EFFECT OF ZnO PARTICLE SIZE ON THE CURING OF CARBOXYLATED NBR AND CARBOXYLATED SBR

G. R. HAMED,* K.-C. HUA

RUBBER RESEARCH CENTER, THE UNIVERSITY OF AKRON AKRON, OH 44325-3909

ABSTRACT
A carboxylated nitrile rubber (XNBR) and a carboxylated SBR (XSBR) were mixed with zinc oxide particles of different specific surface areas (S, 35 m2/g; M, 3.5m2/g; L, 0.5 m2/g) and cure behavior at 165 C studied using oscillating disc rheometry. Without added zinc oxide, both raw rubbers slowly stiffen over many hours of heating. This is probably due to condensation of carboxyl groups to form anhydride crosslinks. XNBR compositions containing the finely divided S crosslink much more rapidly. Full cure is reached after about 10 minutes of heating. Cure rate decreases markedly as the specific surface area of the ZnO decreases. A composition containing M at twice stoichiometry requires about an hour to cure well, while with L, about 10 hours are required. In contrast, curing of the XSBR depends little on the specific surface area of the ZnO, either with S or L, curing is essentially complete after 30 minutes. After simply mixing ZnO into either rubber, it remains as a dispersed particulate. With XNBR, curing appears to be controlled by the rate of dissolution and diffusion of ZnO, while, with XSBR, reaction is not diffusion limited and may be confined to regions near particle surfaces.

INTRODUCTION Pioneering studies of carboxylated rubbers by H. P. Brown1-3 led to commercialization of carboxylated nitrile rubber (XNBR) and carboxylated styrene-butadiene rubber (XSBR). Presently, XNBR is sold as a bulk, dry rubber and is used in engineering applications requiring high resistance to fracture, while XSBR is supplied as a latex and is employed in less severe service, such as in carpet backing and paper coating. Carboxylated rubbers are commonly cured with ZnO, which neutralizes acid groups thereby producing ionomeric elastomers, whose properties have been studied extensively.4-19 Complete neutralization consists of two steps: ZnO + RCOOH RCOOZnOH RCOOZnOH + RCOOH RCOOZnOOCR + H2O (1) (2)

Upon fully reacting, each mole of ZnO neutralizes two moles of acid and a mole of water is produced. In this paper, we examine the effect of ZnO particle size on the cure behavior of an XNBR and an XSBR. EXPERIMENTAL The XNBR was Nipol 1072 (Zeon Chemical), and the XSBR was Dow CP615NA (Dow Chemical), which was supplied as a latex. Prior to use, the latex was dried by pouring it onto a large flat plate in a hood at room temperature. After 48 hours, the latex was essentially dry. As seen in Table I, the XNBR contained 0.075 0.005 ephr (equivalents of acid per hundred parts by weight of rubber), while the XSBR contained 0.12 0.01 ephr, i.e., about 50% more acid functionality than the XNBR. Also shown in Table 1 are properties of Nipol DN2850, a regular NBR.

* Corresponding author. Ph: 330-972-6831; Fax: 300-972-5290; email: hamed@polymer.uakron.edu

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TABLE I PROPERTIES OF XNBR (NIPOL 1072), NBR (NIPOL DN2850), AND XSBR (DOW CP 615NA)

Zinc oxides of different particle size were used (Table II). These are designated S, M and L for small, medium and large particles, respectively. Gum rubbers are designated XNBR-0 or XSBR-0, while compositions containing ZnO have a suffix indicating ZnO type and level, relative to stoichiometry for complete neutralization. For example, XNBR-Sl contains the stoichiometric amount (3 phr) of the small Zinc Oxide 35; XNBR-M5 contains the medium Zinc Oxide FP-Z at five times (15 phr) stoichiometry; XSBR-L3 contains the large Cerox 506 at three times (14.6 phr) stoichiometry.
TABLE II ZINC OXIDE TYPES

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MIXING

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Compositions were prepared in a Haake Rheomix Model 600 Mixer using a rotor speed of 40 rpm and a fill factor of 0.85. The temperature of the mixer wall was about 35 C before rubber was added. No external heating or cooling of the mixer was used. A thermocouple sticking into the rubber mass monitored melt temperature during mixing. It took about one minute to add the raw XNBR or XSBR to the mixer. At three minutes of mixing, ZnO was added and mixing was continued for an additional four minutes. Compositions were removed and (sausage roll) passed 10 times through the nip (~ 2 mm) of a two-roll mill (19 and 23 rpm).
CURE RHEOMETRY

Cure behavior was determined with a Monsanto Model R-100 oscillating disk rheometer (ODR) (165 C, 3 arc) using about 12 g of sample. (Prior to determining the ODR response of XNBR-0 and XSBR-0 (no ZnO), they were masticated in the internal mixer, and on the mill, in order to provide the same processing history as compositions containing ZnO.) RESULTS AND DISCUSSION
INTERNAL MIXING

Torques during the mixing of XNBR-S5 and XSBR-S3 are shown in Figures 1 and 2. Torque increases as rubber is added to the mixer and then decreases. For XNBR-S5, upon addition of 15 phr of the small ZnO, the torque stays about the same for about one minute before continuing to decrease. XSBR-S3 behaves differently. After ZnO addition, mixing torque rises, an indication of the onset of scorch. ODR results, given later, are consistent with the scorchiness of XSBR relative to the XNBR.

FIG. 1 Torque during internal mixing of XNBR-S5.

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FIG. 2 Torque during internal mixing of XSBR-S3.

The raw XNBR-0 and XSBR-0 are transparent, before and after mixing. Compositions containing ZnO are opaque and white becoming brighter as ZnO content increases. After mixing, ZnO is a dispersed particulate in each elastomer.
XNBR CURE BEHAVIOR

Results of cure rheometry at 165 C for the XNBR containing the different zinc oxides are shown in Figures 3-5. In addition, results for XNBR-0 and the raw NBR are given. Figure 3 (Sseries) shows that XNBR-0 undergoes some crosslinking. Upon heating at 165 C for 2 hours, torque rises from a minimum value of 10 dN-m to about 23 dN-m. The XNBR self-crosslinks without added curative, probably due to bimolecular condensation of acid groups to form anhydride crosslinks. (In contrast, the raw NBR shows no increase in torque upon heating.) Up to about 1.5 times (4.5 phr) the stoichiometric amount of ZnO, cure rate and maximum torque increase rapidly with increased ZnO. Cure behavior is little different for compositions containing more than two times the stoichiometric amount of ZnO. (The slightly increased torques of S3 and S5 probably result from excess ZnO acting as particulate filler.) Thus, about twice the stoichiometric amount of S is needed for full cure.

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FIG. 3. Cure rheometry of XNBR containing small (S) ZnO.

Cure results with the large L ZnO are given in Figure 4. Note the much longer time scale compared to Figure 3. Results for the raw XNBR-0 are the same as those shown in Figure 3, but now the behavior at longer times is shown. XNBR-0 continues to self-crosslink up to 20 hours of heating. In contrast to the normal one-step cure seen with the small ZnO, two-step curing occurs with the large ZnO. In early heating, all compositions (0.5-5x stoichiometry) containing L have reduced torque relative to XNBR-0. The large ZnO particles slow thermal crosslinking of the raw XNBR-0. Apparently, some carboxyl groups have reacted with the ZnO (Reaction 1), thereby reducing self-crosslinking. The first neutralization step does not produce elastically effective network chains (at least not at sufficiently low conversions where ionic aggregation is expected to be absent), but, it decreases the concentration of acid groups available to participate in anhydride formation. For compositions with up to the stoichiometric amount of L, torque remains less than that of XNBR-0 over the whole range of heating time. At higher levels (1.5-5x stochiometry) of L, a second curing step takes place, as torque increases rapidly and becomes higher than that of the raw XNBR-0. The second stage occurs earlier as ZnO concentration increases and may be due to: (a) Reaction 2 producing intermolecular links. A further torque increase could result from aggregation of crosslink sites. (b) Sufficient Reaction 1 products to result in ionomeric aggregation. This mechanism is feasible since monovalent cations have been shown to be capable of crosslinking carboxylated rubbers. (Of course, ionomeric aggregation could involve the products of both Reactions 1 and 2.)

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FIG. 4. Cure rheometry of XNBR containing large (L) ZnO.

The finding that cure rate is strongly dependent on ZnO particle size indicates diffusion-controlled reaction(s). With the smaller ZnO, (Figure 3) neutralization is rapid. Indeed, the first step seems to occur so quickly that it cannot be determined by ODR; only the second stage of cure is seen. Moreover, neutralization is so rapid with S that at all levels (0.5-5.0x stoichiometry), and for all cure times, torque exceeds that of XNBR-0. Neutralization occurs before much anhydride linking has taken place. Figure 5 compares (on a log-log plot) the cure behavior of compositions containing S, M, or L at twice stoichiometry. The medium sized ZnO shows intermediate behavior between S and L. With M, curing is much more rapid than with L, but a two-step cure is still apparent.

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FIG. 5. Cure rheometry of XNBR containing different zinc oxides at twice stoichiometry.

Next, diffusion-controlled curing will be considered semi-quantitatively. We begin by defining a time tc when curing is essentially complete. This was done in each case as depicted, for example, in Figure 6. ODR curves were fitted with two straight lines one in the plateau region where torque changes little and another corresponding to the maximum slope. The intersection of the two lines defines tc. Further, we define a characteristic length scale for diffusion as the volume (V) of rubber in a composition divided by the total surface area (A) of the ZnO contained therein. Based on the basic diffusion equation (D = x2/2t), we assume that tc depends directly on (V/A)2 and also inversely on the concentration of ZnO, tc = f ((V/A)2/phr ZnO)

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FIG. 6. Method of tc determination, shown for XNBR-M series.

Figure 7 shows values of tc for compositions containing various phr of the three types of ZnO. Cure time decreases as ZnO concentration increases and is strongly dependent on particle size (or specific surface area). Replotting the data in Figure 7 with (V/A)2/phr ZnO as the abscissa, the mastercurve shown in Figure 8 is obtained. This validates the assumptions made to model the diffusion-controlled neutralization of the XNBR.

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FIG. 7. Values of tc for XNBR containing different zinc oxides.

FIG. 8. Mastercurve of tc for XNBR cured with zinc oxide at 165 C.

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XSBR CURE BEHAVIOR

Figures 9 and 10 show ODR curves for the XSBR containing the S and L zinc oxides, respectively. Like XNBR-0, XSBR-0 undergoes self-crosslinking. We again attribute this to intermolecular anhydride formation. However, in contrast to the XNBR, the effect of particle size is small and the XSBR is scorchy, especially with the S ZnO. XSBR-S3, prior to heating in the ODR, has undergone so much pre-reaction that its minimum torque is about 20 dN-m above that of the XSBR-0, and its maximum torque rise above the minimum is only about 5 dN-m. With L, XSBR compositions are less prone to pre-vulcanization, but they are still scorchier than the XNBR with S (Figure 3)! In addition, although the XSBR contains 50% more carboxyl groups than the XNBR, the maximum torques for the XSBR are much less than those for the XNBR. XSBR begins to neutralize quickly, but does not seem to develop a uniformly crosslinked structure throughout. Rather, the ZnO in XSBR behaves more like a reactive-filler, with neutralization taking place near the surface of ZnO particles, but not effectively throughout the elastomer. In this case, neutralization would, in effect, be like increasing the volume fraction of filler in the composition. (Previously, we have shown that the XNBR becomes much stiffer and stronger after neutralization, while the XSBR shows only a small increase in these properties.) In the next section, we directly compare the cure behavior of the two elastomers.

FIG. 9. Cure rheometry of XSBR containing small (S) ZnO.

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FIG. 10. Cure rheometry of XSBR containing large (L) ZnO.

XNBR COMPARED TO XSBR

Figure 11 gives log-log ODR curves of XNBR and XSBR with S and L at twice stoichiometry. The scorchiness and low maximum torque of XSBR are apparent. (This behavior contrasts to normal curing of rubber (e.g., with sulfur or peroxide), where a rapid onset of crosslinking is followed by a rapid increase in torque.) Finally, Figure 12 shows tc versus level of ZnO (relative to stoichiometry) for the two elastomers containing S or L. For XNBR tc is very much longer with L, while tc is similar for XSBR containing either zinc oxide.

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FIG. 11. Comparison of cure rheometry for XNBR and XSBR.

FIG. 12. Comparison of tc for XNBR and XSBR.

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RUBBER CHEMISTRY AND TECHNOLOGY ACKNOWLEDGEMENT

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These studies were carried out in the Rubber Research Center at The University of Akron. The Center is supported by a consortium of companies and the DIanni Research Endowment. REFERENCES
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