Showing papers on "Epoxide published in 1969"

Copolymerization of carbon dioxide and epoxide with organometallic compounds

Abstract: Attempts to copolymerize carbon dioxide with epoxide led us to the first success in using carbon dioxide as a direct starting material for synthesizing high polymers. Some organometallic catalyst systems were found to catalyze the alternate copolymerization of carbon dioxide and epoxide, resulting in the formation of polycarbonates, the structures of which were confirmed with the aid of IR, NMR and elemental analysis. Diethylzinc-water system produced a methanol insoluble aliphatic polycarbonate of much higher molecular weight than that produced by polycondensation. Thermal properties of the methanol insoluble polycarbonate were studied by differential thermal analysis and thermogravimetric analysis.

Oil-soluble carboxylic acid phenol esters and lubricants and fuels containing the same

Abstract: Additives for lubricating oils, hydrocarbon oils and power transmitting fluids are oil-soluble esters of hydrocarbon substituted succinic acid, the hydrocarbon being saturated and being a polymer containing at least 50 aliphatic carbon atoms. Examples of the ester are the dimethyl ester of polyisobutene succinic anhydride, the polyisobutene succinic anhydride which has been esterified with polyethylene glycol and further reacted with barium oxide to produce a mixed ester-metal salt and the polyisobutene succinic anhydride which has been esterified with a styrene-allyl alcohol copolymer and then reacted with propylene oxide. Examples are given of the addition of these esters to SAE mineral lubricating oils which may also include the usual additives especially the metal phosphor dithioates and their epoxide adducts.ALSO:The invention comprises an oil-soluble ester of a hydrocarbon-substituted succinic acid, the hydrocarbon being saturated and being a polymer containing at least 50 aliphatic carbon atoms. The ester may be prepared by reacting an alcohol or phenol with a hydrocarbon-substituted succinic anhydride or acid, preferably at 150 DEG to 300 DEG C. and in the presence of an esterification catalyst, by reacting an epoxide or a mixture of an epoxide and water with a hydrocarbon substituted succinic anhydride or acid or acid halide, by reacting maleic acid or anhydride with an alcohol and reacting the obtained mono- or di-ester of maleic acid with the polyolefin, and, finally by esterifying itaconic anhydride or acid and then reacting with the polyolefin. The preferred method is by reacting a polyhydric alcohol having 2-10 OH radicals with 0.5-10 moles of hydrocarbon-substituted succinic anhydride, the hydrocarbon being a polymer of a C2- 6 mono-olefin having a M.Wt. of 700-5000. The examples relate to the treatment of polyisobutene succinic anhydride and of the succinic anhydride of the copolymer of 90 isobutene and 10 piperylene. The esters may be used as lubricant addititives.

Selectivity of the epoxide phenol reaction

Abstract: A method for determining the relative amount of alcohol side reaction which occurs in reactions of epoxy compounds with active hydrogen compounds has been investigated. It involves determining the ratio of rates of the successive reaction, epoxide-active hydrogen compound and epoxide-generated secondary alcohol, in the reaction of epoxide and active hydrogen compound at respectively a 2:1 mole ratio. Rate ratios are reported for the bulk reaction of bisphenol-A and the diglycidyl ether of bisphenol-A under different reaction conditions. The data correlated with the properties of high molecular weight polymers. Amines with β-hydroxyl groups were very selective catalysts.

4-(3-secondary amino-2-hydroxy-proxy) 1 2 5-thiadiazoles

Abstract: 4-(3-(SUBSTITUTED AMINO)-2-HYDROXUPROPOXY)-1,2,5-THIADIAZOLE COMPOUNDS, OPTIONALLY SUBSTITUTED IN THE 3-POSITION OF THE THIADIAZOLE NUCLEUS WHICH EXHIBITS B-ADRENERGIC BLOCKING PROPERTIES AND THUS ARE USEFUL IN THE MANAGEMENT OF ANGINA PECTORIS ARE DESCRIBED. THE PRODUCTS ARE PREPARED BY ONE OF FOUR PRINCIPAL METHODS (1) REACTION OF A 4-HYDROXY-1,2,5-THIADIAZOLE WITH EPIHALOYDRINE TO PROVIDE 4-(3 HALO-2-HYDROXYPROPOXY)-1,2,5-THIADIAZOLE WHICH UPON TREATMENT WIHT ALKALI, FORMS THE EPOXIDE WHICH IS THEN REACTED WITH AN AMINE TO PROVIDE THE DESIRED PRODUCT; (2) REACTION OF A 3-CHLORO(OR BROMO)-4-(3-SUBSTITUTED AMINO-2-HYDROXYPROPOXY)-1,2,5-THIADIAZOLE WITH AN AMINE OR AN N-CONTAINING HETEROCYCLE THAT REPLACES THE 3-CHLOROGROUP; (3) REACTION OF 3-CARBOXY-4-ALLYLOXY-1,2,5-THIADIAZOLE WITH N-BROMOSUCCINIMIDE FOLLOWED BY ESTERIFICATION TO GIVE THE ALKYL ESTER OF 3-CARBOXY-4(3-BROMO-2-HYDROXYPROPOXYL)-1,2,5-THIADIAZOLE WHICH UPON TREATMENT WITH AN AMINE FORMS A 3-CARBONOYL-4-(3SUBSTITUTED AMINO-2-HYDROXYPROPOXY)-1,2,5-THIADIAZOLE AND (4) REDUCTIVE ALKYLATION OF AN R-O-CH2-CO-CH-N2, R-O-CH2-CO-CN3, R-O-CH2-CO-CH=N-OH, R-O-CH2-CO-CH2-NO2, R-O-CH2-CH(-OH)-CH2-NO2, R-O-CH2-CH(-OH)-CN, OR R-O-CH2-CO-CN WHEREIN R IS THE 1,2,5-THIADIAZOLE-4-YL GROUP.

Process for producing copolymer of epoxide and carbon dioxide

Abstract: A PROCESS FOR PRODUCING HIGH MOLECULAR WEIGHT COPOLYMERS OF AN EPOXIDE, SUCH AS PROPYLENE OXIDE, ETHYLENE OXIDE, STYRENE OXIDE, ISOBUTYLENE OXIDE OR EPICHLOROHYDRIN, AND CARBON DIOXIDE, WHEREIN THE COPOLYMERIZATION REACTION OCCURS UNDER THE PRESSURE OF CARBON DIOXIDE GAS AND IN THE PRESENCE OF AN ORGANOMETALLIC COMPOUND AS A CATALYST.

Lubricants and fuels containing epoxide treated esters

Abstract: A PROCESS FOR POST-TREATING OIL-SOLUBLE ESTERS OF MONOOR POLYCARBOXYLIC ACIDS AND POLYHYDRIC ALCOHOLS WITH ORGANIC EPOXIDES THE ACYL MOIETY OF THE ESTERS IS DERIVED FROM MONO- OR POLYCARBOXYLIC ACIDS CONTAINING AT LEAST ABOUT FIFTY ALIPHATIC CARBON ATOMS EXCLUSIVE OF THE CARBOXYL CARBON ATOMS THE PRODUCTS ARE USEFUL AS LUBRICANT AND FUEL ADDITIVES A TYPICAL EXAMPLE OF THE PROCESS WOULD BE THE POST-TREATMENT OF A DIESTER OF POLYISOBUTENYL-SUBSTITUTED SUCCINIC ACID AND SORBITOL WITH PROPYLENE OXIDE

Quinone epoxides. V. The biosynthesis of terreic acid.

Abstract: Tracer studies using the 14C-labeled salts of acetic acid, 6-methylsalicylic acid, and orsellinic acid demonstrate that the carbon skeleton of terreic acid (3,4-epoxy-6-hydroxy-2,5-toluquinone), a metabolite of Aspergillus terreus, is biosynthesized by the acetate–malonate pathway and that 6-methylsalicylic acid is an intermediate in this process. Orsellinic acid does not appear to be involved. Molecular 18O is incorporated into the metabolite, and distinction can be made between incorporation at the epoxide oxygen and the three remaining oxygens on the basis of exchange rates. By this method the epoxide oxygen is shown to originate from atmospheric oxygen. The overall biosynthetic pathway is discussed.

Heat-curable compositions of matter

Abstract: Heat-curable epoxide resin mixtures from (1) a polyepoxide with at least one carbocyclic or heterocyclic ring (e.g. ARALDIT CY 175, triglycidylisocyanurate or casting resin F), (2) a polyester containing at least one carbocyclic or heterocyclic ring with terminal carboxyl groups; the ratio of the total chain members Zg to the ring members Zr must be 2 to 13, and the chain contains 2 to 10 recurring structural elements (e.g. polyesters from phthalic acid anhydride and ethyleneglycol 11:10 or from succinic acid and 1,1-bis-(hydroxymethyl)cyclohexane 5:4) in a quantity of 0.2-0.8 equivalent per 1 epoxide equivalent and (3) a polycarboxylic acid anhydride (phthalic acid anhydride, hexahydrophthalic acid anhydride) containing a carbocyclic ring in a quantity of 0.8 to 0.2 equivalent per 1 epoxide equivalent. Cured shaped articles have unexpectedly high tensile strength (to over 900 kg./cm2) and show after gelling very slight shrinkage.

Liquid-phase oxidation of 2-butene in the presence of benzaldehyde

Abstract: The co-oxidation of cis- and trans-2-butene and benzaldehyde at 110 °C has been carried out in benzene and the mechanism of epoxide formation has been investigated by examining the ratio of cis- to trans-epoxides. The results indicate that epoxides were formed by two mechanisms, one involving the benzoylperoxy radical to give about half cis and half trans epoxides and the other by stereospecific epoxidation with perbenzoic acid. Experimental results show that the stereospecific character of epoxidation increases with the reaction time and the concentration of benzaldehyde, but does not depend on the concentration of 2-butene.

Curable compositions containing an epoxide resin and a copolymer o an olefine hydrocarbon with an olefine ester

Abstract: THIS APPLICATION CONCERNS CURABLE COMPOSITIONS COMPRISING: (A) AN EPOXIDE RESIN, (B) DISPERSED IN PARTRICULATE FROM IN (A), A THERMOPLASTIC COPOLYMER OF AN A-OLEFINE HYDROCARBON WITH AN A-OLEFINE WHICH IS AN ETHER OR IS AN ESTER OF A CARBOXYLIC ACID, AND (C) A CURING AGENT FOR EPOXIDE RESINS. THE COPOLYMER (B) IS PREFERABLY AN ETHYLENE-VINYL ACETATE COPOLYMER, AND THE PREFERRED CURING AGENT IS DICYANDIAMIDE. THE COMPOSITIONS MAY ALSO CONAIN A LATENT ACCELERATOR, AND A SECOND THERMOPLAST, SUITABLY A PHENOXY RESIN OR A POLYSULPHONE. FILM ADHESIVES PREPARED FROM THESE COMPOSITIONS FORM BONDS WITH EXCELLENT PEEL STRENGTHS. IN AN EXAMPLE, FILM ADHESIVES WERE EMPLOYED PREPARED FROM BISPHENOL A POLYGLYCIDYL ETHERS HAVING AN EPOXIDE CONTENT OF 5.7 AND 0.25-0.42 EQUIV./KG., DICYANDIAMIDE, IMIDAZOLE (ACCELERATOR), AN ETHYLENE-VINYL ACETATE COPOLYMER, AND A PHENOXY RESIN.

Investigation of the epoxide–carboxylic acid reaction in model compound and polymerization reactions

Abstract: The reaction of epoxide and acid has been studied in the model reaction of bisphenol-A diglycidyl ether and acetic acid with several base catalysts at 60, 95, and 115°C The results suggest that no greater than 5% side reactions occur A series of polyhydroxylester polymers were prepared from bisphenol-A diglycidyl ether and adipic acid The polymers gel rapidly upon heating at 200°C Terpolymers of bisphenol-A diglycidyl ether, bisphenol-A, and azelaic acid were prepared These also gel at 200°C when 50 mole-% of the active hydrogen reactant is azelaic acid

Chromium salicylate catalyzed epoxide-carboxylic acid esterification

Abstract: Esterification reactions between a wide variety of monomeric and polymeric epoxides and carboxylic acids are catalyzed by bis- and tris- chromium(III) complexes with salicylic and substituted salicylic acids.

Carboxyepoxyethyl-1-phosphonic acid and derivatives

Abstract: NOVEL SUBSTITUTED EPOXYETHYLPHOSPHONIC ACIDS AND DERIVATIVES THEREOF ARE PREPARED BY OXIDATIONOF THE CORRESPONDING VINYL COMPOUNDS OR BY TREATING A 1,2-DISUBSTITUTED ETHYLPHOSPHONIC ACID COMPOUND WITH A REAGENT CAPABLE OF EFFECTING EPOXIDE RING CLOSURE. THE NEW SUBSTITUTED EPOXYETHYLPHOSPHONIC ACID COMPOUNDS AND DERIVATIVES SUCH AS THEIR SALTS ARE ANTIBACTERIALS WHICH INHIBIT THE GROWTH OF GRAN-POSITIVE AND GRAM-NEGATIVE BACTERIA.

Epoxidation of olefins with thallic carboxylates

Abstract: THE PROCESS DISCLOSED IS ONE OF OXIDIZING PROPYLENE OR ISOBUTYLENE TO THE CORRESPONDING EPOXIDE. THE OXIDIZING AGENT IS A THALLIC CARBOXYLATE, SUCH A THALLIC ACETATE, AND THE EPOXIDE IS OBTAINED AS PRINCIPAL PRODUCT BY CONTINUOUSLY REMOVING THE VOLATILE OXIDATION REACTION PRODUCTS FROM THE REACTION MIXTURE AS THE OXIDATION PROCEEDS. THE OXIDATION MAY BE CARRIED OUT AT A TEMPERATURE FROM ABOUT 0*C TO ABOUT 170*C.

Advanced addition products containing terminal epoxide groups

Abstract: NEW, SO-CALLED "ADVANCED" ADDUCTS CONTAINING EPOXIDE GROUPS, FROM POLYEPOXIDE COMPOUNDS CONTAINING ON AN AVERAGE MORE THAN ONE EPOXIDE GROUP IN THE MOLECULE AND MONONUCLEAR, FIVE- OR SIX-MEMBERED, UNSUBSTITUTED OR SUBSTITUTED N-HETEROCYLIC COMPOUND WHOSE MOLECULE CONTAINS TWO ENDOCYCLIC NH GROUPS, AND LESS THAN ONE EQUIVALENT NH GROUP FOR EVERY EPOXIDE GROUP EQUIPVALENT OF THE POLYEPOXIDE COMPOUND, OBTAINED BY REACTION OF FOR EXAMPLE 2 MOLS OF DIOMETHANEDIGLYCIDYL EHTER AND 1 MOL OF 5,5-DIMETHYLHYDANTOIN. THE EPOXIDE RESINS "ADVANCED" WITH THE AID OF SUCH NITROGEN COMPOUNDS HAVE A GOOD STORAGE STABLITY IN ADDITION TO EXCELLENT ELECTRICAL PROPERTIES.

Chemistry of the Podocarpaceae. XX. Epoxides of ring-A-unsaturated 12-Methoxypodocarpa-8,11,13-trienes

Abstract: Selective epoxidation of the methoxy alkene mixture (IX) from oxidative decarboxylation of 12-methoxypodocarpa-8,11,13-trien-19-oic acid (I) provides a method of obtaining a high yield of the exocyclic alkene (VII) from the mixture. Isolation of the 3α,4α-epoxide (X) during the epoxidation allows the formation of C 3 oxygenated derivatives of 12- methoxypodocarpa-8,11,13-trien-19-oic acid. Methods for opening the epoxide ring of (X) and of the 4α,5α- and 4α,19-epoxides, (XI) and (XII), have been examined, and the structures of the products from rearrangement of each epoxide with boron trifluoride have been assigned.

Determination of the extent of reaction for the system carboxyl‐terminated polybutadiene‐epoxide beyond the gel point by infrared spectroscopy

Abstract: Curing reactions were investigated after the gel point, using infrared transmittance and reflection spectrophotometric techniques. In the system carboxyl-terminated polybutadiene (CTPB)/Epon X801 or Epotuf STF-6, catalyzed with Fe(III)-acetyl-acetonate (FeAA), at an equivalent ratio of carboxyl to epoxide groups, the final extent of reaction of COOH groups was found to be between 64% and 77% for eight CTPB samples. Increasing the ratio of epoxide to carboxyl groups (up to 1.6) resulted in an increase in the conversion, but the complete reaction of COOH groups could not be accomplished. The final extent of reaction also depends upon the functionality of the crosslinking agent. The lower the functionality of the epoxide, the higher the conversion of COOH groups. The use of chromium naphthenate as a catalyst for epoxide–COOH reactions gave higher conversions than FeAA. This result is related to side reactions catalyzed by the chromium naphthenate. The change in mechanical properties and the change in extent of reaction were followed simultaneously; it was found that no further development of mechanical properties occurred when the curing reaction between COOH and epoxide groups had ceased.

1,6-Anhydro-2-deoxy-β-D-hexopyranoses

Abstract: Three 1,6-anhydro-2-deoxy-β-D-hexopyranoses with the arabino-(XIV), lyxo-(XVIII), and ribo-(XIX) configurations have been synthesized. Hydrolysis of each of these compounds was rapid and proceeded essentially to completion. Their optical rotations are consistent with a chair-like conformation. 1,6:2,3- and 1,6:3,4-Dianhydro-β-D-allopyranoses, (XI) and (XIII), have also been prepared; these complete the series of isomeric epoxide derivatives of the 1,6-anhydro-D-hexopyranoses.

Reactions of organic peroxides. Part XI. Amino-peroxides from cyclic ketones

Abstract: It has been found that reaction of various cyclic ketones (cyclopentanone, 2-methyl-, 3-methyl-, 4-methyl- and 3,3,5-trimethylcyclohexanone and cycloheptanone) with hydrogen peroxide and ammonia produces the corresponding 1,1′-peroxydicycloalkylamine and, in some cases, the 1-hydroperoxycycloalkylamine. From cyclododecanone only the hydroperoxy-amine was obtained, whereas isophorone gave, in addition to its epoxide, both 2,3-epoxy-1-hydroperoxy-3,5,5-trimethylcyclohexylamine and 1,1′-peroxybis(2,3-epoxy-3,5,5-trimethylcyclohexyl)amine. The reactions of these peroxides studied included: (i) the formation of unsymmetrical peroxyamines from 1-hydroperoxy-3,3,5-trimethylcyclohexylamine and carbonyl compounds, and (ii) thermal and base-catalysed decomposition of some of the peroxy-amines, both symmetrical and unsymmetrical.

Storage stable heat-currable soluble and fusible precondenates based on polyepoxide compounds acid polyesters and anhydride curing agents

Abstract: CURABLE B-STAGE FROM (1) A POLYEPOXIDE WITH AT LEAST ONE CARBOCYCLIC OR HETEROCYCLIC RING (FOR EXAMPLE ARALDIT CY 175, TRIGLYCIDYL ISOCYANURATE OR CASTING RESIN F), (2) A POLYESTER CONTAINING AT LEAST ONE CARBOCYCLIC OR HETEROCYCLIC RING, WITH TERMINAL CARBOXYL GROUPS, WITH THE RATIO OF THE TOTAL CHAIN MEMBERS ZG TO RING MEMBERS ZR HAVING TO BE 2 TO 13, AND WITH THE CHAIN POSSESSING 2-10 RECURRING STRUCTURAL ELEMENTS (FOR EXAMPLE POLYESTERS FROM PHTHALIC ANHYDRIDE AND ETHYLENE GLYCOL 11:10 OR FROM SUCCINIC ACID AND 1,1-BIS(HYDROXYMETHYL)-CYCLOHEXANE 5:4) IN AMOUNTS OF 0.2-0.8 EQUIVALENT PER 1 EPOXIDE EQUILVALENT, AND (3) A POLYCARBOXYLIC ACID ANHYDRIDE CONTAINING A CARBOCYCLIC RING (PHTHALIC ANHYDRIDE, HEXAHYDROPHTALIC ANHYDRIDE) IN AN AMOUNT OF 0.8-0.2 EQUIVALENT PER 1 EPOXIDE EQUIVALENT.

Process for retarding the hardening of epoxide resins using a barbituric retarder and retarding compositions

Abstract: A PROCESS FOR RETARDING THE HARDENING OF AN EPOXIDE RESIN AT ELEVATED TEMPERATURES WHICH COMPRISES ADMIXING A RETARDING AMOUNT OF A BARBITURIC COMPOUND HAVING THE FORMULA 1,3-DI-R2,2-Y=,5-R1-PERHYDROPYRIMIDINE-4,6-DIONE WHEREIN Y IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF O AND S, R2 REPRESENTS MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL HAVING FROM 1 TO 8 CARBON ATOMS, PHENYL, AND HALOGEN AND NITRO SUBSTITUTED DERIVATIVES THEREOF, AND R1 REPRESENTS MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, NITRO AND NITROSO, TO A HARDENABLE MIXTURE OF (1) A HARDENABLE EPOXIDE COMPOUND CONTAINING MORE THAN ONE EPOXIDE GROUP IN THE MOLECULE AND (2) AN ORGANIC POLYCARBOXYLIC ACID ANHYDRIDE EPOXIDE RESIN HARDENER, SAID HARDENABLE MIXTURE BEING MAINTAINED AT A TEMPERATURE SUFFICIENT TO CAUSE AN EPOXIDE RESIN HARDENING REACTION. THE COMPOSITIONS CONTAINING THE BARBITURIC COMPOUNDS DELAY THE HARDENING OF THE HARDENABLE EPOXIDE RESIN MIXTURE FOR VARYING TIMES DEPENDING ON THE AMOUNT OF RETARDING COMPOUND UTILIZED AS WELL AS THE HARDENABLE EPOXIDE RESIN AND THE TEMPERATURE.

The mechanism of epoxide reactions. Part XII. Reactions of ethylene oxide with alcohols in the presence of sodium alkoxides and of tertiary amines

Abstract: The kinetics of the base-catalysed solvolyses of ethylene oxide in a series of alcohols have been studied and comparisons made between reactions catalysed by sodium alkoxides and reactions catalysed by tertiary amines. In the former case the reactions take place in a single step and the effects of substituent groups on reactivity tend to cancel, so that in the temperature range 60–70° the rates in nine alcohol–alkoxide combinations are all very similar.The amine-catalysed reactions take place in several stages, the active catalyst in the case of triethylamine at temperatures below 50° being triethyl-2-hydroxyethylammonium alkoxide, formed by an initial relatively slow reaction between triethylamine and ethylene oxide and subsequent rapid equilibration of the resulting zwitterion with solvent. With a series of nuclear-substituted NN-dimethylanilines nucleophilic catalysis was also demonstrated and at higher temperatures this probably constitutes the major reaction route for reactions catalysed by tertiary amines. General base catalysis by tertiary amines was shown to be negligible in all the solvents studied.