US3651098A - Polyglycidyl esters - Google Patents

Polyglycidyl esters Download PDF

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US3651098A
US3651098A US792749*A US3651098DA US3651098A US 3651098 A US3651098 A US 3651098A US 3651098D A US3651098D A US 3651098DA US 3651098 A US3651098 A US 3651098A
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mols
ester
anhydride
theory
glycol
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Alfred Heer
Karl Metzger
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BASF Schweiz AG
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Ciba AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/307—Other macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the subject of the present invention is new long-chain polyglycidyl esters containing aliphatic or cycloaliphatic acid residues, of general formula wherein R and R independently of each another denote a residue, obtained by removal of the carboxyl groups, of an aliphatic or cycloaliphatic polycarboxylic acid having 2 to 4 carboxyl groups, A represents the residue, obtained by removal of the two hydroxyl groups, of a polyalkylene glycol of average molecular weight of at least 200, and wherein m and n denote integers having a value of at least 1 and at most 3, preferably 1 or 2.
  • R and R denote the residue of a mononuclear cycloaliphatic polycarboxylic acid or of an aliphatic polycarboxylic acid having 2 or 3 carboxyl groups and in which the residue A is derived from a polyalkylene glycol which is built up of alkylene glycol units having 2 to 6 carbon atoms are, in addition to being distinguished by easy accessibility, also distinguished by particularly valuable technical properties.
  • Particularly preferred compounds are the symmetrical diglycidyl esters of formula A denotes the residue, obtained by removal of the two hydroxyl groups, of a polyalkylene glycol of formula wherein Alkylene is an alkylene residue having 2 to 6 carbon atoms and the number x is so chosen that the A lkylene- H IT LU;
  • average molecular weight of the polyalkylene glycol is a least 200, preferably 250 to 2500.
  • the polyglycidyl esters according to the invention are as a rule liquid at room temperature.
  • the compounds derived from polyalkylene glycols having higher glycol structural units such as for example polyhexanediol are mostly solid and crystalline.
  • the new polyglycidyl esters of Formula I can be manufactured by reacting a partial ester of formula wherein R R A, m and n have the same significance as in Formula I and Cat denotes a cation, preferably hydrogen or alkali metal, in a single stage or several stages, with an epihalogenohydrin or B-methylepihalogenohydrin with elimination of Cat-Hal, denotes the halogen atom of the epihalogenohydrin or B-methylepihalogenohydrin, in a manner which is in itself known.
  • alkali salts of the partial esters such as for example the di-sodium salt of the half-ester from 1 mol of a polypropylene glycol of molecular weight 425 and 2 mols of hexahydrophthalic anhydride at elevated temperature with an excess of the epihalogenohydrin or B-methylepihalogenohydrin such as epichlorhydrin or fi-methylepichlorhydrin, filtering off the inorganic salt which has separated out and distilling off the excess epichlorhydrin.
  • alkali salts of the partial esters such as for example the di-sodium salt of the half-ester from 1 mol of a polypropylene glycol of molecular weight 425 and 2 mols of hexahydrophthalic anhydride at elevated temperature
  • the epihalogenohydrin or B-methylepihalogenohydrin such as epichlorhydrin or fi-methylepichlorhydrin
  • the partial ester in the form of the free acid with an excess of epihalogenohydrin, that is to say as a rule in an amount of more than 2 mols per free carboxyl group, in the presence of suitable catalysts such as for example tertiary amines quaternary ammonium salts or ion exchanger resins, in a single stage to give the glycidyl ester.
  • suitable catalysts such as for example tertiary amines quaternary ammonium salts or ion exchanger resins
  • the excess epihalogenohydrin then eliminates hydrogen halide from the halogenohydrin ester groups with the formation of glycidyl ester groups and of an equivalent quantity of glycerine dihalogenohydrin.
  • the latter is distilled off after the completion of the reaction, together with epihalogenohydrin, and can be regenerated by treatment with strong alkalis to give the epihalogenohydrin.
  • Such a single-stage catalytic process is for example described in German patent specification 1,165,030.
  • the process sufi'ers from the disadvantage of yielding relatively impure products which, as a result of major proportions of halogenohydrin esters, possess a relatively low epoxide oxygen content and a high halogen or chlorine content.
  • the new glycidyl esters according to the invention, of Formula I are preferably manufactured by reactingan epihalogenohydrin, preferably epichlorhydrin, in the presence of a catalyst such as preferably a tertiary amine or a quaternary ammonium base or a quaternary ammonium salt, with a partial ester of Formula IV and treating the resulting product containing halogenohydrin groups with reagents which remove hydrogen halide.
  • a catalyst such as preferably a tertiary amine or a quaternary ammonium base or a quaternary ammonium salt
  • Suitable catalysts for the addition of epichlorhydrin are above all tertiary amines such as triethylamine, tri-npropylamine, benzyldimethylamine, N,N'-dimethylaniline and triethanolamine; quaternary ammonium bases such as bcnzyltrimethylammonium hydroxide; quaternary ammoiiiumsalts such as tetramcthylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, bcnzyltrimethylammonium acetate, methyltriethylammonium chloride; and furthermore ion exchanger resins having tertiary or quaternary amino groups, and also trialkylhydrazonium salts such as trimethylhydrazonium iodide.
  • quaternary ammonium bases such as bcnzyltrimethylammonium hydroxide
  • Suitable catalysts are furthermore also low molecular thioesters and sulphonium salts or compounds which can change into thioethers or sulphonium compounds with the epihalogenohydrins, such as hydrogen sulphide, sodium sulphide or mercaptans.
  • thioethers or sulphonium salts there may be mentioned: diethyl sulphide, B-hydroxyethyl ethyl sulphide, fi-hydroxypropyl ethyl sulphide, w-hydroxy-tetramethylene ethyl sulphide, thiodiglycol, mono-B-cyanoethyl thioglycol ether, dibenzyl sulphide, benzyl ethyl sulphide, benzyl butyl sulphide, trimethylsulphonium iodide, tris- (fl-hydroxyethyl)sulphonium chloride, dibenzylmethylsulphonium bromide, 2,3-epoxypropylmethylethylsulphonium iodide, dodecyl methyl sulphide and dithiane.
  • Strong alkalis such as anhydrous sodium hydroxide or aqueous sodium hydroxide solution are as a rule used for the dehydrohalogenation but it is also possible to employ other alkaline reagents such as potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate or potassium carbonate.
  • the dehydrohalogenation can in turn be carried out in several stages.
  • Possible epihalogenohydrins are epibromhydrin and above all epichlorhydrin. Good yields are obtained if an excess of epichlorhydrin, and in particular preferably 5 to 40- mols of epichlorhydrin per carboxyl group, are used.
  • a partial epoxidation of the bischlorhydrin ester of the partial ester (IV) already takes place.
  • the epichlorhydrin which acts as a hydrogen chloride acceptor is thereby partially converted to glycerine dichlorohydrin. This is again regenerated to give epichlorhydrin on treatment with alkali.
  • polyglycidyl esters of partial esters from 1 mol of a low molecular polyalcohol or glycol (molecular weight at most about 150) such. as, ethylene glycol, diethylene glycol or triethylene glycol and n or 2 mols of a dicarboxylic acid anhydride such as phthalic anhydride have already been described separately manufactured in one stage and then converted with epichlorohydrin into the polyglycidyl esters (compare German published specification 1,165,030), or the partial esters are produced on glycidylation in situ by reacting a mixture of epichlorhydrin, dicarboxylic acid anhydride and polyalcohol or polyglycol.
  • a low molecular polyalcohol or glycol molecular polyalcohol or glycol
  • the partial esters of Formula ilV used as starting compounds can for example be manufactured according-to known processes by reaction of 2 mols of an aliphatic or cycloaliphatic polycarboxylic acid anhydride with 1 mol of a polyalkylene glycol of formula.
  • HO-A-OH (v) wherein the symbol A has the same significance as in Formula I and wherein the polyalkylene glycol (V) has an average molecular weight of at least 200, preferably 250-2500.
  • aliphatic polycarboxylic acid anhydrides there may be mentioned: succinic anhydride, dodecyl succinic anhydride, adipic acid polyanhydride, sebacic acid polyanhydride; 4-carboxybutane-l,Z-dicarboxylic acid anhydride, maleic anhydride, adducts of maleic anhydride to unsaturated aliphatic hydrocarbons such as dipentene or tetrapropylene.
  • Suitable cycloaliphatic polycarboxylic acid anhydrides are for example: hexahydrophthalic anhydride, 4-methyl-" hexahydrophthalic anhydride, A -tetrahydrophthalic anhydride, 4-methyl-A tetrahydrophthalic anhydride and the isomer mixtures obtained by isomerisation of tetrahydrophthalic anhydride in the presence of suitable catalysts such as metallic palladium or ruthenium (compare U.S. Pat.
  • Possible polyalkylene glycols of Formula V are above all the polyethylene glycols, polypropylene glycols, polybutylene glycols or polyhexanediols having an average molecular weight of at least 200, and prefarably molecular weights of about 250 to about 2500.
  • the new polyglycidyl esters, according to the invention, of Formula I react with the usual curing agents for epoxide compounds and can therefore be cross-linked or cured by adding such curing agents, analogously to other polyfunctional epoxide compounds or epoxide resins.
  • Possible curing agents of this kind are basic or acid compounds.
  • the curing properties of the polyglycidyl esters (I) can vary depending on the acid strength of the polycarboxylic' acid incorporated. Derivatives of strong dicarboxylic acids -value less than 4) as a rule already cure completely in the cold with amine curing agents whilst derivatives of weaker polycarboxylic acids as a rule can only be cured by 'warming.
  • amines or amides such as aliphatic, cycloaliphatic or aromatic, primary, secondary and tertiary amines, for example monoethanolamine, ethylene diamine, hexamethylene diamine, trimethylhexamethylene diamine,
  • diethylene triamine triethylene tetramine, tetraethylene pentamine, N,N-dimethylpropylene diamine-1,3, N,N-diethylpropylene diamine-l,3, 2,2-bis(4'-aminocyclohexyl) propane, 3,5,5-trimethyl-3-(-aminomethyl) cyclohexylamine (isophorone diamine), Mannich bases such as 2,4,6-tris(dimethylaminomethyl)phenol; m-phenylene diamine, p-phenylene diamine, bis(4-aminophenyl)-methane, bis(4-aminophenyl)sulphone and m-xylylene diamine; adducts of acrylonitrile or monoepoxides such as ethylene oxide or propylene oxide, to polyalkylene polyamines such as diethylenetn'amine or triethylenetetramine; adducts from polyamines such as diethylenetriamine or tri
  • curing accelerators in the cure, and in particular when using polyamides, polymeric polysulphides or polycarboxylic acid anhydrides as curing agents;
  • accelerators are for example: tertiary amines, their salts or quaternary ammonium compounds, for example 2,4,6-tris(dimethylaminomethyl) phenol, benzyldimethylamine, 2-ethyl-4-methyl-imidazole, and triamylammonium phenolate; or alkali metal alcoholates such as for example sodium hexanetriolate.
  • the expression curing relates to the conversion of the above-mentioned diepoxides into insoluble and infusible cross-linked products and in fact as a rule with simultaneous shaping to give shaped articles such as castings, pressings or laminates or to give twodimensional articles such as coatings, lacquer films or adhesive bonds.
  • the shaped articles in general show a low water absorption, good notched strength, high tensile strength and high elongation at break.
  • the technical products of low chlorine content of about 0.5% are furthermore distinguished by particularly advantageous corrosion behaviour (for example when used for embedding or cementing metallic conductors).
  • active diluents such as for example styrene oxide, butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and glycidyl esters of synthetic highly branched mainly tertiaryaliphatic monocarboxylic acids (Cardura E), or cycloaliphatic monoepoxides such as 3-vinyl-2,4-dioxaspiro(5,5)-9,10-epoxyundecane can be added to the diepoxides according to the invention in order to lower the viscosity.
  • active diluents such as for example styrene oxide, butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and
  • the diepoxides according to the invention can furthermore be used as mixtures with other curable diepoxide or polyepoxide compounds.
  • polyglycidyl ethers or polyhydric alcohols such as 1,4-butanediol, polyethylene glycols, polypropylene glycols or 2,2-bis(4'-hydroxycyclohexyl) propane
  • polyglycidyl ethers of polyhydric phenols such as 2,2-bis-(4'-hydroxyphenyl)propane (:bisphenol A), 2,2(4-hydroxy-3',5-dibromophenyl)propane, bis(4 hydroxyphenyl)-sulphone, 1,1,2,2 tetrakis(4'-hydroxyphenyl)ethane or condensation products of formaldehyde with phenols manufactured in an acid medium, such as phenol novolacs or cresol novolacs; polyglycidyl esters of polycarboxylic acids such as for
  • Curable mixtures which are suitable for the manufacture of shaped articles including two-dimensional structures and which contain the polyepoxides according to the invention, optionally together with other diepoxide or polyepoxide compounds and furthermore curing agents for epoxide resins such as polyamines or polycarboxylic acid anhydrides are therefore also a subject of the present invention.
  • polyglycidyl esters according to the invention or their mixtures with other polyepoxide compounds and/or curing agents can furthermore, in any stage before curing, be mixed with the usual modifiers such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticisers, levelling agents, agents which confer thixotropy, flame-inhibiting substances or mould release agents.
  • modifiers such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticisers, levelling agents, agents which confer thixotropy, flame-inhibiting substances or mould release agents.
  • extenders reinforcing agents, fillers and pigments which can be employed in the curable mixtures according to the invention: anthracite tar, bitumen, glass fibres, boron fibres, carbon fibres, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, quartz powder, slate powder, aluminium trihydrate, chalk powder, gypsum, antimony trioxide, bentones, silica aerogel (Aerosil), lithopone, barytes, titanium dioxide, carbon black, graphite, iron oxide or metal powder such as aluminium powder or iron powder.
  • organic solvents for the modification of the curable mixtures: toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone-alcohol, ethylene glycol monomethyl ether, monoethyl ether and monobutyl ether.
  • Dibutyl, dioctyl and dinonyl phthalate, tricresyl phosphate, trixylenyl phosphate and also polypropylene glycols can for example be employed as plasticisers for modifying the curable mixtures.
  • the new polyglycidyl esters can furthermore be partially or completely esterified in a known manner with carboxylic acids such as especially higher unsaturated fatty acids. It is furthermore possible to add other curable synthetic resins, for example phenoplastics or aminoplastics, to such lacquer formulations.
  • the curable mixtures can, in the unfilled or filled state, optionally in the form of solutions or emulsions, serve as laminating resins, paints, lacquers, dipping resins, impregnating resins, casting resins, pressing compositions,
  • EXAMPLE 1 (a) Manufacture of the partial ester 616 g. (4 mols) of hexahydrophthalic anhydride and 850 g. (2 mols) of polypropylene glycol having an average molecular weight of 425 and 4.7 equivalents of hydroxyl groups/ kg. were initially introduced into a suitable reaction vessel and warmed to 130 C. whilst stirring. A slightly exothermic reaction set in. After 60 minutes at 130 C. and a further 30 minutes at 140 C. the mixture was cooled to 90 C. and a sample was titrated to determine the acid content. The titration showed 2.75 equivalents/kg. of free acid groups (theory: 2.73 equivalent/ kg.), which is equivalent to practically quantitative forma tion of the half-ester.
  • the pH electrode was removed and a dropping funnel containing 400 g. (5 mols) of aqueous 50% strength sodium hydroxide solution was attached.
  • the reaction mixture was cooled to 55 C. and a further 20 g. of aqueous 50% strength solution of tetramethylammonium chloride were added.
  • the apparatus was subjected to a vacuum and the sodium hydroxide solution was allowed to run in continuously over the course of 80 to 120 minutes at 70 to 100 mm. Hg and at an internal temperature of 52 to 58 C., with the water introduced and the water formed being azeotropically distilled off with epichlorhydrin.
  • the epichlorhydrin was separated from the water in a water separator and continuously returned to the reaction mixture. A total of 300 ml. of water was separated off.
  • the apparatus was vented and the reaction mixture was successively washed in the separating funnel with 1000 ml. of water, 700 ml. of aqueous 5% strength monosodium phosphate solution and 700 ml. of water whilst warm.
  • the epichlorhydrin solution is very concentrated (45% solids content) and can therefore in isolated cases form stable emulsions on washing. It was possible to destroy such emulsions by adding 100 to 250 ml. of ethanol.
  • the epichlorhydrin solution was concen trated in a rotary evaporator under a water-jet vacuum. The residue was dried for 45 minutes at 120 C. under a vacuum of about 1 mm. Hg and then filtered through a pressure filter with Hyfio and filter paper. 1653 g. (97.8% of theory) of a pale yellow clear liquid non-crystallising product were obtained.
  • the analytical values were:
  • Epoxide content 2.3 equivalents/kg. (97.4% of theory) Chlorine content: 0.4% Viscosity (at 25 C.): 1500 cp. (Hoeppler viscometer)
  • the product mainly consisted of the following compound The partial ester from 2'rnols of hexahydrophthalic' anhydride and 1 mol of polypropylene glycol of average molecular weight 1025 was manufactured inan analogous manner to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 1. The following amounts were employed for this purpose: 1025 g.
  • Epoxide content 1.4, equivalents/kg. (99.4%, of theory)
  • Chlorine content 0.2-%.-
  • Crystal transition temperature measured in a differential calorimeter: 42 C.
  • the product mainly consists of the following compound:
  • n about 34.2 (average value).
  • EXAMPLE 6 The partial ester was manufactured from 2 mols of 4- methyl-A -tetrahydrophthalic anhydride and 1 mol of polyethylene glycol of average molecular weight 1450 in an analogous manner to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 1.
  • the following quantities were employed for this purpose: 1450 g. (1 mol) of polyethylene glycol of average molecular weight 1450 (commercial product of Union Carbide obtainable under the registered name Carbowax 1540)--the material was dried for 4 hours at 140 C. under a high vacuum before use and then had 1.38 equivalents of hydroxyl groups/kg; 332 g.
  • Viscosity (at 25 0.): 2100 cp. (Hoeppler viscometer).
  • the product mainly consists of the isomer mixture of the following compounds which are positional isomers (the methyl groups can be in the 4-position or S-position relative to the glycidyl ester groups on the ring).
  • the partlal ester was manufactured from 2 mols of (24 111015) of epichlorhydrin, 200 g, (2% 1 1013) of aquel maleic anhydride and1 mol Of poly-tetram'ethylene' ether 011s sodium hydroxide solution (50% strength) and 2 x20 5 glycol (P y y y of average molecular of mtm thyhmm nim hl idel ti 50% I weight 1000 in an analogous manner to that described strength in water; p in Example 1 and the glycidyl ester was obtained there- 1377, g 93 g% of theory) of light brown clear 1 i "from in the same manner as in Example 1.
  • the product mainly consists of the isomer mixture of epichlorhydrin, 200 g. (2 /2 mols) of aqueous sodium the following compounds which are positional isomers, it hydroxide solution (50% streng h) and 2X g. of tetrabeing possible herein for the methyl groups to be in the methylammonium chloride solution, 50% strength in 3-position, 6-position or 7-position of the bicyclic nucleus: water.
  • the partial ester was manufactured from 2 mols of 3,4,5,6,7,7-hexachlor 3,6 endomethylene-A -tetrahydro- Epoxide content: 1.25 equivalents/kg. (81.8% of theory) phthalic anhydride and 1 mol of polypropylene glycol of Chlorine content: 2.2% average molecular weight 425 in an analogous manner Viscosity (at 25 C.): 7500 cp. (Hoeppler viscometer) to that described in Example 1 and the diglycidyl ester was obtained therefrom in the same manner as in Example 40 The p t is n t Stable and t t peratures above 1. The following quantities were employed: 425 g. (1 100 C. a volatile compound is eliminated which can be mol) of polypropylene glycol of average molecular weight distilled in Vacllo, e epoxide content at the same;
  • Chlorine content 33.6% (101% of theory) f o ollowrng quantities were employed for this purpose: 1025 vlscoslty (at 25 30,000 p. oeppler-vls g.”(1 mol) of polypropylene glycol of average molecular
  • the product mainly consists of the following comweight 1025 and having 1.95 equivalents of hydroxyl pound:
  • Chlorine content 05%
  • the following quantities were employed: 600 g. (1 mol)
  • tered name Carbowax 600)the material was dried for 4 hours at 140 C. under a high vacuum before use and EXAMPLE 12 5 then had 3.35 equivalents of hydroxyl groups per kg.; .
  • the partial ester was manufactured from polysebaclc 870 g. of Admerginat A having an anhydride conten acid anhydride and polyhexamethylene ether glycol of 2.3 equivalents/kg.
  • Epoxide content 2.2 equivalents/kg. (93.2% of theory) Chlorine content: 0.3% Viscosity (at C.): 7900 cp. (Hoeppler viscometer)
  • Glycidyl ester according to Example No 1 1 2 Parts by weight of glycidyl ester 100 100 24 Parts by weight of epoxide resin 0 Parts by weight of hexahydrophthalic anhydride" Parts by weight of benzyldiinetlzlylamlne- 0. 2 0. 2 15 Parts by weight of quartz 0 0 0 '0 0 Tensile strength according to DIN 0. 9 6. 4 6. 0 2. 6 0. r
  • Glycldyl ester according to Example No Parts by weight of glycldyl ester ,p Parts by weight of epoxide resin 0... Parts by weight of triethylene tetramine .5... I Tensile strength according to DIN. kgJmmJ--.
  • Epoxide resin D by way of comparison, the partial; ester was manufactured from 2 mols of hexahydrophthalic anhydride and 1 mol of ethylene glycol in an analogous 17 18 manner to Example 1, and the diglycidyl ester (epoxide We claim: resin D) obtained therefrom in the same manner as in 1.
  • the yield was 91% of theory; the product wherein R and R each represent a residue, obtained by had the following analytical values: removal of the carboxyl groups, of an aliphatic or cycloaliphatic polycarboxylic acid having 2 to 4 carboxyl Total chlorine content: 1.0% (according to Wurzschmitt) 322, 8 g sggi gz gs gi g ggi zigigii a i -Zia: vlscoslty' (at 9700 (Hoeppler vlscometer) age molecular weight of at least 200, and wherein m and Epoxide resm E: the partlal ester Was mauufa fl n are integers having a value of at least 1 and at most 3.
  • the yield was 94% of theory; the prodr t th 'd b not had the followmg analytlc a1 values: groups A epresen s e resl ue o tamed by removal of the two hydroxyl groups, of a polyalkylene glycol of aver- Epoxide content: 4.1 equivalents/kg. (98% of theory) age molecular Wtfight of at least and wherein m and Total chlorine cont nt; 10% (according t W n are integer having a value of at least 1 and at most 2.

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US792749*A 1968-01-29 1969-01-21 Polyglycidyl esters Expired - Lifetime US3651098A (en)

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CH131468A CH502402A (de) 1968-01-29 1968-01-29 Verfahren zur Herstellung von neuen langkettigen, aliphatische oder cycloaliphatische Säurereste enthaltenden Polyglycidylestern

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860541A (en) * 1971-12-24 1975-01-14 Ciba Geigy Corp Storage-stable, rapidly curable epoxide resin composition
US3953479A (en) * 1973-09-04 1976-04-27 Westvaco Corporation Diglycidyl esters of C21 -cycloaliphatic dicarboxylic acid
US4993607A (en) * 1989-07-10 1991-02-19 General Electric Company Transfer tube with in situ heater
US5480960A (en) * 1993-07-15 1996-01-02 Shell Oil Company Process for the preparation of an acid functional polyester resin
US5739213A (en) * 1995-01-06 1998-04-14 Shell Oil Company Acid functional and epoxy functional polyester resins
US6107442A (en) * 1997-02-21 2000-08-22 Shell Oil Company Outdoor durable coating compositions and acid functional polyester resins and polyglycidyl esters thereof usable therefor
US6187875B1 (en) 1997-03-25 2001-02-13 Shell Oil Company Acid functional polyester resins and lower temperature curable powder coating compositions comprising them
US6201070B1 (en) * 1996-11-20 2001-03-13 Union Carbide Chemicals & Plastics Technology Corporation Method for enhancing the toughness of cycloaliphatic epoxide-based coatings
WO2023074390A1 (ja) * 2021-10-27 2023-05-04 日産化学株式会社 液晶配向剤、液晶配向膜、液晶表示素子、及び化合物

Families Citing this family (8)

* Cited by examiner, † Cited by third party
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FR2464245A1 (fr) * 1979-08-27 1981-03-06 Solvay Diacides carboxyliques chlorobromes et procedes pour leur fabrication et leur utilisation
IT1189716B (it) * 1985-02-14 1988-02-04 Asolo Sport Srl Procedimento per la realizzazione di calzature
US5218045A (en) * 1987-03-27 1993-06-08 North Dakota State University Coating binders comprising liquid crystalline enhanced polymers
US5043192A (en) * 1988-03-15 1991-08-27 North Dakota State University Polymeric vehicle for coating
US5171765A (en) * 1987-03-27 1992-12-15 North Dakota State University Water dispersible polymers for coatings based on polymers containing mesogenic groups
US5244699A (en) * 1987-03-27 1993-09-14 North Dakota State University Polymeric vehicle for coatings
US5235006A (en) 1987-03-27 1993-08-10 North Dakota State University Mesogens and polymers with mesogens
GB8825057D0 (en) * 1988-10-26 1988-11-30 Shell Int Research Novel polygycidyl esters their preparation & their use in thermosetting compositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860541A (en) * 1971-12-24 1975-01-14 Ciba Geigy Corp Storage-stable, rapidly curable epoxide resin composition
US3953479A (en) * 1973-09-04 1976-04-27 Westvaco Corporation Diglycidyl esters of C21 -cycloaliphatic dicarboxylic acid
US4993607A (en) * 1989-07-10 1991-02-19 General Electric Company Transfer tube with in situ heater
US5480960A (en) * 1993-07-15 1996-01-02 Shell Oil Company Process for the preparation of an acid functional polyester resin
US5739213A (en) * 1995-01-06 1998-04-14 Shell Oil Company Acid functional and epoxy functional polyester resins
US5811198A (en) * 1995-01-06 1998-09-22 Shell Oil Company Acid functional and epoxy functional polyester resins
US6201070B1 (en) * 1996-11-20 2001-03-13 Union Carbide Chemicals & Plastics Technology Corporation Method for enhancing the toughness of cycloaliphatic epoxide-based coatings
US6107442A (en) * 1997-02-21 2000-08-22 Shell Oil Company Outdoor durable coating compositions and acid functional polyester resins and polyglycidyl esters thereof usable therefor
US6187875B1 (en) 1997-03-25 2001-02-13 Shell Oil Company Acid functional polyester resins and lower temperature curable powder coating compositions comprising them
WO2023074390A1 (ja) * 2021-10-27 2023-05-04 日産化学株式会社 液晶配向剤、液晶配向膜、液晶表示素子、及び化合物

Also Published As

Publication number Publication date
GB1255504A (en) 1971-12-01
CH502402A (de) 1971-01-31
DE1966703C3 (de) 1979-07-26
NL6901372A (en)van) 1969-07-31
BR6905961D0 (pt) 1973-01-11
FR2000897A1 (en)van) 1969-09-19
DE1966703B2 (de) 1978-11-23
DE1904110B2 (de) 1973-12-06
DE1966703A1 (de) 1973-10-11
DE1904110C3 (de) 1974-07-25
DE1904110A1 (de) 1969-11-06
BE727516A (en)van) 1969-07-28
AT289134B (de) 1971-04-13

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