CA1196015A - Resinous salts, their preparation, and their use in coatings - Google Patents
Resinous salts, their preparation, and their use in coatingsInfo
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- CA1196015A CA1196015A CA000418383A CA418383A CA1196015A CA 1196015 A CA1196015 A CA 1196015A CA 000418383 A CA000418383 A CA 000418383A CA 418383 A CA418383 A CA 418383A CA 1196015 A CA1196015 A CA 1196015A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/14—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Resinous salts, prepared by thioalkylation or sulfoalkylation of A phenol obtained by advancement of a polyepoxide, followed by at least partial neutralisation, have the general formula where R- represents a group of formula -S-R1-COO or a group of formula -SO3- ; R1 represents an aliphatic, aromatic or araliphatic divalent group which may contain a further group -COO-M+; R2 represents -H or alkyl; one of R3 and R31 represents a hydroxyl group and the other represents -H, halogen, alkyl, or alkenyl; each R4 represents -H, halogen, alkyl, or alkenyl;
R5 represents -H, halogen, alkyl, alkenyl, or a group -CH(R2)OH, -CH(R2)OR8, or -CHR2-R-M+; R6 represents the residue of a polyepoxide, preferably of average mol. wt. 1000-5000;
each of the groups R7, which may be the same or different, represents -H or a covalent bond linked to the group R6; R8 represents alkyl or alkoxyalkyl; R9 denotes the residue of an optional terminating group; m represents 1, 2, 3, or 4; n and p represent zero or 1, X represents alkylene, carbonyl, sulfonyl, oxygen, sulfur, or a valence bond; and M+ represents a hydrogen ion or a cation derived from an alkali metal, ammonia, an amine or one valence of a polyvalent cation, at least 25% of the ions being a said cation.
Compositions comprising these salts and, if required, a phenoplast, an aminoplast, or a blocked polyisocyanate, are stable when dispersed in water, usually with the aid of a minor amount of an organic solvent, and may be used to form protective films, especially for metal containers.
Resinous salts, prepared by thioalkylation or sulfoalkylation of A phenol obtained by advancement of a polyepoxide, followed by at least partial neutralisation, have the general formula where R- represents a group of formula -S-R1-COO or a group of formula -SO3- ; R1 represents an aliphatic, aromatic or araliphatic divalent group which may contain a further group -COO-M+; R2 represents -H or alkyl; one of R3 and R31 represents a hydroxyl group and the other represents -H, halogen, alkyl, or alkenyl; each R4 represents -H, halogen, alkyl, or alkenyl;
R5 represents -H, halogen, alkyl, alkenyl, or a group -CH(R2)OH, -CH(R2)OR8, or -CHR2-R-M+; R6 represents the residue of a polyepoxide, preferably of average mol. wt. 1000-5000;
each of the groups R7, which may be the same or different, represents -H or a covalent bond linked to the group R6; R8 represents alkyl or alkoxyalkyl; R9 denotes the residue of an optional terminating group; m represents 1, 2, 3, or 4; n and p represent zero or 1, X represents alkylene, carbonyl, sulfonyl, oxygen, sulfur, or a valence bond; and M+ represents a hydrogen ion or a cation derived from an alkali metal, ammonia, an amine or one valence of a polyvalent cation, at least 25% of the ions being a said cation.
Compositions comprising these salts and, if required, a phenoplast, an aminoplast, or a blocked polyisocyanate, are stable when dispersed in water, usually with the aid of a minor amount of an organic solvent, and may be used to form protective films, especially for metal containers.
Description
This invention relates to new~ water~soluble or water-dispersible resinous salts, to aqueous compositions coDtaining them, and to surfaces coated with such compositions.
To ob~ain a corrosion-resistant coating for metal containers it is conventional to coat the metal surface with a crosslinkable resin formulation dissolved in an organic solvent and then to heat the coating to evaporate the solvent and to crosslink the resin. Crosslinking the coating converts it into a tough, adherent, flexible, and protective film. During heating, the solvent is usually evaporated into the atmosphere. Since or~anic solvents are relatively expensive, inflammable, and usually en~ironmentally objectionable, there e~ists a need for coatings which may be applied using minimal proportions of such solvents, particularly useful being coating compositio~s which contain a high proportion of water.
We have now found that stable, aqueous compositions which cure to give coatings having excellent mechanieal properties and chemical resistance may be prepared from new resinous salts. These salts are prepared fr~m a phenol-terminated
To ob~ain a corrosion-resistant coating for metal containers it is conventional to coat the metal surface with a crosslinkable resin formulation dissolved in an organic solvent and then to heat the coating to evaporate the solvent and to crosslink the resin. Crosslinking the coating converts it into a tough, adherent, flexible, and protective film. During heating, the solvent is usually evaporated into the atmosphere. Since or~anic solvents are relatively expensive, inflammable, and usually en~ironmentally objectionable, there e~ists a need for coatings which may be applied using minimal proportions of such solvents, particularly useful being coating compositio~s which contain a high proportion of water.
We have now found that stable, aqueous compositions which cure to give coatings having excellent mechanieal properties and chemical resistance may be prepared from new resinous salts. These salts are prepared fr~m a phenol-terminated
2~ resin~either by thioalk~lation ~ith a mercaptocarboxylic acid and an aldehyde followed ~y at least par~ial neutralisation of the carboxylic acid group(s~ introduced by the ~ercapto-carboæylic acid, or by sulphoalkylation with sulphurous acid (or a water soluble salt thereof) and an aldehyde followed, if necessary, by at least partial neut-ralisation of the sulphonic ~3~
acid group(s~ introduced b~ sulphLIrous ac~d or its salt. They may be used with an aminoplast, a phenol~formaldehyde resin, or a blocked polyisocyanate as aqueous surface coating compositions. In cer~ain cîrcumstances the addition of such a coreactant is not, however, necessary.
The use of YariouS reactions to obtain from phenols or epoxides water--soluble or water~dispersible resins ~or use as coatings has previously been described.
For ~xa~ple, British Patent Specifica~ion No. 1 254 528 discloses carboxyl group-co~taining polyethers said to be suitable for use in water~d;lutafile coating compositions and which are obtained by reaction of a glycidyl e~her, a phenol-aldehyde condensate containing methylol groups, and a hydro~ycarboxylic acid. The product ;s a polyether phenol~aldehyde resin etherified with the hydroxycarboxylic acid. Use of a mercaptocarboxylic acid to give a thioether-carboxylic acid is not enYisaged. United States Patent ~o. 4 153 586 describes producing a water-dispersible resin by reaction of a polyepoxide with a mercaptocarboxylic acid in the presence of a tin-containing catalyst.
Reaction between a phenol, an aldehyde, and an alkali metal bisulphite is also known (see, for example, Suter et al., J. Org. Chem., 1945, 10, 470-478) but, so far as we are aware, has not been carried out hitherto using a phenol-tipped advanced polyepoxide.
This invention accordingly provides new, water~soluble or water-dispersible resinous salts of formula ~ 4 ~
lP ~ X ~ _ where R represents either a group of formula -S Rl COO- II
or a group of formula ~S03 III
wherein Rl represents an aliphatic, aromatic, or araliphatic divalent group of 1 to 10 carbon atoms which may contain a further group of formula -CCO M , R represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, ! one of R and R3 represents a hydro~yl group and the other represents a hydrogen a~om, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, each -R4, which may be the same or different, represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, R represents an atom or a group bonded to a ring carbon atom which is ortho or para to the group R3 or R13 that represents ~ s ~
a hydroxyl group, and is a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, a group of formula -('H(R )OH, a group of formula -CH(R )oR8, or a group of formula -CH-R M IV
R6 represents the residue of a polyepoxide after removal of (m-~) 1,2~epoxide groups, each oE the substituents R , which may be the same or different, represents either a hydrogen atom or a covalent bond linked to the group R6 to form a cycloaliphatic ring which may be substituted by one or more aliphatic,cycloaliphatic and/or hetero-cyclic g~oups, R8 represents either an alkyl group of from 1 to 6 carbon atons or an alkoxyalkyl group wherein the alkoxy group and the alkyl group each have from 1 to 6 carbon atoms, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the carboxylic acid group, or the secondary amino group 9 m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that ~m~p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulphonyl group, an oxygen or sulphur D ~5 ~ 6 ato~ or a valency bond, and M represents a hydrogen ion, a cation derived from an alkali metal9 ammonia, or an amine, including quaternary ammoni~n cations, or one ~alency of a polyvalent catlon, with the proviso tha~ at least 25% of the ions M are a said cation.
Preferred salts of formNla I are those wherein, wherl R represents a group of formula II, R represents an alkylene group of 1 or 2 carbon atoms~ those wEIerein R6 represents a residue having an average molecular Yeight of fro~ 1000 to 5000, and those wherein (m~p) represents 2. C~lorine and ~romine are tEle preferred ~alogen atoms within t~ definitions of R3, R31, R4, and R5.
Prefera~ly the salts of formula I are further of formula R3 ~ X ~ OCH2CHCH2 - R CH2¦HCH2 M R - CH 4 (R )4 Rl /
R3 ~ X ~
R2 (R4)4 V
o~
Rl OH OH
R ~ 4 ~ X ~ ~ CH2CHCH2 -R - CH2~HCH2R
* M R ~ CH R (R )4 VI
where R , R2, R3, R3 , R4, R5, R9, X, and M are as hereinbefore defined and R10 represents the residue of an aliphatic, cycloaliphatic, or aromatic diglycidyl ether or ester after removal of both glycidyl groups.
It is further preferred that R10 in the compounds of formula V or formula VI is itself of formula ~: _ _ ~ ~ X ~ OH ~ ~ -O-(R )4 (R4)4 (R )4 (R4)4 q VII
where R and X are as hereinbefore defined and q is zero or an inte~er of from 1 to 20, and is preferably from 2 to 10~
Salts of formula I, V~ and VI wherein the group R r,epresents a hydroxyl group are part.icularly preferred, as are those in which R2 and R4 both represent a hydrogen atom.
.
Another aspect of this invention is a process for the preparation of water~soluble or water-dispersible resinous salts which comprises ~eac~ion oE a phenol-terminated resirl of formula R -CH-CH ~ R6 ~ CH - C~10 k ~ X ~ oa l (R4)4 ~n (R )3 J m VIII
wherein R4, R6, R7, R~, ~, ~, n, and p are as hereinbefore defined, wi~h the proviso that at least ~ne of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydroxyl group is unsubstituted, by thio~
alkylation in the presence of a source of M (where M is as i previously defined) ions with an aldehyde of formula R CHO IX
where R2 is as hereinbefore defined, and a mercaptocarboxylic acid of formula 15HS-Rl-COOH X
where Rl is as hereinbefore defined for Rl but may contain a carboxylic acid (-COOH) substituent instead of a -COO M
substituent.
_ 9 ~
This reaction is preferably effected by heating the reactants, usually in an inert solvent, in the presence of sufficient of a base at least partially to neutralise the mercaptocarboxylic acid. The reaction temperature is preferably within the range 60 to 180 C, especially 75 to l40C, and the reaction is usually complete within 15 minutes to 8 hours. Suitable inert so1vents include hydrocarbons, ethers, alcohols, and esters; amongst these toluene, xylene, tetrahydrofuran, butanols, ethyl acetate, and especially 2-butoxyethaDol and 2-etho~yethanol, are preferred.
A fu~ther aspect of t~is inYenti`on is a process for the preparation of water-solub~e or water~dispersihle resinous salts which comprises reaction of a phenol~terminated resin of formula VIII (whe~e R4, R 9 R ~ R ~ X, m, n~and p are as hereinbefore ~eflned~ with an aldehyde of formula IX (wherein R is as hereinbefore defined) and sulphurous acid or a water~
soluble salt of sulphurous acid,such as sodium or potassium sulphite, bisulphite, or metabisulphite, This reaction is preferably effected by heating the reactants, usually in an inert solvent, if necessary in the presence of sufficient of a base at least partially to neutralise any free acid, and optionally in the presence of a surfactant. The preferred reaction temperatures and suitable sol~ents are as described above for ~he reaction with a mercaptocarboxylic acid.
Suitable bases for the at leas~ partial neutralisation include sodium hydroxide, sodium carbonate, potassium carbonate, ammonia, triethylamine, and triethanolamine. 2-(dimethylamino~-2-methylpropan-s ~ 10 ~l-ol and 2~Cdlmethylamlno~ethanol are particularly preferred.
Usually 0.3 to 2.0 moles of the mercaptocarboxylic acid of formula X or of sulphurous acid or its salt are employed per mole of phenolic hydroxyl groups in the resin of formula VIII. An excess of the aldehyde of formula IX is usually employed, especially 1.1 to 4~0 moles of the aldehyde per mole of the mercaptocarboxylic acid of form~la X or of sulphurous acid or its salt, since t~e products then exhibit greater stahility to storage at room temperature.
The preferred aldehyde of formula IX is formaldehyde;
conveniently this is generated in situ from paraformaldehyde.
Preferred acids of formula ~ are 2- or 3-mercaptopropionic acid, thioglycolic acid, and thiomalic acid.
The phenol-terminated resins of formula VIII used as starting materials are themselves prepared by the reaction of a polyepoxide, preferably a diepoxida, with an excess of a dihydric phenol using known methods. This reaction results in adYancement of the polyepoxide through reaction with ~oth hydroxyl groups of the dihydric phenol. There must be at least as much dihydric phenol present as there is polyepoxide, on a molar basis, in order to give a product having at least one terminal phenolic group. The lar ratio o~ polyepoxide to dihydric phenol is usually within the range 1:1.02 to 1:1.6, and especially 1:1.1 to 1:1.5. The preferred method of advancement is ~y heating the reactants at 100~200C, and in the presence of a base, which may be a tertiary amine but is preferably an alkali metal hydroxide. An inert solvent may be present if desired.
The dihydric phenol used for advancement may be mononuclear, e.g., hydroquinone, but is preferably a bisphenol, especially one of formula HO ~ X ~ _ OH
(R4~4 CR4~4 where X and R4 are as hereinbefore defined, such as bis(4-hydro~y~
phenyl)~ethane and 252-~bis(4~hydroxyphenyl~propane.
Polyepo~ides preferred for adYancement to form the starting material of formula VIII are those containing two terminal groups of formula ~0 CH~C~-~I2 XII
directly attached to an atom or atoms of oxygen, nitrogen, or sulphur.
As examples of such resins may ~e mentioned polyglycidyl esters obtainable by reaction of a compound containing two carboxylic acid groups per molecule with epichlorohydrin or glycerol dichlorohydrin in the presence of an alkali. Such polyglycidyl esters may be derived from alipha~ic polycarboxylic - 12 ~
acids, e.g.g oxalic acid, succinic acid~ glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimerised linoleic acid; from cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4~methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid;
and fr~m aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid, Further examples are polyglycidyl ethers obtainable by reaction of a compound containing at least two free alcoholic hydroxyl or phenolic hydrox~l groups per molecule with epichlorohydrin or glycerol dichlorohydrin under alkaline conditions or, alternatively, in the presence of an acid catalyst and subsequent treatment with alkali. These ethers may be made from acyclic alcohols such as ethylene glycol, diethylene glycol~ and higher poly(oxyethylene2 glycols, propane-1,2-diol and poly(oxypropylene~ glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene~
glycols, pentane-l,S-diol, and polyepichlorohydrins; from cycloalipha~ic alcohols such as resorcitol, quinitol, bisC4~
hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and l,l-bis(hydroxymethyl)cyclohex-3-ene; and from alcohols having aromatic nuclei, such as N,N-bisC2~hydroxyethyl~aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. Or they may be made from mononuclear phenols, such as resorcinol and hydroquinone, and fro~ polynuclear phenols, such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxy-phenyl) sulphone, 2,2-bis~4-hydroxyphenyl)propane, 2,2-bis(3,5-- 13 ~
dibromo~4-hydroxyphenyl~propane and 2 9 2-bis(2~allyl-4-hydroxyphenyl)-propane.
Poly(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination of ~he reaction products of epichlorohydrin with amines co~taining two amino-hydrogen atoms such as aniline, n butylamine, and bis(4-methylaminophenyl)methane; and N,N'-diglycidyl derivatives of cyclic aLkylene ureas, such as ethylene-urea and 1,3~propyleneurea, and of hydan~oins such as 5,5 dimethylhydantoin.
Examples of poly(S-glycidyl~ compounds are di-S-glycidyl derivatives of dithiols such as ethane-1,2-dithiol and bis(4-mercaptomethylphenyl~ ether.
Polyepoxides having the 1,2-epoxide groups attached to different kinds of hetero atoms may be employed, e.g., the glycidyl ether-gl~cidyl ester of salicylic acid, N-gly~idyl-N~-(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-1,3 bis(5,5~dimethyl-1-glycidylhydantoin-3~yl)propane.
Polyepoxides containing non-terminal epoxide groups may also be employed, such as ~i~ylcyclohexene dio~ide, limonene dioxide9 dicyclopentadiene oxide, 4-oxatetracyclo [6,2,1,02'7,0 ' ~-undec-9-yl glycidyl ether, the bis(4-oxatetracyclo [6,~,1,02'7903'5~-undec-9-yl) e~her of ethylene glycol. 3,4-epoxycyclohexylmethyl
acid group(s~ introduced b~ sulphLIrous ac~d or its salt. They may be used with an aminoplast, a phenol~formaldehyde resin, or a blocked polyisocyanate as aqueous surface coating compositions. In cer~ain cîrcumstances the addition of such a coreactant is not, however, necessary.
The use of YariouS reactions to obtain from phenols or epoxides water--soluble or water~dispersible resins ~or use as coatings has previously been described.
For ~xa~ple, British Patent Specifica~ion No. 1 254 528 discloses carboxyl group-co~taining polyethers said to be suitable for use in water~d;lutafile coating compositions and which are obtained by reaction of a glycidyl e~her, a phenol-aldehyde condensate containing methylol groups, and a hydro~ycarboxylic acid. The product ;s a polyether phenol~aldehyde resin etherified with the hydroxycarboxylic acid. Use of a mercaptocarboxylic acid to give a thioether-carboxylic acid is not enYisaged. United States Patent ~o. 4 153 586 describes producing a water-dispersible resin by reaction of a polyepoxide with a mercaptocarboxylic acid in the presence of a tin-containing catalyst.
Reaction between a phenol, an aldehyde, and an alkali metal bisulphite is also known (see, for example, Suter et al., J. Org. Chem., 1945, 10, 470-478) but, so far as we are aware, has not been carried out hitherto using a phenol-tipped advanced polyepoxide.
This invention accordingly provides new, water~soluble or water-dispersible resinous salts of formula ~ 4 ~
lP ~ X ~ _ where R represents either a group of formula -S Rl COO- II
or a group of formula ~S03 III
wherein Rl represents an aliphatic, aromatic, or araliphatic divalent group of 1 to 10 carbon atoms which may contain a further group of formula -CCO M , R represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, ! one of R and R3 represents a hydro~yl group and the other represents a hydrogen a~om, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, each -R4, which may be the same or different, represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, R represents an atom or a group bonded to a ring carbon atom which is ortho or para to the group R3 or R13 that represents ~ s ~
a hydroxyl group, and is a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, a group of formula -('H(R )OH, a group of formula -CH(R )oR8, or a group of formula -CH-R M IV
R6 represents the residue of a polyepoxide after removal of (m-~) 1,2~epoxide groups, each oE the substituents R , which may be the same or different, represents either a hydrogen atom or a covalent bond linked to the group R6 to form a cycloaliphatic ring which may be substituted by one or more aliphatic,cycloaliphatic and/or hetero-cyclic g~oups, R8 represents either an alkyl group of from 1 to 6 carbon atons or an alkoxyalkyl group wherein the alkoxy group and the alkyl group each have from 1 to 6 carbon atoms, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the carboxylic acid group, or the secondary amino group 9 m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that ~m~p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulphonyl group, an oxygen or sulphur D ~5 ~ 6 ato~ or a valency bond, and M represents a hydrogen ion, a cation derived from an alkali metal9 ammonia, or an amine, including quaternary ammoni~n cations, or one ~alency of a polyvalent catlon, with the proviso tha~ at least 25% of the ions M are a said cation.
Preferred salts of formNla I are those wherein, wherl R represents a group of formula II, R represents an alkylene group of 1 or 2 carbon atoms~ those wEIerein R6 represents a residue having an average molecular Yeight of fro~ 1000 to 5000, and those wherein (m~p) represents 2. C~lorine and ~romine are tEle preferred ~alogen atoms within t~ definitions of R3, R31, R4, and R5.
Prefera~ly the salts of formula I are further of formula R3 ~ X ~ OCH2CHCH2 - R CH2¦HCH2 M R - CH 4 (R )4 Rl /
R3 ~ X ~
R2 (R4)4 V
o~
Rl OH OH
R ~ 4 ~ X ~ ~ CH2CHCH2 -R - CH2~HCH2R
* M R ~ CH R (R )4 VI
where R , R2, R3, R3 , R4, R5, R9, X, and M are as hereinbefore defined and R10 represents the residue of an aliphatic, cycloaliphatic, or aromatic diglycidyl ether or ester after removal of both glycidyl groups.
It is further preferred that R10 in the compounds of formula V or formula VI is itself of formula ~: _ _ ~ ~ X ~ OH ~ ~ -O-(R )4 (R4)4 (R )4 (R4)4 q VII
where R and X are as hereinbefore defined and q is zero or an inte~er of from 1 to 20, and is preferably from 2 to 10~
Salts of formula I, V~ and VI wherein the group R r,epresents a hydroxyl group are part.icularly preferred, as are those in which R2 and R4 both represent a hydrogen atom.
.
Another aspect of this invention is a process for the preparation of water~soluble or water-dispersible resinous salts which comprises ~eac~ion oE a phenol-terminated resirl of formula R -CH-CH ~ R6 ~ CH - C~10 k ~ X ~ oa l (R4)4 ~n (R )3 J m VIII
wherein R4, R6, R7, R~, ~, ~, n, and p are as hereinbefore defined, wi~h the proviso that at least ~ne of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydroxyl group is unsubstituted, by thio~
alkylation in the presence of a source of M (where M is as i previously defined) ions with an aldehyde of formula R CHO IX
where R2 is as hereinbefore defined, and a mercaptocarboxylic acid of formula 15HS-Rl-COOH X
where Rl is as hereinbefore defined for Rl but may contain a carboxylic acid (-COOH) substituent instead of a -COO M
substituent.
_ 9 ~
This reaction is preferably effected by heating the reactants, usually in an inert solvent, in the presence of sufficient of a base at least partially to neutralise the mercaptocarboxylic acid. The reaction temperature is preferably within the range 60 to 180 C, especially 75 to l40C, and the reaction is usually complete within 15 minutes to 8 hours. Suitable inert so1vents include hydrocarbons, ethers, alcohols, and esters; amongst these toluene, xylene, tetrahydrofuran, butanols, ethyl acetate, and especially 2-butoxyethaDol and 2-etho~yethanol, are preferred.
A fu~ther aspect of t~is inYenti`on is a process for the preparation of water-solub~e or water~dispersihle resinous salts which comprises reaction of a phenol~terminated resin of formula VIII (whe~e R4, R 9 R ~ R ~ X, m, n~and p are as hereinbefore ~eflned~ with an aldehyde of formula IX (wherein R is as hereinbefore defined) and sulphurous acid or a water~
soluble salt of sulphurous acid,such as sodium or potassium sulphite, bisulphite, or metabisulphite, This reaction is preferably effected by heating the reactants, usually in an inert solvent, if necessary in the presence of sufficient of a base at least partially to neutralise any free acid, and optionally in the presence of a surfactant. The preferred reaction temperatures and suitable sol~ents are as described above for ~he reaction with a mercaptocarboxylic acid.
Suitable bases for the at leas~ partial neutralisation include sodium hydroxide, sodium carbonate, potassium carbonate, ammonia, triethylamine, and triethanolamine. 2-(dimethylamino~-2-methylpropan-s ~ 10 ~l-ol and 2~Cdlmethylamlno~ethanol are particularly preferred.
Usually 0.3 to 2.0 moles of the mercaptocarboxylic acid of formula X or of sulphurous acid or its salt are employed per mole of phenolic hydroxyl groups in the resin of formula VIII. An excess of the aldehyde of formula IX is usually employed, especially 1.1 to 4~0 moles of the aldehyde per mole of the mercaptocarboxylic acid of form~la X or of sulphurous acid or its salt, since t~e products then exhibit greater stahility to storage at room temperature.
The preferred aldehyde of formula IX is formaldehyde;
conveniently this is generated in situ from paraformaldehyde.
Preferred acids of formula ~ are 2- or 3-mercaptopropionic acid, thioglycolic acid, and thiomalic acid.
The phenol-terminated resins of formula VIII used as starting materials are themselves prepared by the reaction of a polyepoxide, preferably a diepoxida, with an excess of a dihydric phenol using known methods. This reaction results in adYancement of the polyepoxide through reaction with ~oth hydroxyl groups of the dihydric phenol. There must be at least as much dihydric phenol present as there is polyepoxide, on a molar basis, in order to give a product having at least one terminal phenolic group. The lar ratio o~ polyepoxide to dihydric phenol is usually within the range 1:1.02 to 1:1.6, and especially 1:1.1 to 1:1.5. The preferred method of advancement is ~y heating the reactants at 100~200C, and in the presence of a base, which may be a tertiary amine but is preferably an alkali metal hydroxide. An inert solvent may be present if desired.
The dihydric phenol used for advancement may be mononuclear, e.g., hydroquinone, but is preferably a bisphenol, especially one of formula HO ~ X ~ _ OH
(R4~4 CR4~4 where X and R4 are as hereinbefore defined, such as bis(4-hydro~y~
phenyl)~ethane and 252-~bis(4~hydroxyphenyl~propane.
Polyepo~ides preferred for adYancement to form the starting material of formula VIII are those containing two terminal groups of formula ~0 CH~C~-~I2 XII
directly attached to an atom or atoms of oxygen, nitrogen, or sulphur.
As examples of such resins may ~e mentioned polyglycidyl esters obtainable by reaction of a compound containing two carboxylic acid groups per molecule with epichlorohydrin or glycerol dichlorohydrin in the presence of an alkali. Such polyglycidyl esters may be derived from alipha~ic polycarboxylic - 12 ~
acids, e.g.g oxalic acid, succinic acid~ glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimerised linoleic acid; from cycloaliphatic polycarboxylic acids such as tetrahydrophthalic acid, 4~methyltetrahydrophthalic acid, hexahydrophthalic acid, and 4-methylhexahydrophthalic acid;
and fr~m aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid, Further examples are polyglycidyl ethers obtainable by reaction of a compound containing at least two free alcoholic hydroxyl or phenolic hydrox~l groups per molecule with epichlorohydrin or glycerol dichlorohydrin under alkaline conditions or, alternatively, in the presence of an acid catalyst and subsequent treatment with alkali. These ethers may be made from acyclic alcohols such as ethylene glycol, diethylene glycol~ and higher poly(oxyethylene2 glycols, propane-1,2-diol and poly(oxypropylene~ glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene~
glycols, pentane-l,S-diol, and polyepichlorohydrins; from cycloalipha~ic alcohols such as resorcitol, quinitol, bisC4~
hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and l,l-bis(hydroxymethyl)cyclohex-3-ene; and from alcohols having aromatic nuclei, such as N,N-bisC2~hydroxyethyl~aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane. Or they may be made from mononuclear phenols, such as resorcinol and hydroquinone, and fro~ polynuclear phenols, such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxy-phenyl) sulphone, 2,2-bis~4-hydroxyphenyl)propane, 2,2-bis(3,5-- 13 ~
dibromo~4-hydroxyphenyl~propane and 2 9 2-bis(2~allyl-4-hydroxyphenyl)-propane.
Poly(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination of ~he reaction products of epichlorohydrin with amines co~taining two amino-hydrogen atoms such as aniline, n butylamine, and bis(4-methylaminophenyl)methane; and N,N'-diglycidyl derivatives of cyclic aLkylene ureas, such as ethylene-urea and 1,3~propyleneurea, and of hydan~oins such as 5,5 dimethylhydantoin.
Examples of poly(S-glycidyl~ compounds are di-S-glycidyl derivatives of dithiols such as ethane-1,2-dithiol and bis(4-mercaptomethylphenyl~ ether.
Polyepoxides having the 1,2-epoxide groups attached to different kinds of hetero atoms may be employed, e.g., the glycidyl ether-gl~cidyl ester of salicylic acid, N-gly~idyl-N~-(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-1,3 bis(5,5~dimethyl-1-glycidylhydantoin-3~yl)propane.
Polyepoxides containing non-terminal epoxide groups may also be employed, such as ~i~ylcyclohexene dio~ide, limonene dioxide9 dicyclopentadiene oxide, 4-oxatetracyclo [6,2,1,02'7,0 ' ~-undec-9-yl glycidyl ether, the bis(4-oxatetracyclo [6,~,1,02'7903'5~-undec-9-yl) e~her of ethylene glycol. 3,4-epoxycyclohexylmethyl
3'~4'-epoxycyclohexanecarboxylate and its 6,6'-dimethyl derivative, the bis~3,4-epoxycyclohexanecarboxylate~ of ethylene glycol, and 3-(3,4-epoxycyclohe~yl)-~,9-epoxy-294-dioxaspiror5~5]undecane.
~ 14 ~
Also, if desired, a mixture of diepo~icles ~ay be used.
Polyepo~ides containing more than ~wo epoxide groups ~ay be advanced but, as those skilled in the art of epo~ide resi~s are aware, advanc~ment of such polyepuxides is more difficult, there 5 being a risk or gelation.
Preferred diepoxides are d;~lycidyl ethers and diglycidyl esters. Specific preferred diepoxides are diglycidyl ethers of 2,2-bis(4-hydroxyphe~yl)propane or bis(4-hydroxyphenyl)Dethane, having a 1,2-epoxide content of more than 1.0 equivalent per kilogra~
The dihydric p~enol ~y be used alone or, if desired, i~
the presence of a compound which reacts with an epoxide group of the polyepo~ide ~ut will not ~eact further, so preventing further chain~length~ning reaction. Suitable such Ichain~
terminators' are secondary monoamines, monocarbo~ylic acids and, more especially, nohydric phenols, p~tert.butylphenol being particularly preferred. If a chain terminator i5 added it must be in such a quantity that at least one epoxide group per average molecule of the polyepoxide is left free to react with the dihydric phenol.
As already stated, the salts of this invention may be used, in the form of heat-curable compositions, to form surEace coatings~
3~
~- 15 ~
This in~e~tion accordingly further provides heat-curable composition~ comprisin~ 100 parts by ~eight of a salt o~ formula I~ calculatet o~ its ~olids co~te~l: (as here;nafter def;ned) and 2 to 200 parts, pre~er~hly 23 to 150 part~, by weight, calculated oa its solids co~tent~ of an smi~oplast~ a phe~ol-formaldehyde resin, or a blocked p~lyisocy~nate1 ~he aminoplast or phenol-for~aldehyde resi~ ha~i~g at les~t 2 groups of formula ca o~ll XIII
attached directly to an amidic nitrogen ato~ or atoms or direc~ly attached ~o carbon atoms of a phenolic ring, where R
represents a hydrogen atom or a~ alkyl group of from 1 to 6 carbo~ ato~s.
Such compositio~s i~ a form suitable for application ~ill u~ually also contain ~ater a~d a mQnor proportion, compared with the volume of water, of a~ organic solvent, such as a~ ether, alcokol, k~one,or ester, esp~cially 2-~u~7ethanol or 2-ethoxyethanol. ~Iethylolated compouuds which may be used to form the coDpositions include urea.-fon~aldehyde condensates, æmino-triazine-formaldehyde condensates, especially mela~ine-formaldehyde and benzoguana~i~e-formaldehyde condensates, and phenol-formaldehyde condensatesO These may be etherified if desired, e.g., the ~butyl ethers may be used. In many cases the methylolated compo-lnds and their ethers are not the~selves water-soluble or water-dispersible. Tncorporation of a compound of formula I aids the dispersion or solution of such ~ 16 ~
m~erials in wate~ giving stable solutions or dis~ersio~s of the mix~ures.
Examples of suitable blocked polyisocyanates (i.e., those which are stable in the aqueous dispersion at room tem~erature but which react with the compound of formu]a I on heatîng) include di~
and poly-isocy~nates blocked with caprolactam, an o~i~e (e.g., cyclohexanone oxime), a monohydric phenol (e.g., phenol itself, p-cresol, and p~tert,~utylphenol~, or a monohydr;c aliphatic, cycloaliphatic, or araliphatic alcohol (e.g., methanol, n-butanol, decanol, l-phenylethanol~ 2-ethoxyethanol, and 2-n-butoxyethanol).
Suitable isocyanates include aromatic di-isocyanates such as m-phenylene, 1,4-naphthylene, 2,4- and 2,6-tolylene, and 4,4l_ methylenebis(phenylene) di-isocyanates, and also their prepolymers with glycols (e.g., ethylene and propylene glycol), glycerol, trimethylolpropane, pentaerythritol~ diethylene glycol, and adducts of alkylene oxides with these aliphatic di- and polyhydric alcohols.
The compositions may be cured by heating at lOO C to 275C, preferably 150C to 225 C, for from 30 seconds to 1 hour, preferably from 2 to 30 minutes.
Other water-soluble or water-dispersible film-formin~
substances may also be included9 such as alkyd resins and acrylic resins. The amount of such materials may vary between wide limits, but should not be so great as to mask the advantageous properties of the compositions of this invention. Typically, additions of up to 50%, and preferably not more than 30% may be used, these - 17 ~
percentages being based on t}le solids conteat of the materials.
By the term "solids content", as used throughout the present specification and the clai~s thereto, is meant the percentage residue left after a 1 g sample of the material has been heated i~ a 5 cm diameter open dish in an oven at 120C for 3 hours a~ atmospheric pressure.
Ne ~e further found that if, in formula I, R5 denotes a group of formula -~M(R2)0~ the salts may be heat-cured without including an aminoplast~ a phenol-formaldehyde resin~ or a blocked polyisocyanate.
A further aspect of this invention accordingly provides a method of coating a surface ~hich comprises applying thereto a salt of formula I w~erein ~5 denotes a group of ormula -CH(R2)0 and heating the coated surface ~o a temperature within the range 15 100 C to 275 C, preferably lSO C to 225 C, for from 30 seconds to 1 hour and prefera~ly for ~rom 2 to 30 minutes, to cure the salt.
Surfaces to ~e coated with a composition of this invention are preferably of primed or unprimed metal, especially a ferrous ~etal, hut ~ay~be, e~., g~ w~od ~ a ~eat~esistant synt~etic ~ater-i`al.
The compositions may be applied by immersion, brushing, rollering, spraying (including electroctatic spraying~, by electrodeposition, or by any other conventional means. They may9 if desired, include pigments and dyes. Other materials which may ~ 18 ~
be ;ncorporated ;nclude e~tender~ ~uch as calcium carbonate, çalcium s~lphate, barium sulphate, and magnesium silicate, surface-active agen~s, flow additives, and plasticisers. They may also contain a strong acid, e.g., an aromatie sulphonic acid or its salt with an amine or a~monia, as catalyst.
This invention is illustrat~d by the following Examples in wh;ch all percentages are by weight.
Starting materials used in the F.xamples were prepared as ~ollows:
lQ Phenol I
Epoxide resin I, i.e., a liquid glycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane~(760 g; epoxide group content 5.25 equiv./kg), 2,2-bis(4-hydroxyphenyl)propane (684 g), and 10% aqueous sodium hydroxide solution (1.6 g~ were stirred and heated under nitrogen to 160 C. The mola~ ratio of epoxide .esin to bisphenol was 1:1.5. An exothermic reaction commenced and the temperature of the ~ixture rose spontaneously to 197C. The mixture W25 cooled to 180C and stirred at this temperature for a further 3 hours to gi~e Phenol I, a phenolic hydroxyl group terminated resin having negligible epoxide group content (not more than 0.02 equiv./kg) and an average molecular weight of 1370.
henol II
Epoxide resin I (35.9 kg), 2,2-bis(4-hydro~-yphenyl~propane (24.6 kg~, p-tert.butylphenol (2.0 kg), and 10% aqueous sodium hydroxide solution (39 g) were stirred and heated under nitrogen to 180 C. The molar ratio of epoxide resin to bisphenol to ~ 19 -monoh~dric phenol was 1:1.14:0.14. AQ e~othermic reaction commenced and the temperature of the mixture rose spontaneously to 207C. The mixture was cooled to 180 C and st:irred at this temperature for 3~ hours to give Phenol II, a phe~olic hydroxyl group~terminated resin having a negligible epo~ide group content and an average molecular weight of 1880.
Phenol III
~
3,4-Epoaycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (200 g; epoxide group content 7.00 equiv./kg), 2,2-bis(4-hydroxy-phenyl)propane (199.5 g), and 50% aqueous ~etramethylammonium chloride (2.4 g) were stirred and heated to 120C. The molar ratio of the epoxide resin to bisphenol was 1:1.25. An exothermic reaction commenced and the temperature of the mixture rose spontaneously to 132 C. The mixture was cooled to 120C and stirred at this temperature for a further 2 hours followed by 3 hours at 160C to gi~e Phenol III, a phenolic hydroxyl group-terminated resin having a negligible epoxide group content (0.08 equiv./kg) and an average molecular weigh~ of 1220.
Phenol IV
Epoxide resin I (114.3 g), hydroquinone (44 g), and 50%
aqueous tetr~methylammonium chloride (l g) were stirred and heated to 130C. The molar ratio of Epoxide resin I to hydroquinone was 1:1.33. An exothermic reaction commenced and the temperature of the mixture rose spontaneously to l90 C. The mixture was cooled to 160C and stirred at this temperature for 3~ hours to give 20 ~
Phenol Xv9 a p~enolic hydroxyl group~terminated resin having a negli~ible epoxide group content (no~ mo~e than 0.02 equiv./kg) and an average molecular weight of 152C)o Phen~l V
_ .
. 5 Epoxide resin I (256.0 g), 2,2-bis~4-hydroxyphenyl) sulphone (254.0 g)~ and 50Z aqueous tetra~ethylammonium chloride (3.3 g) were stirred and heated ~o 1~0C. The molar ratio of Epoxide resin I ~o the bisphenol was 1:1~5. An exother~ic reaction c~mmenced and the tempera~ure of the mixture rose spontaneously to 170C. The mix~ure was heated further to 180C and held at this temperatur~ for 2l hours tp give Phenol V, a phenolic hydroxyl g~oup-terminated resi~ having a negligible epoxide group content (not more than 0.02 equiv~/kg) and a~ average molecular weight of 14G0.
Phen~l VI
Epoxide resin II, i.e,, a solid glycidyl polyether of 2,2-bis~4-hydro~yphenyl~propane ~100 g; epoxide group content 1.40 equi~.tkg2, 2-butoxyet~anol ao g~, and acetic acid (2.1 g;
0.035 mol.~ were stirred and heated to 120C and maintained at 120C for 4 hours by which ~.ime the epoxide group content had 20 fallen to 0.58 equiv./kg. There were added 2 9 2-bis(4 hydroxyphenyl)-propane (24 g~ and 10% aqueous sodium hydroxide solution (0.2 g~, and the mixture was heated under nitrogen to 170C and maintained at 170 C for 6 hours to g;ve a solution in 2-butoxyethanol of Phenol VI, a phenolic hydroxyl group-termlnated resin having a negli`glble epoxide 25 groupcontent, ~3~
~e~
This is a water-soluble, methylated hexamethylolmelamine ~esin of 1002 solids content which contains~ on average, 4.0 ~ethoxymethyl residues per aminotriazine nucleus, and has a viscosity of 10 Pa s at 25C;
Phenoplast I
This is a co~mercially available butylated phenol-formaldehyde resin~ supplied as a solution (56% sollds content) in n-butanol containing a small amount of toluene. It is not soluble nor dispersible in water.
~]ocked rsocyana e r A mixture C43.9 gg 0.25 mol~ of 2,4~ and 2,6~diisocyanato-toluene (ra~io 4:1~ was s~irred in a reactor and 2-ethylhexanol C7l.5 g, 0~55 mol.~ containing 2 drops of dibutyltin dilaura~e 1~ catalyst was added slowly, ~aintaining the reaction temperature below 60C.
Free formaldehyde ~as determined by the following method:
About 1~5 g of the resin ~as ~ei~het accurately and placed i~ a conical flask. Distilled water (30 ml~ ~as added and the contents were mixed thoroughly. Thymolphthalei~ indicator (3 drops) was adted and the mixture was adjusted to neutrality ~lth N/10 hydrochloric acid or sodium hydroxide if necessary. The mi~ture was cooled in ice, and ice-cold sodium sulphite solution (25 ml, 12.5% w/~) ~as added. The mixture was shaken ~i~orously ~ 22 -and then titrated against N/10 hydroehloric acid until the hl~e clolour disappeared. The percentage free formaldehyde =
titre (ml) x ~ormality of HCl x 3.001 sample weight (g) - ~3 -E~A~IE 1 -A solutior- of Phenol I C50.0 g; 0,036 mole) in 2-~utoxyethanol (16.7 g) wa.s mixed ~ith thioglycolic acid (9.2 g; 0.10 mole) and heated to 100C- After 30 minutes a~ 100C, the mixture was cooled tD 80C a~d paraformaldehyde (3.6 g; 91% ac~ive content, 0.11 mole~
and 2~(dimethylamano)ethanol ~5.3 g; 0.060 mole) were added. This soluti~n was then gently heated to reflux at 140C and maintained a~ reflux for 8 hours by which time the measured free formaldehyde content had fallen to 0.22~. The produe~
1~ had a solids content o 73.7% and was fully dilutable with water.
The product is su~stantiall~ of a~erage formula I, where R denotes a group of formula II, Rl denotes eC~2~, R2, R31, R4, and P~7 each denote H, R3 denotes ~OH, some ~f R5 denot~ -H and the remainder denote a group ~ ~S~C~2COO M ortho to R ~ R
denotes a residue co~prising u~its of formula 2 ~ 2 0~ ~ 2 ~ oc~2 CH3 r CH3 XIV
wherein r has an average value 2.3, m is 2, p is zero, n is l, ~
denotes isopropylidene para to ~3, and 60% of the groups M denote a group o~ formula HOCH2CH2NHCCH3~2, the re~ainder denoting H .
A solution of Phenol II ~350 g; 0,186 mole~ in 2~uto~yethanol (191 g~ was mixed with thioglycolic acid (47.9 g; 0.52 mole~ and heated to 100C. After 30 minutes at 100C the mixture was S cooled to 80 C and paraformaldehyde (20.6 g; 91% ac~ive content, 0.62 mole) and 2-(dimethylamino~ethanol (46.2 g; 0.52 mole) were added. This solution was then gently heated to reflux at 130C
and maintained a~ re~lux for S hours by which time the measured free formaldehyde content had fallen ~o 0.6%. The product had a solids conten~ of 63.5% and was f~lly dllutable with water.
T~e product is sufis~antially of a~erage ~rmula I, where R denotes a group of formula rI, Rl denotes ~CH2-, R2, R31, R4, and R7 each de~ote -H, R3 denotes ~0~, some of R5 denote ~
and the remainder deno~e a group ~SH2-S~CH2COO ~ ortho to R , R6 denotes a residue comprising un~ts of formulz XIV wherein r is of average Yalue 4.0, (m+p2 is 2, n is 1, R deno~es p~tert.~
butylpheno~y~ X denotes isopropylidene para to R , and M denotes a group of formula ~OC~2C~2NH(CH3~2.
A solution of Phenol I {50.0 g, 0.036 mole~ in 2-butoxyethanol (16.7 g~ was mixed with thiomalic acid (15.0 g; 0.10 mole) and heated to 120C. After 30 minutes at 120C, the mixture was cooled to 80C and paraformaldehyde ~0 g; 91% active content, 0.30 mole) and 2-(dimethylamino)ethanol (18.0 g; 0.20 le) were added. .This solution was then gently heated to reflux at 138C
and maintained at reflux for 6 hours hy which time the measured free formaldehyde had fallen to 0.9%. The product had a solids content of 67.5% and was fully dilutable with water.
The product is substantially of average formula I, where R
S denotes a group of formula II, R denotes ~~ ~ R2 R3 R4 H2COO'Mt and R7 each denote -~, R3 denotes -OH, some of R5 denote -H and the remainder denote a group -CH20H or -CH2-S~CH-COO M ortho to ~ I2COO M
R3, R6 denotes a residue co~prising units of formula XIV wherein r is of a~erage value 2.3, m is 2, p is zero, n is 1, X denotes isopropylidene para to R3, and M denotes a group of formula Hoc~2c~2NH(cH3)2o E~AMPLE 4 A solution of Phenol I (50.0 g, 0.036 mole) in 2-butoxyethanol (25 g) was mixed with 3-mercaptopropionic acid ~15.9 g; 0.15 mole) lS and heated to 80C. To this solution was added paraformaldehyde (7.2 g; 91% active content, 0.22 mole) and 2~(dimethylamino~ethanol (13.3 g; 0.15 mole) and the mixture was gently heated to reflux at 125C and m~intained at reflux for 5 hours by which time the measured free formaldehyde had fallen to 1.3%. The product had a 20- solids content of 65.1~ and was fully dilutable with water.
The produc~ is substantially o average formula I9 where R denotes a group of formula II, R denotes CH2CH2-, R , R 1' R~ a~d R7 each denote -H, R3 denotes ~OH9 some of R5 denote a group -CH20H and the remainder denote a group ~ ~ -S~CH2-CH2COO M ortho to R , R denotes a residue com~rising Ullits of formula XIV wherein r is of aYerage value 2,3, m is 2, .p is æero, n is 1, X denotes isop;ropylidene para to R , and M
denote3 a group of formula HOCH2C~12NH(CH3)2.
E~AMPIE S
S Phe~l III C5~ g; 0.041 mwle2 w~ mi~ed ~ith 2~buto~yetha~ol (20 ~) and heated t~ 110C. When the phenol had compl2tely dis~olved the mlxture was cooled to 80C and thioglycolic acid (9.2 g, 0.10 mole), 2~ methylamlno)ethanol (8.9 g; 0.10 mole), and 91% para~ormaldehyde C4 g; 0.12 m~le2 were added. The mixture 0 WA~ gently heated to reflux at 133C and maintained a~ this temperature for Z hours by w~ich time the measured free formaldehyde conte~t had fallen to 0.9%. The product had a solids content o~
68.62 and wa~ ully dilutahle ~ith ~ater.
The produc~ is substantially of average formula T, w~ere R
denotes a group of iormula II, R denotes ~CH2-, R , R 1~ and R4 denote -H, R deno~es -OH, some of R denote -H and the remainder denote a group -CH2SC~2C00 ~ or -CH20H ortho to R , R represents a covalent bond with R6 which, toge~her with the indicated hydroxyethylene group, represents a group of formula zO ~C~2Ct,x C~ 20Co~
~ 27 -(in which every terminal bond of the indicated groups -CH20CO~
is posi~ioned 3~ or 4- to the indicated hydro~yl groups~, m is 2, p is ~ero, n is 1~ ~ denotes isopropylidene para to R3, and M denotes a group of formula HOC~2CH2N~I(CH3)2.
Phenol IV (50 g; 0.033 mole~ was m.ixed with 2~butoxyethanol (25 g) and heated to 120C. When the phenol had completely dissolved, the. mîxture was cooled to 80 C and thioglycolic acid (9.2 g; 0.10 ~ole), 91% paraformaldehyde (5.0 g~ 0.15 mole~, and 2-(dimethylamino)e~hanol (9.0 g; 0.10 mole~ were added.
The solution was then gently heated to reflux at 140C and maintaiued at reflux for 4 hours, by which time the measured free formaldehyde conterlt had fallen to 0.44%~ The product had a solids content of 64.9% and was fully diluta~le with water.
The product is subs~antially of aYerage formula I, where R
denotes a group of formula II, R denotes -CH2~, R , R 1' R4, and R denote -H~ R3 denotes -OH, s~me of R denote -H and the remainder denote a group -CH20H or -CH2-S-CH2COO M ortho to R3, m is 2, n and p are ~ero, R denotes a residue containing 2,2-bis(4-oxyphenyl)propane groups, -CH~CH(OH~CH2- groups, and p-phenylenedioxy groups, and M~denotes a group of formula OCH2 2 (CE13)2.
Phenol V (50 g; 0.036 mole~ was mixed with 2-butoxyethanol (20 g~
and heated to 140C. When the phenol had completely dissolved the mixture was cooled to 90 C and thioglycolic acid (9.2 g; 0 10 - 28 ~
~ole), 91~ paraformaldehyde (4.0 g; O.:L2 mole),and 2-(dimethyl-amino)ethanol (8.9 g; 0 10 mole) were added. The solution was the~ hea~ed ~o reflux at 140 C and maintained at reflux for 4 hours by which time the free formaldehyde content had fallen to 0.40%. The product had a solids content of 68.6% and was flllly dilutable with water.
T~e product is su~stantially of average formula I, where R
denotes a group of for~ula II, Rl denotes ~H2~, R2, R31, R4, and R7 each denote ~H, R3 denot~s ~OH~ some of R5 denote ~ and the remainder denote a group ~CH20H or ~CH2-S~CH2COO M ortho to R3, R denotes a residue containing 2~2~-~isC4~oxyphenyl~propane groups9 ~CH2CM~OH~CH2~ g~oup~ and 2,2-bis(4~oxyp~enyl~ sulphone groups, m is 2, p is zero, n is 1, X denotes ~S02~ para to R39 and M denotes a group uf formula H0CH2CH2NHCCH~2.
Sodium sulphite (7.3 g; 0.58 mole) was dissolved in water (20 ml3 and 38~1% formaldehyde solution ~10.5 g; 0.120 mole of CH20) was added. The mixture was stirred at room temperature for one hour and then added to a solution of Phenol I (25 g;
0.018 mole) in 2-butoxyethanol (36.3 g) held at 100C. Dioctyl succinate s~llphonic acid sodium salt (3 g) was added to the mixture, which was heated to reflux (103C) and held at reflux for 2 hours. The product had a solids content of 34% and was ully dilutable with water.
~ 2~ -The product is substantially of.average formula I, where R denotes a group of formula III, R , R 1~ R , and R denote ~H9 R denotes -OH, some of R denote -H and the remainder denote ~CH20H ortho to to R , R denotes a residue compris~.ng units of formula XIV wherein r has an average value of 2.3, p is zero, m is 2, n is 1, X denotes isopropylidene para to R , and M denotes Na .
EX~MPLE 9.
-- ~7_.
The solution C50 g) of Phenol ~I was mi~ed wit~ thloglycolic acid (4.2 g; 0.046 mol) and 2-(d;methylamino~ethanol (4.1 g; 0.046 mol? and heated to 100C, Uhen the ~i~ture reached 100C, paraformaldehyde C3.0 g; 91% active content, 0,09 ~ol) was added and heating was continued to a temperature of 140 C~ The mixture was ~aintained a~ 140C for 3 hours, ~y which ti~e the measured free formaldeh~de cont.ent had fallen to 0.5%. T~le product had a solids content of 64.3% and was fully dilutable with water.
The product is su~stantially of aYerage formula I, where R denotes a group of formula II, R de~otes -C~2~9 R , R 1' R , and R7 each denote -H, R3 denotes ~OH9 some of R5 denote -H
and the remainder denote a group of formula -C~2-S~CH2COO M
ortho to R3, R6 denotes a residue compris~ng u~its of formula XIV
wherein r is of average value of 3-9, (~+P2 is 2, n is l, R
denotes CH3COO-, X denotes isopropylidene para to R3, and M
denotes a group of formula HOCH2CH2NH(CH3~2.
6~
- 30 ~
~ 0 A solution of Phenol I (64,4 ~; 0.046 mol) in 2~butoxyethanol (2105 g) was mixed with thiogl~colic acid (5.5 g; 0.06 mol~ a~d heated to 100C. After 30 minutes at 100C the mixture was cooled to 80C and paraformaldeh~de t4 g; 91~ acti~e content, 0.12 mol) and 2-(dimethylamino~eth,anol (5.3 ~; 0.64 mol~ were added This solution was then gently heated to reflux at 140C and ~aintained at reflux for 4 hours ~y which time the measured free formaldehyde content had fallen to 0.20%~ The product had a solids content of 74.0% and was ully dilutable with water.
The prod~ct is substantially of aYerage formula I, where R
denotes a group of formula II, R denotes ~CH2~J R , R 1~ R ~ and R7 each denote -H~ R3 denotes ~OH, some of R5 denote -~120H and ~he remainder denote a group of formula ~CH2-S~CH2COO M ortho to ~ 15 R , R denotes a residue comprising units of Xormula ~IV wherein ; r has an average value of 2,3, m is 2, p is zero, n is 1, X deno~es isopropylidene para to R , and M denotes a group of formula HOCH2C~2NHtC~3)2 EXAMPLES 11~13 In thPse Exa~ples car~oxylate salts of this in~ention are cured by heating with an aminoplast.
Coating formulations were prepared by mi~ing the produc~s of, respectively, Examples 1, 2, and 4 with Aminoplast I in th~
ratio 80:20 calculated on tne solids contents. The resulting ~5 solutions were dilu~ed with water and applied to tin-coated steel ~3~
plates by spin-coating, leaving a coating 2 ~m thick. The plates were then he~ted at 215 C for 3 minutes and tested. The results are shown in Table 1.
~YAMPLE 14 In ~his E~ample a carboxylate salt of this invention is cured by heating with a phenolic resin.
A coating ~ormulation was prepared by mixing the product of Example 2 with Phenoplast I in the ratio 72:2~ calculated on the solids contents. The resulting solution was diluted with water and applied to tin-coat&d steel plates by spin-coating, lea~ing a coating 2-4 ~m thick. I~e plates were then heated at 200 C for 10 minutes and tested. The results are also shown in ! . Table l.
~ 32 -Test Exam~le E~a~le E~am~le E~3mple ll 12 13 14 ~___ _ ~ r~ ~ Pass Pass Pass pass at 55~ 80~ 5S~ 88Z
__ ___ ___ Pas~aurlsatlon in water Pa~s Pass Pass 75~C/45 min.3 ___~ __ ~ater boil ; l~O~C/l hour3~ail Pass Soite~ed . .~ ._ 3:~ ace~ic aci~
100C/6 hour~3 ~ ~ ~ Pass _~ _ ~
A dash (w) indicates that the test was ~ot carried out lThe E~IK rub tes~ comprised givirlg the coated surface 50 double rnbs ~ith C~ttOIl wool soaked i~ ethyl me~hyl ketone a~d - e~ami~ing the surface for removal or softening. 'Pass~ indicates that no P~fect wax obsen~ed l~e wedge ~e~d test comprised impact~ending the specimens o~er a mandrel 10 cm long~ having an outside di~eter of 6 mm at one end a~d tapering to a point at the other. The specimens were then examined to determine the percentage of the le~gth of the sample fr~m which ~he coati~g did not flake of~.
3The pasteurisation a~d ~oili~g tests eom~rised heating the ~ ~3 -~
samples in water or aceeic acid for the give~ time a~d t~mperature and examini~g the coated surface for an~ defects. IPass' lndicated that ~o d~fects were observed .
EXAMPI~E ~lS
In this Example a car~oxylate salt of this invention is cured by heating alone, i.e., in the a6sence of an aminoplast or phenoplast.
The product of Example 10 was diluted with water as required to give a viscosity at 25C of 20~30 ~Pa s and applied to tin coated steel plates by spin coating leaving a coating 2 to 4 ~m thick. The coating was cured by heating at 215C for 10 minutes.
The coating passed the EMK rub test and pasteurisation in water test described above.
In this Example a carbo~ylate salt of this invention is cured by heating with a blocked isocyanate.
A formulation for coatings c~prising the product of Example I (10 g~, Blocked Isocyanate I C1.8 g2, and water as required to giYe a vîscosity at 25~C o 20~30 mPa s was applied to tin-coated steel plates by spin-coa~ing, leaving a coating 2 to 4 ~m thick. The plates were heated at 180C for 20 ~inutes, The coating passed the EMK rub test and pasteurisation in water test as described above~ ,
~ 14 ~
Also, if desired, a mixture of diepo~icles ~ay be used.
Polyepo~ides containing more than ~wo epoxide groups ~ay be advanced but, as those skilled in the art of epo~ide resi~s are aware, advanc~ment of such polyepuxides is more difficult, there 5 being a risk or gelation.
Preferred diepoxides are d;~lycidyl ethers and diglycidyl esters. Specific preferred diepoxides are diglycidyl ethers of 2,2-bis(4-hydroxyphe~yl)propane or bis(4-hydroxyphenyl)Dethane, having a 1,2-epoxide content of more than 1.0 equivalent per kilogra~
The dihydric p~enol ~y be used alone or, if desired, i~
the presence of a compound which reacts with an epoxide group of the polyepo~ide ~ut will not ~eact further, so preventing further chain~length~ning reaction. Suitable such Ichain~
terminators' are secondary monoamines, monocarbo~ylic acids and, more especially, nohydric phenols, p~tert.butylphenol being particularly preferred. If a chain terminator i5 added it must be in such a quantity that at least one epoxide group per average molecule of the polyepoxide is left free to react with the dihydric phenol.
As already stated, the salts of this invention may be used, in the form of heat-curable compositions, to form surEace coatings~
3~
~- 15 ~
This in~e~tion accordingly further provides heat-curable composition~ comprisin~ 100 parts by ~eight of a salt o~ formula I~ calculatet o~ its ~olids co~te~l: (as here;nafter def;ned) and 2 to 200 parts, pre~er~hly 23 to 150 part~, by weight, calculated oa its solids co~tent~ of an smi~oplast~ a phe~ol-formaldehyde resin, or a blocked p~lyisocy~nate1 ~he aminoplast or phenol-for~aldehyde resi~ ha~i~g at les~t 2 groups of formula ca o~ll XIII
attached directly to an amidic nitrogen ato~ or atoms or direc~ly attached ~o carbon atoms of a phenolic ring, where R
represents a hydrogen atom or a~ alkyl group of from 1 to 6 carbo~ ato~s.
Such compositio~s i~ a form suitable for application ~ill u~ually also contain ~ater a~d a mQnor proportion, compared with the volume of water, of a~ organic solvent, such as a~ ether, alcokol, k~one,or ester, esp~cially 2-~u~7ethanol or 2-ethoxyethanol. ~Iethylolated compouuds which may be used to form the coDpositions include urea.-fon~aldehyde condensates, æmino-triazine-formaldehyde condensates, especially mela~ine-formaldehyde and benzoguana~i~e-formaldehyde condensates, and phenol-formaldehyde condensatesO These may be etherified if desired, e.g., the ~butyl ethers may be used. In many cases the methylolated compo-lnds and their ethers are not the~selves water-soluble or water-dispersible. Tncorporation of a compound of formula I aids the dispersion or solution of such ~ 16 ~
m~erials in wate~ giving stable solutions or dis~ersio~s of the mix~ures.
Examples of suitable blocked polyisocyanates (i.e., those which are stable in the aqueous dispersion at room tem~erature but which react with the compound of formu]a I on heatîng) include di~
and poly-isocy~nates blocked with caprolactam, an o~i~e (e.g., cyclohexanone oxime), a monohydric phenol (e.g., phenol itself, p-cresol, and p~tert,~utylphenol~, or a monohydr;c aliphatic, cycloaliphatic, or araliphatic alcohol (e.g., methanol, n-butanol, decanol, l-phenylethanol~ 2-ethoxyethanol, and 2-n-butoxyethanol).
Suitable isocyanates include aromatic di-isocyanates such as m-phenylene, 1,4-naphthylene, 2,4- and 2,6-tolylene, and 4,4l_ methylenebis(phenylene) di-isocyanates, and also their prepolymers with glycols (e.g., ethylene and propylene glycol), glycerol, trimethylolpropane, pentaerythritol~ diethylene glycol, and adducts of alkylene oxides with these aliphatic di- and polyhydric alcohols.
The compositions may be cured by heating at lOO C to 275C, preferably 150C to 225 C, for from 30 seconds to 1 hour, preferably from 2 to 30 minutes.
Other water-soluble or water-dispersible film-formin~
substances may also be included9 such as alkyd resins and acrylic resins. The amount of such materials may vary between wide limits, but should not be so great as to mask the advantageous properties of the compositions of this invention. Typically, additions of up to 50%, and preferably not more than 30% may be used, these - 17 ~
percentages being based on t}le solids conteat of the materials.
By the term "solids content", as used throughout the present specification and the clai~s thereto, is meant the percentage residue left after a 1 g sample of the material has been heated i~ a 5 cm diameter open dish in an oven at 120C for 3 hours a~ atmospheric pressure.
Ne ~e further found that if, in formula I, R5 denotes a group of formula -~M(R2)0~ the salts may be heat-cured without including an aminoplast~ a phenol-formaldehyde resin~ or a blocked polyisocyanate.
A further aspect of this invention accordingly provides a method of coating a surface ~hich comprises applying thereto a salt of formula I w~erein ~5 denotes a group of ormula -CH(R2)0 and heating the coated surface ~o a temperature within the range 15 100 C to 275 C, preferably lSO C to 225 C, for from 30 seconds to 1 hour and prefera~ly for ~rom 2 to 30 minutes, to cure the salt.
Surfaces to ~e coated with a composition of this invention are preferably of primed or unprimed metal, especially a ferrous ~etal, hut ~ay~be, e~., g~ w~od ~ a ~eat~esistant synt~etic ~ater-i`al.
The compositions may be applied by immersion, brushing, rollering, spraying (including electroctatic spraying~, by electrodeposition, or by any other conventional means. They may9 if desired, include pigments and dyes. Other materials which may ~ 18 ~
be ;ncorporated ;nclude e~tender~ ~uch as calcium carbonate, çalcium s~lphate, barium sulphate, and magnesium silicate, surface-active agen~s, flow additives, and plasticisers. They may also contain a strong acid, e.g., an aromatie sulphonic acid or its salt with an amine or a~monia, as catalyst.
This invention is illustrat~d by the following Examples in wh;ch all percentages are by weight.
Starting materials used in the F.xamples were prepared as ~ollows:
lQ Phenol I
Epoxide resin I, i.e., a liquid glycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane~(760 g; epoxide group content 5.25 equiv./kg), 2,2-bis(4-hydroxyphenyl)propane (684 g), and 10% aqueous sodium hydroxide solution (1.6 g~ were stirred and heated under nitrogen to 160 C. The mola~ ratio of epoxide .esin to bisphenol was 1:1.5. An exothermic reaction commenced and the temperature of the ~ixture rose spontaneously to 197C. The mixture W25 cooled to 180C and stirred at this temperature for a further 3 hours to gi~e Phenol I, a phenolic hydroxyl group terminated resin having negligible epoxide group content (not more than 0.02 equiv./kg) and an average molecular weight of 1370.
henol II
Epoxide resin I (35.9 kg), 2,2-bis(4-hydro~-yphenyl~propane (24.6 kg~, p-tert.butylphenol (2.0 kg), and 10% aqueous sodium hydroxide solution (39 g) were stirred and heated under nitrogen to 180 C. The molar ratio of epoxide resin to bisphenol to ~ 19 -monoh~dric phenol was 1:1.14:0.14. AQ e~othermic reaction commenced and the temperature of the mixture rose spontaneously to 207C. The mixture was cooled to 180 C and st:irred at this temperature for 3~ hours to give Phenol II, a phe~olic hydroxyl group~terminated resin having a negligible epo~ide group content and an average molecular weight of 1880.
Phenol III
~
3,4-Epoaycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (200 g; epoxide group content 7.00 equiv./kg), 2,2-bis(4-hydroxy-phenyl)propane (199.5 g), and 50% aqueous ~etramethylammonium chloride (2.4 g) were stirred and heated to 120C. The molar ratio of the epoxide resin to bisphenol was 1:1.25. An exothermic reaction commenced and the temperature of the mixture rose spontaneously to 132 C. The mixture was cooled to 120C and stirred at this temperature for a further 2 hours followed by 3 hours at 160C to gi~e Phenol III, a phenolic hydroxyl group-terminated resin having a negligible epoxide group content (0.08 equiv./kg) and an average molecular weigh~ of 1220.
Phenol IV
Epoxide resin I (114.3 g), hydroquinone (44 g), and 50%
aqueous tetr~methylammonium chloride (l g) were stirred and heated to 130C. The molar ratio of Epoxide resin I to hydroquinone was 1:1.33. An exothermic reaction commenced and the temperature of the mixture rose spontaneously to l90 C. The mixture was cooled to 160C and stirred at this temperature for 3~ hours to give 20 ~
Phenol Xv9 a p~enolic hydroxyl group~terminated resin having a negli~ible epoxide group content (no~ mo~e than 0.02 equiv./kg) and an average molecular weight of 152C)o Phen~l V
_ .
. 5 Epoxide resin I (256.0 g), 2,2-bis~4-hydroxyphenyl) sulphone (254.0 g)~ and 50Z aqueous tetra~ethylammonium chloride (3.3 g) were stirred and heated ~o 1~0C. The molar ratio of Epoxide resin I ~o the bisphenol was 1:1~5. An exother~ic reaction c~mmenced and the tempera~ure of the mixture rose spontaneously to 170C. The mix~ure was heated further to 180C and held at this temperatur~ for 2l hours tp give Phenol V, a phenolic hydroxyl g~oup-terminated resi~ having a negligible epoxide group content (not more than 0.02 equiv~/kg) and a~ average molecular weight of 14G0.
Phen~l VI
Epoxide resin II, i.e,, a solid glycidyl polyether of 2,2-bis~4-hydro~yphenyl~propane ~100 g; epoxide group content 1.40 equi~.tkg2, 2-butoxyet~anol ao g~, and acetic acid (2.1 g;
0.035 mol.~ were stirred and heated to 120C and maintained at 120C for 4 hours by which ~.ime the epoxide group content had 20 fallen to 0.58 equiv./kg. There were added 2 9 2-bis(4 hydroxyphenyl)-propane (24 g~ and 10% aqueous sodium hydroxide solution (0.2 g~, and the mixture was heated under nitrogen to 170C and maintained at 170 C for 6 hours to g;ve a solution in 2-butoxyethanol of Phenol VI, a phenolic hydroxyl group-termlnated resin having a negli`glble epoxide 25 groupcontent, ~3~
~e~
This is a water-soluble, methylated hexamethylolmelamine ~esin of 1002 solids content which contains~ on average, 4.0 ~ethoxymethyl residues per aminotriazine nucleus, and has a viscosity of 10 Pa s at 25C;
Phenoplast I
This is a co~mercially available butylated phenol-formaldehyde resin~ supplied as a solution (56% sollds content) in n-butanol containing a small amount of toluene. It is not soluble nor dispersible in water.
~]ocked rsocyana e r A mixture C43.9 gg 0.25 mol~ of 2,4~ and 2,6~diisocyanato-toluene (ra~io 4:1~ was s~irred in a reactor and 2-ethylhexanol C7l.5 g, 0~55 mol.~ containing 2 drops of dibutyltin dilaura~e 1~ catalyst was added slowly, ~aintaining the reaction temperature below 60C.
Free formaldehyde ~as determined by the following method:
About 1~5 g of the resin ~as ~ei~het accurately and placed i~ a conical flask. Distilled water (30 ml~ ~as added and the contents were mixed thoroughly. Thymolphthalei~ indicator (3 drops) was adted and the mixture was adjusted to neutrality ~lth N/10 hydrochloric acid or sodium hydroxide if necessary. The mi~ture was cooled in ice, and ice-cold sodium sulphite solution (25 ml, 12.5% w/~) ~as added. The mixture was shaken ~i~orously ~ 22 -and then titrated against N/10 hydroehloric acid until the hl~e clolour disappeared. The percentage free formaldehyde =
titre (ml) x ~ormality of HCl x 3.001 sample weight (g) - ~3 -E~A~IE 1 -A solutior- of Phenol I C50.0 g; 0,036 mole) in 2-~utoxyethanol (16.7 g) wa.s mixed ~ith thioglycolic acid (9.2 g; 0.10 mole) and heated to 100C- After 30 minutes a~ 100C, the mixture was cooled tD 80C a~d paraformaldehyde (3.6 g; 91% ac~ive content, 0.11 mole~
and 2~(dimethylamano)ethanol ~5.3 g; 0.060 mole) were added. This soluti~n was then gently heated to reflux at 140C and maintained a~ reflux for 8 hours by which time the measured free formaldehyde content had fallen to 0.22~. The produe~
1~ had a solids content o 73.7% and was fully dilutable with water.
The product is su~stantiall~ of a~erage formula I, where R denotes a group of formula II, Rl denotes eC~2~, R2, R31, R4, and P~7 each denote H, R3 denotes ~OH, some ~f R5 denot~ -H and the remainder denote a group ~ ~S~C~2COO M ortho to R ~ R
denotes a residue co~prising u~its of formula 2 ~ 2 0~ ~ 2 ~ oc~2 CH3 r CH3 XIV
wherein r has an average value 2.3, m is 2, p is zero, n is l, ~
denotes isopropylidene para to ~3, and 60% of the groups M denote a group o~ formula HOCH2CH2NHCCH3~2, the re~ainder denoting H .
A solution of Phenol II ~350 g; 0,186 mole~ in 2~uto~yethanol (191 g~ was mixed with thioglycolic acid (47.9 g; 0.52 mole~ and heated to 100C. After 30 minutes at 100C the mixture was S cooled to 80 C and paraformaldehyde (20.6 g; 91% ac~ive content, 0.62 mole) and 2-(dimethylamino~ethanol (46.2 g; 0.52 mole) were added. This solution was then gently heated to reflux at 130C
and maintained a~ re~lux for S hours by which time the measured free formaldehyde content had fallen ~o 0.6%. The product had a solids conten~ of 63.5% and was f~lly dllutable with water.
T~e product is sufis~antially of a~erage ~rmula I, where R denotes a group of formula rI, Rl denotes ~CH2-, R2, R31, R4, and R7 each de~ote -H, R3 denotes ~0~, some of R5 denote ~
and the remainder deno~e a group ~SH2-S~CH2COO ~ ortho to R , R6 denotes a residue comprising un~ts of formulz XIV wherein r is of average Yalue 4.0, (m+p2 is 2, n is 1, R deno~es p~tert.~
butylpheno~y~ X denotes isopropylidene para to R , and M denotes a group of formula ~OC~2C~2NH(CH3~2.
A solution of Phenol I {50.0 g, 0.036 mole~ in 2-butoxyethanol (16.7 g~ was mixed with thiomalic acid (15.0 g; 0.10 mole) and heated to 120C. After 30 minutes at 120C, the mixture was cooled to 80C and paraformaldehyde ~0 g; 91% active content, 0.30 mole) and 2-(dimethylamino)ethanol (18.0 g; 0.20 le) were added. .This solution was then gently heated to reflux at 138C
and maintained at reflux for 6 hours hy which time the measured free formaldehyde had fallen to 0.9%. The product had a solids content of 67.5% and was fully dilutable with water.
The product is substantially of average formula I, where R
S denotes a group of formula II, R denotes ~~ ~ R2 R3 R4 H2COO'Mt and R7 each denote -~, R3 denotes -OH, some of R5 denote -H and the remainder denote a group -CH20H or -CH2-S~CH-COO M ortho to ~ I2COO M
R3, R6 denotes a residue co~prising units of formula XIV wherein r is of a~erage value 2.3, m is 2, p is zero, n is 1, X denotes isopropylidene para to R3, and M denotes a group of formula Hoc~2c~2NH(cH3)2o E~AMPLE 4 A solution of Phenol I (50.0 g, 0.036 mole) in 2-butoxyethanol (25 g) was mixed with 3-mercaptopropionic acid ~15.9 g; 0.15 mole) lS and heated to 80C. To this solution was added paraformaldehyde (7.2 g; 91% active content, 0.22 mole) and 2~(dimethylamino~ethanol (13.3 g; 0.15 mole) and the mixture was gently heated to reflux at 125C and m~intained at reflux for 5 hours by which time the measured free formaldehyde had fallen to 1.3%. The product had a 20- solids content of 65.1~ and was fully dilutable with water.
The produc~ is substantially o average formula I9 where R denotes a group of formula II, R denotes CH2CH2-, R , R 1' R~ a~d R7 each denote -H, R3 denotes ~OH9 some of R5 denote a group -CH20H and the remainder denote a group ~ ~ -S~CH2-CH2COO M ortho to R , R denotes a residue com~rising Ullits of formula XIV wherein r is of aYerage value 2,3, m is 2, .p is æero, n is 1, X denotes isop;ropylidene para to R , and M
denote3 a group of formula HOCH2C~12NH(CH3)2.
E~AMPIE S
S Phe~l III C5~ g; 0.041 mwle2 w~ mi~ed ~ith 2~buto~yetha~ol (20 ~) and heated t~ 110C. When the phenol had compl2tely dis~olved the mlxture was cooled to 80C and thioglycolic acid (9.2 g, 0.10 mole), 2~ methylamlno)ethanol (8.9 g; 0.10 mole), and 91% para~ormaldehyde C4 g; 0.12 m~le2 were added. The mixture 0 WA~ gently heated to reflux at 133C and maintained a~ this temperature for Z hours by w~ich time the measured free formaldehyde conte~t had fallen to 0.9%. The product had a solids content o~
68.62 and wa~ ully dilutahle ~ith ~ater.
The produc~ is substantially of average formula T, w~ere R
denotes a group of iormula II, R denotes ~CH2-, R , R 1~ and R4 denote -H, R deno~es -OH, some of R denote -H and the remainder denote a group -CH2SC~2C00 ~ or -CH20H ortho to R , R represents a covalent bond with R6 which, toge~her with the indicated hydroxyethylene group, represents a group of formula zO ~C~2Ct,x C~ 20Co~
~ 27 -(in which every terminal bond of the indicated groups -CH20CO~
is posi~ioned 3~ or 4- to the indicated hydro~yl groups~, m is 2, p is ~ero, n is 1~ ~ denotes isopropylidene para to R3, and M denotes a group of formula HOC~2CH2N~I(CH3)2.
Phenol IV (50 g; 0.033 mole~ was m.ixed with 2~butoxyethanol (25 g) and heated to 120C. When the phenol had completely dissolved, the. mîxture was cooled to 80 C and thioglycolic acid (9.2 g; 0.10 ~ole), 91% paraformaldehyde (5.0 g~ 0.15 mole~, and 2-(dimethylamino)e~hanol (9.0 g; 0.10 mole~ were added.
The solution was then gently heated to reflux at 140C and maintaiued at reflux for 4 hours, by which time the measured free formaldehyde conterlt had fallen to 0.44%~ The product had a solids content of 64.9% and was fully diluta~le with water.
The product is subs~antially of aYerage formula I, where R
denotes a group of formula II, R denotes -CH2~, R , R 1' R4, and R denote -H~ R3 denotes -OH, s~me of R denote -H and the remainder denote a group -CH20H or -CH2-S-CH2COO M ortho to R3, m is 2, n and p are ~ero, R denotes a residue containing 2,2-bis(4-oxyphenyl)propane groups, -CH~CH(OH~CH2- groups, and p-phenylenedioxy groups, and M~denotes a group of formula OCH2 2 (CE13)2.
Phenol V (50 g; 0.036 mole~ was mixed with 2-butoxyethanol (20 g~
and heated to 140C. When the phenol had completely dissolved the mixture was cooled to 90 C and thioglycolic acid (9.2 g; 0 10 - 28 ~
~ole), 91~ paraformaldehyde (4.0 g; O.:L2 mole),and 2-(dimethyl-amino)ethanol (8.9 g; 0 10 mole) were added. The solution was the~ hea~ed ~o reflux at 140 C and maintained at reflux for 4 hours by which time the free formaldehyde content had fallen to 0.40%. The product had a solids content of 68.6% and was flllly dilutable with water.
T~e product is su~stantially of average formula I, where R
denotes a group of for~ula II, Rl denotes ~H2~, R2, R31, R4, and R7 each denote ~H, R3 denot~s ~OH~ some of R5 denote ~ and the remainder denote a group ~CH20H or ~CH2-S~CH2COO M ortho to R3, R denotes a residue containing 2~2~-~isC4~oxyphenyl~propane groups9 ~CH2CM~OH~CH2~ g~oup~ and 2,2-bis(4~oxyp~enyl~ sulphone groups, m is 2, p is zero, n is 1, X denotes ~S02~ para to R39 and M denotes a group uf formula H0CH2CH2NHCCH~2.
Sodium sulphite (7.3 g; 0.58 mole) was dissolved in water (20 ml3 and 38~1% formaldehyde solution ~10.5 g; 0.120 mole of CH20) was added. The mixture was stirred at room temperature for one hour and then added to a solution of Phenol I (25 g;
0.018 mole) in 2-butoxyethanol (36.3 g) held at 100C. Dioctyl succinate s~llphonic acid sodium salt (3 g) was added to the mixture, which was heated to reflux (103C) and held at reflux for 2 hours. The product had a solids content of 34% and was ully dilutable with water.
~ 2~ -The product is substantially of.average formula I, where R denotes a group of formula III, R , R 1~ R , and R denote ~H9 R denotes -OH, some of R denote -H and the remainder denote ~CH20H ortho to to R , R denotes a residue compris~.ng units of formula XIV wherein r has an average value of 2.3, p is zero, m is 2, n is 1, X denotes isopropylidene para to R , and M denotes Na .
EX~MPLE 9.
-- ~7_.
The solution C50 g) of Phenol ~I was mi~ed wit~ thloglycolic acid (4.2 g; 0.046 mol) and 2-(d;methylamino~ethanol (4.1 g; 0.046 mol? and heated to 100C, Uhen the ~i~ture reached 100C, paraformaldehyde C3.0 g; 91% active content, 0,09 ~ol) was added and heating was continued to a temperature of 140 C~ The mixture was ~aintained a~ 140C for 3 hours, ~y which ti~e the measured free formaldeh~de cont.ent had fallen to 0.5%. T~le product had a solids content of 64.3% and was fully dilutable with water.
The product is su~stantially of aYerage formula I, where R denotes a group of formula II, R de~otes -C~2~9 R , R 1' R , and R7 each denote -H, R3 denotes ~OH9 some of R5 denote -H
and the remainder denote a group of formula -C~2-S~CH2COO M
ortho to R3, R6 denotes a residue compris~ng u~its of formula XIV
wherein r is of average value of 3-9, (~+P2 is 2, n is l, R
denotes CH3COO-, X denotes isopropylidene para to R3, and M
denotes a group of formula HOCH2CH2NH(CH3~2.
6~
- 30 ~
~ 0 A solution of Phenol I (64,4 ~; 0.046 mol) in 2~butoxyethanol (2105 g) was mixed with thiogl~colic acid (5.5 g; 0.06 mol~ a~d heated to 100C. After 30 minutes at 100C the mixture was cooled to 80C and paraformaldeh~de t4 g; 91~ acti~e content, 0.12 mol) and 2-(dimethylamino~eth,anol (5.3 ~; 0.64 mol~ were added This solution was then gently heated to reflux at 140C and ~aintained at reflux for 4 hours ~y which time the measured free formaldehyde content had fallen to 0.20%~ The product had a solids content of 74.0% and was ully dilutable with water.
The prod~ct is substantially of aYerage formula I, where R
denotes a group of formula II, R denotes ~CH2~J R , R 1~ R ~ and R7 each denote -H~ R3 denotes ~OH, some of R5 denote -~120H and ~he remainder denote a group of formula ~CH2-S~CH2COO M ortho to ~ 15 R , R denotes a residue comprising units of Xormula ~IV wherein ; r has an average value of 2,3, m is 2, p is zero, n is 1, X deno~es isopropylidene para to R , and M denotes a group of formula HOCH2C~2NHtC~3)2 EXAMPLES 11~13 In thPse Exa~ples car~oxylate salts of this in~ention are cured by heating with an aminoplast.
Coating formulations were prepared by mi~ing the produc~s of, respectively, Examples 1, 2, and 4 with Aminoplast I in th~
ratio 80:20 calculated on tne solids contents. The resulting ~5 solutions were dilu~ed with water and applied to tin-coated steel ~3~
plates by spin-coating, leaving a coating 2 ~m thick. The plates were then he~ted at 215 C for 3 minutes and tested. The results are shown in Table 1.
~YAMPLE 14 In ~his E~ample a carboxylate salt of this invention is cured by heating with a phenolic resin.
A coating ~ormulation was prepared by mixing the product of Example 2 with Phenoplast I in the ratio 72:2~ calculated on the solids contents. The resulting solution was diluted with water and applied to tin-coat&d steel plates by spin-coating, lea~ing a coating 2-4 ~m thick. I~e plates were then heated at 200 C for 10 minutes and tested. The results are also shown in ! . Table l.
~ 32 -Test Exam~le E~a~le E~am~le E~3mple ll 12 13 14 ~___ _ ~ r~ ~ Pass Pass Pass pass at 55~ 80~ 5S~ 88Z
__ ___ ___ Pas~aurlsatlon in water Pa~s Pass Pass 75~C/45 min.3 ___~ __ ~ater boil ; l~O~C/l hour3~ail Pass Soite~ed . .~ ._ 3:~ ace~ic aci~
100C/6 hour~3 ~ ~ ~ Pass _~ _ ~
A dash (w) indicates that the test was ~ot carried out lThe E~IK rub tes~ comprised givirlg the coated surface 50 double rnbs ~ith C~ttOIl wool soaked i~ ethyl me~hyl ketone a~d - e~ami~ing the surface for removal or softening. 'Pass~ indicates that no P~fect wax obsen~ed l~e wedge ~e~d test comprised impact~ending the specimens o~er a mandrel 10 cm long~ having an outside di~eter of 6 mm at one end a~d tapering to a point at the other. The specimens were then examined to determine the percentage of the le~gth of the sample fr~m which ~he coati~g did not flake of~.
3The pasteurisation a~d ~oili~g tests eom~rised heating the ~ ~3 -~
samples in water or aceeic acid for the give~ time a~d t~mperature and examini~g the coated surface for an~ defects. IPass' lndicated that ~o d~fects were observed .
EXAMPI~E ~lS
In this Example a car~oxylate salt of this invention is cured by heating alone, i.e., in the a6sence of an aminoplast or phenoplast.
The product of Example 10 was diluted with water as required to give a viscosity at 25C of 20~30 ~Pa s and applied to tin coated steel plates by spin coating leaving a coating 2 to 4 ~m thick. The coating was cured by heating at 215C for 10 minutes.
The coating passed the EMK rub test and pasteurisation in water test described above.
In this Example a carbo~ylate salt of this invention is cured by heating with a blocked isocyanate.
A formulation for coatings c~prising the product of Example I (10 g~, Blocked Isocyanate I C1.8 g2, and water as required to giYe a vîscosity at 25~C o 20~30 mPa s was applied to tin-coated steel plates by spin-coa~ing, leaving a coating 2 to 4 ~m thick. The plates were heated at 180C for 20 ~inutes, The coating passed the EMK rub test and pasteurisation in water test as described above~ ,
Claims (16)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Salts of formula where R- represents either a group of formula or a group of formula wherein R1 represents an aliphatic, aromatic, or araliphatic divalent group of 1 to 10 carbon atoms, R2 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, one of R3 and R? represents a hydroxyl group and the other represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, each R4 represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, R5 represents an atom or a group bonded to a ring carbon atom which is ortho or para to the group R3 or R? that represents a hydroxyl group and is a hydrogen atom, a halogen atom, an alkyl group of l to 4 carbon atoms, an alkenyl group of 2 of 4 carbon atoms, a group of formula -CH(R2)OH, a group of formula -CH(R 2)OR8, or a group of formula IV
wherein R8 represents either an alkyl group of from 1 to 6 carbon atoms or an alkoxyalkyl group wherein the alkoxy group and the alkyl group each have from 1 to 6 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups, each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal therefrom of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents l, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, and M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation.
wherein R8 represents either an alkyl group of from 1 to 6 carbon atoms or an alkoxyalkyl group wherein the alkoxy group and the alkyl group each have from 1 to 6 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups, each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal therefrom of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents l, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, and M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation.
2. A salt as claimed in claim 1, wherein R6 in formula I represents a said residue having an average molecular weight of from 1000 to 5000.
3. A salt as claimed in claim 1 or 2 wherein R- in formula I
represents a group of formula II in which R1 represents an alkylene group of 1 or 2 carbon atoms.
represents a group of formula II in which R1 represents an alkylene group of 1 or 2 carbon atoms.
4. A salt as claimed in claim 1 or 2 which is also of formula V
or VI
where R10 represents the residue of an aliphatlc, cycloaliphatic, or aromatic diglycidyl ether or ester after removal of both glycidyl groups.
or VI
where R10 represents the residue of an aliphatlc, cycloaliphatic, or aromatic diglycidyl ether or ester after removal of both glycidyl groups.
5. A process for the preparation of resinous salts which are at least dispersible in water, comprising reaction of a phenol-terminated resin of formula . VIII
with the proviso that at least one of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydrolxyl group is unsubstituted, in the presence of a source of M+ ions with an aldehyde of formula and a mercaptocarboxylic acid of formula X
where R2 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, each R4 represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of to 4 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups 9 each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation, and R? represents an aliphatic, aromatic, or araliphatic divalent group of t to 10 carbon atoms.
with the proviso that at least one of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydrolxyl group is unsubstituted, in the presence of a source of M+ ions with an aldehyde of formula and a mercaptocarboxylic acid of formula X
where R2 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, each R4 represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkenyl group of to 4 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups 9 each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation, and R? represents an aliphatic, aromatic, or araliphatic divalent group of t to 10 carbon atoms.
6. The process of claim 5, wherein 1.1 to 4.0 moles of the aldehyde of formula IX are used per mole of the mercaptocarboxylic acid of formula X.
7. The process of claim 5 or 6, wherein 0.3 to 2.0 moles of the mercaptocarboxylic acid of formula X are used per mole of phenolic hydroxyl groups in the phenol-terminated resin of formula VIII.
8. The process of claim 5 or 6, wherein the mercaptocarboxylic acid of formula X is 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid, or thiomalic acid.
9. A process for the preparation of resinous salts which are at least dispersible in water, comprising reaction of a phenol-terminated resin of formula VIII
with the proviso that at least one of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydroxyl group is unsubstituted, in the presence of a source of M+ ions with an aldehyde of formula and sulfurous acid or a water-soluble salt of sulfurous acid, where R2 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, each R4 represents a hydrogen atom, a halogen atom, an alkyl group of l to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups, each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, and M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation.
with the proviso that at least one of the two carbon atoms ortho, or the one carbon atom para, to the carbon atom bearing the indicated phenolic hydroxyl group is unsubstituted, in the presence of a source of M+ ions with an aldehyde of formula and sulfurous acid or a water-soluble salt of sulfurous acid, where R2 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, each R4 represents a hydrogen atom, a halogen atom, an alkyl group of l to 4 carbon atoms, or an alkenyl group of 2 to 4 carbon atoms, R6 represents the residue of a polyepoxide after removal of (m+p) 1,2-epoxide groups, each R7 represents either a hydrogen atom or a covalent bond which is linked to the group R6 to form a cycloaliphatic ring, R9 represents the residue of a monohydric phenol, a secondary monoamine, or a monocarboxylic acid after removal of the hydrogen atom of the phenolic hydroxyl group, the secondary amino group, or the carboxylic acid group, m represents 1, 2, 3, or 4, n represents zero or 1, p represents zero or 1, such that (m+p) is at least 2 and at most 4, X represents an alkylene or alkylidene group of 1 to 3 carbon atoms, a carbonyl or sulfonyl group, an oxygen or sulfur atom, or a valence bond, and M+ represents a hydrogen ion, a cation derived from an alkali metal, ammonia, or an amine, or one valence of a polyvalent cation, with the proviso that at least 25% of the ions M+ are a said cation.
10. The process of claim 9, wherein 1.1 to 4.0 moles of the aldehyde of formula IX are used per mole of sulfurous acid or its salt,
11. The process of claim 9 or 10. wherein 0.3 to 2.0 moles of sulfurous acid or a water-soluble salt thereof are used per mole of phenolic hydroxyl groups in the phenol-terminated resin of formula VIII.
12. Curable compositions comprising 100 parts by weight of a salt as claimed in claim 1, calculated on its solids content, and 2 to 200 parts by weight, calculated on its solids content, of an aminoplast, a phenol-formaldehyde resin, or a blocked polyisocyanate, the aminoplast or phenol-formaldehyde resin having at least 2 groups of formula which are attached directly to an amidic nitrogen atom or atoms or which are attached directly to carbon atoms of a phenolic ring, where R11 represents a hydrogen atom or an alkyl group of from l to 6 carbon atoms.
13. Curable compositions comprising 100 parts by weight of a salt produced by the process of claim 5, calculated on its solids content, and 2 to 200 parts by weight, calculated on its solids content, of an aminoplast, a phenol-formaldehyde resin, or a blocked polyisocyanate, the aminoplast or phenol-formaldehyde resin having at least 2 groups of formula which are attached directly to an amidic nitrogen atom or atoms or which are attached directly to carbon atoms of a phenolic ring, where R11 represents a hydrogen atom or an alkyl group of from 1 to 6 carbon atoms.
14. Curable compositions comprising 100 parts by weight of a salt produced by the process of claim 9, calculated on its solids content, and 2 to 200 parts by weight, calculated on its solids content, of an aminoplast, a phenol-formaldehyde resin, or a blocked polyisocyanate, the aminoplast or phenol-formaldehyd resin having at least 2 groups of formula which are attached directly to an amidic nitrogen atom or atoms or which are attached directly to carbon atoms of a phenolic ring, where R11 represents a hydrogen atom or an alkyl group of from 1 to 6 carbon atoms,
15. A method of coating a surface which comprises applying a composition as claimed in claim 12, 13, or 14 and heating at from 100° to 275°C.
16. A method of coating a surface which comprises applying a salt of formula I as defined in claim 1 where R5 denotes a group of formula -CH(R2)OH, and heating at from 100° to 275°C.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8138979 | 1981-12-04 | ||
| GB8138979 | 1981-12-24 | ||
| GB8209094 | 1982-03-27 | ||
| GB8209094 | 1982-03-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196015A true CA1196015A (en) | 1985-10-29 |
Family
ID=26281630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000418383A Expired CA1196015A (en) | 1981-12-24 | 1982-12-22 | Resinous salts, their preparation, and their use in coatings |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1196015A (en) |
| DE (1) | DE3247281A1 (en) |
| FR (1) | FR2519011A1 (en) |
| GB (1) | GB2127414B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8407283D0 (en) * | 1984-03-21 | 1984-04-26 | Ciba Geigy Ag | Preparation of resinous products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029621A (en) * | 1975-08-07 | 1977-06-14 | Ppg Industries, Inc. | Reaction products of a polyepoxide with a thiol having a group hydroyzable to carboxyl, and aqueous solubilized products |
| US4153586A (en) * | 1978-03-13 | 1979-05-08 | Ppg Industries, Inc. | Process of making epoxy resins modified with mercaptocarboxylates |
| US4362853A (en) * | 1980-10-24 | 1982-12-07 | Ciba-Geigy Corporation | Resinous salts, their preparation, and their use in coatings |
-
1982
- 1982-11-30 GB GB08234035A patent/GB2127414B/en not_active Expired
- 1982-12-21 DE DE19823247281 patent/DE3247281A1/en not_active Withdrawn
- 1982-12-22 CA CA000418383A patent/CA1196015A/en not_active Expired
- 1982-12-24 FR FR8221752A patent/FR2519011A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3247281A1 (en) | 1983-07-07 |
| GB2127414B (en) | 1985-01-03 |
| FR2519011A1 (en) | 1983-07-01 |
| GB2127414A (en) | 1984-04-11 |
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