Polyisobutylenes

Derivatives of polyisobutylene (6. in Figure 9.1) offer the advantage of control over the molecular weight of the polyisobutylene obtained by cationic polymerization of isobutylene. Condensation on maleic anhydride can be done directly either by thermal activation ( ene-synthesis reaction) (2.1), or by chlorinated polyisobutylene intermediates (2.2). The condensation of the PIBSA on polyethylene polyamines leads to succinimides. Note that one can obtain mono- or disuccinimides. The mono-succinimides are used as... 

The polyispbptylenes (PIB) having molecular weights ranging from 1000 to 2000 are substituted by maleic anhydride, and the polyisobutylene succinic anhydride (PIBSA) formed is neutralized by a polyethylene-polyamine as indicated in Figure 9.10. 

Figure 3.4 Uj versus M" for polyisobutylene samples with three different degrees of crosslinking (T and a constant). [Reprinted with permission from P, J. Flory, Ind. Eng. Chem. 38 417 (1946). Copyright 1946, American Chemical Society.]...

Figure 3.9 Log-log plots of modulus versus time for polyisobutylene at 25 C and polystyrene at 135°C. Note the different units of time for the two substances. (From data of A. V. Tobolsky and E. Catsiff and of H. Fujita and K. Ninomiya. From Ref. 4.)...

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... 

Use the graphical method outlined above to evaluate and and, from these, X for polyisobutylene in diisobutylketone. 

Polybutenes. Polybutenes are produced by controlled polymerization of butenes and isobutene (isobutylene) (see Butylenes). A typical polyisobutylene stmcture is... 

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. 

Other Uses. Large quantities of hydrocarbon resins are used in mastics, caulks, and sealants (qv). Polymers for these adhesive products include neoprene, butyl mbber, polyisoprene, NR, SBR, polyisobutylene, acryHcs, polyesters, polyamides, amorphous polypropylene, and block copolymers. These adhesives may be solvent or water-borne and usually contain inorganic fillers. 

Synthetic oils have been classified by ASTM into synthetic hydrocarbons, organic esters, others, and blends. Synthetic oils may contain the following compounds diaLkylben2enes, poly(a-olefins) polyisobutylene, cycloaUphatics, dibasic acid esters, polyol esters, phosphate esters, siUcate esters, polyglycols, polyphenyl ethers, siUcones, chlorofluorocarbon polymers, and perfluoroalkyl polyethers. 

Fig. 1. Polymerization of isobutyiene with various initiating ions in conjunction with (C2H )2A1C1 (3). PIB =polyisobutylene.

Viscosity (Viscosity-Index) Improvers. Oils of high viscosity index (VI) can be attained by adding a few percent of ahnear polymer similar to those used for pour-point depressants. The most common are polyisobutylenes, polymethacrylates, and polyalkylstyrenes they are used in the molecular weight range of about 10,000 to 100,000 (18). A convenient measure for the viscosity-increasing efficiency of various polymers is the intrinsic viscosity Tj, as given by the function... 

Lubrication oil additives represent another important market segment for maleic anhydride derivatives. The molecular stmctures of importance are adducts of polyalkenyl succinic anhydrides (see Lubrication and lubricants). These materials act as dispersants and corrosion inhibitors (see Dispersants Corrosion and corrosion control). One particularly important polyalkenyl succinic anhydride molecule in this market is polyisobutylene succinic anhydride (PIBSA) where the polyisobutylene group has a molecular weight of 900 to 1500. Other polyalkenes are also used. Polyalkenyl succinic anhydride is further derivatized with various amines to produce both dispersants and corrosion inhibitors. Another type of dispersant is a polyester produced from a polyalkenyl succinic anhydride and pentaerythritol [115-77-5]. 

The susceptibihty of dialkyl peroxides to acids and bases depends on peroxide stmcture and the type and strength of the acid or base. In dilute aqueous sulfuric acid (<50%) di-Z fZ-butyl peroxide is resistant to reaction whereas in concentrated sulfuric acid this peroxide gradually forms polyisobutylene. In 50 wt % methanolic sulfuric acid, Z fZ-butyl methyl ether is produced in high yield (66). In acidic environments, unsymmetrical acychc alkyl aralkyl peroxides undergo carbon—oxygen fission, forming acychc alkyl hydroperoxides and aralkyl carbonium ions. The latter react with nucleophiles,... 

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

Thermoplastics. There are five elastomeric membranes that are thermoplastic. Two materials, chlorinated polyethylene (CPE) and polyisobutylene (PIB), are relatively obscure. Thermoplastic materials can be either heat-fused or solvent-welded. In contrast to Hypalon and uncured EPDM, this abiHty to fuse the membranes together remains throughout the life of the material. However, cleaning of the membrane surface after exposure to weather is required. Correct cleaning procedures for specific membranes are available from the individual manufacturer. 

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