Polybutene-1

Olefin polymers alpha-olefin polymers (PAO), polybutenes and alkylaromatics, in particular the dialkylbenzenes (DAB). This class of compounds is the most widespread and accounted for 44% of the synthetic base market in France in 1992. 

Hydrocarbons. Synthesized hydrocarbons are the most popular of the synthetic base stocks. These are pure hydrocarbons (qv) and are manufactured from raw materials derived from cmde oil. Three types are used olefin oligomers, alkylated aromatics, and polybutenes. Other types, such as cycloahphatics, are also used in small volumes in specialized apphcations. 

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. 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Alkylated aromatic lubricants, phosphate esters, polyglycols, chlorotrifluoroethylene, siUcones, and siUcates are among other synthetics that came into production during much that same period (28,29). Polyphenyl ethers and perfluoroalkyl polyethers have followed as fluids with distinctive high temperature stabiUty. Although a range of these synthetic fluids find appHcations which employ their unique individual characteristics, total production of synthetics represent only on the order of 2% of the lubricant market. Poly(a-olefin)s, esters, polyglycols, and polybutenes represent the types of primary commercial interest. 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

Polybutene can be cross-linked by irradiation at ambient temperature with y-rays or high energy electrons in the absence of air. The performance of articles manufactured from polybutene is only slightly affected by ionizing radiation at doses below 30 kGy (3 Mrad) (26). PMP is also relatively stable to P-and y-radiation employed in the sterilization of medical suppHes (27). 

Above 100°C, most polyolefins dissolve in various aHphatic and aromatic hydrocarbons and their halogenated derivatives. For example, polybutene dissolves in benzene, toluene, decalin, tetralin, chloroform, and chlorobenzenes. As with other polyolefins, solubiHty of PB depends on temperature, molecular weight, and crystallinity. 

Table 4. Properties of Pipe-Grade Polybutene Resin ...

Polybutene. The largest share of commercially produced crystalline PB is used for manufacturing pipe and tubing. 

Amoco developed polybutene olefin sulfonate for EOR (174). Exxon utilized a synthetic alcohol alkoxysulfate surfactant in a 104,000 ppm high brine Loudon, Illinois micellar polymer small field pilot test which was technically quite successful (175). This surfactant was selected because oil reservoirs have brine salinities varying from 0 to 200,000 ppm at temperatures between 10 and 100°C. Petroleum sulfonate apphcabdity is limited to about 70,000 ppm salinity reservoirs, even with the use of more soluble cosurfactants, unless an effective low salinity preflush is feasible. 

Although these polymers have iaadequate stabiUty and processibiUty for most plastics appHcations, the abiUty to undergo scission back to the gaseous monomers has afforded some utility ia fabrication of electron-beam resists for photoUthography. Polybutene sulfone (251) and polyhexene sulfone (252) have been developed for this small-volume but high value appHcation. 

Polyisobutylene is produced ia a range of mol wts, and has found a host of uses. The low mol wt Hquid polybutenes have appHcations as adhesives, sealants, coatings, lubricants, and plasticizers, and for the impregnation of electrical cables (7). Moderate mol wt polyisobutylene was one of the first viscosity-iadex modifiers for lubricants (8). High mol wt polyisobutylene is used to make uncured mbbery compounds, and as an impact additive for thermoplastics. 

Monomers for manufacture of butyl mbber are 2-methylpropene [115-11-7] (isobutylene) and 2-methyl-l.3-butadiene [78-79-5] (isoprene) (see Olefins). Polybutenes are copolymers of isobutylene and / -butenes from mixed-C olefin-containing streams. For the production of high mol wt butyl mbber, isobutylene must be of >99.5 wt % purity, and isoprene of >98 wt % purity is used. Water and oxygenated organic compounds iaterfere with the cationic polymerization mechanism, and are minimized by feed purification systems. 

Polybutenes. Copolymerization of mixed isobutylene and 1-butene containing streams with a Lewis acid catalyst system yields low mol wt (several hundred to a few thousand) copolymers that are clear, colorless, viscous Hquids. The chain-ends are unsaturated, and they are often chemically modified through this functionaUty (7,73). 

Plasticizers and Processing Aids. Petroleum-based oils are commonly used as plasticizers. Compound viscosity is reduced, and mixing, processing, and low temperature properties are improved. Air permeabihty is increased by adding extender oils. Plasticizers are selected for their compatibihty and low temperature properties. Butyl mbber has a solubihty parameter of ca 15.3 (f /cm ) [7.5 (cal/cm ) ], similar to paraffinic and naphthenic oils. Polybutenes, paraffin waxes, and low mol wt polyethylene can also be used as plasticizers (qv). Alkyl adipates and sebacates reduce the glass-transition temperature and improve low temperature properties. Process aids, eg, mineral mbber and Stmktol 40 ms, improve filler dispersion and cured adhesion to high unsaturated mbber substrates. 

Polybutenes enjoy extensive use as adhesives, caulks, sealants, and glaring compounds. They are used as plasticizers in mbber formulations with butyl mbber, SBR, and natural mbber. In linear low density polyethylene (LLDPE) blends they induce cling to stretch-wrap films. Polybutenes when modified at their unsaturated end groups with polar fiinctionahty are widely employed in lubricants as dispersants. Blends of polybutene with polyolefins produce semisoHd gels that can be used as potting and electrical cable filling materials. 

Chemical degradation can be avoided by using closed stmctures, which may have protective covets or which may be fully hermetic, as well as by using unreactive metals. Barrier coatings ate effective in some cases, and polyethylene—polybutene grease (8) is used in some splicing connectors for telecommunications cable. 

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