Alkylene oxides propylene oxide

Alkylene Oxides Propylene Oxide Butylene Oxide... 

Propylene Oxide. Propylene oxide is another basic chemical used in manufacturing intermediates for urethane foams (cushioning and insulation), coatings, brake fluids, hydraulic fluids, quenchants, and many other end uses.23 The classic industrial synthesis of this chemical has been the reaction of chlorine with propylene to produce the chloro-hydrin followed by dehydrochlorination with caustic to produce the alkylene oxide, propylene oxide, plus salt. 

Thiess AM, Schwegler H, Fleig I, Stocker WG. Mutagenicity study of workers exposed to alkylene oxides (ethylene oxide/propylene oxide) and derivatives. J Occup Med 1981 23(5) 343-7. 

It is claimed that styrene/butadiene diblock polymers bring about an improvement in the hardness, strength, and processability of polybutadiene elastomers (27), as well as an improvement in the ozone resistance of neoprene rubber (28). Styrene diblock polymers have also been made with isoprene, a-methyIstyrene, methyl methacrylate, vinylpyridine, and a-olefins. Block copolymers of ethylene, propylene, and other a-olefins with each other have been made as well. Heteroatom block copolymers based on styrene or other hydrocarbons and alkylene oxides, phenylene oxides, lactones, amides, imides, sulfides, or slloxanes have been prepared. 

By the judicious selection of diols or glycols for reaction with ethylene oxide, propylene oxide, or higher alkylene oxides (or other 1,2-epoxides) as well as mixtures of such reactants, a large variety of polymers may be formed. 

Speranza and coworkers (143) modified cationically initiated ethylene oxide/propylene oxide copolymers by coreacting them, during the alkylene oxide copolymerization, with the diglycidyl... 

Poly(alI lene glycol)s. While these can be made from polymeri2ation of any alkylene oxide, they are usually prepared either from propylene oxide as the water-insoluble type, or as water-soluble copolymers of propylene oxide and up to 50% ethylene oxide (35,36) (see Polyethers, propylene OXIDE polymers). Current worldwide production is estimated to be about 45,000 t. 

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. 

These products are characterized in terms of moles of substitution (MS) rather than DS. MS is used because the reaction of an ethylene oxide or propylene oxide molecule with ceUulose leads to the formation of a new hydroxyl group with which another alkylene oxide molecule can react to form an oligomeric side chain. Therefore, theoreticaUy, there is no limit to the moles of substituent that can be added to each D-glucopyranosyl unit. MS denotes the average number of moles of alkylene oxide that has reacted per D-glucopyranosyl unit. Because starch is usuaUy derivatized to a considerably lesser degree than is ceUulose, formation of substituent poly(alkylene oxide) chains does not usuaUy occur when starch is hydroxyalkylated and DS = MS. 

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... 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

Sheratte55 reported the decomposition of polyurethane foams by an initial reaction with ammonia or an amine such as diethylene triamine (at 200°C) or ethanolamine (at 120°C) and reacting the resulting product containing a mixture of polyols, ureas, and amines with an alkylene oxide such as ethylene or propylene oxide at temperatures in the range of 120-140°C to convert the amines to polyols. The polyols obtained could be converted to new rigid foams by reaction with the appropriate diisocyanates. 

Phosphoric acid esters based on alkylene oxide adducts are of great interest. Their properties can be altered by the length and structure of the hydrophobic alkyl chain. But they are also controlled by the kind and length of the hydrophilic alkyleneoxide chain. The latter can easily be tailored by selection between ethylene oxide and propylene oxide and by the degree of alkoxylation. 

Anionic polymerization of alkylene sulfides was extensively studied by Sigwalt and collaborators. In contrast to propylene oxide, anionic polymerization of pro-... 

A drilling fluid additive, which acts as a clay stabilizer, is the reaction product of methylglucoside and alkylene oxides such as ethylene oxide, propylene oxide, or butylene oxide. Such an additive is soluble in water at ambient conditions, but becomes insoluble at elevated down-hole temperatures [386], Because of their insolubility at elevated temperatures, these compounds concentrate at important surfaces such as the drill bit cutting surface, the borehole surface, and the surfaces of the drilled cuttings. 

Wood wafers were treated with mixtures of propylene oxide and oligomeric isocyanate (Guevera and Moslemi, 1983). The best treatment was found to be a mixture of 9 1 propylene oxide to isocyanate. In another study, Guevera and Moslemi (1984) studied the swelling properties of wood modified with propylene or butylene oxide and compared the data with modifications using a furan resin, or vinylpyrrolidinone. The best results were obtained by the use of alkylene oxides in combination with a cross-linking agent (trimethylol propane trimethacrylate). 

On the basis of this principle, a process involving oxidation of unsaturated hydrocarbons and other organic compounds, more readily oxidized than alkenes, contribute substantially to solving problems in direct single-stage production of propylene and higher alkylene oxides. 

Polyethers are prepared by the ring opening polymerization of three, four, five, seven, and higher member cyclic ethers. Polyalkylene oxides from ethylene or propylene oxide and from epichlorohydrin are the most common commercial materials. They seem to be the most reactive alkylene oxides and can be polymerized by cationic, anionic, and coordinated nucleophilic mechanisms. For example, ethylene oxide is polymerized by an alkaline catalyst to generate a living polymer in Figure 1.1. Upon addition of a second alkylene oxide monomer, it is possible to produce a block copolymer (Fig. 1.2). 

Polyethers are typically products of base-catalyzed reactions of the oxides of simple alkenes. More often than not, ethylene oxides or propylene oxides and block copolymers of the oxides are used. A polypropylene oxide-based polymer is built and then capped with polyethylene oxides. An interesting aspect of this chemistry is the use of initiators. For instance, if a small amount of a trifunctional alcohol is added to the reactor, the alkylene oxide chains grow from the three alcohol end groups of the initiator. Suitable initiators are trimethylol propane, glycerol or 1,2,6 hexanetriol. The initiator is critical if one is to make a polyether foam for reasons that we will discuss shortly. 

We had studied mainly the propylene oxide polymerization, because the requirement for stereoregulation imposed on the catalyst was supposed to be severest for this monomer among alkylene oxides. The catalysts extensively studied are R2A10A1R2 and EtZnNBu ZnEt, which are composed of two metal atoms (59). The latter catalyst, being a crystalline compound, is characterized by giving an isotactic poly-propylen oxide in high yield. 

Poly(propylene oxide) [25322-69-4] may be abbreviated PPO and copolymers of PO and ethylene oxide (EO) are referred to as EOPO. Diol poly(propylene oxide) is commonly referred to by the common name poly(propylene glycol) (PPG). Propylene oxide [75-56-9] and poly(propylene oxide) and its copolymers, with ethylene oxide, have by far the largest volume and importance in the polyurethane (PUR) and surfactant industry compared to all other polyepoxides. Articles reviewing propylene oxide (1), poly(propylene oxide) (2—4), other poly(alkylene oxides) (4), and polyurethanes (5—7) are cited to lead the interested reader to additional detail not in the scope of this article. 

Alkylene Oxides and Azuidines. Alkyleneamines react readily with epoxides, such as ethylene oxide or propylene oxide, to form mixtures of hydruxyalkyl derivatives. A/iridincs react in an analogous fashion to epoxides. 

Copolymerisation of propylene oxide as well as other oxiranes with carbon dioxide in the presence of zinc-based coordination catalysts is generally accompanied with the formation of a cyclic five-membered carbonate, propylene carbonate or another alkylene carbonate [147,206,207,210,212,230]. The alky-lene carbonate, however, is not the precursor for poly(alkylene carbonate), since it hardly undergoes a polymerisation under the given conditions [142-146],... 

The oldest surfactant is soap, which may be traced back to the ancient Egyptians and beyond. Synthetic surfactants had been produced in the first half of the 20th century but it was only after World War II, with the development of the modern petrochemical industry, that alternative feedstocks to oleochemicals became readily available. Hence chloroparaf-fins and/or alphaolefins and benzene were used to produce alkylbenzene (or alkylate ), processes were developed to produce a range of synthetic fatty alcohols and alkylene oxide chemistry resulted in ethylene oxide and propylene oxide building blocks becoming readily available. 

A major trend in industrial chemistry has been an emphasis on improved processes for the production of major chemicals such as ethylene, propylene, vinyl chloride, styrene, alkylene oxides, methanol, terephthalates, and so on. The necessity for higher efficiency, lower cost processes has been accentuated by the relatively slow growth rates of major industrial chemicals over the past two decades or so. The fertilizer portion of the agricultural chemicals market as described in Table 2.6 is an example of the slow growth. 

Polyether polyols are prepared by the anionic polymerization of alkylene oxides, such as propylene oxide and/or ethylene oxide, in the presence of an initiator and a catalyst, as shown in the following equation ... 

The most widely used catalyst for the stepwise ring-opening polymerization of alkylene oxides is potassium hydroxide. This reaction (KOH catalyst), however, is accompanied by side reactions, e.g., the formation of allyl alcohol brought about by the isomerization of propylene oxide. 

Alkylene oxide(s) The vast majority of commercialised polyalkylene glycols are based on ethylene oxide only, propylene oxide only or copolymers incorporating the two. Copolymers can be synthesised as random (oxides added as a mixture giving a statistical distribution throughout the chain) or block (oxides added separately). Due to the more reactive nature of ethylene oxide, random copolymers will tend to preferentially incorporate propylene oxide units at the chain extremities. 

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