Petroleum resins

The first resins to be produced on a commercial scale were the coumarone—indene or coal-tar resins (1) production in the United States was started before 1920. These resins were dominant until the development of petroleum resins, which were estabHshed as important raw materials by the mid-1940s. Continued development of petroleum-based resins has led to a wide variety of aHphatic, cyclodiene, and aromatic hydrocarbon-based resins. The principal components of petroleum resins are based on piperylenes, dicyclopentadiene (DCPD), styrene, indene, and their respective alkylated derivatives. 

Terpene-based hydrocarbon resins are typically based on natural products such as a-pinene, P-pinene, and ti-limonene [5989-27-5] which are obtained from the wood and citms industries, respectively. These resins, which were originally the preferred tackifiers for natural mbber appHcations, possess similar properties to aHphatic petroleum resins, which were developed later. Terpene-based resins have been available since the mid-1930s and are primarily used in the adhesives industry. 

Petroleum resins are low molecular weight thermoplastic hydrocarbon resins synthesized from steam cracked petroleum distillates. These resins are differentiated from higher molecular weight polymers such as polyethylene and polypropylene, which are produced from essentially pure monomers. Petroleum resin feedstocks are composed of various reactive and nonreactive aliphatic and aromatic components. The resins are usually classified as C-5... 

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-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

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). 

Catalyst systems used in the commercial synthesis of aromatic petroleum resins are very similar to those systems used in the manufacture of C-5 and C-5—C-9 type resins. The principal catalysts are AlCl and BF and their respective complexes. BF catalysis usually yields resins with improved color over AlCl catalyzed systems. 

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. 

Terpene resins, because of their low odor and acceptable FDA clearance, are used as tackifiers for the natural and synthetic gum bases used in chewing gum. Selected petroleum resins are also used as gum bases. 

Polyterpenes, coumarone-indene resins, and so-called petroleum resins are produced commercially using cationic polymerization. These are used as additives for rubber, coatings, floor coverings, and adhesives. 

Till this time, polymer science was largely empirical, instinctive, and intuitive. Several polymers were commercially available prior to World War I celluloid, shellac, Galalith (casein), Bakelite, and cellulose acetate plastics hevea rubber, cotton, wool, and silk rayon fibers Glyptal polyester coatings bitumen or asphalt, and coumarone-indene and petroleum resins. However, as evidenced by the chronological data shown in Table 1.1, there was little... 

Tile is based mainly on vinyl chloride and vinyl acetate copolymers. Some polypropylene tile systems have recently been introduced. A petroleum resin is usually employed as an extender and processing aid conventional vinyl plasticizers and stabilizers also are incorporated. Reinforcing fibers and limestone constitute the remainder of the tile composition the fibers contribute hot strength for processing and dimensional stability in the finished tile, limestone supplies bulk at an economical cost. Stable pigments are also incorporated. Since tile is installed on and below grade level, it is important that the finished product be resistant to the effects of moisture and alkali. 

The resins and asphaltenes from tar sands and from the other synthetic fuels have not been analyzed beyond the extent shown by the tables. The resins can be fractionated and analyzed in more detail using methods developed for petroleum resins by Jewell (46) and McKay (47), but more extensive work is necessary to have definitive analysis methods for these materials. 

Toluene Toluene Toluene 20% w/v petroleum resin none 20% w/v petroleum resin none 20% w/v aluminum stearate 10% w/v aluminum stearate L = 12.9 D11 L = 10 D2-2 L = 49D1-75... 

Alkyd Silver-Brite Sherwin- Williams Metallic aluminum in petroleum resin... 

Historically the very first prepared were the coal-tar indene-couma-rone resins which came on the market in the early 1900s and are still produced even if they are now largely surpassed by other types. They were followed by the terpene resins obtained from turpentine distillates, and then in the 1940s by the petroleum resins prepared from Cs and C8-Cio streams. The so-called pure monomer resins were developed only recently. 

J. Findley, Petroleum resins, Encyclopedia of Polymer Science and Technology (EPST), Wiley-Interscience, New York, 1966, Vol. 9, pp. 863-860. 

A tackifier is hard low-molecular weight resin with a Tg higher than room temperature. It can give the highest tack to the adhesive when added at the proper amount. Petroleum resin, polyterpene, and rosin esters are typical tackifiers, which are all commercially available. 

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