MXPA99001263A - Polyglycidyl ethers of secondary alcohols - Google Patents

Abstract

The present invention relates to polyglycidyl ether compounds containing at least three mono- or divalent radicals A of general formula (A) wherein R1 represents (i) a straight chain or branched alkyl groups of 1 to 16 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (ii) a straight chain or branched alkenyl group of 2 to 6 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (iii) a phenyl or naphthyl group, optionally substituted in the ring or rings by one or two chlorine atoms or by one or two alkyl groups, each of 1 to 10 carbon atoms, and having in all from 7 to 30 carbon atoms, or (iv) a phenylalkyl or naphthylalkyl group, optionally substituted in the ring or rings by one or two chlorine or bromine atoms or by one or two alkyl groups, each of 1 to 10 carbon atoms, said phenylalkyl or napthylalkyl group having in all from 7 to 30 carbon atoms, or (v) a mononuclear cycloalkyl group of 3 to 6 carbon atoms, or (vi) a mononuclear cycloalkylalkyl group of from 4 to 10 carbon atoms and R2 represents hydrogen or a straight chain or branched alkyl groups of 1 to 9 carbon atoms. They are prepared by either reacting a polyglycidylether of a polyphenolic compound like an epoxy novolac with an alcohol and then glycidylating the resulting polysecondary hydroxy compound with epichlorohydrin or by reacting the polyphenolic compound with a monoglycidyl ether and then with epichlorohydrin. The invention further relates to processes for making and using the polyglycidyl ether compounds.

Description

POLYGLYCYDIYL ETHES OF SECONDARY ALCOHOLS It has now been found that certain new polyglycidyl ethers of secondary alcohols are curable resins having low viscosity when compared for example with the widely used commercial resin EPNMR 1180 having a viscosity of 20,000 centipoise at 52 ° C. The cured products made from the new compounds present also show improved flexibility and solvent resistance. The resins according to the present invention can be used widely, especially in the fields of coating and encapsulation and specifically electrical coatings. The present invention relates to polyglycidyl ether compounds containing at least three mono- or divalent radicals A of the general formula wherein Ra represents (i) straight or branched chain alkyl groups with 1 to 16 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (ii) a straight or branched chain alkenyl group with 2 to 4 carbon atoms; to 6 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (iii) a phenyl group Naphthyl, optionally substituted on the ring or rings with one or two chlorine or bromine atoms, or on one or two alkyl groups, each having 1 to 10 carbon atoms, and having a total of 7 to 30 carbon atoms , or (iv) a phenyl alkyl or naphthyl alkyl group, optionally substituted in the ring or rings with one or two chlorine or bromine atoms, or by one or two alkyl groups, each with 1 to 10 carbon atoms, the phenyl alkyl or naphthyl group has in total from 7 to 30 carbon atoms, or (v) a mononuclear cycloalkyl group with 3 to 6 carbon atoms, or (vi) a mononuclear cycloalkylalkyl group with from 4 to 10 carbon atoms and R2 represents hydrogen or straight or branched chain alkyl groups with 1 to 9 carbon atoms. The present invention furthermore relates to polyglycidyl ether compounds containing at least three divalent radicals A as previously defined having the following general formulas A-CH2- [A-CH2] n (I) or (A) 3C-R3 (II ) or (A) 2CH-CH (A) 2 (III) wherein n is a number equal to or greater than 1, more preferably from 1 to 50, especially from 1 to 5, and R 3 is hydrogen or CH 3. In a preferred embodiment, R represents straight or branched chain alkyl groups with 1 to 16 carbon atoms and R2 is hydrogen. In a more preferred embodiment, the polyglycidyl ether compound may be represented by the general formula A-CH2- [A-CH2] n-A (I) wherein n is a number from 1 to 5, Rx is C4H9 and R2 is hydrogen. The present invention also relates to a process for the preparation of a polyglycidyl ether compound as previously described, containing at least three mono- or divalent radicals A as defined above, comprising (a) reacting at least an equimolar amount with respect to the glycidyl radicals of the formula B, of an alcohol of the formula X RiOH (X) wherein R 1 was defined as above, with a polyglycidyl ether of a polyhydric phenol containing at least three mono- or divalent radicals B of the general formula wherein R2 is defined as above, in the presence of a basic catalyst or a Lewis acid catalyst that produces a poly-secondary alcohol; and (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst, to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A or (b2) ) reacting the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step, and then in a second step, treating the poly (chlorohydrin) intermediate with an alkali to produce the polyglycidyl ether compound containing the minus three mono- or divalent radicals of the general formula A. In a still further embodiment, the present invention relates to a process for the preparation of a polyglycidyl ether compound as previously described which contains at least three mono- or divalent radicals A , as defined above, comprising (a2) reacting a polyhydric phenol containing a radical R2 and at least three OH- groups with a monoglycidyl ether of the formula XII wherein Rt was previously defined, optionally in the presence of a phase transfer catalyst that produces a poly-secondary alcohol of the formula XIII containing at least three mono- or divalent radicals of the general formula C and (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst, to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A or (b2) ) react the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step and then in a second step, treat the intermediate poly (chlorohydrin) with an alkali, to produce the polyglycidyl ether compound containing the minus three mono- or divalent radicals of the general formula A. Accordingly, this invention provides polyglycidyl ether compounds containing at least three mono- or divalent radicals A of the general formula wherein R2 represents (i) straight or branched chain alkyl groups with 1 to 16 carbon atoms, which may be substituted by one to four chlorine atoms or bromine atoms, or (ii) a straight or branched chain alkenyl group with 2 to 6 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (iii) a phenyl or naphthyl group, optionally substituted in the ring or rings with one or two chlorine or bromine atoms or by one or two alkyl groups, each of 1 to 10 carbon atoms and having in total from 7 to 30 carbon atoms, or (iv) a phenylalkyl or naphthylalkyl group, optionally substituted on the ring or rings by one to two chlorine or bromine atoms and by one or two alkyl groups, each having 1 to 10 carbon atoms, the phenylalkyl or naphthylalkyl group has in total from 7 to 30 carbon atoms, or (v) a mononuclear cycloalkyl group of 3 to 6 carbon atoms, or (vi) a mononuclear cycloalkyl group with 4 to 10 carbon atoms and R2 represents hydrogen or a straight or branched chain alkyl group with 1 to 9 carbon atoms. Preferably, the R1 groups are the same and in particular each represents a straight or branched chain alkyl group with 1 to 14 carbon atoms, an alkyl group, a cyclohexyl group, or a benzyl group. R- is particularly preferred. which is C4H9.

Preferably, R2 is hydrogen. Preferably, the compounds present are of the general formula A-CH2- [A-CH2] nA (I) or (A) 3C-R3 (II) or (A) 2CH-CH (A) 2 (III) wherein n is a number equal to or greater than 1 and R3 is hydrogen or CH3. Preference is given to compounds of the formula (I). In the formula (I), the monovalent radicals A are preferably linked in the m or p position, with respect to the ether group, with the CH2- group. In the formula (I), the CH2- groups are preferably in the position o u o and p, with respect to the ether group in the radical or divalent radicals A. Examples of compounds of the formulas (I), (II) and (III) are: fifteen where E is the radical Additional preferred compounds of the formula (I) are those in which n is a number between 1 and 50 and more preferred a number between 1 and 5. Particularly preferred are compounds of the formula (I) wherein n is a number from 1 to 5, Ri is C4H9 and R2 is hydrogen. The invention also relates to a process for the preparation of a polyglycidyl ether compound containing at least three mono- or divalent radicals A, as previously defined, comprising (a) reacting at least an equimolar amount with respect to the glycidyl radicals of the formula B, of an alcohol of the formula X RxOH (X) wherein Rx is as previously defined, with a polyglycidyl ether of a polyhydric phenol containing at least three mono- or divalent radicals B of the general formula wherein R2 is as previously defined in the presence of a basic catalyst or a Lewis acid catalyst, producing a poly-secondary alcohol; (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst to produce the polyglycidyl ether compound containing at least three < mono- or divalent radicals of the general formula A; or (b2) reacting the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step and then in a second step treating the poly (chlorohydrin) intermediate with an alkali, to produce the polyglycidyl ether compound which it contains at least three mono- or divalent radicals of the general formula A.

Preferably, alcohols are used in which R-_ is an alkyl group with 1 to 14 carbon atoms, an allyl group, a cyclohexyl group, or a benzyl group. Particular preference is given to alcohols in which Rx is an alkyl group having 1 to 14 carbon atoms. Preferred polyglycidyl ethers of a polyhydric phenol are those in which the monovalent radicals B are linked in the m or p position, with respect to the ether group, and the radical or divalent radicals B are bonded in the position o u o and p, with respect to the ether group. Especially preferred polyglycidyl ethers of a polyhydric phenol are of the formula where E is the radical -O S. 1 At least one equimolar amount is employed, with respect to the glycidyl radicals of the formula B of the alcohol, preferably an equimolar amount to a triple molar excess of the alcohol and more preferably a double molar excess of the alcohol. Suitable basic catalysts include tertiary amine, quaternary ammonium base, alkali hydroxide and quaternary ammonium salt. Suitable Lewis acid catalysts include boron trifluoride or its complex, stannic chloride or a compound of the formula [MX], wherein M is a metal of groups IB to VIIB or a metal or metalloid of Groups IIA to VA, of the Periodic Table of the Elements or an ammonium ion and X is an anion selected from the group consisting of BF4 ~, PFS ~, AsF6", A1F4 ~, TiF62 ~, SiF62", and ZrF62. "A preferred catalyst is BF3- etherate or BF3.2H20 Preferred catalysts of the formula [MX] are those wherein M is a metal selected from the group consisting of copper, zinc, iron, magnesium, silver, calcium or a metalloid such as tin or arsenic or an ion Ammonium and X is BF4 ~, SiF62 ~ or PF6 ~ Particularly preferred compounds are Sn (BF4) 2, Fe (BF4) 2, Ca (BF4) 2, Zn (BF4) 2, Mg (BF4) 2, Cu (BF4). ) 2 / NH2BF4, MgSiF6 and AgPF6 More particularly Sn (BF4) 2 / Fe (BF4) 2, Ca (BF4) 2, Zn (BF4) 2, Mg (BF4) 2, Cu (BF4) 2, H4BF4 are preferred. , and AgPF6.The reaction of alcohol with polyglycidyl ether d and a polyhydric phenol is carried out by heating the reactants at a temperature in the range of about 50 to 130 ° C, preferably about 70 to about 120 ° C, and more preferably about 90 to about 110 ° C, without solvent. In the preparation of the polyglycidyl ether compound containing at least three mono or divalent radicals of the general formula A, the remaining residual alcohol after completion of step (a) is conveniently removed by distillation.

The poly-secondary alcohol can then be reacted in step (bl) with an equimolar amount to an eight-fold excess with respect to the secondary alcohol groups, preferably a three-fold excess to a six-fold excess, more preferably a five times excess of epichlorohydrin in the presence of an equimolar amount to an excess of 50%, with respect to the secondary alcohol groups, preferably an equimolar amount to an excess of 10% of an alkali and in the presence of a catalyst phase transfer at a temperature in the range of about 30 to 90 ° C, preferably about 35 to about 75 ° C and more preferably about 40 to about 65 ° C. The poly-secondary alcohol can alternatively then be reacted in step (b2) with an equimolar amount to a five-fold excess, with respect to secondary alcohol groups, preferably an equimolar amount to a 50% excess, of epichlorohydrin in the presence of a Lewis acid catalyst at a temperature in the range of about 30 to 90 ° C, preferably about 35 to about 75 ° C, and more preferably about 40 to about 65 ° C. In both methods (bl or b2) the reaction can be carried out in the presence of a solvent such as a hydrocarbon, an ether or an acetone, but the use of an excess of epichlorohydrin as the solvent is preferred. The reaction is typically conducted at a pressure of 70 to 260 torr in order to maintain an azeotropic reflux of epichlorohydrin-vigorous water. Suitable alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or a mixture thereof. Sodium hydroxide is preferred. Suitable phase transfer catalysts include tetraalkylammonium halide such as ethyltrioctylammonium chloride, methyltridecylammonium chloride or tetramethylammonium chloride, or a tertiary amine or quaternary ammonium base such as benzyltrimethylammonium or quaternary ammonium salt such as benzyltrimethylammonium chloride . Benzyltrimethylammonium chloride is preferred. The phase transfer catalyst is generally employed in an amount of from about 0.1 to about 5% by weight, preferably about 0.5 to about 2.0% by weight and more preferably from about 1.0 to about 1.5% by weight, based on the total weight of the reagents.

Suitable Lewis acid catalysts include boron trifluoride or a complex thereof or stannic chloride. The invention furthermore relates to a process for the preparation of a polyglycidyl ether compound containing at least three mono- or divalent radicals A as defined above, comprising: (a2) reacting a polyhydric phenol containing a radical R2 and minus three OH- groups with a monoglycidyl ether of the formula XII wherein R1 was defined as above, optionally in the presence of a phase transfer catalyst yielding a poly-secondary alcohol of the formula XIII containing at least three mono- or divalent radicals of the general formula C 02 (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A; or (b2) reacting the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step and then in a second step treating the poly (chlorohydrin) intermediate with an alkali to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A. Preferably, monoglycidyl ethers are used in which R-_ is an alkyl group with 1 to 14 carbon atoms, an allyl group, a cyclohexyl group or a benzyl group. Particularly preferred are monoglycidyl ethers wherein Ra is an alkyl group with 1 to 14 carbon atoms. In the preparation of the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A, the monoglycidyl ether is reacted in step (a2) with about 0.2 mol to an equimolar amount, preferably 0.6 to an equimolar amount , more preferably about 0.9 to an equimolar amount, with respect to the OH? phenolic groups, of the polyhydric phenol in the presence of a phase transfer catalyst at a temperature in the range of about 30 to 90 ° C, preferably about 35 ° C. at about 75 ° C, and more preferably about 40 to about 65 ° C. Preferred polyhydric phenols are those in which the monovalent phenol radicals are linked in the m or p position, with respect to the OH group, and the radical or the divalent phenol radicals B are bonded in the position o u o and p to the OH group. Especially preferred polyhydric phenols are of the formula Suitable phase transfer catalysts include tetraalkylammonium halides, such methyltrioctylammonium chloride, methyltridecylammonium chloride or tetramethylammonium chloride or a tertiary amine or quaternary ammonium base such as a benzyltrimethylammonium or quaternary ammonium salt such as benzyltrimethylammonium chloride. Benzyltrimethylammonium chloride is preferred. The phase transfer catalyst is generally employed in an amount of about 0.1 to about 5% by weight, preferably about 0.5 to about 2.0% by weight and more preferably about 1.0 to about 1.5% by weight, based on the weight total of the reagents.

The poly-secondary alcohol can then be reacted in step (bl) with an equimolar amount to an eight-fold excess, with respect to the secondary alcohol groups, preferably a three-fold excess to a six-fold excess, in particular a five times excess of epichlorohydrin in the presence of an equimolar amount to an excess of 50%, with respect to the secondary alcohol groups, preferably in an equimolar amount to a 10% excess of an alkali and in the presence of a phase transfer catalyst at a temperature in the range of about 30 to 90 ° C, preferably about 35 to about 75 ° C, and more preferably about 40 to about 65 ° C. The poly-secondary alcohol can alternatively then be treated in step (b2) with an equimolar amount to a five-fold excess with respect to the secondary alcohol groups, preferably in an equimolar amount to 50% excess, of epichlorohydrin in the presence of a Lewis acid catalyst at a temperature in the range of about 30 to 90 ° C, preferably about 35 to about 75 ° C, and preferable to about 40 to about 65 ° C. In both methods (bl or b2) the reaction can be carried out in the presence of a solvent such as a hydrocarbon, an ether or a ketone, but use of an excess of epichlorohydrin as a solvent is preferred. The reaction is typically conducted at a pressure of 70 to 260 torr in order to maintain an azetropic reflux of water-vigorous epichlorohydrin. Suitable alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or a mixture thereof. Sodium hydroxide is preferred. Suitable phase transfer catalysts include tetraalkylammonium halides such as methyltrioctylammonium chloride, methyltridecylammonium chloride or tetramethylammonium chloride or a tertiary amine or quaternary ammonium base such as benzyltrimethylammonium or quaternary ammonium salt such as benzyltrimethylammonium chloride. Benzyltrimethylammonium chloride is preferred. The phase transfer catalyst is generally employed in an amount of from about 0.1 to about 5% by weight, preferably from about 0.5 to about 2.0% by weight and more preferably from about 1.0 to about 1.5% by weight based on the total weight of the reagents.

Suitable Lewis acid catalysts include boron trifluoride or a complex thereof or stannic chloride. The polyglycidyl ether complexes of the present invention can be cured, i.e. hardened, with substances employed as curing agents for epoxy resins, to form insoluble, infusible products having valuable technical properties. If desired, the polyglycidyl ethers of the present invention can be cured in the presence of other epoxy resins. According to this, additional curable compositions are provided which comprise a polyglycidyl ether compound and a curing agent and optionally another epoxy resin. As examples of curing agents there may be mentioned those which are conveniently employed as curing agents for epoxy resins, including aliphatic, cycloaliphatic, aromatic and heterocyclic amines such as m- and p-phenylenediamine, bis (4-aminophenyl) methane, aniline formaldehyde resins, bis (4-aminophenyl) sulfone, ethylenediamine, propan-1,2-diamine, propan-1,3-diamine, N, N-diethylethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (2-hydroxyethyl) -, N - (2-hydroxypropyl) -, and N- (2-cyanoethyl) -diethylenetriamine, 2, 2, -trimethylhexan-1, 6-diamine, 2,3,3-trimethylhexan-1,6-diamine, m-xylylenediamine, N, N-dimethyl- and N, N-diethylpropan-l, 3-diamine, ethanolamine, bis (4-aminociclohexyl) methane, 2,2-bis (4-aminociclohexyl) ropano, 2, 2-bis (4-amino) 3-me-ilcyclohexyl) propane, 3-aminomethyl-3,5,5,5-trimethyl-cyclohexylamine (isophoronadiamine) and N- (2-aminoethyl) piperazine; dicyandiamide, polyaminoamides, for example those prepared from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids; amine adducts with stoichiometric deficits of polyepoxides such as diglycidyl ether; isocyanates and isothiocyanates; polyhydric phenols, for example resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, phenol-aldehyde resins and phenol-aldehyde resins modified with oil, phosphoric acid; polythiols such as "Thiokol" ("Thiokol" is a registered trademark); and polycarboxylic acids and their anhydrides, for example phthalic anhydride, tetrahydrophthalic anhydride, methylenediethylenetetrahydrophthalic anhydride, non-innylsuccinic anhydride, dodecenylsuccinic anhydride, anhydride, and anhydride, anhydride, tetrahydrophthalic anhydride, and its mixtures; maleic anhydride, succinic anhydride, pyromellitic acid dianhydride and benzophenone-3, 3 ', 4,4'-tetracarboxylic acid dianhydride, polybasic anhydride, polyazelaic anhydride, acids corresponding to the aforementioned anhydrides and also isophthalic acid, terephthalic acid , citric acid and mellitic acid. Particularly preferred anhydride or polycarboxylic acid curing agents are those which, if necessary mixed, are liquids at temperatures below 60 ° C. Catalytic polymerizing agents, such as tertiary amines (for example 2,4,6-tris (dimethylaminoethyl) phenol and other Mannich bases, N-benzyldimethylamine and triethanolamine) may also be employed; alkoxides of alkali metals of alcohols (for example, 2,4-dihydroxy-3-hydroxymethylpentane sodium alcoholate), stannous salts of alkanoic acids (for example stannous octanoate), Friedel-Crafts catalysts such as trifluoro boron and their complexes; and chelates formed by the boron trifluoride reaction, with for example 1,3-diketones. In conjunction with the curing agents, suitable accelerators may also be employed. When poly (aminoamides), dicyandiamides, polythiols or polycarboxylic acid anhydrides are used to cure, tertiary amines or their salts, quaternary ammonium compounds or alkali metal alkoxides can serve as accelerators. Examples of specific accelerators are N-benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, imidazoles and triamlylammonium phenoxides.

Other accelerators that may be employed include metal nitrates, particularly magnesium nitrate and manganese nitrate, fluorinated and chlorinated carboxylic acids and their salts, such as magnesium trifluoroacetate, sodium trifluoroacetate, magnesium trichloroacetate and sodium trichloroacetate, trifluoromethanesulfonic acid and their salts, such as the salts of manganese, zinc, magnesium, nickel and cobalt and magnesium perchlorate and calcium perchlorate. An effective amount of the curing agent is employed. The proportion will depend on the chemical nature of the curing agent and the properties sought of the curable composition and its cured product; the optimal ratio can easily be determined by familiar methods for those skilled in the art. By way of illustration, however, when the curing agent is an amine, normally about 0.75 to 1.25 amino-hydrogen equivalents of the amine will be employed per 1,2-epoxide equivalent of the epoxide resin. When polycarboxylic acids or their anhydrides are used, usually about 0.4 to 1.1 equivalents of carboxylic acid or carboxylic acid anhydride are taken per 1,2-epoxy equivalent, while about 0.75 to 1.25 equivalents of phenolic hydroxyls are used with polyhydric phenols. curing agent for 1,2-epoxy equivalent. In general, from 1 to 40 parts by weight of a catalytic polymerization agent are used per 100 parts by weight of the epoxide resin. The curing can be carried out depending on the nature of the curing agent, the ambient temperature (18 ° to 25 ° C) or at higher temperatures (50 ° to 180 ° C, for example). If desired, the curing or hardening can be carried out in two steps, for example by stopping the curing reaction, or if a curing agent which requires a high temperature for complete curing is used, by only partially curing at a lower temperature to give a curable preconditioning to a meltable and soluble or "B-stage" product, for use in producing molding powders, sintering coating powders or prepregs in a well-known form. As already indicated, the compounds of this invention can be employed with conventional epoxide resins. In the usual methods of making many epoxide resins, mixtures of compounds of different molecular weight are obtained, these mixtures ordinarily contain a proportion of compounds whose epoxide groups have been subjected to partial hydrolysis or where the epoxidation has not proceeded to completion. The average number of 1,2-epoxide groups per molecule of an epoxide resin does not need to be at least 2 and does not need to be integral; in general it is a fractional number, but in any case it must be greater than 1.0. Of the epoxide resins which can be used in mixture with the polyglycidyl ether compound, the most suitable ones are those in which the epoxide groups are also terminal, ie of the formula wherein R 4 denotes a hydrogen atom or a methyl group, and especially those wherein the groups are present as glycidyl or β-methylglycidyl groups, directly connected to an oxygen, nitrogen or sulfur atom. These resins include polyglycidyl and poly (β-methylglycidyl) esters which are obtained by the reaction of a substance containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin or β-methylepichlorohydrin in the presence of alkali. The polyglycidyl esters can be derived from aliphatic carboxylic acids, for example oxalic acid, succinic acid, adipic acid, sebasic acid or dimerized or trimerized linoleic acid, from cycloaliphatic carboxylic acids such as hexahydrophthalic acid, 4-methyl-hexahydroftalic, tetrahydroftalic and 4-methyltetrahydrofonic acid, or from aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. Other epoxy resins that can be used include polyglycidyl and poly (β-methylglycidyl) ethers that are obtained by the reaction of substances they contain per molecule, two or more alcoholic hydroxy groups or two or more phenolic hydroxy groups, with epichlorohydrin, glycerol dichlorohydrin, or β-methylepichlorhydrin, under alkaline conditions or alternatively in the presence of an acidic catalyst with subsequent alkali treatment. These polyglycidyl ethers may be derived from aliphatic alcohols, for example ethylene glycol and poly (oxyethylene) glycols such as diethylene glycol and triethylene glycol, propylene glycol and poly (oxypropylene) glycols, propane-1,3-diol, butan-1, 4- diol, pentan-1, 5-diol, hexan-1,6-diol, hexan-2, 6-triol, glycerol, 1,1,1-trimethylolpropane, and pentaerythritol; of cycloaliphatic alcohols such as quinitol, 1,1-bis (hydroxymethyl) cyclohex-3-ene, bis (4-hydroxycyclohexyl) methane, and 2,2-bis (4-hydroxycyclohexyl) propane; or alcohols containing aromatic nuclei, such as N, N-bis- (2-hydroxyethyl) -aniline, and 4,4'-bis (2-hydroxyethylamino) diphenylmethanol. Preferably, the polyglycidyl ethers are derived from substances containing two or more phenolic hydroxy groups per molecule, for example resorcinol, catechol, hydroquinone, bis (4-hydroxyphenyl) -methane, 1,1,2,2-tetrakis (4 - hydroxyphenyl) -ethane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone and especially phenol-formaldehyde or cresol-formaldehyde novolak resins, 2,2-bis (4-hydroxyphenyl) propane (otherwise known as bisphenol A ), and 2, 2, -bis (3, 5-dibromo-4-hydroxyphenyl) propane. Furthermore, poly (N-glycidyl) compounds such as those obtained by the dehydrochlorination of reaction products of epichlorohydrin and amines containing at least two hydrogen atoms, directly connected to nitrogen, such as aniline, n-butylamine, can be employed. , bis (4-aminophenyl) methane, bis (4-aminophenyl) sulfone, and bis (4-methylaminophenyl) methane. Other poly (N-glycidyl) compounds that can be employed include triglycidyl isocyanurate, N, N'-diglycidyl derivatives of cyclic alkylene ureas such as ethyleneurea and 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins such as 5, 5-dimethylhydantoin. Epoxy resins obtained by the epoxidation of cyclic and acrylic polyolefins can also be used such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 3,4-epoxydihydrodicyclopentadienyl glycidyl ether, the bis (3,4-epoxydihydrodicyclopentadienyl) ether of ethylene glycol, 3,4-epoxycyclohexylmethyl 3,4 '-epoxycyclohexanecarboxylate and its derivative is 6,6'-dimethyl, the bis (3,4-epoxycyclohexancarboxylate) of ethylene glycol, the acetal formed between 3,4-epoxycyclohexanecarboxyaldehyde and 1,1 bis (hydroxymethyl) -3,4-epoxycyclohexane, bis (2,3-epoxycyclopentyl) ether and epoxidized butadiene or butadiene copolymers with ethylenic compounds such as styrene and vinyl acetate. Epoxide resins particularly suitable for mixing with the polyglycidyl ether compounds of the present invention are polyglycidyl ethers of 2,2-bis (4-hydroxyphenyl) propane or of a phenol novolak (which may be substituted on the ring by a chlorine atom) or an alkyl group of 1 to 4 carbon atoms) and formaldehyde and having an epoxide content of at least 1.0 equivalent 1,2-epoxide per kilogram. The compositions of the invention may further contain plasticizers such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate, inert diluents and diluents so-called reagents, such as diglycidyl formal and especially mono-epoxides such as butyl glycidyl ether, iso-octyl glycidyl ether, phenyl glycidyl ether, styrene oxide, glycidyl acrylate, glycidyl methacrylate, and glycidyl esters of aliphatic, predominantly tertiary, highly branched synthetic monocarboxylic acids. They may also contain additives such as fillers, reinforcing materials, coloring matter, flow control agents, flame retardants and mold lubricants. Suitable spreaders, fillers and reinforcement materials include asbestos, asphalt, bitumen, glass fibers, textile fibers, carbon fibers, boron fibers, mica, alumina, gypsum, titanium oxide, chalk, quartz flour, cellulose, kaolin, ground dolomite, wollastonite, colloidal silica having a large specific surface such as that available under the trademark of "Aerosil" clays modified by treatment with long chain amines (such as those available under the trademark "Bentone"), poly ( powdery vinyl chloride), pulverulent polyolefin hydrocarbons, powdery cured aminoplasts and metal powders such as aluminum or iron powder. Flame retardants such as antimony trioxide can also be incorporated. In the examples, as in the remaining part of the description, percentages are given as percentages by weight and the ranges include the established limits, unless otherwise noted.

Example 1: 1515 g of n-butanol and 4.68 g of BF3-2H20 are charged to a 4-neck round bottom flask with three liters capacity, equipped with a mechanical stirrer. Using a heating tape, 900 g of GY 1180 (Epoxy Cresol Novolac: Ciba) are added over a period of three hours to the stirred solution which is maintained at 110 ° C. The container temperature is raised to 115 ° C and maintained until the epoxy value is less than 0.001 eq / lOOg. The vessel is cooled to 80 ° C and 4.68 g of 50% NaOH (aqueous solution) are added. After stirring for 15 minutes, the excess n-butanol is removed by distillation under reduced pressure, so that the temperature of the vessel is lower than 110 ° C. After the residue is cooled to about 60 ° C, 1768.6 g of epichlorohydrin, followed by 25.2 g of 50% benzyltrimethylammonium chloride (aqueous solution), add with vigorous stirring. The mixture is heated to 50-55 ° C under a vacuum of 70 torr with rx of water-epichlorohydrin. Over a period of two hours, 195 g of 50% NaOH (aqueous solution) are added during which the water-epichlorohydrin azeotrope is distilled to a Dean-Stark trap, where the water is retained and the epichlorohydrin is returned to the reactor . The azeotropic water removal is continued for another two hours. The product is washed three times with 300 g of water so that between the first and second washing the pH of the solution is adjusted to 6 with 10% aqueous acetic acid. The excess epichlorohydrin is distilled off to dryness under reduced pressure (less than 5 torr) such that the pot temperature is lower than 150 ° C. It gives a light yellow liquid as the product (1450 grams, 87% yield). The analytical data are in accordance with the desired product having an epoxy value of 0.282 eq./lOO g (PE: 355) and a viscosity of 24,000 cps at 25 ° C.

Claims (11)

1. CLAIMS 1. A polyglycidyl ether compound containing at least three mono- or divalent radicals A of the general formula wherein R1 represents (i) straight or branched chain alkyl groups with 1 to 16 carbon atoms, which may be substituted by one to four chlorine atoms or bromine atoms, or (ii) a straight or branched chain alkenyl group with 2 to 6 carbon atoms, which may be substituted by one to four chlorine or bromine atoms, or (iii) a phenyl or naphthyl group, optionally substituted in the ring or rings with one or two chlorine or bromine atoms or by one or two alkyl groups, each having 1 to 10 carbon atoms and having a total of 7 to 30 carbon atoms, or (iv) a phenylalkyl or naphthylalkyl group, optionally substituted on the ring or rings by one or two atoms of chlorine or bromine and by one or two alkyl groups, each having 1 to 10 carbon atoms, the phenylalkyl or naphthylalkyl group has in total 7 to 30 carbon atoms, or (v) a mononuclear cycloalkyl group of 3 to 6 carbon atoms, or (vi) a mononuclear cycloalkyl group with 4 to 10 volumes of carbon and R2 represents hydrogen or an alkyl group of straight or branched chain with 1 to 9 carbon atoms.
2. 2. A compound according to claim 1 of the general formula A-CH2- [A-CH2] nA (I) or (A) 3C-R3 (II) or (A) 2CH-CH (A) 2 ( III), where n is a number equal to or greater than 1 and R3 is hydrogen or CH3. .
3. A compound according to claim 1, characterized by the general formula A-CH2- [A-CH2] nA (I) wherein n is a number from 1 to 50.
4. 4. A compound according to claim 1, characterized by the general formula A-CH2- [A-CH2] nA (I) wherein n is a number from 1 to 5.
5. 5. A compound according to claim 1, characterized in that R_ represents straight or branched chain alkyl groups. with 1 to 16 carbon atoms and R2 is hydrogen.
6. 6. A compound according to claim 1, of the general formula A-CH2- [A-CH2] n-A (I) wherein n is a number from 1 to 5, Rx is C4H9 and R2 is hydrogen.
7. 7. A process for the preparation of a polyglycidyl ether compound according to claim 1, characterized in that it contains at least three mono- or divalent radicals A as defined above, characterized in that it comprises (a) reacting at least an equimolar amount with respect to to the glycidyl radicals of the formula B, of an alcohol of the formula X wherein Rx is as defined above, with a polyglycidyl ether of a polyhydric phenol containing at least three mono- or divalent radicals B of the general formula wherein R2 is defined as above, in the presence of a basic catalyst or a Lewis acid catalyst that produces a poly-secondary alcohol; and (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst, to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A.
8. 8. A process for the preparation of a polyglycidyl ether compound according to claim 1, characterized in that it contains at least three mono- or divalent radicals A as defined previously, comprising (a) reacting at least an equimolar amount with respect to the radicals glycidyl of the formula B, of an alcohol of the formula X RxOH (X) wherein R? was defined as above, with a polyglycidyl ether of a polyhydric phenol containing at least three mono- or divalent radicals B of the general formula wherein R2 is defined as above, in the presence of a basic catalyst or a Lewis acid catalyst that produces a poly-secondary alcohol; and (b2) reacting the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step, and then in a second step, treating the intermediate poly (chlorohydrin) with an alkali to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A.
9. 9. A process for the preparation of a polyglycidyl ether compound according to claim 1, characterized in that it contains at least three mono- or divalent radicals A as defined previously, comprising (a2) reacting a polyhydric phenol containing a radical R2 and at least three OH- groups with a monoglycidyl ether of the formula XII R, -0 ^ (X ") wherein R2 was previously defined, optionally in the presence of a phase transfer catalyst that produces a poly-secondary alcohol of the formula XIII containing at least three mono- or divalent radicals of the general formula C 2 and (bl) reacting the poly-secondary alcohol with epichlorohydrin in the presence of an alkali and a phase transfer catalyst, to produce the polyglycidyl ether compound containing at least three mono- or divalent radicals of the general formula A.
10. A process for the preparation of a polyglycidyl ether compound according to claim 1, characterized in that it contains at least three mono- or divalent radicals A, as previously defined, comprising (a2) reacting a polyhydric phenol containing a radical R2 and at least three OH- groups with a monoglycidyl ether of the formula XII wherein Rx is as defined above, optionally in the presence of a phase transfer catalyst that produces a poly-secondary alcohol of the formula XIII containing at least three mono- or divalent radicals of the general formula C and (b2) reacting the poly-secondary alcohol with epichlorohydrin in the presence of a Lewis acid catalyst in a first step and then in a second step treating the poly (chlorohydrin) intermediate with an alkali, to produce the polyglycidyl ether compound which contains at least three mono- or divalent radicals of the general formula A.
11. 11. A process for preparing substrate having a hardened coating, characterized in that it comprises: (a) combining a polyglycidyl ether compound according to claim 1, with an agent of curing to produce a formulation; and (b) applying at least one layer of the formulation on the substrate.