Alkylene

HN —R —NH —R ),. Hydrophilic polar substances formed by reacting alkylene polyamines or simple amines with alkylene dihalides. Used as flocculants, for, e.g. cellulose fibre and mineral ore suspensions. 

Cyclic compounds capable of undergoing ring opening (alkylene oxides, lactones, lactams, anhydrides, etc.). 

The hydroxyl groups can be alkylated with the usual alkylating agents. To obtain aryl ethers a reverse treatment is used, such as treatment of butynediol toluenesulfonate or dibromobutyne with a phenol (44). Alkylene oxides give ether alcohols (46). 

The hydroxyl groups can be alkylated in the usual manner. Hydroxyalkyl ethers may be prepared with alkylene oxides and chloromethyl ethers by reaction with formaldehyde and hydrogen chloride (86). The terminal chlorides can be easily converted to additional ether groups. 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

The next significant strength improvement followed the 1950 Du Pont (19) discovery of monoamine and quaternary ammonium modifiers, which, when added to the viscose, prolonged the life of the ziac cellulose xanthate gel, and enabled even higher stretch levels to be used. Modifiers have proliferated siace they were first patented and the Hst now iacludes many poly(alkylene oxide) derivatives (20), polyhydroxypolyamines (21—23), and dithiocarbamates (24). 

Alternative technology for modifying a poly(aLkylene terephthalate) by incorporation of a phosphinate stmcture has been developed by Enichem. Phosphinate units of the stmcture —P(CgH5) (0)CH20— are introduced into a polyester such as PET or PBT by transesterification with an oligomer comprised of the aforementioned units (136). 

Manufacture. The manufacture of 1,4-cyclohexanedimethanol can be accompHshed by the catalytic reduction under pressure of dimethyl terephthalate ia a methanol solution (47,65). This glycol also may be prepared by the depolymerization and catalytic reduction of linear polyesters that have alkylene terephthalates as primary constituents. Poly(ethylene terephthalate) may be hydrogenated ia the presence of methanol under pressure and heat to give good yields of the glycol (see Polyesters) (66,67). 

HydroxyethyUiydrazine (11) is a plant growth regulator. It is also used to make a coccidiostat, furazoHdone, and has been proposed, as has (14), as a stabilizer in the polymerization of acrylonitrile (72,73). With excess epoxide, polysubstitution occurs and polyol chains can form to give poly(hydroxyaLkyl) hydrazines which have been patented for the preparation of cellular polyurethanes (74) and as corrosion inhibitors for hydrauHc fluids (qv) (75). DialkyUiydrazines, R2NNH2, and alkylene oxides form the very reactive amineimines (15) which react further with esters to yield aminimides (16) ... 

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. 

Poly(alkylene glycol)s have a number of characteristics that make them desirable as lubricants. Compared to petroleum lubricants, they have lower pour points, a higher viscosity index, and a wider range of solubilities including water, compatibility with elastomers, less tendency to form tar and sludge, and lower vapor pressure (35). 

Poly(alkylene glycol)s are also used as lubricity additives ia water-based synthetic cutting and grinding fluids (36), and ia aqueous metalworking fluids. Under the high frictional heating at the tool or die contact with the workpiece, the polyalkylene glycol comes out of solution ia fine droplets which coat the hot metal surfaces. 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

A process variation of the extraction of 2-isopropylnaphthalene hydroperoxide from the cmde oxidation product with an alkylene glycol has been patented (71). The 2-naphthalenol plant of American Cyanamid, which was using the hydroperoxidation process and had a 14 x 10 t /yr capacity (72), ceased production in 1982, leaving the United States without a domestic producer of 2-naphthol. The 2-naphthol capacity in the Western world is approximately 50 x 10 t/yr, with ACNA, Italy and Hoechst AG, Germany operating the largest plants. China produces about 7 x 10 t/yr. Other important producing countries are Poland, Romania, the former Czechoslovakia, and India (35,52). 

Dialkyl peroxides have the stmctural formula R—OO—R/ where R and R are the same or different primary, secondary, or tertiary alkyl, cycloalkyl, and aralkyl hydrocarbon or hetero-substituted hydrocarbon radicals. Organomineral peroxides have the formulas R Q(OOR) and R QOOQR, where at least one of the peroxygens is bonded directly to the organo-substituted metal or metalloid, Q. Dialkyl peroxides include cyclic and bicycflc peroxides where the R and R groups are linked, eg, endoperoxides and derivatives of 1,2-dioxane. Also included are polymeric peroxides, which usually are called poly(alkylene peroxides) or alkylene—oxygen copolymers, and poly(organomineral peroxides) (44), where Q = As or Sb. 

Hydroxyalkyl hydroperoxides from cycHc ketones (1), where X = OH, R =, H and R, R = alkylene, apparentiy exist in solution as equihbrium mixtures of the cycHc ketone, hydrogen peroxide, and other peroxides, eg, the dihydroperoxide (1) in which X = OOH, and dialkyl peroxides (2) where X = OH and Y = OH or OOH. Due to the existence of this equihbrium, the latter two dialkyl peroxides react as mixtures of monomeric hydroperoxides in solution. 

Acidic hydrolysis of these hydroxyaLkyl hydroperoxides yields carboxyUc acids, whereas basic hydrolysis regenerates the parent aldehyde, hydrogen peroxide, and often other products. When derived from either aldehydes or cycHc ketones, peroxides (1, X = OH, = H, R, = alkylene or... 

As with other hydroperoxides, hydroxyaLkyl hydroperoxides are decomposed by transition-metal ions in an electron-transfer process. This is tme even for those hydroxyaLkyl hydroperoxides that only exist in equiUbrium. For example, those hydroperoxides from cycHc ketones (R, R = alkylene) form an oxygen-centered radical initially which then undergoes ring-opening -scission forming an intermediate carboxyalkyl radical (124) ... 

When derived from cycHc ketones, dihydroperoxides (1, X = OOH R = H, R and R = alkylene) react with vinyl monomers in the presence of Cr, V, or Ti salts to form difimctional compounds (145) ... 

Work had gone on in both the United States and Europe, notably at Du Pont and ICI Ltd. in the United Kingdom, on exploring the whole series of alkylene terephthalate polymers in connection with new synthetic fibers. Poly(l,4-butylene terephthalate) (PBT) was investigated in detail, as it had very... 

Hydroxyhydroquinone and pyrogaHol can be used for lining reactors for vinyl chloride suspension polymerization to prevent formation of polymer deposits on the reactor walls (98). Hydroxyhydroquinone and certain of its derivatives are useful as auxiUary developers for silver haUde emulsions in photographic material their action is based on the dye diffusion-transfer process. The transferred picture has good contrast and stain-free highlights (99). 5-Acylhydroxyhydroquinones are useful as stabilizer components for poly(alkylene oxide)s (100). 

The biodegradation of poly(alkylene glycols) is hindered by their lack of water solubiUty, and only the low oligomers of poly(propylene glycol) are biodegradable with any certainty (179—181), as are those of poly(tetramethylene glycol) (182). A similar xo-oxidation mechanism to that reported for poly(ethylene glycol) has been proposed. 

Many specific reaction conditions using otiiei alkylene oxides (14) oi combinations of alkylene oxides (15) may be found in tiie patent Hteiatuie. DiaZotlZatlon. The general reactions of o-diamines with an alkali nitrite and an acid with subsequent ting closure are well known. 

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). 

Ethylenediamine Alkoxylates. The reaction 1,2-alkylene oxides with ethylenediamine forms the basis of a series of surfactants of the following general stmcture ... 

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