Polymerization of petroleum

The mesophase pitches used for high-modulus carbon fiber production can be formed either by the thermal polymerization of petroleum- or coal tar-based... 

Polybutene resins. These liquid resins are obtained by cationic polymerization of petroleum C4 streams in the presence of AICI3 at relatively low temperature. Temperature and AICI3 concentration are important factors as they influence the molecular weight and viscosity of the final resin. After reaction, the mixture is deactivated with water, methanol, ammonia or aqueous sodium hydroxide. The organic layer is separated and distilled to remove solvent and unconverted material. 

The generic name hydrocarbon resins designates several families of low molar mass polymers (M from 600 to 104) obtained by polymerization of petroleum, coal tar, and turpentine distillates [80-82], In most cases, these products are obtained by cationic polymerization of mixtures either of aliphatic and/or aromatic mono and diolefins present in the more or less enriched Cs and C9 feedstreams, or of pure aromatic monomers generally of the styrene type. They are complex mixtures of polymers ranging from viscous liquids and tacky fluids to hard, brittle thermoplastics, and are used as additives in adhesives, printing inks, rubbers, coatings, etc. [80-82], They are obviously amorphous and are characterized by their softening point (0 to —150° C), determined by standardized methods (i.e.,... 

They are obtained from the derivatization of rosin or by polymerization of petroleum distillates, turpentine fractions, coal tar and pure monomers. 

Deposits due to chemical reactions at a heat transfer surface will inhibit the transfer of heat. Two important examples are the polymerization of petroleum refinery feedstocks and the protein denaturalization that occurs in foodstuffs which come in contact with heated surfaces. Another situation of this type could be the chemical reactions that take place subsequent to the deposition of the foulant. This occurs, for example, in corrosion products particularly in the presence of boiling heat transfer. 

The tackifying (or modifying) resins which are used in formulating elastomer-based adhesives are obtained by the polymerization of petroleum and terpene feedstreams, as well as... 

Hydrocarbon resin is a broad term that is usually used to describe a low molecular weight thermoplastic polymer synthesized via the thermal or catalytic polymerization of coal-tar fractions, cracked petroleum distillates, terpenes, or pure olefinic monomers. These resins are used extensively as modifiers in the hot melt and pressure sensitive adhesive industries. They are also used in numerous other appHcations such as sealants, printing inks, paints, plastics, road marking, carpet backing, flooring, and oil field appHcations. They are rarely used alone. 

The feedstocks used ia the production of petroleum resias are obtaiaed mainly from the low pressure vapor-phase cracking (steam cracking) and subsequent fractionation of petroleum distillates ranging from light naphthas to gas oil fractions, which typically boil ia the 20—450°C range (16). Obtaiaed from this process are feedstreams composed of atiphatic, aromatic, and cycloatiphatic olefins and diolefins, which are subsequently polymerized to yield resias of various compositioas and physical properties. Typically, feedstocks are divided iato atiphatic, cycloatiphatic, and aromatic streams. Table 2 illustrates the predominant olefinic hydrocarbons obtained from steam cracking processes for petroleum resia synthesis (18). 

G-5 Aliphatic Petroleum Resins. Carbocationic polymerization of C-5 feedstreams has been accomptished with various Friedel-Crafts catalyst systems. Table 3 compares the efficiencies of selected Lewis acids ia the polymerization of a typical C-5 stream containing 43 wt % C-5—C-6 diolefias and 47 wt % C-5—C-6 olefins (20). Based on weight percent yield of resia at equimolar coaceatratioas of catalyst (5.62 mmol/100 g), efficieacy follows AICI3 AlBr3 > BF3etherate-H20 > TiCfy > SnCl. The most commonly used catalyst in petroleum resin synthesis is AlCl. ... 

G-9 Aromatic Petroleum Resins. Feedstocks typically used for aromatic petroleum resin synthesis boil in the approximate range of 100—300°C at atmospheric pressure, with most boiling in the 130—200°C range. The C-9 designation actually includes styrene (C-8) through C-10 hydrocarbons (eg, methylindene). Many of the polymerizable monomers identified in Table 1 for coumarone—indene type cmdes from coal tar are also present in aromatic fractions from cracked petroleum distillates. Therefore, the technology developed for the polymerization of coal-tar cmdes is also appHcable to petroleum-derived aromatic feedstocks. In addition to availabiHty, aromatic petroleum resins offer several advantages over coumarone—indene resins. These include improved color and odor, as weU as uv and thermal stabiHty (46). 

Gyclopentadiene/Dicyclopentadiene-Based Petroleum Resins. 1,3-Cyclopentadiene (CPD) is just one of the numerous compounds produced by the steam cracking of petroleum distillates. Due to the fact that DCPD is polymerized relatively easily under thermal conditions without added catalyst, resins produced from cycloaHphatic dienes have become a significant focus of the hydrocarbon resin industry. 

In 1929, polymerized olefins were the first synthetic oils to be produced commercially in an effort to improve on the properties of petroleum oils. Interest in esters as lubricants appears to date back to 1937 in Germany, and their production and use expanded rapidly during and following World War II to meet the needs of the military and the newly developed jet engines (2). 

Solvents. Petroleum naphtha is a generic term appHed to refined, pardy refined, or unrefined petroleum products. Naphthas are prepared by any of several methods, including fractionation of distillates or even cmde petroleum, solvent extraction, hydrocracking of distillates, polymerization of unsaturated (olefinic) compounds, and alkylation processes. Naphtha can also be a combination of product streams from more than one of these processes. 

Researchers at Phillips Petroleum Company developed a commercially viable process for the synthesis of PPS involving the polymerization of /)-dich1orohenzene and a sodium sulfide source in a polar organic compound at elevated temperature and pressure. This Phillips process was patented in 1967 (18). Between 1967 and 1973, Phillips built and operated a pilot plant, estabhshed market demand, and constmcted a hiU-scale commercial plant. In 1973, the world s first PPS plant came on-stream in Phillips faciUty in Borger, Texas. 

The polymerization process of coal tar and petroleum fraction (from which aromatic hydrocarbon resins are obtained) are similar. The process is extensively described in the book by Mildenberg et al. [25]. There are three basic steps in the polymerization of coumarone-indene and hydrocarbon resins. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

These are semisolid or solid substances formed in nature from crude oils after the volatile components have evaporated and the remainder has undergone oxidation and polymerization. They are also referred to as bitumens, waxes, and pitch. These materials are believed to consist of mixtures of complex organic molecules of high molecular weight. As with crude oils, which contain thousands of different chemical compounds, an exact chemical analysis for identification and composition is impractical to perform on the solid deposits of petroleum. 

In the early 1950s there was the quite contemporary discovery—in three different laboratories—of processes for the polymerization of ethene at low pressure using solid catalysts The catalyst used by the Standard Oil of Indiana was Mo(VI) oxide supported on aluminum oxide the one by Phyllips Petroleum was Cr(VI) oxide still supported on silica/alumina the catalyst studied by Ziegler and his co-workers at the Max Planck Institute at Miihlheim... 

---