Classifications

• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
• • 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
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
  • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
• • 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
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
• • 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
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds

Definitions

• Novolacs the acid-catalyzed condensation products of phenols with less than 1 mole of formaldehyde per mole of phenol, constitute a well-known class of phenolic resins and have found wide use.
• the novolacs in commercial use are derived preponderantly from mononuclear, monohydric phenols, .such as phenol itself, cresol, p-t-butylphenol, octylphenol and xylenol. Large amounts of resorcinol, a mononuclear, dihydric phenol, are also used, however, in novolac manufacture.
• a relatively recently developed novolac is derived from bisphenol A and contains eight aromatic nuclei (benzene rings), each having a phenolic hydroxyl attached to it.
• This novolac is marketed by Celanese Corporation in the form of its octaglycidyl ether, a high molecular weight epoxy resin known by the tradename SU-8.
• the unadvanced novolac may be represented by the following ideal structure: ( 1 )
• novolac of formula (1) is actually linear in structure, i.e., is not branched.
• SU-8 is a hard, high melting epoxy resin which reacts rapidly, has good heat resistance and cold-flows to a lesser extent than more conventional high molecular weight epoxy novolacs.
• it not only is brittle but also contains low molecular weight epoxide species derived from the free bisphenol inevitably present in novolacs prepared by the reaction of formaldehyde with bisphenols. The latter species are present in sufficient amount so that the epoxy will still cold flow, albeit to a limited extent.
• Also inevitably present in conventional bisphenol novolacs are species of sufficiently high molecular weight to undesirably increase the gelling speed of the epoxidized novolac.
• the epoxy novolacs of the present invention consist at least partially of a monomeric, polynuclear polyglycidyl ether of the formula (2):
• R is H or CH 3 ,
• R 1 is H, a C 1 -C 20 alkyl, alkenyl, cycloalkyl, cycloalkenyl , aralkyl, aralkenyl, aryl, alkaryl, alkenylaryl, alkoxy or alkenyloxy group or a halo or nitro group, independently in each occurrence,
• R 2 is H or OH, independently in each occurrence
• J is H, an R 1 group as above-defined or is a fourth group, and
• Q is the residue of a poly(methylol and/or alkoxymethyl) difunctional phenol of either of the following formulas:
• n 0 or 1
• y is 1 or 2
• -Z- is a valence bond, a C 1 -C 4 alkylene or alkenylene group, or a
• R 3 - independently in each occurrence- is H or a
• R 1 , R 2 and the latter ⁇ difunctional phenol being as defined hereinbefore.
• oligomeric epoxy novolacs of the invention It is not possible to represent the oligomeric epoxy novolacs of the invention by a single, ideal formula. It is believed that oligomerization during novolac formation involves reaction of methylol groups with methylol or alkoxymethyl groups in different molecules and reaction of more than one ring hydrogen in a reactive phenol molecule with as many methylol
• oligomeric novolacs of the invention are believed to include "abnormal" linkages such as are shown in the following segment hypothesized for a novolac derived from tetramethylol hydroquinone and phenol. It will be noted that such segments may contain substantially more than 10 phenolic hydroxyls.
• the novolacs may also include some -CH 2 OCH 2 - groups formed by intramolecular reactions of adjacent methylol groups on the same aromatic ring. To the extent that this occurs, the phenolic equivalent weight of the novolac may be raised other than by oligomerization. That is, this reaction would result in a molecular weight decrease, rather than an increase. Reaction of an alkoxymethyl group with an adjacent methylol group is less likely but appears possible - at least when the alkoxymethyl group is a methoxymethyl group. However, interaction of two adjacent alkoxymethyl groups is improbable and this is another advantage of poly(alkoxymethyl) diphenols as novolac precursors.
• Such oligomerization as occurs during epoxidation will result from adduction of otherwise t ⁇ nconverted phenolic hydroxyls with oxirane groups in established glycidyl ether groups. That is, "advancement" to a higher molecular weight epoxy resin may occur. Any undesired tendency in this direction can generally be suppressed by employing a higher epichlorohydrin (or methylepichlorohydrin) to phenolic hydroxyl ratio in the epoxidation mixture, as is illustrated subsequently herein.
• the epoxy novolacs of this invention are prepared from difunctional phenols ring-substituted with three or four methylol and/or alkoxymethyl groups.
• the precursor novolacs are prepared by reacting the substituted phenol in the presence of an acid with a mono- or diphenol to convert the methylol and/or alkoxymethyl groups to mono- or dihydroxybenzyl groups.
• a typical novolac produced by this method is derived from tetramethylol bisphenol A and ordinary phenol.
• the most preferred method of preparing the novolacs is a "one-pot" process which includes, as a first step, preparation of a poly(methylol- and/or alkoxymethyl) dihydric phenol, by whatever method, as a precursor to the novolac.
• hexaglycidyl ether of the latter novolac will have a branched, rather than a linear structure and will accordingly provide a more closely knit structure than SU-8.
• difunctional phenol includes both dinuclear diphenols (bisphenols) and mononuclear diphenols (simply diphenols hereinafter).
• poly(methylol and/or alkoxymethyl)difunctional phenol as used herein is intended to denote a bis- or diphenol ring substituted with at least three methylol and/or alkoxymethyl groups.
• alkoxymethyl as used herein denotes a monovalent radical of the formula R-O-CH 2 - in which R is an alkyl, aralkyl or cycloalkyl group of from 1 to 30 carbons, preferably a 1 to 4 carbon alkyl group.
• methylol- or alkoxymethyl-reactive phenol is used herein to denote a mono- or dihydric phenol having at least one ring hydrogen capable of condensing with a methylol or alkoxymethyl group attached directly to a hydroxy-substituted benzene ring - to eliminate a molecule of water or of the corresponding alcohol, R-OH (R being defined as above).
• epoxidize means to form the polyglycidyl ether of the novolac.
• the branched novolacs useful to prepare the epoxy novolacs of the present invention may be prepared by reacting a poly(methylol and/or alkoxymethyl)difunctional phenol with at least one molecular proportion of a methylol- and/or methoxymethyl-reactive phenol per methylol (etc.) group, in the presence of an acidic catalyst for the reaction of active ring hydrogens with the methylol and/or alkoxymethyl groups.
• Preferred such products are those derived from phenol itself and from p,p' bisphenols substituted with a methylol or alkoxymethyl group in each of the four ortho positions therein.
• Suitable reactants for the preparation of the precursor novolacs are as follows.
• the formaldehyde may be provided in the form of any suitable formaldehyde source material, such as, for example, formalin, paraformaldehyde or s-trioxane.
• suitable polymethylol difunctional phenols for use, as such or as precursors to corresponding alkoxymethyl derivatives, in the method of the present invention are bis- or diphenols ring-substituted with at least 3 - preferably 4 - methylol groups. Otherwise unsubstituted phenols, such as tetramethylol hydroquinone or tetramethylol bisphenols of the formula
• bisphenols having four active hydrogens can be prepared from meta-substituted phenols - such as m-cresol, for example - and, at least as the p,p' isomers, can be converted to the tetramethylol derivatives.
• the bisphenol employed consists 100% of the p,p' isomer (known as para Bis A, for example).
• para Bis A the p,p' isomer
• the presence of minor amounts of the o,p' isomer is not necessarily detrimental.
• the latter isomers may be preferred for the preparation of tri-methylol bisphenols .
• the polymethylol compound preparations are generally carried out by allowing from 30 to 120 minutes for formation of the bis-phenate slurry and then reacting it for 2 to 4 hours with a 5-10% excess of the formaldehyde source material at temperatures within the range of from 50 to 70°C (60°C, preferably).
• trimethylol bisphenols may be somewhat difficult to prepare simply by the standard base-catalyzed reaction of the unsubstituted diphenols or p,p' -bisphenols with an excess of formaldehyde. That is, they may be obtained only in admixture with di- and/or tetramethylol derivatives.
• the content of the trimethylol compounds in such mixtures may be increased by using little or no excess of formaldehyde, employing bases which are less effective catalysts than NaOH and by terminating the reaction short of completion. As a general proposition, this will be done only when a novolac having an average functionality of less than 6 is desired.
• the trimethylol derivative can more readily be prepared (so long as said group does not interfere, i.e., does not excessively deactivate the ring hydrogens expected to react with the formaldehyde).
• unsymmetrical bisphenols having the single substituent in a position ortho (or para) to one of the two phenol groups may be reacted with an excess of formaldehyde under somewhat more severe conditions than those used for the preparation of tetramethylol derivatives of unsubstituted bisphenols.
• the requisite monosubstituted bisphenol starting material may be prepared either by direct substitution in the bisphenol or by reacting an aldehyde or ketone with a mixture of substituted and unsubstituted phenols in proportions appropriate to their relative reactivities, and then isolating the desired monosubstituted bisphenol, as by preparative chromatography.
• the dihydric phenol is resorcinol
• one of the ring hydrogens will be meta to both hydroxyls and should be substantially less reactive than the other three ring hydrogens.
• the trimethylol derivative should be directly preparable.
• all four ring hydrogens are reactive and monosubstitution with a non-interfering group is advisable if a trimethylol derivative of either of these diphenols is desired.
• substituent groups known or believed to be essentially non-interfering are C 1 -C 20 alkoxy or alkenyloxy, C 1 -C 20 alkyl, alkenyl, cycloalkyl or cycloalkenyl groups, and phenyl, benzyl, halo and nitro groups.
• a given mono- or dihydric phenol is methylol- or alkoxymethyl-reactive. This does not necessarily require testing the phenol with the polymethylol (etc.) difunctional phenol to be used. If the candidate phenol will condense - for example with the methylol group(s) in saligenin (o-hydroxybenzyl alcohol), 2,4- or 2,6-dimethylol phenol or 2,4,6-trimethylolphenol, it should be suitable as a methylol reactive phenol for the practice of the present invention.
• methylol-substituted monophenols which may be more representative of particular polymethylol difunctional phenols are monomethylol xylenols, the 2,6-dimethylol derivative of p-benzylphenol, the dimethylol derivatives of o-chlorophenol and 2-nitro-4methylolphenol.
• the corresponding methoxymethyl derivatives of the foregoing methylol-substituted monophenols may similarly be used to test for the requisite reactivity of a candidate alkoxymethyl-reactive phenol.
• tetramethylol difunctional phenols are tetramethylol bisphenol A and tetramethylol hydroquinone. By reaction with a several fold excess of phenol or a dihydroxy benzene, the latter, tetramethylol compound (or the corresponding mono- to tetraalkoxy derivatives thereof) may be converted to novolacs, for use in the present invention, having the following formula:
• R 1 is H or p-OH (the same in each occurrence, unless a mixture of mono- and diphenols is used).
• novolacs of the latter formula are not only branched but are even more compact than those of formula (6). If R 1 is -OH in each occurence, the novolac has a phenolic hydroxyl functionality of 10.
• the presence of the substituent in a position ortho to a phenolic hydroxyl is preferred.
• novolacs of either of formulas (6) or (8) should be amenable to ring-substitution with halo- or nitro groups (either of which should increase the reactivities of the phenolic hydroxyl groups). This would also be true of novolacs like those of formulas (6) or (8) but derived from mono- or dihydric phenols monosubstituted with alkyl, alkenyl, alkoxy groups, etc.
• the poly(methylol and/or alkoxymethyl)dihydric phenol from which the novolac is derived may be made from a similarly substituted difunctional phenol.
• the methylol- and/or alkoxymethyl-substituted diphenol may be pre-prepared or made in situ.
• the alkoxymethyl-containing species are conveniently made from the tri- or tetramethylol compounds by reaction of the latter with an excess of an alkanol or cycloalkanol in the presence of an acid catalyst in a manner similar to that employed in converting the methylol derivatives to the novolacs used in the invention.
• the alkoxymethyl compounds are substantially less reactive than the methylol compounds but this is actually an advantage.
• the polymethylol compounds must be stored in a freezer (and even then self-react, albeit slowly) whereas the poly(alkoxymethyl) compounds are stable - but still reactive enough to be used to make the novolacs.
• the basic methylolation mixture is carefully neutralized with CO 2 (under pressure) or a dilute mineral acid, such as 3N HCl and is then made just slightly acid (with dilute HCl, for example).
• a dilute mineral acid such as 3N HCl
• the resulting brine layer is separated and a methylol-reactive mono- or dihydric phenol (or an alcohol) is mixed with the organic phase before the catalytic acid is added. If an alcohol is to be reacted with the -CH 2 OH groups, the mixture (or the separate components thereof) should also be dried first.
• Suitable acids for catalysis of the novolacforming reaction include those, such as oxalic acid, for example, generally used in the preparation of conventional novolacs (from HCHO and phenols).
• HCl is convenient but acids such as p-toluene sulfonic acid, oxalic acid or acid-form ion exchange resins are also suitable.
• the amount of acid introduced as the condensation catalyst should be at least enough to lower the pH to about 1.0. Greater amounts of (anhydrous) acids tend to complex the water eliminated in the condensation but are not otherwise beneficial.
• the methylol-reactive phenol should be employed in the amount of at least 1 molecular proportion per methylol or alkoxymethyl group to be reacted out.
• the novolac produced will generally be predominantly oligomeric and will have a relatively high molecular weight.
• a high purity monomeric novolac having the ideal structure of formula (5) can be obtained with phenol itself at phenol/-CH 2 OH ratios of 8-10 (mole ratios of 36:1 to 40:1 for a tetramethylol difunctional phenol). Even higher ratios can be used, but to little or no advantage.
• Monomeric novolacs containing only minor amounts of oligomers can be obtained at ratios of from 2.0 to 7.5 depending on the relative reactivities of the phenol and the methylol groups, the reaction temperature and the method of combining the reactants.
• the novolacs low in oligomers are soft.
• the predominantly oligomeric novolacs are hard.
• poly(alkoxymethyl) diphenols Another advantage of using poly(alkoxymethyl) diphenols is that self-reaction is considerably less of a problem and substantially less oligomerization should result at a given phenol/reactive-group ratio. That is, essentially monomeric novolacs should be preparable from most phenols at ratios as low as 2.5, even when employing the reactant combination method of Example IV-A.
• novolacs used in the practice of the invention having really high contents of oligomeric products generally have higher average molecular weight ranges than are desirable for most uses they would find in the form of their epoxidized derivatives. Accordingly, novolacs made at phenol to methylol ratios of at least 2.5 are preferred as epoxy resin precursors.
• the novolacs obtained from phenol per se at ratios in the range of 2 to 3 molecules of phenol per methylol group are more preferred, by reason of providing epoxides (polyglycidyl ethers) of sufficient hardness to be non-sintering, yet low enough in melt viscosity to give good flow properties in molding compounds. When the phenol is cresol, ratios of 2.5 to 5.0 are preferred.
• Some polymethylol difunctional phenols - such as tetramethylol bisphenol A, for example - tend strongly to crystallize and are most easily utilized when made in situ and mixed with the methylol-reactive phenol immediately after the brine layer has been removed. This is also advantageous in drastically reducing the rate of self-reaction on the part of highly reactive methylol compounds. Further, it is essential to pre-mix the reactants before the catalyst is introduced because self-reaction of the methylol compounds is inherently faster than the desired reaction of methylol groups with ring hydrogens and both reactions are speeded up by the catalyst. The methylol/phenol reaction may be started by slightly warming the catalyst-containing mixture of reactants but, once under way, is very exothermic.
• the mixture is heated (at reflux, conveniently) for an arbitrary period of from one to several hours, to ensure completion of the reaction. Less of an exotherm would be expected when at least one of the methylol groups has first been converted to an alkoxymethyl group.
• Suitable reaction temperatures for the novolacforming condensation extend from the lowest temperature at which adequate stirring and a practical reaction rate can be attained to the highest temperature at which the extent of side-reaction and/or degradation is not intolerable. In general, however, temperatures including the peak temperature allowed during the exotherm - within the range of from 40° to 70°C are preferred when the methylol - or alkoxymethyl-reactive phenol is phenol itself. When the phenol is a cresol, temperatures within the range from 60° to 107°C are preferred.
• azeotroping alcohol can be charged initially to leave enough for the reaction after azeotroping is complete.
• the acid catalyst is either concentrated (c HCl, for example) or anhydrous.
• the reactant/catalyst mixture is then stirred at a temperature of 65° to 80°C for at least several hours.
• methanol - the most preferred alcohol - is used, the reaction mixture is refluxed for as long as 10 hours or more when a high degree of conversion of -CH 2 OH to -CH 2 OCH 3 groups is desired.
• the alcohol concentration is reduced, as by dissolution in an inert solvent, and/or the contact time and/or reaction temperature is reduced.
• the reaction mixture may be worked up for the novolac in any suitable manner.
• a simple and effective workup is to neutralize the acid with 50% aq. NaOH, separate the resulting brine, strip off most of the unconverted methylol- or alkoxymethyl-reactive phenol in a rotary evaporator under reduced pressure, complete phenol removal by steam stripping and dry the residual product in a rotary evaporator under reduced pressure allowing the final pot temperature to reach about 150°C.
• the novolac produced can be removed from the vessel - usually with the ai4 of a hot-air gun - as a viscous but flowable melt.
• the epoxy novolac of the present invention is defined as a polyglycidyl ether of the foregoing formula (5) which may be prepared by reacting the corresponding novolac with an epihalohydrin of the formula
• R is H or CH 3 and X is Cl or Br.
• the epihalohydrin is epichlorohydrin and the first step of the epoxidation - coupling, or -OH/oxirane adduction - is catalyzed with a quaternary ammonium compound such as BTMAC (benzyl trimethylammonium chloride).
• BTMAC benzyl trimethylammonium chloride
• the molecular weight of the epoxide can be controlled not only by manipulating reactant ratios (in the novolac and epoxide-forming steps) but also by the choice of the methylol-reactive (capping) phenol used. That is, optimization of molecular weight-dependent properties may be achieved by selecting alkyl substituted phenols (ortho-alkyl phenols, preferably) in which the size of the alkyl group is larger or smaller. Also, the proportion of the alkyl phenol in mixtures of the same with ordinary phenol can be varied.
• the reaction mixture was transferred to a 2-liter, 3-neck flask and there was added 457 grams of "liquid phenol" - 90% phenol, 10% water (4.37 g moles of phenol; 2.5 moles per -CH 2 OH).
• the mixture was neutralized with 72 ml of 1-2N HCl and another 28 ml. of the acid was added as a catalyst.
• the acidified mixture was then refluxed, with stirring, for 1-1/2 hours, neutralized with 50% NaOH and made acid with acetic acid.
• the resulting brine layer was separated and the organic phase freed of phenol by steam stripping to a final pot temperature of 150°C.
• the stripped residue weighed 278 grams (97.3% of theoretical for the desired 6-functional novolac) and therefore was presumed to consist essentially of the monomeric novolac of formula (2) herein.
• Epoxides of the type made in Run 1 have Mettler softening (dropping) points of between 60 and 70°C and melt viscosities of about 240 centistokes (0.000240 m 2 /s) at 150°C (Brookfield HAT microviscometer).
• the epoxidation was carried out by the following procedure.
• the novolac was stirred in a 2-liter, 3-neck, round-bottom flask with the epichlorohydrin.
• 2.8 Grams of 60% benzyltrimethyl- ammonium chloride was added as a coupling catalyst to the resulting solution, which was refluxed for one hour and then cooled to 25°C.
• Dehydrochlorination was done in two steps, the first step being mainly dehydrochlorination of the glycerine dichlorohydrin present after the coupling reaction. 222.6 Grams of 25% aq. NaOH was slowly added to the solution at 25°.
• Table I is a compilation of data for twelve, 3-step epoxide preparations (Runs 2-13) starting from bisphenol A and using phenol to cap the tetramethylol compound.
• the preparations were carried out essentially in the manner of the preceding example but at various phenol to methylol ratios and epichlorohydrin to novolac ratios. Also, two different methods of achieving coupling and dehydrochlorination were used in carrying out the epoxidations, as indicated in the Table.
• the epoxy novolac made in Run 2 was formulated and cured as indicated in the following Table II. For comparison, data are also given for the commercial epoxy resin, SU-8.
• novolac preparations described earlier herein are preferred for small scale preparations but do not permit sufficiently reliable control of the initial exotherm in large scale operations.
• the following continuous addition method affords more positive temperature control and is therefore preferred for larger scale preparations, even though it results in a somewhat higher proportion of higher molecular weight oligomers in the novolac product. More conventional methods of limiting heat evolution resulted in substantially higher molecular weights.
• the novolac was epoxidized in the following manner. 69.6 Grams of the novolac is dissolved in 546 grams of epichlorohydrin (7 mols per phenolic OH) and 0.7 grams of BTMAC coupling-catalyst added. The solution is refluxed 2.5 hours and cooled to ambient temperature. 52 Grams of 25% aq. NaOH is added and the mixture stirred 1 hour at ambient temperature. Water and unconverted epichlorohydrin are removed by distillation in vacuo. The residue is dissolved in 70 grams of 75/25 MEK/toluene and heated to 60°C. Another 52 grams of 25% NaOH is then added at 60°C in one hour and the reaction mixture stirred another hour at 60°C.
• More MEK/toluene is added in an amount equal to twice the weight of the novolac charged and half that amount of water is added, with stirring. Phase disengagement is permitted and the aqueous phase removed. The organic phase is dried (as with MgSO 4 ), mixed bentonite (20%; to remove BTMAC) and filter-aid, filtered and stripped.
• the epoxide (nominally 6-functional, polyglycidyl ether) had an EEW of 179 (vs. 165 theoretical).
• the HDT values obtained when this epoxide was cured 1:1 with each of two different curing agents are given in Table III following. Also included in the Table, for comparison, are the HDT values obtained with each of four different curing agents for a similar epoxide made essentially by the procedure of Example I but at a phenol/methylol ratio of 7.5 to 1 and epi/phenolic OH ratio of 7 to 1.
• a novolac was prepared essentially in the manner of Example IIIA but employing o-cresol as the methylol-reactive phenol and in a ratio of 5 molecules per methylol group. It was epoxidized in the manner of Example IIIB but with an epichlorohydrin/OH ratio of 10:1.
• HDT values of the epoxide, cured 1:1 and 0.7:1 with MDA (methylene dianiline), are included in Table III. Also included, for comparison, is an HDT value for the commercial 6-functional epoxy resin, "ECN-1280" (registered tradename; Ciba-Geigy, Epoxy
• Cresol Novolac cured 1:1 with nadic methyl anhydride (NMA) + 2% BDMA (benzyl dimethyl amine).
• novolac epoxides More specific end uses contemplated for the present novolac epoxides are: for the lower molecular weight products, in adhesives, laminates and potting compounds; and for the higher molecular weight products, in molding compounds and powder coatings.
• the epoxides of the present invention may of course be employed for various purposes in admixture with other epoxides, such as those derived from monoor dihydric phenols or with polynuclear polyphenols such as phenol/formaldehyde novolacs, bisphenol/formaldehyde novolacs, or C 1 -C 6 alkanes or alkenes substituted with from two to four hydroxyphenyl groups.
• epoxide mixtures may be made by blending the separately-preformed epoxides or by epoxidizing mixtures of the novolacs disclosed herein with other phenols, polyphenols, etc., as above indicated.

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• 1983
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