CHAPTER I

INTRODUCTION

1.1

BACKGROUND

Isobutylene (or 2-methylpropene) is a hydrocarbon of significant industrial importance. It is a four-carbon branched alkene (olefin), one of the four isomers of butylene. Isobutylene is a chemical compound with chemical formula C4H8 and the related compounds include isobutene, 2-methylpropene, and 1-dimethylethylene. The structural formula of isobutylene is shown below.

Figure 1.1

The structural formula of Isobutylene

1.2

PHYSICAL PROPERTIES

At standard temperature and pressure, isobutylene is a colorless, highly flammable gas with unpleasant odor. It is soluble in alcohols, diethyl ether, hydrocarbons and practically insoluble in water. The important physical properties for isobutylene are shown in the table below.

Table 1.1 Physical Properties of Isobutylene Properties Melting point, C (101.3kPa) Boiling point, C Density of liquid at 25 C, g/L Density of gas at 0C, 101.3kPa, kg/ Vapor pressure (Antoine equation constants) Temperature range, C A B C Heat of vaporization, J/g at 25C at boiling point Isobaric specific heat at 25C gas in ideal state, J/kg.K liquid at 101.3kPa, J/kg.K Enthalpy of formation, Free enthalpy of formation, at 25 C, 101.3kPa, kJ/mol at 25 C, 101.3kPa, kJ/mol 1589 2336 -16.9 58.11 -2702.3 144.75 4000.3 0.239 2.507 367.46 394.78 -18 to +12 7.71644 932.2 240.0 -140.337 -6.896 587.9 2.582

Heat of combustion at constant pressure and 25 C, kJ/mol Critical temperature, C Critical pressure, kPa Critical volume, L/mol Heat of combustion at constant pressures and 25C, J/mol Isobaric specific heat at 25C, J/kg.K gas in ideal state liquid at101.3kPa Surface tension at 20 C, mN/m (=dyn/cm) Source: Encyclopedia of Chemical Technology.

1590.5 2338.0 0.01242

1.3

CHEMICAL PROPERTIES

Isobutylene behave as typical olefins. The main reactions are acid-catalyzed addition reactions, isomerization, and polymerization. Isobutylene, the lowest branched-chain olefin, can exhibits higher reactivity, especially in addition and polymerization reactions. Hydration. Acid-catalyzed hydration of isobutylene is one of the commercially most important processes. Both gas and liquid phase processes are used. For example, hydration of isobutylene yields tert-butyl alcohol (TBA). Sulfuric acid (45wt%) is commonly used as a protonating agent. Hydration is commercially used for separating isobutylene from from mixed butenes. Etherification. The acid-catalyzed addition of alcohols to isobutylene yields alkyl butyl ethers. Reaction of isobutylenes with methanol, yielding methyl tert-butyl ether (MTBE), is of technical importance. Liquid phase and ion exchange resins as catalysts are commonly used. Halogenation. Isobutylene readily reacts with chlorine at low temperatures forming methallyl chloride. Hydroformylation. Hydroformylation of isobutylene in the presence of cobalt or rhodium catalysts gives 3-methylbutanol. Polymerization and Oligomerization. Polymerization of isobutylene in the presence of Al between -10 and 80C yields polybutenes. Oligomerization of isobutylene to dimers and trimers is done by extracting isobutylene from mixed butenes using 65-70wt% sulphuric acid and subsequent heating to100C. An alternative process uses acid ion-exchange resins instead of sulphuric acid. The resulting isobutene oliogomers, mainly 2,2,4-trimethylpentenes. Oxidation. Air oxidation of isobutylene over complex mixtures of transition metal oxides gives methacrylic acid. Oxidation of isobutylene with ammonia and oxygen to produce methacrylonitrile. Prins reaction. The acid-catalyzed reaction of isobutylene with formaldehyde is the most important synthetic route for isoprene production.

Alkylation. Friedel-Crafts alkylation of aromatics, primarily phenol, p-cresol, and catechol, with isobutylene in the presence of acid catalysts yields tert-butylaromatics.