MELTING AND GLASS TRANSITIONS IN POLYISOBUTYLENE * R. M. Kext, Bamey Bennert, anp P. B. Stickney Barreuun Memonian Inerimure, Covumnvs, O10 INTRODUCTION The purpose of this work was to investigate the crystallization behavior of uncompounded, unstressed polyisobutylene and butyl rubber. Glass transition data obtained during the work are also reported. The data were determined dilatometrically. The work was prompted by a literature survey! which col- lected transition data on elastomers. It was found that crystallization informa- tion for polyisobutylene and butyl rubber was based largely on x-ray studies of these polymers under high elongation. In fact, it has been assumed generally that these polymers would crystallize only when highly oriented, as by stretch- ing. Because of the resistance of polyisobutylene to ordering when in the un- stressed state, no measurements of optimum crystallization temperature or melting temperature, 7’, have previously been reported. Information of this type is important because of its bearing on the mechanical behavior of a poly- mer. Many types of elastomers will crystallize readily if oriented by a large stress. However, only those having relatively simple structures crystallize readily under zero stress. Such behavior is, of course, a limiting factor in low-tempera- ture serviceability. Polyisobutylene might seem at first to have the required simplicity of structure; however, steric hindrance of the side methyl group forces the chain to crystallize in a helical configuration having a molecular re- peat distance of 18.6 A, as shown by Fuller, Frosch, and Pape®. This is the greatest repeat distance of any of the elastomers, suggesting that a lengthy exposure period would be required if ordering were to occur at all. A clue to ordering in an isobutylene copolymer was furnished by Gehman, Woodford, and Wilkinson’, who reported that s butyl tread stock showed a greatly in- creased torsional stiffness after storage for about 40 days at —30° C. The aged butyl sample exhibited an x-ray diffraction pattern suggestive of erystal- lization. These results may be the first showing crystallization in a butyl polymer essentially free of stress. In other work, Radi and Britt‘, using equilibrium temperature-retraction techniques with samples elongated 300 per cent initially, found that two types of butyl polymers showed optimum erystal- lization rates at —30° and —41° C. The aggregate of these results suggests that crystallization might occur in unstressed polyisobutylene if sufficient time were allowed, and indicates an optimum rate in the range of —30° to —40° C. This is reasonable by comparison with natural rubber, which has a glass transi- tion temperature very close to that of butyl rubber, and an optimum crystalliza- tion rate at about —25°C. .n original publication. Presented before the Rubber Division of the American Chemical Society, Cincitnall Obie, May 14-16, 1058" 499500 RUBBER CHEMISTRY AND TECHNOLOGY EXPERIMENTAL Dilatometric techniques described by Bekkedahl* were followed in this work. The capillary tubing of the dilatometers of about 2 mm inside diameter was of the precision-bore type supplied by the Fischer and Porter Company, Hatsboro, Pennsylvania. During calibration, the bore volume of this tubing was found to be constant within =+0.0001 ml/mm over its entire length. ‘This degree of precision falls within experimental error and makes it unnecessary to correct the volume of the confining fluid for variations in the bore. Each raw polymer sample was first pressed into a 6 X 6 X 0.075-inch sheet for 15 minutes at 120° to 135°C, This procedure removed nearly all of the air and rendered the sample transparent so that any remaining air bubbles could easily be excluded. It was necessary to handle the samples as small pieces, because the polymers were so tacky that large strips or chunks could not be pushed into the dilatometer bulb without entrapping large amounts of air. Therefore, the deaerated samples were cut into small cubes and about 5 to 7 grams were charged into the dilatometer with tweezers. Silicone Oil Type SF (81)-40 (General Electric Company) was used as the confining fluid. This oil has previously been shown to be suitable for such a purpose’. It has a low vapor pressure, low surface tension, and no swelling effect on the polymers as determined by a three-month swell test at room temperature. It was deter- mined experimentally that the linear expansivity coefficient of this oil is con- stant from 25° to —100°C. Each dilatometer was cleared of air under vacuum, and was considered to be properly evacuated if the oil meniscus changed no more than 1 mm between atmospheric pressure and full vacuum. Meniscus and reference heights for the dilatometer were measured with a cathetometer to £0.01 em, Long-term exposures at low temperature were carried out in a cold bar pat- terned after a device originally described by Mooney and Wolstenholme’. ‘This consists of 16 separate cold baths operating between 0° and —60° CG, con- trolled by the temperature gradient between a water bath at 0° C and a dry-ice bath at —72°C. With this cold bar, temperatures were maintained within +1 degree for months at a time. Temperatures were measured to +0.1° C by means of thermocouples. Variations in the height of the meniscus were converted to density changes foreach sample. The data were corrected for the emergent stem and for volume changes in the silicone oil and Pyrex bulb. The emergent stem correction be- comes quite significant with silicone oil or other organic fluids that are used in low-temperature dilatometry, because their expansivity is often greater than that of the sample. It was shown during this work that the usual assumption that the temperature inside the entire emergent stem approaches the surround- ing air temperature is not strictly correct. Measurements made inside the capillary by means of fine thermocouple wires showed that there was a temper- ature gradient extending as much as 12 cm above the bath liquid level, even though the entire emergent stem was exposed to ambient temperatures. Taking this gradient into account, a corrected emergent stem formula was obtained as follows: Emergent-stem correction = 0.94 K N (T's — Ta), where K is the difference between expansivity coefficients of the confining fluid and Pyrex glassTRANSITIONS IN POLYISOBUTYLENE 501 N is the height of the meniscus above bath level Ty is bath temperature 74 is air temperature ‘The quantity 0.94 was found to be applicable as an average factor at all bath temperatures, to correct for the temperature gradient in the lower part of the capillary tubing. RESULTS Expansivity curves were determined for Vistanex L-100 and L-140 and for uncompounded butyl rubbers including Enjay Butyls 035, 150, 215, 217, 218, and 325. For these measurements, the samples were cooled from 25° to —95° C at the rate of 0.5 degree per minute. The temperature was maintained constant at each 5-degree interval for 10 minutes before taking a reading. As expected, no evidence of crystallization in any of the polymers was found in these initial rapid cooling tests. However, glass-transition temperatures were observed, and since it is believed that these have not all been published before, they are reported here in Table I. Taste I Gass-Transirion Temperatures or PouyisoBUTYLENES anp Buryt Ruppers Unsaturation, Polymer mole per cent 7, °C Butyl 325 21-25 -70 Butyl 215 1.5-2.0 -71 Butyl 217 1.5-2.0 71 Butyl 218 15-20 7 Butyl 150 1.0-1.4 72 Butyl 035, 0.6-1.0 -3 Vistanex L-100 0 76 Vistanex 1-140 0 76 The difference in slope of the cooling curve above and below T, is very small and a certain amount of subjectivity is involved in determining the breaking point. However, it is felt that these values of T, are accurate to within 1 degree. ‘As can be seen in Table I, the 7, values of these polymers are in the same range as those of cis-1,4-polyisoprene (natural rubber). It is not certain why relatively small amounts of isoprene can increase 7, of the copolymer as much as 6 degrees. It might be concluded that isoprene enters the copolymer in the 1,2 configuration since 1,2-polyisoprene could be expected to have a relatively high T,. However, ozonolysis studies® indicate only 1,4 polymerization of the isoprene in butyl rubber. ‘The change in T, may imply then that isoprene assumes the trans 1,4 configuration in the copolymer, since in this form, in the homopolymer, its 7, also is higher than in natural rubber. However, the differ- ence in 7, between trans-1,4-isoprene and polyisobutylene is probably not enough to account for the large effect of the small isoprene content of the butyl rubbers. The 7, results were taken from only one set of samples, but the trend of 7, with the degree of unsaturation seems real. ‘The application of data of this kind to aid in the analysis of the structure of a copolymer provides interesting specula~ tion. The first observation of crystallization in polyisobutylene was made on samples in the cold bar, as shown in Figure 1. Vistanex I-100 and L-140 began502 RUBBER CHEMISTRY AND TECHNOLOGY ° § g 02 Vistanex L-I40 ot -36C g ° 5° Vistanex L-100 of -42¢ & § o6 s os a a a a a a a a Time, days Fra, 1.—Crystallization of polyisobutylene. to show a characteristic volume decrease after about 10 days at —42° and 36°, respectively. An approximate degree of crystallinity for Vistanex L-100 after equilibration at —42° C was calculated from the density of the amorphous polymer (0.918 g/cm’), the density of the partially crystallized material extra- polated to 20° C (0.926), and the density of the unit crystal, which, according to Bunn’, is 0.96. ‘These data indicate that the polymer was about 20 to 25 per cent crystalline, which is reasonable by comparison with results for other elastomers. Measurements of the rate of crystallization of Vistanex L-100 at various temperatures are shown in Figure 2. The sample exposed at —55° did not crystallize in 18 months. ‘This left only three curves from which the rate could be determined. However, the rate data are known to follow what appears to be a normal distribution curve, as shown first by Wood” for natural rubber. The half-time for crystallization plotted against temperature, as in Figure 3, Volume Decrease, percent ° ° 2 5 S & 2 ® ° 10 Er er a) 70 80 90 Time, doys, Fre, 2,—Volume-time relations during crystallization of polyisobutylene,TRANSITIONS IN POLYISOBUTYLENE 503, 020; ~40) “30 720 ‘Temperature, C Fro, 3.—The crystallization rate of polyisobutylene as a function of temperature. indicates that the maximum rate of crystal formation occurs near ~33° C. It is assumed that essentially the same optimum temperature would be found for butyl rubber, since the small percentage of unsaturation in butyl should not significantly change the effect of temperature on crystallization rate, even though it can retard materially the rate of crystal growth. The effect of copolymerization in polyisobutylene on the rate of erystal growth can be seen by examining the results of attempts to crystallize butyl rubbers. Over a period of a year and a half, at temperatures of —20° to —40°, only one sample crystallized. ‘This sample was Butyl 035, which contains the least unsaturation of all the butyl polymers. In this material (exposed at an average temperature of —25°), evidences of crystallinity first began to appear after about 6 months, and the decrease in specific volume then continued to an apparent maximum after an additional 6 months. In view of the lengthy test period required, it is not surprising that previous efforts to detect crystallization in unstressed butyl rubbers have not been sucessful. Melting-point. determinations for crystallized samples of Vistanex L-100 and L-140 were made following the slow melting technique prescribed by Evans, ‘Mighton, and Flory". Melting was carried out at an average heating rate of 1 degree per day, and over the last 5 degrees at 0.5 degree or less per day. The temperature was increased only when it appeared that the equilibrium volume had been attained at each temperature. Results for Vistanex L-100 are shown in Figure 4. A melting temperature of 1.5 +t 0.5 degrees was indicated by three Sas Specific Volume, ce 4am 102030 o Temperature,C Fra, 4.—Melting curve of polyisobutylene.504 RUBBER CHEMISTRY AND TECHNOLOGY samples of L-100 and one of L-140. Efforts to determine a melting temperature using the sample of crystallized Butyl 035 were not successful. The crystallites were melted below their equilibrium melting temperature due to an equipment failure and could not be induced to reform within a reasonable period at a lower temperature. Thus, no confirming melting data were obtained for butyl rub- ber. However, the results should serve as a base line in studying the effect of stress and of compounding variables on crystallization in butyl polymers. ACKNOWLEDGMENT We wish to thank the Office of the Chief of Ordnance, Department of the Army, and the Detroit Arsenal for sponsoring this work and for permission to publish the results. BIBLIOGRAPHY i944), ttt O85, taersonce, ae. Now York, 1940 . +» Yo, Th Tntarlanes, ‘then Now Yorks 1040, pp. 87-08. I, I. Ain, Chem, Bee. 72, 2018 (1950).