Alkylene Oxide Research Articles

Poly(alkylene oxide) ionomers. XII. Hydrolysis of polymers and copolymers of methyl 10,11‐epoxyundecanoate

AbstractEster‐substituted oxyethylene polymers and copolymers of methyl 10,11‐epoxyundecanoate were prepared with an aluminumalkyl–water coordination initiator system modified with acetylacetone. Poly(ethylene oxide) ionomers, polyelectrolytes, and polycarboxylic acids were obtained by alkaline hydrolysis of the pendant carbomethoxy groups and by neutralizations with acetic acid. The high molecular weight substituted poly(ethylene oxide)s were characterized by spectral, thermal, and dilute solution measurements. The infrared spectra of carboxylate substituted poly(ethylene oxide)s, both homo‐ and copolymers, show the typical shifts in the carboxyl absorption when going from the ester to the carboxylate group to the free acid. Polymer transitions temperatures, as measured by DSC, changed accordingly. Wide‐angle x‐ray diffraction measurements strongly suggest the existence of ionic domains in the oxyethylene polymer matrix. Dilute solution properties of the ionomers show typical polyelectrolyte behavior, including a substantial change in viscosity when ionic solute is added.

非イオン界面活性剤の石炭‐水スラリー高濃度化性能

For highly loaded coal-water slurry (CWS), the authors first eval-uatedthe effect of nonionic surface active agents on highly loaded CWS. Two kinds of bituminous coals different in carbonization degree, such as Tatung coal and Blair Athol coal, were subjected to examination to obtain the following results:1) With Tatung coal more carbonized, CWS of high concentration can more easily be produced than with Blair Athol coal.2) Adducts of alkylphenol, aliphatic alcohol or fatty acid, with ethylene oxide (hereinafter simply called EO), exhibited almost no effect on highly loaded CWS.And besides those with a small number of moles of EO added had effect on reducing the concentration of CWS.3) A block copolymer obtained by adding EO equivalent to a molecular weight of 6, 400 to both ends of polypropylene glycol with a molecular weight of 3, 200 had a good effect on highly loaded CWS.Second, the above alkylene oxide copolymers and sodium salt of formalin conden-sate of naphthalenesulfonic acid and sodium salt lignosulfonate were compared for effect on highly loaded CWS. As a result, alkylene oxide copolymers were found to be muchbetter in such effect.

A review of miscibility enhancement via ion‐dipole interactions

AbstractIt is shown that ion‐dipole interactions induce considerable miscibility enhancement in blends of styrene ionomers with poly(alkylene oxides). Dynamic mechanical studies, in conjunction with transparency and brittleness of the samples, are used to evaluate miscibility. The effect is clearly thermodynamics in that phase separation can be induced in miscible samples by raising the temperature, with miscibility reestablished ons cooling. The miscibility enhancement in these systems is compared with that resulting from hydrogen bonding. In addition to the styrene/alkylene oxide system, ion‐dipole interactions are found to be effective in enhancing the miscibility of many ionic polymer/polar polymer pairs. The ionomers used in this study were styrene lithium methacrylate and ethyl acrylate lithium acrylate copolymers, while polyethers, polysulfides, polyesters, polyimines, and substituted polyethylenses served as polar polymers.

Poly(alkylene oxide) ionomers. XIII. Copolymers of trioxane with the epoxide and 1,3‐dioxolane of methyl 10‐undecenoate

AbstractCationic copolymerization of 1,3,5‐trioxane with methyl 10,11‐epoxyundecanoate or methyl 7,8‐epoxyoctanoate and terpolymerization with 1,3‐dioxolane was successfully carried out. Co‐and terpolymerization of 1,3,5‐trioxane with 4‐(1‐carbomethoxynonyl)‐1,3‐dioxolane was also achieved. Feed compositions of the functional comonomers were varied from 5 to 40 mol %; in all cases the isolated copolymers contained less than 5% of the functional mer units. The composition of the copolymers showed that the methyl ω‐epoxyalkanoates were much less reactive than 1,3,5‐trioxane. A similar trend was observed with the functional dioxolane monomer, although significantly shorter induction periods were observed in comparison with the epoxy/trioxane copolymerizations. The oxymethylene copolymers and terpolymers were characterized primarily by their infrared spectra; however, the thermal and base stabilities of selected copolymers were also determined.

Poly(alkylene oxide) ionomers VIII. Synthesis of methyl ω‐alkenoates and methyl ω‐epoxyalkanoates

Abstractω‐Alkenoic acids, either commercially available or synthesized, were esterified to their corresponding methyl esters. They were characterized by their infrared, 1H‐, and 13C‐NMR spectra. The ω‐alkenoates prepared were: propenoate (acrylic acid), butenoate, pentenoate, hexenoate, heptenoate, octenoate, nonenoate, and decenoate. These compounds were epoxidized with m‐chloroperoxybenzoic acid to the corresponding methyl ω‐epoxyalkanoates. The rate of epoxidation of the double bond is found to increase as the double bond is separated from the carbomethoxy group by increasing numbers of methylene groups. When at least three methylene groups are inserted, the rate of epoxidation becomes constant and is similar to the epoxidation of ω‐olefins. The methyl ω‐epoxyalkanoates were characterized by their infrared, 1H‐, and 13C‐NMR spectra. Methyl ω‐alkenoates and methyl ω‐epoxyalkanoates were prepared and characterized, and their purification was studied in preparation for their investigation as monomers for olefin or epoxide polymerization using corrdination initiators.

Poly(alkylene oxide) ionomers. VII. Use of triethylaluminum/water/acetylacetone (1.0:0.5:1.0) for the polymerization of oxiranes

AbstractPolymerization studies of oxiranes were conducted using a modified aluminumalkyl initiator, derived from the low‐temperature reaction by chelating agents (5°C) and hydrolysis products of triethylaluminum. The stoichiometric reaction product of acetylacetone and triethylaluminum, after partial hydrolysis with water, gave a homogeneous initiator that polymerized the oxides of ethylene, propylene, 1‐butene, 1‐hexene, 3‐chloro‐1‐propene, and 4,4,4‐trichloro‐1‐butene to the corresponding high molecular weight poly(alkylene oxides). The initiator, similar in nominal composition to the classical trialkylaluminum/water/acetylacetone (1.0/0.5/1.0) initiator developed by Vandenberg, retained a high level of activity, when properly stored, for nearly 4 weeks. The composition was inactive when the sequence of chelation and hydrolysis was reversed. Inclusion of a proton‐trapping agent in polymerization experiments of propylene oxide provided evidence that protons do not play a role in the initiation of oxirane polymerizations with modified organoaluminum oxides. Characterization of the various alkylene oxide polymers was carried out by spectroscopic, solution, and thermal techniques.

Miscibility enhancement via ion-dipole interactions. 1. Polystyrene ionomer/poly(alkylene oxide) systems

Abstract : It is shown that ion-dipole interactions can lead t miscibility enhancement in polymer blends. While polystyrene is not miscible with poly(ethylene oxide) or poly(propylene oxide), styrene ionomers show very high miscibility with these materials at low alkylene oxide contents (10 wt %) and high, though not complete, miscibility at higher loading levels. For these systems it is seen that the glass transition temperature (from G' peak positions) of the styrene ionomer is depressed dramatically with increasing alkylene oxide contents and that the glass transition of the alkylene oxide rises appreciably (in most cases) with increasing styrene ionomer content. Increases in ion content at constant styrene levels increase the miscibility. The degree of miscibility enhancement is comparable to that achieved in hydrogen-bonded system. Finally, molecular weight effects observed here are quite similar to those seen in other blend systems.

ChemInform Abstract: INDOLE SYNTHESES UTILIZING O‐METHYLPHENYL ISOCYANIDES

AbstractUnter optimierten Versuchsbedingungen reagiert das o‐Methylisocyanid (Ia) nach Lithiierung mit den Alkylhalogeniden (II) zu den Derivaten (IV), die zu den lndolen (V) cyclisiert werden.

Indole Syntheses Utilizing o-Methylphenyl Isocyanides

Abstract New indole synthesis starting with o-methylphenyl isocyanides such as o-tolyl, 2,4-xylyl, and 2,6-xylyl isocyanide is described in full detail. Treatment of o-tolyl isocyanide with LDA in diglyme at −78 °C generated selectively o-(lithiomethyl)phenyl isocyanide in an almost quantitative yield, which on warming up to room temperature was cyclized to indole after aqueous workup. Similary, 2,4-xylyl and 2,6-xylyl isocyanides were cyclized to 5-methylindole and 7-methylindole quantitatively. The o-(lithiomethyl)phenyl isocyanides reacted with electrophiles such as alkyl halides and alkylene oxides to give o-alkylphenyl isocyanides, which were cyclized via the lithiation at the orthobenzylic carbon to afford 3-substituted indoles. On the other hand, the o-(lithiomethyl)phenyl isocyanides generated in situ at −78 °C was first warmed up to room temperature and then treated with electrophiles to furnish 1-substituted indoles. The o-(lithiomethyl)phenyl isocyanides were acylated in a fairly good yield with N-acylaziridines to give o-(acylmethyl)phenyl isocyanides, which were readily alkylated in the presence of sodium hydride to produce o-(1-acylalkyl)phenyl isocyanides. On acid hydrolysis followed by neutralization, o-(1-acylalkyl)phenyl isocyanides were converted to 2,3-disubstituted indoles.

The effect of alkylene oxides, furan resin and vinylpyrrolidinone on wood dimensional stability

The effect of propylene oxide, butylene oxide, furan resin, and vinylpyrrolidinone in controlling wood dimensional stability have been examined. Wood in the green or ovendry condition was treated with various chemicals using a vacuum-pressure procedure. Treated specimens were tested for tangential swelling, moisture gain, and changes in sorption hysteresis. Results indicate that propylene oxide and butylene oxide enhanced with the crosslinking agent trimethylol propane trimethacrylate, applied to ovendry wood were the most efficient chemical treatments in controlling hygroscopic dimensional changes. The sorption behavior of treated wood as depicted by the ratios of sorption was “very favorable” in most instances. In the case of treatments with furan resin, ratios of sorption were improved from 25 to 100 percent as compared to those of untreated wood.

Recent trends in the stabilisation of polymers

AbstractPolymers are subject to oxidation during processing due to the application of mechanical stress (shear) which leads to the scission of the polymer backbone and the formation of initiating macroalkyl radicals. Under the conditions of low oxygen concentration in commercial mixing operations, a catalytic redox antioxidant mechanism can operate which involves the alternating oxidation of alkyl radicals and reduction of alkylperoxyl radicals.‘Stable’ free radicals (A) notably phenoxyl and nitroxyl radicals and inorganic radicals such as I are very effective melt stabilisers for polyolefins because of their ability to undergo reversible oxidation and reduction. magnified imageA similar mechaism has been shown to operate during the mechano‐oxidation of rubbers in service (fatigue) and during the photo‐oxidation of polyolefins.

Oxidative alkyl- and aryl-aminomercuriation of prop-2-ynyl alcohols. Synthesis of N-substituted α-iminoketones, α-di-imines, and α-aminopropionamidines

Addition of primary aliphatic or aromatic amines to prop-2-ynol (1a), 1-phenylprop-2-ynol (5a), and oct-1-yn-3-ol (5b) in the presence of mercury(II) acetate leads to the precipitation of metallic mercury and the formation of the corresponding oxidation products. The oxidation of alcohols (5a) and (5b) in the presence of aromatic amines leads to α-aminoketones (6), whereas α-di-imines (7) are obtained from aliphatic amines. The reaction of alcohol (1a) and aliphatic amines yields α-di-imines (2); in contrast, α-di-imines (2) or α-aminoamidines (3) can, alternatively, be synthesized from aromatic amines. A mechanism involving the mercury(II) acetate-promoted addition of an amine to a carbon–carbon triple bond and an allylic oxidation, followed by the successive formation of α-iminoketones, α-di-imines, and α-aminoamidines is proposed.

Oxidative alkylation of acetonitrile with methanol: V. A. Kolesnikov, R. V. Yefremov, S. M. Danov and N. V. Lashmanova, Neftekhimiya 23, No. 5, 655–658, 1983

Oxidative alkylation of acetonitrile with methanol: V. A. Kolesnikov, R. V. Yefremov, S. M. Danov and N. V. Lashmanova, Neftekhimiya 23, No. 5, 655–658, 1983

Highly reactive wood pulps for cellulose acetate production

AbstractWood pulps highly reactive in both high‐ and low‐catalyst cellulose acetate processes can be prepared by mercerization and then treatment with alkylene oxides; only trace levels of substitution are required. The fiber inactivating effects of mercerization after drying are overcome, and several acetate properties are improved by this process. The reactivity characteristics cannot be duplicated by similar modifications of nonmercerized fibers; in low catalyst processes such pulps actually show reduced reactivity.

Liquid crystalline polymers, 8. Structurally ordered thermotropic polyesters of glycol ethers

AbstractA series of polysters based on a triad aromatic ester mesogenic unit but containing different poly(alkylene oxide) flexible spacers in the main chain was prepared and its properties examined. The flexible spacers consisted of poly(alkylene oxide)s of varying lengths based on either oligomers of ethylene oxide or propylene oxide. The spacer types, lengths and distributions were found to strongly affect the mesophase and melting behaviors of the polymers. Polymers with spacers having more than 10 units were not liquid crystalline, whereas those of shorter length exhibited mesophase properties. The polymers containing spacers with two, three, or four oxyethylene units showed two mesophases, and the textures of their mesophases suggested that both smectic and nematic phases were formed.

Configurational characteristics of the polysulfides, . Dipole moments and gauche effects in poly (1,3‐dithiocane)

AbstractSeveral earlier studies of poly(alkylene sulfides) have not yielded evidence for a sulfur gauche effect, in contrast to the large attractive gauche effect found particularly in the lower members of the poly(alkylene oxides). In this study the dipole moments at 25°C and the corresponding temperature coefficient of poly(1,3‐dithiocane)Structure based name: poly(thiomethylonethiopentamethylene). [SCH2S(CH2)5]x are calculated in the rotational isomeric‐state approximation, and the results compared to the values determined by experiment. In the calculations the energy Eσ′ = [Eg± − Et] associated with S. . .CH2 interactions in the SCH2SCH2 segment is adjusted to attain agreement between theory and experiment. The results indicate that an extra stabilization energy of ca. 0,9 kcal . mol−1 must be added to these gauche states relative to the trans state (beyond that determined by conformational energy calculations based on semiempirical potential energy functions). This provides the first evidence of a large attractive sulfur gauche effect in the polysulfides, about equal in magnitude to that found for the analogous poly(methylene oxide).

The Preparation and Some Surfactant Properties of Long Chain Alcohol - Alkylene Oxide - Ethylene Oxide (RAE) Block Polymer Nonionics

Three series of RAE block polymers with a general formula, CnAxEy [R : C4C12, A : 1, 2- epoxybutane (BO), styrene oxide (SO), and phenyl glycidyl ether (PGE), x : 211, E : ethylene oxide (EO), y : 540] were prepared by the usnal polyoxyethylatioa of the prodncts obtained by the polyaddition of A to long chain alcohols under the following conditions, catalyst : metallic K, temperature : 110150°C, pressure in N2 atmosphere : 24 atm. The base catalyzed addition of SO mainly gave normal ring-opening products (secondary alcohols). The least EO content required to give a water-soluble product was 3040% for BO series and 45 50% for SO, PGE series. Hydrophobicity of A block was found to increase in the order, propyleae oxide<BO<SO≈PGE, based on the relationship between cloud point and EO content of the products. With respect to surface-tension lowering, foaming and wettiag, BO series showed high ability close to that of alkyl poly (oxyethylene) ethers (CnEy), but, many of PGE series were less efficient. Some of SO amld PGE series with aromatic rings in the A block had a good suspending power for carbon and phthalocyanine. In emulsifying power for xylene, RAE polymers were superior to CnEy and Pluranics. Some discussions were presented on the relation of the structure in RAE polymer to the surfactant properties.

New phosphorus containing cellulose derivatives

The reactions of carboxyl containing cellulose derivatives with trihydroxymethylphosphine and alkylene oxides or aldehydes have yielded phosphonium cellulose derivatives with β and α hydroxyalkyl groups at the phosphorus atom. The use of various carboxycelluloses distinguished by the number and position of the carboxyl groups in the glucopyranose unit showed that they possess high reactivity and the conversions occur at the carboxyl group. In di- and tricarboxylcelluloses steric hindrances are absent since after rupture of the glucopyranose ring the macromolecules have a linear structure. Depending on the structure of the alkylene oxide or aldehyde and also the ratio of the reagents the phosphonium cellulose derivatives obtained are soluble or insoluble in water and retain a fibrous structure in the conditions of phosphorylation and possess reduced combustibility and bactericidal properties.

Retention behaviour of alkylene oxides in reversed-phase high-performance liquid chromatography

Retention behaviour of alkylene oxides in reversed-phase high-performance liquid chromatography

Studies on the synthesis of flame retardants for plastics. Part III. Investigation of products of reaction of phosphorus oxychloride with alkylene oxides by conductometry

Studies on the synthesis of flame retardants for plastics. Part III. Investigation of products of reaction of phosphorus oxychloride with alkylene oxides by conductometry