7. Table III Curing Characteristics of HMM-filled NR Compounds” Properties Rheometric Max torque Optimum Scorch time (lb-in.00 0.0 6.8 10.2 8.0 0.14 1. The absorption band in the range of 35003700 cm. As expected.79 1.75 1.48 67 150”C. This behavior could possibly be explained by the formation of an intermediate in situ in the rubber matrix with hydroxyl groups of HMM.80 1.5 0.74 t 2. 0.95 0.) (rein) (rein) (rein-’) rate constant (K) specific and Physical and Mechanical Properties S-I S-II S-III 61 9 4 20 0.2 6.27 1.8 7.69 (%) 964 12.8 5.) 1. RESULTS AND FTIR Spectra DISCUSSION Optimum Dose The spectra of the melamine derivative is shown in Figure 1.1 is due to the presence of hydroxyl groups.6 4.06 1.97 R.8 3.4 5.25 70 77 7.13 1. The optimum dose of HMM in the presence of the sulfur–accelerator was shown to be 2.6 6.6 8.75 1.1794 16. Relative Cure Rate and Scorch Kinetic and Rheometric Investigations Investigation of the reactivity order of HMM indicates that the material containing hydroxyl groups is reactive in the NR vulcanizate in the presence of From Figure 2.0 8.) 1.81 0.08 0.87 1. the absorption band in the range 35003700 cm.8 7. 76 6.26 1.0 4. Cure condition: temperature .86 1.51 1. the sulfur–accelerator system. pressure 45 kg/cm2.

. . .) (1) Vu.$ . S-II S-III for 2 X 10-’ Nm Relative cure rate and scorch at 150”C of compound (a) time over minimum.. + (3) s-I S-II The plot ln(~. ~ a.. The constant of proportionality changes with different stocks.0 40 h n 6? ‘8 ~ 1.** . cure time for HMM-filled NR compound.*. .t) (2) m I ::. .. . .. .0 (m[n) 11. So. The compounds using HMM show a fast cure rate and give a vulcanizate of high crosslink densities.. . . t gives a straight line. .0 5.5 u m 3 . .. S-I Figure 5 HMM-filled NR .. On integration. . ..0 Figure 4 Log(R= – R.... the increase in the torque reading can be considered as a measure of the relative crosslink density. TENSILE FIRST STRENGTH MODULUS AT SREAK . the negative slope of which gives the first-order specific rate (K) of the crosslinking reaction. . at any rate..) = –K(t – ti) in R.0. and Vu= are the crosslink density at time t and after completion of the cure and tiis the delay time.. .K(t – .... h(Vum – V%) = in VU..236 KONAR 2...*. 111 :111 : Ill : Ill : Ill s .. . . ... ti: dV ~ dt of the rheogram. 1 a..... . the crossformation kinetics is first order after an inducperiod...) vs....fij ELONGATION HARDNESS The rheometer torque is proportional to crosslink density (V.. . Therefore. ... .0.0 2.. = K(vua – vu. eq. . (1) gives Vut = Vu={ 1 – e~(ti-’)}.0 ..1 1. .* . ( b ) slope of the ascending Cure Properties and Cross/ink Formation rise of torque portion We link link tion adopted Coran’s modellb to evaluate the crossformation.. .*.O = cuRE cJ(-~~~~ RATE . or The observed test results depicted in Tables II and III and Figures 4 and 5 show that the crosslink density increases with the use of HMM in the sultimaccelerator NR black-filled vulcanizate.0. – R. H ::: . . According to this model. – R.) vs.0 CURE TIME 8.0. (2) gives ln(l?.. eq.).. ..III Figure 6 Physical and mechanical properties of HMMfilled NR vulcanizate. ~.

Conf.. Dunn Physics London.Sjothun. 08L 61/00) U. P. J. Houwink and J.. The higher strain (100%) moduli increase with the addition of HMM (2. M. J. (1958). DeJong 643 (1952). 1. S. L. C. p... Rubber Age 83. Trau. Butterworth. Science Technol. 197 (1990). R. Peterson. 1978. 71. 1963. Nippon 9. but decrease at higher doses. 8. T. in Proceedings of the IRI Conference of Polymer 1969. ~J. 1996 . Pat. Tawney. O. 10.S. Chem.CURE OF NATURAL RUBBER COMPOUNDS 237 Physical and Mechanical Properties of Vulcanized 3.. and J.5 phr optimum). B. W. Mark. Appl.. 307 ( 1950). in Vulcanizatwn of Elastomers. Sci. Technology. A. Eng. A. Proc. Hodgins 11. Plastics Materials. Y. R. 689 ( 1964).. 2nd cd. 3rd Rubber 5. Bateman. Little. Encyclopedia 1958). Polym. Van Alphen. Viohl. 7. of Polymer Rubb. and N. A. (Jan. G..892. Rec. Bikalus. 12. It is well known that compounding which produces an increase in hardness also produces increases in higher strain moduli values. Coran. K. 1990). Wiley -Interscience. Alliger and 1. Polym. Brydson. et al.. 18. The physical and mechanical properties of vulcanized NR samples containing HMM are summarized in Table III and Figure 6. R. 4. P. G. J. 33. New York.. 1970. J. 670 (1954). Tech. 6. Durairaj (C1-525-168C 215. F. The tensile strength and elongation at break decrease with increasing dose of HMM. Sate. Van Amerongen. De Jonge. and A. Chem. 230. 14. The HMM vulcanized samples show an increase in hardness. J. 2. 7. ACS Diu. Renner in The Chemistry and Ed. and Reinforcement.. NR System 16. 101 2. and 37. Kirk-othmer. Van Alphen. Scanlan. J. New York. 4. The HMM vulcanized samples show that one part of HMM is required to increase hardness by 10 for black-filled NR over the central part of the hardness range of 50°-800 Shore A. on Advances Loughborough. Kaguku and J. of Rubber Line Substances.395.05 13. 15. 121 (1955). H. Rubber Chem. Received Accepted April 18. Blends Kaishi. Chap. Sci.. Smith. 2.908 (Juty 1988) 5 PP.769 9. et al. of Chemical REFERENCES 1. (Cincinnati and P. Gaylord. Ind. Chim. 249. Chap. Eds. 1996 July 29. Eda. J. Vol. 6. (1941). Encyclopedia N. J.

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