Polyisobutylene temperatures

Inspection of Fig. 3.9 suggests that for polyisobutylene at 25°C, Ti is about lO hr. Use Eq. (3.101) to estimate the viscosity of this polymer, remembering that M = 1.56 X 10. As a check on the value obtained, use the Debye viscosity equation, as modified here, to evaluate M., the threshold for entanglements, if it is known that f = 4.47 X 10 kg sec at this temperature. Both the Debye theory and the Rouse theory assume the absence of entanglements. As a semi-empirical correction, multiply f by (M/M. ) to account for entanglements. Since the Debye equation predicts a first-power dependence of r) on M, inclusion of this factor brings the total dependence of 77 on M to the 3.4 power as observed. 

Figure 8.13 shows the reduced osmotic pressure for solutions of polyisobutylene in benzene plotted against C2 at several different temperatures. The... 

The low molecular weight materials produced by this process are used as lubricants, whereas the high molecular weight materials, the polyisobutylenes, are used as VI improvers and thickeners. Polybutenes that are used as lubricating oils have viscosity indexes of 70—110, fair lubricating properties, and can be manufactured to have excellent dielectric properties. Above their decomposition temperature (ca 288°C) the products decompose completely to gaseous materials. 

Fig. 49. Illustration of the time—temperature superposition principle as based on stress—relaxation data for polyisobutylene (299,300). To convert Pa to...

Whereas polyisobutylene and butyl mbber exhibit chain cleavage on free-radical attack, halobutyls, particulady bromobutyl and CDB, are capable of being cross-linked with organic peroxides. The best cure rate and optimal properties are achieved using a suitable co-agent, such as y -phenjiene bismaleimide. This cure is used where high temperature and steam resistance is required. 

In the case of symmetrical molecules such as carbon tetrachloride, benzene, polyethylene and polyisobutylene the only polarisation effect is electronic and such materials have low dielectric constants. Since electronic polarisation may be assumed to be instantaneous, the influence of frequency and temperature will be very small. Furthermore, since the charge displacement is able to remain in phase with the alternating field there are negligible power losses. 

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

Polyurethane networks based on triisocyante and diisocyanate connected by segments consisting of polyisobutylene are rubbery and exhibit high temperature properties, hydrolyic stability, and barrier characteristics. ... 

Further, while conventional Friedel-Crafts halides produce high molecular weight polyisobutylenes or polyisobutylene copolymers (e.g., butyl rubbers, HR) only at relatively low ( —100 °C) temperatures, alkylaluminum-based initiator systems produce high molecular weight materials at much higher ( —40 °C) temperatures. 

In previous papers1,2 we described reactivity studies of cationic isobutylene polymerization using r-butyl halide initiators, alkylaluminum coinitiators and methyl halide solvents. The effects of these reagents as well as temperature on the overall rate of polymerization and polyisobutylene (PIB) yield were studied and reactivity orders were established. These results were explained by a modified initiation mechanism based on an earlier model proposed by Kennedy and co-workers3,4. This paper concerns the effects of f-butyl halide, alkylaluminums and methyl halide, as well as temperature and isobutylene concentration on PIB molecular weights. 

These experimental results show conclusively that the deformation factor occurring in the theoretical equation of state offers only a crude approximation to the form of the actual equilibrium stress-strain curve. The reasons behind the observed deviation are not known. It does appear, however, from observations on other rubberlike systems that the type of deviation observed is general. Similar deviations are indicated in TutyP rubber (essentially a cross-linked polyisobutylene) and even in polyamides having network structures and exhibiting rubberlike behavior at high temperatures (see Sec. 4b). 

Fig. 119.—A2 for a series of polyisobutylene fractions in benzene plotted against the absolute temperature. The molecular weights of the fractions are as follows A, 102,000 193,000 O, 210,000 3, 723,000. (Results of...

Reciprocals of the critical temperatures, i.e., the maxima in curves such as those in Fig. 121, are plotted in Fig. 122 against the function l/x +l/2x, which is very nearly 1/x when x is large. The upper line represents polystyrene in cyclohexane and the lower one polyisobutylene in diisobutyl ketone. Both are accurately linear within experimental error. This is typical of polymer-solvent systems exhibiting limited miscibility. The intercepts represent 0. Values obtained in this manner agree within experimental error (<1°) with those derived from osmotic measurements, taking 0 to be the temperature at which A2 is zero (see Chap. XII). Precipitation measurements carried out on a series of fractions offer a relatively simple method for accurate determination of this critical temperature, which occupies an important role in the treatment of various polymer solution properties. 

Fig. 122.—A plot of the reciprocal of the critical temperature against the molecular size function occurring in Eq. (7) for polystyrene fractions in cyclohexane (O) and for polyisobutylene fractions in diisobutyl ketone (0). (Shultz and Flory. )...

The results of intrinsic viscosity measurements for four polymer-solvent systems made at the -temperature of each are shown in Fig. 141. The four systems and their -temperatures are polyisobutylene in benzene at 24°C, polystyrene in cyclohexane at 34°C, poly-(di-methylsiloxane) in methyl ethyl ketone at 20°C, and cellulose tricapry-late in 7-phenylpropyl alcohol at 48°C. In each case a series of poly-... 

The results for polyisobutylene indicate a small but significant decrease of K with temperature. For the silicone K is the same, within experimental error, in two different 0-solvents in spite of a 63° temperature difference. 

Fig. 143.—The intrinsic viscosity of a polyisobutylene fraction of high molecular weight plotted against temperature in four solvents cyclohexane, diisobutylene (DIB), toluene and benzene. The lines shown have been calculated according to theory. (Fox and Flory. )...

Fig. 144.—The treatment of expansion factor-temperature data obtained from intrinsic viscosities of polyisobutylene fractions in three pure solvents and in ethyl-benzene-diphenyl ether mixtures. Data for fractions having molecular weights Xl6 of 1.88, 1.46, and 0.180 are represented by O,, and Q, respectively. (Fox and Flory. 2)...

High-Temperature Defoamers. Polyisobutylene compounds are particularly effective in high-temperature (300° to 1 XX)° F) treatments of hydrocarbon fluids [786,788], such as during the distillation of crude oil and coking of crude oil residues. Polyisobutylene compounds are less expensive than silicone-based compounds. 

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