Ethylene derivatives vinyl chloride

Chlorine cannot be stored economically or moved long distances. International movements of bulk chlorine are more or less limited to movements between Canada and the United States. In 1987, chlorine moved in the form of derivatives was 3.3 million metric tons or approximately 10% of total consumption (3). Exports of ethylene dichloride, vinyl chloride monomer, poly(vinyl chloride), propylene oxide, and chlorinated solvents comprise the majority of world chlorine movement. Countries or areas with a chlorine surplus exported in the form of derivatives include Western Europe, Bra2il, USA, Saudi Arabia, and Canada. Countries with a chlorine deficit are Taiwan, Korea, Indonesia, Vene2uela, South Africa, Thailand and Japan (3). 

The term liquefied petroleum gas (LPG) is often used to describe those liquefied flammable gases that are derived from petroleum. The term LFG is preferred when the discussion applies to all liquefied flammable gases. It includes materials such as ethylene oxide, vinyl chloride, and methylamines, which behave similarly so far as their flashing and flammable properties are concerned. 

The chemical uses for ethylene prior to World War II were limited, for the most part, to ethylene glycol and ethyl alcohol. After the war, the demand for styrene and polyethylene took off, stimulating ethylene production and olefin plant construction. Todays list of chemical applications for ethylene reads like the WTiat s What of petrochemicals polyethylene, ethylbenzene (a precursor to styrene), ethylene dichloride, vinyl chloride, ethylene oxide, ethylene glycol, ethyl alcohol, vinyl acetate, alpha olefins, and linear alcohols are some of the more commercial derivatives of ethylene. The consumer products derived from these chemicals are found everywhere, from soap to construction materials to plastic products to synthetic motor oils. 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

IR, Raman and 13C NMR spectroscopic studies have been performed on various [Ir(acac)(L)2] complexes (L = ethylene, propene, vinyl chloride, vinyl acetate, methyl acrylate, styrene) for the elucidation of the bonding between Ir and the alkene ligand.142 Also, the square planar iridium(I) acetylacetonate complexes [Ir(LL)(L )2], where LL is a /J-diketonate and L is CO or ethylene, have been studied by UVPES.143 The enthalpies of reaction of the crystalline [Ir(acac)(L)2] complexes with gaseous CO (reaction 28) have been determined by differential scanning calorimetry. The enthalpies for the gaseous reaction have been derived from these results and Ir—L bond strengths estimated.143... 

With the second approach to the preparation of the catalytic system, only methylenebis(dichloroaluminium) was prepared by an electrolytic reaction31. In the flow sheet proposed in the patent, between the electrolytic cell and the polymerization vessel a mixing reactor is interposed, where the various transition metal derivatives are added to the aluminium containing solution. Following this method other monomers, such as butadiene, 1-butene (copolymerized with ethylene), and vinyl chloride were successfully polymerized. 

Substances that have terminal double or triple bonds, if unconjugated to other multiple bonds, are oxidized by P-450 in the e.r. to toxic substances which attack this porphyrin and deactivate it. Examples are ethylene, acetylene, vinyl chloride and the hypnotic ethchlorvynol which is l-chloro-3-ethylpent-l-en-4-yn-3-ol. Thus, ethylene leads to the A-2-hydroxyethy 1-derivative of P-450. A further adverse effect is that other drugs, if given at the same time, escape the usual metabolic transformation and so build up in the patient (Ortiz de Montellano, Beilan and Matthews, 1982). 

Mer is derived from the Greek word meros meaning part. Therefore, a monomer means one part or one unit dimer means two units oligomer means a few units and polymer means many units. A polymerization involves the reaction of a monomer to connect many monomer units. If the reaction is additive, where one monomer adds to the next as in the polymerization of styrene, the polymer is called an addition polymer. Polymerizations of olefins, such as ethylene, propylene, vinyl chloride, or styrene, are addition polymerizations. In an addition polymer, all of the atoms of the monomer remain in the polymer. If the monomers are connected in a condensation reaction such as when a carboxylic acid and an alcohol react to remove water and form an ester linkage, then the polymer is called a condensation polymer. Recognize that in this type of polymer all of the monomer atoms are not incorporated into the final polymer. 

ATRP is successfully employed in the polymerization of a large variety of vinyl monomers such as styrenes, methacrylates, acrylates, acrylonitrile, and some others [2,9-15]. However, at present, available catalytic systems seem to be unsuitable for the less reactive monomers such as ethylene, olefines, vinyl chloride, and vinyl acetate. In the polymerization of monomers with strong electron-donating groups such as /7-methoxy styrene, some side reactions arising from the involvement of cationic intermediate are observed. Acrylic and methacrylic acids are also not prone to ATRP because they form Cu(II) carboxylates, which are inefficient deactivators. However, hydroxy derivatives such as hydroxyethyl acrylate and hydroxyethyl methacrylate can be polymerized by ATRP. 

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics hexanol and 2-ethylhexanol are used as part of the catalyst system in the polymerization of acrylates, ethylene, and propylene (55) the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization initiator for vinyl chloride various trialkyl phosphites find usage as heat and light stabHizers for plastics organotin derivatives are used as heat stabHizers for PVC octanol improves the compatibHity of calcium carbonate filler in various plastics 2-ethylhexanol is used to make expanded polystyrene beads (56) and acrylate esters serve as pressure sensitive adhesives. 

Chlorination of various hydrocarbon feedstocks produces many usehil chlorinated solvents, intermediates, and chemical products. The chlorinated derivatives provide a primary method of upgrading the value of industrial chlorine. The principal chlorinated hydrocarbons produced industrially include chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), chloroethene (vinyl chloride monomer, VCM), 1,1-dichloroethene (vinylidene chloride), 1,1,2-trichloroethene (trichloroethylene), 1,1,2,2-tetrachloroethene (perchloroethylene), mono- and dichloroben2enes, 1,1,1-trichloroethane (methyl chloroform), 1,1,2-trichloroethane, and 1,2-dichloroethane (ethylene dichloride [540-59-0], EDC). 

The leading derivative of ethylene dichloride is vinyl chloride [75-01-4] monomer (VCM), which is subsequently used to produce poly(vinyl chloride) and chloriaated hydrocarbons. Viayl chloride is obtaiaed by dehydrochloriaatioa of ethyleae dichloride ia the gas phase (500—600°C and 2.5—3.5 MPa). 

The decade 1930-1940 saw the initial industrial development of four of today s major thermoplastics polystyrene, poly(vinyl chloride) (PVC), the polyolefins and poly(methyl methacrylate). Since all these materials can be considered formally as derivatives of ethylene they have, in the past, been referred to as ethenoid plastics however, the somewhat inaccurate term vinyl plastics is now usually preferred. 

In addition to the above materials a number of copolymers containing vinyl acetate have been marketed. Ethylene-vinyl acetate (EVA) copolymers are discussed in Chapter 11 and vinyl chloride-vinyl acetate copolymers in Chapter 12. On the other hand, the commercial ethylene-vinyl alcohol copolymers, although derived from EVA, are considered briefly in this chapter since in weight terms the ethylene component is usually the minor one. 

A second major use for chlorine derives from its reactivity with organic materials, in particular with hydrocarbons. Two chlorinated hydrocarbons, ethylene dichloride (lUPAC name 1,2-dichloroethane) and vinyl chloride (lUPAC... 

Vinyl Chloride. A second process by which petroleum-derived ethylene may be employed in the production of polymeric products is by conversion to vinyl chloride and subsequent polymerization or copolymerization with other vinyl monomers. The process involves the reaction of ethylene with chlorine followed by catalytic dehydrochlorination of ethylene dichloride. 

A competing process produces vinyl chloride from acetylene, which also can be derived from petroleum feed stocks but is usually made from calcium carbide. It has been estimated (17) that 45% of current production of vinyl chloride is from ethylene, the remainder from acetylene. 

Another major chlorinated hydrocarbon is vinyl chloride. For many years acetylene was the sole raw material for the production of vinyl chloride by a catalytic fixed bed vapor-phase process. This process is characterized by high yields and modest capital investment. Nevertheless, the high relative cost of acetylene provided an incentive to replace it in whole or in part by ethylene. The first step in this direction was the concurrent use of both raw materials. Ethylene was chlorinated to di-chloroethane, and the hydrogen chloride derived from the subsequent dehydrochlorination reacted with acetylene to form additional vinyl chloride. 

Although acetylene still is used in a number of organic syntheses on an industrial scale, its use on a high-tonnage basis has diminished because of the lower cost of other starting materials, such as ethylene and propylene. Acetylene has been widely used in the production of halogen derivatives, acrylonitrile, acetaldehyde, and vinyl chloride. Within recent years, producers of acrylonitrile switched to propylene as a starting material. 

The most common molecules from which polymers are made are ethylene (chemical formula CH2=CH2) and its derivatives. The key to its polymerisation is the double bond, which opens to form bonds to other ethylenes and the end result is a chain of CH2 groups, -CH2-CH2-CH2-CH2-CH2- which can be millions of carbons long. This is polyethylene. Another common polymer is poly(vinyl chloride) which is made from vinyl chloride (chemical formula CH2=CHCl) and is better known as PVC. See also PPMA and HEMA. The following table lists various common polymers headed by those based on ethylene and its derivatives ... 

PVC is a product based on two of the earth s natural resources, salt and oil. Salt water electrolysis yields chlorine (in addition to caustic soda and hydrogen). Ethylene can be derived from naphtha when oil is refined. Chlorine and ethylene can be combined to form the monomer, vinyl chloride (VCM). PVC results from the polymerisation of vinyl chloride. 

Several procedures exists for calculating the heats of polymerization for various monomers but they are not very important. It is still more useful to consider the experimentally measured values as the best basis both for theoretical studies and for practical calculations. For ethylene derivatives, the value of — AHlc (from liquid monomer to amorphous solid polymer) ranges from 33.5 kJ mol-1 for a-methylstyrene, through ca. 96 kJ mol-1 for vinyl chloride, to 174 kJ mol-1 for tetrafluoroethylene. 

---