Derivates, Propylene Oxide

Substitutive lUPAC nomenclature names epoxides as epoxy derivatives of alkanes According to this system ethylene oxide becomes epoxyethane and propylene oxide becomes 1 2 epoxypropane The prefix epoxy always immediately precedes the alkane ending it is not listed m alphabetical order like other substituents... 

PROPENE The major use of propene is in the produc tion of polypropylene Two other propene derived organic chemicals acrylonitrile and propylene oxide are also starting materials for polymer synthesis Acrylonitrile is used to make acrylic fibers (see Table 6 5) and propylene oxide is one component in the preparation of polyurethane polymers Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable indus trial chemicals acetone and phenol... 

Propylene Oxidation. The propylene oxidation process is attractive because of the availabihty of highly active and selective catalysts and the relatively low cost of propylene. The process proceeds in two stages giving first acrolein and then acryUc acid (39) (see Acrolein and derivatives). 

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). 

Etliyleiie oxide [75-21-8] propylene oxide [75-56-9] or butylene oxide [106-88-7] react widi aminonia to produce alkanolainines (Table 1). Etlianolainines, (n = 1, 2,3, mono-, di-, and tri-), are derived from the reaction of ammonia witli ethylene oxide. Isopropanolamines,... 

Worldwide propylene production and capacity utilization for 1992 are given in Table 6 (74). The world capacity to produce propylene reached 41.5 X 10 t in 1992 the demand for propylene amounted to 32.3 x 10 t. About 80% of propylene produced worldwide was derived from steam crackers the balance came from refinery operations and propylene dehydrogenation. The manufacture of polypropylene, a thermoplastic resin, accounted for about 45% of the total demand. Demand for other uses included manufacture of acrylonitrile (qv), oxochemicals, propylene oxide (qv), cumene (qv), isopropyl alcohol (see Propyl alcohols), and polygas chemicals. Each of these markets accounted for about 5—15% of the propylene demand in 1992 (Table 7). 

The uses of propylene may be loosely categorized as refinery or chemical purpose. In the refinery, propylene occurs in varying concentrations in fuel-gas streams. As a refinery feedstock, propylene is alkylated by isobutane or dimerized to produce polymer gasoHne for gasoHne blending. Commercial chemical derivatives include polypropylene, acrylonitrile, propylene oxide, isopropyl alcohol, and others. In 1992, ca 64% of U.S. propylene suppHes were consumed in the production of chemicals (74). Polypropylene has been the largest consumer of propylene since the early 1970s and is likely to dominate propylene utilization for some time. 

Acrolein can be obtained by propylene oxidation in a process similar to ammoxidation (109) (see Acrolein and derivatives). 

Ammonia, and Amines. Isopropanolamine is the product of propylene oxide and ammonia ia the presence of water (see Alkanolamines). Propylene oxide reacts with isopropanolamine or other primary or secondary amines to produce A/- and A/,A/-disubstituted isopropanolamines. Propylene oxide further reacts with the hydroxyl group of the alkanolamines to form polyether polyol derivatives of tertiary amines (50), or of secondary amines ia the presence of a strong base catalyst (51). 

Carbon Dioxide and Carbon DisulUde. Propylene oxide and carbon dioxide react ia the presence of tertiary amine, quaternary ammonium haUdes, or calcium or magnesium haUde catalysts to produce propylene carbonate (52). Use of catalysts derived from diethyUiac results ia polycarbonates (53). 

Similarly, carbon disulfide and propylene oxide reactions are cataly2ed by magnesium oxide to yield episulftdes (54), and by derivatives of diethyUiac to yield low molecular weight copolymers (55). Use of tertiary amines as catalysts under pressure produces propylene trithiocarbonate (56). 

Peracid Processes. Peracids, derived from hydrogen peroxide reaction with the corresponding carboxyUc acids in the presence of sulfuric acid and water, react with propylene in the presence of a chlorinated organic solvent to yield propylene oxide and carboxyUc acid (194—196). 

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

Polyall lene Oxide Block Copolymers. The higher alkylene oxides derived from propjiene, butylene, styrene (qv), and cyclohexene react with active oxygens in a manner analogous to the reaction of ethylene oxide. Because the hydrophilic oxygen constitutes a smaller proportion of these molecules, the net effect is that the oxides, unlike ethylene oxide, are hydrophobic. The higher oxides are not used commercially as surfactant raw materials except for minor quantities that are employed as chain terminators in polyoxyethylene surfactants to lower the foaming tendency. The hydrophobic nature of propylene oxide units, —CH(CH2)CH20—, has been utilized in several ways in the manufacture of surfactants. Manufacture, properties, and uses of poly(oxyethylene- (9-oxypropylene) have been reviewed (98). 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerisation is usually initiated by alkah hydroxides, especially potassium hydroxide. In the base-catalysed polymerisation of propylene oxide, some rearrangement occurs to give aHyl alcohol. Further reaction of aHyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly diftmctional. By using sine hexacyano cobaltate as catalyst, a more diftmctional polyol is obtained (20). Olin has introduced the diftmctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalysed homopolymerisation of tetrahydrofuran. Copolymers derived from tetrahydrofuran and ethylene oxide are also produced. 

In addition, polyester polyols are made by the reaction of caprolactone with diols. Poly(caprolactone diols) are used in the manufacture of thermoplastic polyurethane elastomers with improved hydrolytic stabiHty (22). The hydrolytic stabiHty of the poly(caprolactone diol)-derived TPUs is comparable to TPUs based on the more expensive long-chain diol adipates (23). Polyether/polyester polyol hybrids are synthesized from low molecular weight polyester diols, which are extended with propylene oxide. 

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

All lene Oxides and Aziridines. Alkyleneamines react readily with epoxides, such as ethylene oxide [75-21-8] (EO) or propylene oxide [75-56-9] (PO), to form mixtures of hydroxyalkyl derivatives. Product distribution is controlled by the amine to epoxide mole ratio. If EDA, which has four reactive amine hydrogens, reacts at an EDA to EO mole ratio which is greater than 1 4, a mixture of mono-, di-, tri,-, and tetrahydroxyethyl derivatives of EDA are formed. A 10 1 EDA EO feed mole ratio gives predominandy 2-hydroxyethylethylenediamine [111-41-1], the remainder is a mixture of bis-(2-hydroxyethyl)ethylenediamines (7). If the reactive NH to epoxide feed mole ratio is less than one and, additionally, a strong basic catalyst is used, then oxyalkyl derivatives, like those shown for EDA and excess PO result (8,9). 

Other Derivatives. Ethylene carbonate, made from the reaction of ethylene oxide and carbon dioxide, is used as a solvent. Acrylonitrile (qv) can be made from ethylene oxide via ethylene cyanohydrin however, this route has been entirely supplanted by more economic processes. Urethane intermediates can be produced using both ethylene oxide and propylene oxide in their stmctures (281) (see Urethane polymers). 

The manufacture and uses of oxiranes are reviewed in (B-80MI50500, B-80MI50501). The industrially most important oxiranes are oxirane itself (ethylene oxide), which is made by catalyzed air-oxidation of ethylene (cf. Section 5.05.4.2.2(f)), and methyloxirane (propylene oxide), which is made by /3-elimination of hydrogen chloride from propene-derived 1-chloro-2-propanol (cf. Section 5.05.4.2.1) and by epoxidation of propene with 1-phenylethyl hydroperoxide cf. Section 5.05.4.2.2(f)) (79MI50501). 

Synthesis of New Propellants Explosives , Quarterly Progress Rept No 5, US Rubber Co, Passaic, Contract Nord 10129 (1948), 36-37 4a) G.O. Curme, Jr F. Johnston, Glycols , ACS Monograph No 114, Reinhold, NY (1952) 4b) A.F, Gait, "Propylene Oxide in E.G. Hancock, Ed, Propylene and Its Industrial Derivatives , Wiley Sons, NY (1973), 273-97 5) R.C. Crews, Effects of Propylene Oxide on Selected Species of Fishes , AFATL TR-74-183 (1974) 6) Bretherick (1975), 364 7) Anon,... 

If primary alcohols with a straight chain of 10-20 carbon atoms are initially alkoxylated by a mixture of ethylene and propylene oxides followed by phosphorylation, a pour point depression to 8°C will occur, whereas phosphate esters derived from nonylphenol are liquid at temperatures as low as 2°C. Phosphoric acid esters on the base of linear primary alcohols (Cn-Cl5) generally solidify below 24°C [50] (Table 2). 

Thermoplastic xylan derivatives have been prepared by in-hne modification with propylene oxide of the xylan present in the alkaline extract of barley husks [424,425]. Following peracetylation of the hydroxypropylated xylan in formamide solution yielded the water-insoluble acetoxypropyl xylan. The thermal properties of the derivative quahfy this material as a potential biodegradable and thermoplastic additive to melt-processed plastics. Xylan from oat spelts was oxidized to 2,3-dicarboxyhc derivatives in a two-step procedure using HI04/NaC102 as oxidants [426]. 

The hydroxypropyl derivative of guar GaM (HPG) was prepared with propylene oxide in the presence of an alkaline catalyst. HPG was subsequently etherified as such with docosylglycidyl ether in isopropanol and presence of an alkaline catalyst [432]. The peculiar features of the long-chain hydrophobic derivatives were ascribed to a balance between inter- and intramolecular interactions, which is mainly governed by the local stress field. 

Propylene glycol, i.e., 1,2-propanediol (1,2-PDO), is an important commodity chemical. It is used as biodegradable functional fluids and as precursors for the syntheses of unsaturated polyester resins and pharmaceuticals (9-10). Propylene glycol is currently produced from petroleum-derived propylene via oxidation to propylene oxide and subsequent hydrolysis (9, 11). However, the rising cost of propylene provides an incentive to find a substitute to propylene for this... 

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