EP0483352A1 - Compositions de resine epoxy traditionnelles et non traditionnelles, leurs derives nucleophiles et leurs compositions polymerisables et de revetement - Google Patents

Compositions de resine epoxy traditionnelles et non traditionnelles, leurs derives nucleophiles et leurs compositions polymerisables et de revetement

Info

Publication number
EP0483352A1
EP0483352A1 EP91912798A EP91912798A EP0483352A1 EP 0483352 A1 EP0483352 A1 EP 0483352A1 EP 91912798 A EP91912798 A EP 91912798A EP 91912798 A EP91912798 A EP 91912798A EP 0483352 A1 EP0483352 A1 EP 0483352A1
Authority
EP
European Patent Office
Prior art keywords
group
independently
carbon atoms
value
bisphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP91912798A
Other languages
German (de)
English (en)
Inventor
Robert A. Dubois
Duane S. Treybig
Allyson Malzman
Pong Su Sheih
Alan R. Whetten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/691,881 external-priority patent/US5147905A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0483352A1 publication Critical patent/EP0483352A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention concerns advanced and unadvanced resins or compounds wherein the unadvanced resins or compounds and at least a portion of the advanced resins or compounds contains at least one -O- R 1 -O- or -(O-CH 2 -CHR 2 ) n -O- group as a bridge between two groups selected independently from the group consisting of (1) a saturated or unsaturated cycloaliphatic group, (2) an aromatic group, (3) a group represented by the formula
  • compositions and coating compositions containing the advanced or unadvanced epoxy resins or compounds or nucleophilic modified advanced or unadvanced epoxy resins or compounds are examples of the advanced or unadvanced epoxy resins or compounds or nucleophilic modified advanced or unadvanced epoxy resins or compounds.
  • Advanced epoxy resins have been employed to prepare either water-borne or solvent-borne coating compositions. They are usually prepared by reacting a diglycidyl ether of a bisphenol with the same bisphenol; however, sometimes a different bisphenol is employed. While these resins usually produce coatings with good adhesion and chemical resistance properties, the
  • coatings are often not as flexible or formable as desired. It would be desirable to increase the
  • One aspect of the present invention pertains to an advanced resin or an unadvanced compound or mixture of such advanced resins and/or unadvanced compounds in any combination represented by the following formulas IA, IB, IC, ID, IE or IF
  • each A is independently a single bond, -O-, -S-, -S-S-, -SO-, -SO 2 -, -CO-, -O-CO-O-, -O-R 1 -O-,
  • each Q is independently a divalent group represented by the formulas
  • each Q' is independently a divalent saturated or
  • each Q 1 is independently a divalent group represented by the formula
  • each Q 2 is independently a group represented by the formula
  • R 1 is a divalent hydrocarbyl group having from 1 to 36, preferably from 2 to 24, more preferably from 2 to 12, most preferably from 2 to 8, carbon atoms
  • R 2 is hydrogen, methyl, ethyl or phenyl
  • R 3 is a divalent hydrocarbyl group having from 1 to 36, preferably from 1 to 24, more preferably from 1 to 12, carbon atoms
  • T is -OR 1 O- or -(O-CH 2 - CHR 2 -) n -O-; each Y 1 is independently -(Q-T) m -Q-; each Y 2 is independently -(Q-T) m -Q- or -(Q'-T) m -Q', or -(Q-T) m - Q-(O-CH 2 -C(OH) (R)-CH 2 -O-(Q-T) m -Q) n 3; each Y 3 is independently a divalent hydrocarbyl group having from
  • each X is independently hydrogen, a halogen, -SO-R 4 , - SO 2 -R 4 , -CO-R 4 , -CO-O-R 4 , -O-CO-R 4 , -S-R 4 ,-OR 4 , or -R 4 ;
  • R 4 is a monovalent hydrocarbyl group having from 1 to 12, preferably from 1 to 10, more preferably from 1 to 8, most preferably from 1 to 6, carbon atoms; each a independently has a value from 1 to 25, preferably from 1 to 15, more preferably from 1 to 10; each m
  • n independently has a value from zero to 25, preferably from zero to 10, more preferably from zero to 5; ml has a value from 1 to 25, preferably from 1 to 10, more preferably from 1 to 5; n has a value from 1 to 10, preferably from 2 to 8, more preferably from 2 to 5; nl has a value from 1 to 100, preferably from 1 to 80, more preferably from 2 to 60, most preferably from 2 to 30; n 2 has a value of 1 or 3; n 3 has a value from zero to 10, preferably from 0.1 to 5; and x has a value from 2 to 19, preferably from 3 to 10, more preferably from 3 to 5; with the proviso that at least one of said
  • advanced resins or unadvanced compounds contains at least one -O-R 1 -O- or -(O-CH 2 -CHR 2 ) n -O- group as a bridge between two groups selected independently from the group consisting of (1) a saturated or unsaturated
  • Another aspect of the present invention pertains to an advanced resin prepared by reacting a composition comprising
  • components (1) and (2) are employed in amounts which provide a- ratio of phenolic hydroxyl groups per epoxide group of from 0.5:1 to 2:1; and with the proviso that at least one of the components (1) or (2) contains at least one -O-R 1 -O- group or an -(O-CH 2 -CHR 2 ) n -O- group as a bridge between two groups selected independently from the group consisting of (1) a saturated or unsaturated aliphatic group, (2) an aromatic group, (3) a group represented by the formula
  • R 1 is a divalent hydrocarbyl group having from 1 to 36, preferably from 2 to 24, more preferably from 2 to 12, most preferably from 2 to 8, carbon atoms and R 2 is hydrogen, methyl, ethyl or phenyl.
  • Another aspect of the present invention pertains to an acidified advanced resin or an acidified unadvanced compound resulting from reacting a
  • composition comprising
  • A, Q, Q', R, R', R a , R b , R 1 , R 2 , R 3 , T, X, Y 1 , Y 2 , Y 3 , a, m, m 1 , n, n 1 , n 2 , n 3 and x are as hereinbefore defined;
  • n -O- group contains at least one -O-R 1 -O- or -(O-CH 2 - CHR 2 ) n -O- group is present as a bridge between two groups selected independently from the group consisting of (1) a saturated or
  • Another aspect of the present invention pertains to an acidified advanced resin comprising the product resulting from reacting a composition comprising
  • components (1) and (2) are employed in amounts which provide a ratio of phenolic hydroxyl groups per epoxide group of from 0.5:1 to 2:1; and with the proviso that at least one of the components (1) or (2) contains at least one -O-R 1 -O- group or -(O-CH 2 -CHR 2 ) n -O- group as a bridge between two groups selected
  • R 1 is a divalent hydrocarbyl group having from 1 to 36 carbon atoms
  • R 2 is hydrogen, methyl, ethyl or phenyl
  • n has a value from 1 to 10
  • Another aspect of the present invention pertains to an aqueous dispersion comprising the aforementioned acidified advanced resin or acidified unadvanced resin and water.
  • Another aspect of the present invention pertains to curable compositions comprising (I) any of the aforementioned advanced resin compositions and (II) a curing amount of at least one suitable curing agent therefor.
  • Another aspect of the present invention pertains to a process for coating an aqueous cationic epoxy resin based composition onto an object having an electroconductive surface by steps comprising immersing the electroconductive object into a coating bath comprising an aqueous dispersion of cationic particles of the epoxy based composition, passing an electric current through said bath sufficient to electrodeosite a coating of said composition on the object by providing a difference of electric potential between the object and an electrode that is (a) spaced apart from said object, (b) is in electrical contact with said bath, and (c) is electrically positive in relation to said object;
  • composition contains any of the aforementioned cationic epoxy-containing compositions and a curing amount of a suitable curing agent therefor.
  • a further aspect of the present invention pertains to a coating composition comprising any of the aforementioned curable compositions.
  • a still further aspect of the present invention pertains to an article coated with the aforementioned coating compositions which coating has subsequently been cured.
  • the present invention provides coating with good flexibility or formability as exhibited by good flexural or formable properties determined by reverse impact, T-bend and wedge-bend tests, chip resistance, and with good corrosion resistance and throwpower.
  • the present invention may suitably comprise, consist of, or consist essentially of, the
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the element to which it is attached.
  • divalent hydrocarbyl group refers to the aforementioned hydrocarbyl groups minus an additional hydrogen atom.
  • cycloaliphatic groups can be saturated or unsaturated. These hydrocarbyl groups can also contain substituent groups such as halogens including chlorine bromine, fluorine, iodine, nitro, nitrile. Also, these groups can be specifically free of any one or more of such substituent groups.
  • the cyclic group with an S in the middle of the ring indicates a saturated or unsaturated cyclohexyl group wherein the cyclohexyl group can contain one or two unsaturated groups in the ring.
  • the advanced resins of the present invention can be either terminated in epoxy groups or phenolic hydroxyl groups as desired.
  • the advanced resins of the present invention can be prepared by reacting the appropriate epoxy resin with the appropriate phenolic hydroxyl-containing compound at a temperature of from 25°C to 280°C, preferably from 75°C to 240°C, more preferably from 100°C to 220°C for a time sufficient to complete the reaction, usually from 0.025 to 48, preferably from 0.05 to 24, more preferably from 0.01 to 10, hours. Higher reaction temperatures require less time than the lower reaction temperatures.
  • the pressure is not particularly
  • reaction is conducted at pressures which will maintain the reactive components and any solvents or reaction medium employed in the liquid phase.
  • the epoxy resin and the phenolic hydroxyl- containing compound are employed in amounts which provide a ratio of phenolic hydroxyl groups to epoxide groups of from 0.5:1 to 2:1, preferably from 0.7:1 to 1:1, more preferably from 0.75:1 to 0.95:1.
  • a ratio of phenolic hydroxyl groups to epoxide groups of from 0.5:1 to 2:1, preferably from 0.7:1 to 1:1, more preferably from 0.75:1 to 0.95:1.
  • the advanced resins can be prepared employing catalytic quantities of a suitable catalyst for the reaction between the epoxide groups and the phenolic hydroxyl groups.
  • a suitable catalyst for the reaction between the epoxide groups and the phenolic hydroxyl groups.
  • catalysts include metal hydroxides, tertiary amines, phosphines, quaternary ammonium and phosphonium compounds, combinations thereof. Preferred such
  • catalysts include, for example,
  • butyltriphenylphosphonium bicarbonate triethylamine, tripropylamine, tributylamine, 2-methylimidazole, combinations thereof.
  • These catalysts are employed in catalytic amounts and the particular amount depends upon the particular reactants and catalyst being employed. However, usually the amount is from 0.0001 to 10, preferably from 0.05 to 1, more preferably from 0.1 to 0.5, percent by weight based upon the weight of the epoxy resin.
  • the advancement reaction can be conducted in the presence of a solvent such as, for example, alcohols, glycol ethers, aromatic hydrocarbons, aliphatic hydrocarbons, ketones, amides, sulfones, cyclic ethers, any combination thereof.
  • Preferred such solvents include, for example, isopropanol, ethanol, butylene glycol methyl ether, diethylene glycol n-butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether, toluene, xylene, decane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, any combination thereof.
  • Suitable epoxy resins which can be employed to prepare the advanced resins of the present invention include those represented by the aforementioned formula IE and the following formula II and III
  • R, R', Y 2 , Y 3 , a, and n 2 are as hereinbefore defined.
  • the glycidyl ethers of the oxyalkylated diols are produced by the condensation of an epihalohydrin with an oxyalkylated polyol represented by the following Formula IV:
  • the oxyalkylated diols of Formula IV are produced by reacting a diol of the following Formula V
  • ethylene oxide propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or an alkyl or aryl glycidyl ether or mixtures thereof. Combinations of these oxides added in sequential manner can also be used so as to form block copolymers rather than random polymers.
  • useful diols include, bisphenol A, bisphenol F, hydroquinone,
  • Particularly suitable epoxy resins include, for example, the diglycidyl ethers of biphenol, bisphenol A, bisphenol F, bisphenol K, bisphenol AP (1,1-bis(4- hydroxyphenyl)-1-phenyl ethane), 1,2-bis(3- hydroxyphenoxy)ethane, 1,4-bis(3-hydroxyphenoxy)butane, 1,4-bis(4-hydroxyphenoxy)butane, 1,8-bis(3- hydroxyphenoxy)octane, 1,8-bis(4-hydroxyphenoxy)octane, 1,10-bis(4-hydroxyphenoxy)decane, 1,12-bis(4- hydroxyphenoxy)decane, the reaction product of bisphenol A or bisphenol F with from 2 to 6 moles of propylene oxide or ethylene oxide, poly(bisphenol A)ether of ethylene glycol, poly(bisphenol F)ether of ethylene glycol, any combination thereof.
  • Suitable phenolic hydroxyl-containing compounds which can be employed herein include, for example, those represented by the aforementioned formula IB and following formula VIA or VIB Formula VIA HO— Y 1 — OH
  • Particularly suitable phenolic hydroxyl- containing compounds which can be employed herein include, for example, biphenol, bisphenol A, bisphenol F, bisphenol K, bisphenol AP (1,1-bis(4-hydroxyphenyl)- 1-phenyl ethane), 1,2-bis(3-hydroxyphenoxy)ethane, 1,4- bis(3-hydroxyphenoxy)butane, 1,4-bis(4- hydroxyphenoxy)butane, 1,8-bis(3-hydroxyphenoxy)octane, 1,8-bis(4-hydroxyphenoxy)octane, 1,10-bis(4- hydroxyphenoxy)octane, 1,12-bis(4- hydroxyphenoxy)dodecane, poly(bisphenol A)ether of ethylene glycol, poly(bisphenol F)ether of ethylene glycol, any combination thereof.
  • scavenging compound for a time sufficient to complete the reaction, usually from 0.1 to 24, preferably from 0.5 to 10, more preferably from 1 to 5, hours.
  • the higher reaction temperatures require less time to complete the reaction whereas the lower temperatures require more time to complete the reaction.
  • reaction is usually conducted in the presence of water or ethanol so as to reduce the viscosity of the slurried reaction mixture and make it more susceptible to
  • the particular amount of water being that amount which provides the desired stirring viscosity, and can vary from as little as 2 to as much as 30, preferably from 3 to 20, more preferably from 5 to 10, percent by weight based upon the amount of phenolic hydroxyl-containing compound employed.
  • the particular amount of ethanol can vary from 2 to 500, preferably from 10 to 200, more preferably from 50 to 150 percent by weight based upon the amount of phenolic hydroxyl-containing compound employed.
  • Hydrogen halide scavenging compounds which can be employed herein include, for example, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates.
  • Preferred hydrogen halide scavenging compounds include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, any combination thereof.
  • the advanced resin can be rendered water compatible i.e. water soluble or miscible. This can be accomplished by reacting the advanced resins of the present invention including mixtures of these advanced resins with a different epoxy resin having an average of more than one vicinal epoxide group per molecule with one or more nucleophilic compounds.
  • the nucleophilic compound is suitably employed in an amount sufficient to convert at least a portion of the epoxy groups to cationic groups or cation-forming groups.
  • a cationic group is formed.
  • the nucleophilic compound is usually employed in an amount which provides a ratio of moles of
  • nucleophilic compound per epoxide group of from 0.15:1 to 1.1:1, preferably from 0.4:1 to 1:1, more preferably from 0.7:1 to 0.9:1, in the presence of a Brönsted acid.
  • an unstable aqueous dispersion iss usually obtained because it has a low charge density.
  • an aqueous solution is usually obtained. Whether this stoichiometry results in an aqueous solution or dispersion depends upon the molecular weight of the epoxy resin. With a low
  • the 1.1:1 stoichiometry may give a dispersion rather than a solution.
  • the reaction is usually conducted at
  • temperatures of from 25°C to 110°C, preferably from 60°C to 100°C, more preferably from 70°C to 90°C, for a time sufficient to complete the desired reaction, usually from 0.5 to 24, preferably from 1 to 12, more preferably from 2 to 8, hours.
  • the higher reaction temperatures require less time than the lower reaction temperatures.
  • the charge density of the solid resin is used to determine the quantity of nucleophilic compound per epoxy group contained in the epoxy resin.
  • the charge density is the milliequivalents of nucleophilic compound per gram of solid.
  • a larger charge density is required for a high molecular weight epoxy resin than a low epoxy resin to obtain a
  • the charge density may vary from 0.08 to 1.4, preferably from 0.35 to 0.6, more preferably from 0.35 to 0.45, milliequivalents of nucleophilic compound per gram of solid.
  • nucleophilic compound/Br ⁇ nsted acid is variable so long as the reaction mixture is at neutral or acid pH.
  • the amount of water that is included in the reaction mixture, for water-borne compositions, can be varied to convenience so long as there is sufficient acid and water present to stabilize nucleophilic
  • aqueous compositions of the present invention can also contain any amount of an organic solvent such as ethylene glycol monobutyl ether. These solvents are usually employed in amounts of from 1 to 75, preferably from 4 to 35, more preferably from 6 to 18, percent by weight based upon the weight of the aqueous dispersion or solution.
  • an organic solvent such as ethylene glycol monobutyl ether.
  • the Brönsted acid is employed in amounts which provides a ratio of moles of acid to moles of nucleophilic compound of from 0.2:1 to 10:1,
  • nucleophilic compounds which are used advantageously in forming the cations required for forming the cationic resins in this invention are represented by the following classes of compounds, sometimes called Lewis bases:
  • R 5 and R 6 individually are lower alkyl, hydroxy lower alkyl or are combined as one divalent acyclic aliphatic radical having 3 to 5 carbon atoms;
  • R 7 -N-R 8 wherein R 8 and R 9 individually are lower alkyl, hydroxy lower alkyl, or are combined as one divalent acyclic aliphatic radical having from 3 to 5 carbon atoms, R 10 is a divalent acyclic aliphatic group having from 2 to 10 carbon atoms, R 11 and R 12 individually are lower alkyl and R 7 is hydrogen or lower alkyl, aralkyl or aryl, except that when R 8 and R 9 together are a divalent acyclic aliphatic group then R 7 is hydrogen, lower alkyl or hydroxyalkyl and when either or both of R8 and R 9 is
  • R 7 is hydrogen
  • R 13 -N-R 14 wherein R 13 , R 14 and R 15 individually are lower alkyl, hydroxy lower alkyl or aryl, By the term lower it is meant a group having from 1 to 10, preferably from 1 to 6, more preferably from 1 to 4, carbon atoms.
  • Suitable pyridine compounds which can be employed herein as the nucleophilic compound include monopyridine compounds and polypyridine compounds.
  • Monopyridine compounds which can be employed herein include, for example, those represented by the following formulas VII-IX
  • each R c and R d is independently hydrogen, a halogen atom, particularly chlorine or bromine, a hydrocarbyl or hydrocarbyloxy or a hydroxy substituted hydrocarbyl group having from 1 to 10, preferably from 1 to 4, carbon atoms, a carbamoyl group (-CO-NH 2 ), or a hydroxyl group.
  • Preferred monopyridine compounds include nicotinamide, pyridine, 2-picoline, 3-picoline, 4-picoline, 4-ethylpyridine, 3,4-dimethylpyridine, 3,5- dimethylpyridine, 4-phenylpyridine, 4-propanolpyridine, quinoline, 4-methylquinoline, isoquinoline, mixtures thereof.
  • the most preferred monopyridine compound is nicotinamide.
  • Polypyridines which can be employed include any compound having more than one pyridine group per molecule.
  • Particularly suitable such pyridine- containing compounds include those represented by the following formulas X-XII
  • each R c is independently hydrogen, a halogen atom, particularly chlorine or bromine, a hydrocarbyl or hydrocarbyloxy or a hydroxy substituted hydrocarbyl group having from 1 to 10, preferably from 1 to 4,carbon atoms, a carbamoyl group (-CO-NH 2 ), or a hydroxyl group; each R e is independently an alkyl group having from 1 to 10 carbon atoms, an amine group, a urea group, a thiourea group, a carbonyl group, -S-S- group, -S-CH 2 - CH 2 -S- group, -C(OH)H-CO-group, or an amide group; and each y independently has a value from 1 to 5.
  • Particularly suitable polypyridine compounds include, for example, 1,2-bis(4-pyridyl)ethane, 4,4'- trimethylenedipyridine, 3, 3'-bipyridine, 4,4'- bipyridine, 4,4'-bipyridinehydrate, 2,3'-bipyridine, 2,4'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 1,3-di- (3-picolyl)urea, 1,3-di-(3-picolyl)thiourea, di-(2- picolyl)amine, 2,2'-(3,6- dithiaoctamethylene)
  • 2,2',6',2"-terpyridine aldrithiol-4, 2,2'-bipyridine, alpha-methyl-1,2-di-3-pyridyl-1-propanone, alpha- pyridoin, any combination thereof.
  • nucleophilic compounds are pyridine, nicotinamide, quinoline, isoquinoline, tetramethyl thiourea, tetraethyl thiourea, hydroxyethylmethyl sulfide, hydroxyethylethyl sulfide, dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, methyl-n-propyl sulfide, methylbutyl sulfide, dibutyl sulfide, dihydroxyethyl sulfide, bis-hydroxybutyl sulfide, trimethylene sulfide, thiacyclohexane,
  • Substantially any organic acid can be used in the conversion reaction to form onium salts so long as the acid is sufficiently strong to promote the reaction between the nucleophilic compound and the vicinal epoxide group(s) on the
  • the acid should be sufficiently strong to protonate the resultant amine product to the extent desired.
  • Suitable Br ⁇ nsted acids which can be employed include any such acid or combination of acids which promotes the reaction between the pyridine compound and the epoxide group and provides a compatible anion in the final product.
  • compatible anion it is meant one which exists in close association with the cationic nitrogen of the pyridine compound for an indefinite period.
  • Monobasic acids are usually preferred.
  • the Bronsted acids can be inorganic or inorganic acids.
  • Preferred inorganic acids which can be employed include, for example, phosphoric acid, hydrochloric, acid, hydrobromic acid, nitric acid, sulfuric acid, any combinations thereof.
  • Organic acids which can be employed herein include, for example, those saturated or unsaturated acids having from 2 to 30, preferably from 2 to 6, more preferably from 2 to 3 carbon atoms. Also suitable are the hydroxy-functional carboxylic acids (e.g., glycolic acid, lactic acid, etc.) and organic sulfonic acids (e.g., methanesulfonic acid).
  • the preferred organic acids include, for example, acetic acid, propionic acid, acrylic acid, methacrylic acid, itaconic acid, ethanesulfonic acid, decanoic acid, triacontanoic acid, lactic acid, any combination
  • the conversion reaction to form cationic resins is normally conducted by merely blending the reactants together and maintaining the reaction mixture at an elevated temperature until the reaction is complete or substantially complete. The progress of the reaction is easily monitored.
  • the reaction is normally conducted with stirring and is normally conducted under an
  • inert gas e.g., nitrogen
  • Satisfactory reaction rates occur at temperatures of from 25°C to 100°C, with preferred reaction rates being observed at temperatures from 60° to 100°C.
  • the amount of water that is also included in the reaction mixture can be varied to convenience so long as there is sufficient acid and water present to stabilize the cationic salt formed during the course of the reaction. Normally, it has been found preferable to include water in the reaction in amounts of from 5 to 30 moles per epoxy equivalent.
  • the nucleophilic compound is a
  • the water can be added before, during, or after the resin epoxy group/nucleophile reaction.
  • the preferred range of charge density of the cationic, advanced epoxy resin is from 0.2 to 0.8 milliequivalent of charge per gram of the resin, calculated assuming complete salting of the limited reagent (acid or amine).
  • any excess nucleophilic compound can be removed by standard methods, e.g., dialysis, vacuum stripping and steam distillation.
  • the cationic, advanced epoxy resins of this invention in the form of aqueous dispersions are useful as coating compositions, especially when applied by electrodeposition.
  • the coating compositions containing the cationic resins of this invention as the sole resinous component are useful but it is preferred to include crosslinking agents in the coating composition so that the coated films, when cured at elevated
  • the most useful sites on the resin for crosslinking reactions are the secondary hydroxyl groups along the resin backbone.
  • Materials suitable for use as crosslinking agents are those known to react with hydroxyl groups and include blocked polyisocyanates; amine-aldehyde resins such as melamine-formaldehyde, urea-formaldehyde, benzoguanine-formaldehyde, and their alkylated analogs; polyester resins; and phenol-aldehyde resins.
  • the advanced resins of the present invention can be cured by any suitable curing agent for curing epoxy resins, e.g. those resins containing a vicinal epoxide group as well as those curing agents which cure through the secondary hydroxyl groups appearing along the backbone of either the epoxy terminated resins and the hydroxyl terminated resins.
  • suitable curing agent for curing epoxy resins e.g. those resins containing a vicinal epoxide group as well as those curing agents which cure through the secondary hydroxyl groups appearing along the backbone of either the epoxy terminated resins and the hydroxyl terminated resins.
  • Suitable curing agents which cure through the epoxide groups include, compounds containing at least two primary or secondary amine hydrogen atoms such as, for example primary and secondary aliphatic,
  • cycloaliphatic or aromatic amine compounds compounds containing at least two carboxylic acid groups per molecule (organic polybasic acids) and their anhydrides such as for example, saturated an unsaturated aliphatic or cycloaliphatic carboxylic acids and aromatic
  • Suitable primary or secondary amine-containing compounds which can be employed as the epoxy curing agent include, for example, ethylenediamine,
  • tetraethylenepentamine isophoronediamine, N- aminoethylpiperazine, menthanediamine, 1,3- diaminocyclohexane, xylylenediamine, m-phenylenediamine, 1,4-methylenedianiline, metaphenylenediamine,
  • diaminodiphenylsulfone diaminodiphenyl ether, 2,4- toluenediamine, 2,6-diaminopyridine, bis(3,4- diaminophenyl)sulfone, resins prepared from aniline and formaldehyde, aminated polyglycols, any combination of any two or more such curing agents.
  • Organic polybasic acid curing agents include, for example, oxalic acid, phthalic acid, maleic acid, aconitic acid, carboxyl terminated polyesters, any combination of any two or more such curing agents.
  • Anhydrides of polycarboxylic acids include, for example, phthalic anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride,
  • dodecenylsuccinic anhydride Nadic Methyl Anhydride (methylbicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride isomers), pyromellitic dianhydride,
  • curing agents include, for example, amides and polyamides, urea-aldehyde resins, melamine- aldehyde resins, hexamethoxymethylmelamine,
  • curing agents which can be employed herein include, for example, dicyandiamide, 2-methylimidazole, phenol- formaldehyde resins, cresol-formaldehyde resins, any combination thereof.
  • Curing agents which cure through the secondary hydroxyl groups along the backbone of the advanced resins include, for example, polyisocyanates, blocked polyisocyanates, urea-aldehyde resins, melamine-aldehyde resins, phenol-aldehyde novolac resins, alkylated phenol-aldehyde novolac resins, any combination thereof.
  • Preferred such curing agents include, for example, hexamethoxymethylmelamine, urea-formaldehyde resins, melamine-formaldehyde resins, aromatic or cycloaliphatic or aliphatic polyisocyanates, blocked polyisocyanates, a mixture of the allyl ethers of mono-, di- and tri- methylol phenol, a mixture of the allyl ethers of methylol phenol partially polymerized, phenol- formaldehyde novolac resins and cresol-formaldehyde novolac resins, any combination thereof.
  • Blocked polyisocyanates include, for example, those blocked with alcohols, phenols, oximes, lactams and N,N-dialkylamides or esters of alpha-hydroxyl group- containing carboxylic acids.
  • Particularly suitable polyisocyanates include, for example, isocyanurate trimer of hexamethylene diisocyanate, toluene
  • Preferred blocked polyisocyanates are those blocked with oximes of ketones also known as ketoximes.
  • the preferred ketoximes is methyl ethyl ketoxime, acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, methyl isobutyl
  • ketoxime cyclohexanone ketoxime
  • the blocked polyisocyanates are prepared by reacting equivalent amounts of the isocyanate and the blocking agent in an inert atmosphere such as nitrogen at temperatures between 25° to 100°C, preferably below 70°C to control the exothermic reaction. Sufficient blocking agent is used so that the product contains no residual, free isocyanate groups.
  • a solvent compatible with the reactants, product, and the coating composition can be used such as a ketone or an ester.
  • a catalyst can also be employed such as dibutyl tin dilaurate.
  • the blocked polyisocyanate crosslinking agents are incorporated into the coating composition at levels corresponding to from 0.2 to 2.0 blocked isocyanate groups per hydroxyl group of the cationic resin.
  • the preferred level is from 0.3 to 1 blocked isocyanate group per resin hydroxyl group.
  • a catalyst can, optionally, be included in the coating composition to provide faster or more complete curing of the coating.
  • Suitable catalysts for the various classes of crosslinking agents are known to those skilled in the art.
  • suitable catalysts include dibutyl tin
  • Amounts used typically range between 0.1 and 3 weight percent of binder solids.
  • the curing agents are employed in amounts which will generally cure the advanced resin, i.e. that amount which is sufficient to render the resultant cured coating composition non-tacky. In those instances where the curing agent cures by reacting with the epoxide groups, they are employed in amounts which provide a ratio of equivalents of curing agent per epoxide group of from 0.01:1 to 10:1, preferably from 0.1:1 to 5:1, more preferably from 0.5:1 to 1.5:1.
  • the curing agent is employed in amounts which provide a ratio of equivalents of curing agent per secondary hydroxyl group of from 0.05:1 to 5:1, preferably from 0.1:1 to 3:1, more preferably from 0.3:1 to 2:1.
  • the advanced resins of the present invention can be blended with other materials such as solvents or diluents, fillers, pigments, dyes, flow modifiers, thickeners, reinforcing agents, antifoam agents, slip agents, adhesion promoters, flexibility promoters, surface tension modifiers, stress release agents, gloss reducing agents, rheology modifiers, stabilizers, surfactants, plasticizers, or any combination thereof.
  • other materials such as solvents or diluents, fillers, pigments, dyes, flow modifiers, thickeners, reinforcing agents, antifoam agents, slip agents, adhesion promoters, flexibility promoters, surface tension modifiers, stress release agents, gloss reducing agents, rheology modifiers, stabilizers, surfactants, plasticizers, or any combination thereof.
  • the amount of additive depends on the
  • additives are usually employed in amounts of from 0.00001 to 10, preferably from 0.001 to 5, more preferably from 0.01 to 0.05 percent by weight based upon the weight of total solids.
  • Fillers are added in amounts up to 60
  • Plasticizers are added in quantities of from10 to 40 percent by weight.
  • Solvents or diluents which can be employed herein include, for example, alcohols, hydrocarbons, ketones, glycol ethers, or any combination thereof.
  • Particularly suitable solvents or diluents include, for example, methanol, ethanol, isopropanol,
  • glycol methyl ether dipropylene glycol methyl
  • Reinforcing materials which can be employed herein include natural and synthetic fibers in the form of woven cloth , mat, monofilament,
  • Suitable fillers which can be employed herein include, for example, inorganic oxides,
  • the advanced resins of the present invention are particularly useful in the preparation of coatings; however, they may also find utility in castings, laminates, encapsulants.
  • the coating compositions can be applied by any conventional method known in the coating industry.
  • Spraying is the preferred technique for the aqueous .coating compositions.
  • the coating is thermally cured at temperatures of from 95°C to 280°C or higher, for periods in the range of from 0.08 to 60 minutes.
  • the resultant films can be dried at ambient temperatures for longer periods of time.
  • Unpigmented coating compositions are prepared by blending the resinous product with the crosslinking agent and optionally any additives such as catalysts, solvents, surfactants, flow modifiers, plasticizers, defoamers, or other additives. This mixture is then dispersed in water by any of the known methods.
  • a preferred method is the technique known as phase- inversion emulsification, wherein water is slowly added with agitation to the above mixture, usually at
  • the solids content of the aqueous dispersion is usually between 5 and 45 percent by weight and
  • Pigmented coating compositions are prepared by adding a concentrated dispersion of pigments and
  • This pigment dispersion is prepared by grinding the pigments together with a suitable pigment grinding vehicle in a suitable mill as known in the art.
  • Pigments and extenders known in the art are suitable for use in these coatings including pigments which increase the corrosion resistance of the coatings. Examples of useful pigments or extenders include
  • titanium dioxide titanium dioxide, talc, clay, lead oxide, lead silicates, lead chromates, carbon black, strontium chromate, and barium sulfate.
  • Pigment grinding vehicles are known in the art.
  • electrodepositable coatings consists of a water-soluble cationic resinous product, water, and a minor amount of water-compatible solvent.
  • the cationic resinous product is prepared by reacting an epichlorohydrin/bisphenol A condensation product having an epoxide group content of 8 percent with a nucleophilic compound, an acid, and water in a similar fashion as described above for the cationic resins used in the preferred embodiment of the invention.
  • the water-soluble product can be diluted with water to form a clear solution useful as a pigment grinding vehicle.
  • the pH and/or conductivity of the coating compositions can be adjusted to desired levels by the addition of compatible acids, bases, and/or electrolytes known in the art.
  • Other additives such as solvents, surfactants, defoamers, anti-oxidants, bactericides, etc. can also be added to modify or optimize properties of the compositions or the coating in accordance with practices known to those skilled in the art.
  • the coating compositions of the invention can be applied by any conventional technique for aqueous coatings, they are particularly useful for application by cathodic electrodeposition, wherein the article to be coated is immersed in the coating composition and made the cathode, with a suitable anode in contact with the coating composition.
  • cathodic electrodeposition wherein the article to be coated is immersed in the coating composition and made the cathode, with a suitable anode in contact with the coating composition.
  • a film of the coating deposits on the cathode and adheres.
  • Voltage can range from 10 to 1,000 volts, typically 50 to 500. The film thickness achieved generally increases with increasing voltage.
  • suitable films may be achieved at higher voltages than for compositions using resins prepared by a one-step preparation.
  • Current is allowed- to flow for between a few seconds to several minutes, typically two minutes over which time the current usually decreases.
  • Any electrically conductive substrate can be coated in this fashion, especially metals such as steel and aluminum.
  • Other aspects of the electrodeposition process, such as bath maintenance, are conventional. After deposition, the article is removed from the bath and typically rinsed with water to remove that coating composition which does not adhere.
  • the uncured coating film on the article is cured by heating at elevated temperatures, ranging from 200°F to 536°F (93°C to 280°C), for periods of 0.08 to 60 minutes.
  • a five neck five liter round bottom flask equipped with a mechanical stirrer, two condensers, and a dropping funnel was purged with nitrogen then charged under a nitrogen blanket with 1.5 kg (13.6 moles) resorcinol, 120 grams deionized water, and 138.75 grams (0.64 moles) 1 ,4-dibromobutane.
  • the reaction slurry was slowly heated with stirring to reflux under a slow nitrogen purge; then a solution of 109 grams (1.64 moles) 85 percent KOH pellets in 109 grams water was added dropwise under a nitrogen blanket over a two hour period. After an additional hour of refluxing, the reaction mixture was allowed to cool enough to pour the contents into 10 liters deionized water.
  • the water slurry was acidified with 30 percent sulfuric acid and allowed to stand at room temperature overnight before filtering under reduced pressure and washing with several portions of warm water.
  • the residue 80 grams of yellow amorphous solid, was then extracted with large quantities of boiling water to remove oils. After cooling to room temperature, the water extracts (14 liters) yield 28 grams of white, shiny platelets. HPLC analysis revealed 92 percent purity by peak area.
  • a five neck five liter round bottom flask equipped with a mechanical stirrer, two condensers, and a dropping funnel was purged with nitrogen then charged under a nitrogen blanket with 1.25 kg (11.36 moles) hydroquinone, 350 grams deionized water, and 231.25 grams (1.07 moles) 1,4-dibromobutane.
  • the reaction mass becomes a stirable slurry as it was slowly heated to reflux under a slow nitrogen purge.
  • a solution of 180 grams (2.7 moles) 85 percent KOH pellets in 180 grams water was added dropwise under a nitrogen blanket over a two hour period.
  • a five neck five liter round bottom flask equipped with a mechanical stirrer, two condensers, and a dropping funnel was purged with nitrogen then charged under a nitrogen blanket with 1.1 kg (10.0 moles) hydroquinone, 350 grams deionized water, and 272.0 grams (1.0 moles) 1,8-dibromooctane.
  • the reaction mass becomes a stirable slurry as it was slowly heated to reflux under a slow nitrogen purge.
  • a solution of 184 grams (2.7 moles) 85 percent KOH pellets in 184 grams water was added dropwise under a nitrogen blanket over a period of 75 minutes.
  • the slurry had converted to a tea colored solution; then, after.most of the KOH had been added, a white material precipitates in increasing amounts as the refluxing was continued an additional 90 minutes.
  • the reaction mixture was quenched with one liter of water then poured into 4 liters of water.
  • the water slurry was acidified with 30 percent sulfuric acid and filtered under reduced pressure.
  • the filter cake was slurried in warm (50-70°C) water, filtered again and washed with several portions of boiling water. It was then dried in a vacuum oven at 120°C and 310 grams of crude white product was recovered. The product was treated with 8 liters of boiling ethanol and filtered to remove oligomers.
  • the filtrate yields a total of 134 grams (41 percent Yield based on the dibromide) of white, shiny, "mica-like" crystals more than 95 percent pure by HPLC peak area and GPC analysis.
  • a final crystallization from 1.1 liters boiling ethanol gives product more than 99 percent pure by HPLC peak area (m.p. 151- 153.5°C) for use in preparation of the
  • reaction mixture was refluxed an additional hour after all the KOH had been added.
  • the pH of the reaction mixture was basic.
  • the reaction was quenched with 1.5 liters of water and acidified with 40 percent sulfuric acid.
  • the reaction mixture was then poured into 4 liters of water, cooled in an ice bath to a temperature of 10°C and filtered to recover a tan colored solid which was slurried in 1.2 liters boiling water to wash out resorcinol and KBr.
  • UV ultraviolet spectroscopy
  • reaction mixture dissolves into a dark purple solution then it becomes increasingly clouded as NaBr was produced. Increasing amounts of water was collected in the Dean Stark trap. A sample taken near the end of caustic addition was neutral to pH test paper and showed 95 percent conversion of the starting diphenol. The remaining caustic along with a 5-10 percent excess was added over a twenty minute period and refluxing was continued another 15 minutes. The reaction mixture at this point was basic to pH test paper and it showed better than 99.8 percent conversion of the starting diphenol by UV analysis. The heating mantle was removed and the reaction was quenched by acidifying with CO 2 chips.
  • the cooled reaction mass was filtered under reduced pressure and the residue was taken up into boiling acetone and was filtered to remove NaBr, then the acetone was stripped under reduced pressure and a white solid was recovered.
  • the reaction mixture filtrate was stripped of epichlorohydrin and propylene glycol methyl ether under reduced pressure and a white solid was recovered.
  • the two portions of white solid product were taken up in 1.5 liters of methylene chloride and washed with three portions of 200 ml each of distilled water then passed through 2V filter paper twice to remove most of the suspended water, then the methylene chloride was removed by stripping under reduced pressure and the white solid product was dissolved in 450 mL hot acetone and allowed to crystallize at 10°C.
  • propylene glycol methyl ether in epichlorohydrin while retaining the less dense layer of water, a glycol cooled condenser, a thermometer, and a dip tube for adding caustic solution fed by a peristaltic pump was charged with 2,500 grams of a 20 wgt. percent solution of propylene glycol methyl ether in epichlorohydrin (21.6 moles epichlorohydrin) and 248.2 grams (1.008 moles) of 1,2-Bis(3-hydroxyphenoxy)ethane from example 1.
  • the Dean Stark trap was filled with a 20 wgt.
  • Reflux was continued an additional 45 minutes after adding the remainder of the caustic and a sample then tests basic to pH test paper.
  • the heating mantle was removed and the reaction was quenched by acidifying with CO 2 chips.
  • the reaction mixture was then filtered under reduced pressure to remove the salt.
  • the filtrate was concentrated under reduced pressure to a volume of 1,500 ml, washed with three portions of 300 ml each of
  • propylene glycol methyl ether in epichlorohydrin while retaining the less dense layer of water, a glycol cooled condenser, a thermometer, and a dip tube for adding caustic solution fed by a peristaltic pump was charged with 2,500 grams of a 20 wgt. percent solution of propylene glycol methyl ether in epichlorohydrin (21.6 moles epichlorohydrin) and 333.0 grams (1.008 moles) of 1,8-Bis(3-hydroxyphenoxy)octane from example 5.
  • the Dean Stark trap was filled with a 20 wgt. percent solution of propylene glycol methyl ether in
  • the filtrate was then stripped of most of the epichlorohydrin and propylene glycol methyl ether under reduced pressure and 2.5 liters methylene chloride was added.
  • the resulting solution was washed with three portions of 300 ml each of distilled water, then passed through 2V filter paper twice to remove most of the suspended water before stripping the methylene chloride and the remaining epichlorohydrin and propylene glycol methyl ether under reduced pressure.
  • the light brown liquid product was dissolved in 1.2 liters warm acetone and allowed to crystallize overnight in a refrigerator.
  • the first crop of white solid (331 grams, m.p. 75 to 80°C) was 94 percent pure by HPLC peak area and
  • the reactor was then charged with 1,368 grams (6.0 moles) bisphenol A (polycarbonate grade) under a nitrogen streaiff, then it was heated to reflux before 159.7 grams (0.85 moles) ethylene dibromide in 100 mis ethanol was added from the addition funnel in a rapid dropwise fashion.
  • the reaction mixture was refluxed twenty hours, then most of the ethanol was distilled out before adding 1.5 liters toluene which was used to distill out the remaining ethanol as an azeotrope with toluene.
  • the toluene was replenished occassionally to maintain a reaction volume of about 3 liters.
  • reaction mixture was neutralized with aqueous HC1 and water was removed as an azeotrope with toluene through a Dean Stark trap.
  • the reaction mixture was filtered hot by gravity filtration, then the salt residue was washed with more hot toluene and the filtrates were combined (207 grams of KBr was recovered). After standing overnight at room temperature, the clear toluene
  • the reactor was then charged with 400 grams (2.0 moles) bisphenol F under a nitrogen stream, then it was heated to reflux before 150.2 grams (0.80 moles) ethylene dibromide in 200 mis ethanol was added from the addition funnel in a rapid dropwise fashion.
  • the reaction mixture was refluxed forty-eight hours, then neutralized with aqueous HCl, and filtered warm under reduced pressure.
  • the gummy residue was extracted with boiling methylene chloride and the ethanol filtrate was stripped under reduced pressure and the resulting residue was extracted with boiling methylene chloride.
  • the methylene chloride extracts were stripped under reduced pressure and the brown gummy residue was treated with several portions of boiling water totaling 2 liters.
  • the reactor was then charged with 400 grams (2.0 moles) bisphenol F under a- nitrogen stream, then it was heated to reflux before 150.2 grams (0.80 moles) ethylene dibromide in 200 mis ethanol was added from the addition funnel in a rapid dropwise fashion.
  • the reaction mixture was refluxed forty-eight hours, then neutralized with 130 mis 10 percent aqueous HCl.
  • the reaction mixture was decanted from the salt and concentrated by distillation to 750 mls. More salt was removed and the reaction mixture was concentrated to 700 mls before it was added 1.5 liters of water and a gummy layer forms.
  • the aqueous mixture was boiled 3 to 5 minutes, the water was decanted off and the water washing was repeated twice more.
  • HPLC analsis showed about 66 percent by peak area of unreacted bisphenol F.
  • a three-neck 250 ml round bottom flask equipped with a condenser, a thermometer, and an air driven steel stirrer shaft was charged with 130.58 grams of the diglycidyl ether of bisphenol A having an EEW of 180.6, and heated to about 90°C under a nitrogen purge of 200 ml/min. Then, 83-12 grams (0.303 moles) 1,4-Bis(3- hydroxyphenoxy) butane prepared in example 2 was added and dispersed well before adding 0.286 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate.acetic acid complex catalyst in methanol. The temperature was increased over a 70 minute period to 190°C.
  • reaction temperature peaks at 196°C.
  • the reaction mixture was cooked at about 185°C for nearly 30 minutes before quickly heating to 210°C and pouring out the relatively viscous contents on a sheet of aluminum foil to cool. Samples were removed at 15 minutes and thirty minutes after the beginning of the exotherm to determine extent of reaction and the EEW's of each was 2098 and 2108 respectively and the final EEW was 2118.
  • a three-neck 250 ml round bottom flask equipped with a condenser, a thermometer, and an air driven steel stirrer shaft was charged with 130.58 grams of the diglycidyl ether of bisphenol A having an EEW of 180.6, and heated to about 100°C under a nitrogen purge of 200 ml/min. Then, 83-12 grams (0.303 moles) 1,4-Bis(4- hydroxyphenoxy)butane prepared in example 3 was added and dispersed well before adding 0.286 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate.acetic acid complex catalyst in methanol. The temperature was increased over a one hour period to 190°C.
  • the reaction mixture was cooked at about 185°C for another 90 minutes before quickly heating to 210°C and pouring out the relatively viscous contents on a sheet of aluminum foil to cool. Samples were removed at 15, 30, 60, and 90 minutes after the peak temperature of 190°C to determine extent of reaction and the EEW's of the first three were 1587, 1599, and 1617 respectively and the final EEW was 1706.
  • a three-neck 250 ml round bottom flask equipped with a condenser, a thermometer, and an air driven steel stirrer shaft was charged with 113.86 grams of the diglycidyl ether of bisphenol A having an EEW of 180.6, and 88.14 grams (0.267 moles) 1,8-Bis(4- hydroxyphenoxy)octane prepared in example 4.
  • the mixture was heated with stirring to about 120°C to obtain a well mixed slurry.
  • 0.572 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate-acetic acid complex catalyst in methanol was added under a nitrogen purge of 200 ml/min.
  • a three-neck 250 ml round bottom flask equipped with a condenser, a thermometer, and an air driven steel stirrer shaft was charged with 130.58 grams of the diglycidyl ether of bisphenol A having an EEW of 180.6, and 83.12 grams (0.303 moles) 1,4-Bis(4- hydroxyphenoxy)butane prepared in example 3.
  • the mixture was heated with stirring to about 81°C before adding 0.572 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol under a nitrogen purge of 200 ml/min.
  • the temperature was increased over a fifty- three minute period to 190°C.
  • the reaction mixture was cooked for another two hours at about 185°C, then another 0.572 grams of the catalyst solution was added and the reaction was continued another hour at 185°C before pouring out the contents on a sheet of aluminum foil to cool.
  • the corresponding epoxide equivalent weights of the samples were 2028, 2047, and 2067, respectively.
  • the final EEW was 2087.
  • the temperature was increased over a forty-six minute period to 187°C then cooked at that temperature another thirty-nine minutes before pouring out the contents on a sheet of aluminum foil to cool. Samples were removed at 15 and 30 minutes after the peak temperature of 187°C was reached to determine extent of reaction by measuring the EEW's which were 1770 and 1784 respectively. The final EEW was 1799.
  • the temperature was increased over an eleven minute period to 120°C then over a five minute period to 130°C.
  • the reaction peaks briefly at 150°C and was then cooked at 120 to 130°C before pouring 'out the contents on a sheet of aluminum foil to cool fifty minutes after the temperature first reaches 120°C.
  • a five-neck 1000 ml round bottom flask equipped with a thermometer and an air driven steel stirrer shaft was charged with 420.37 grams (2.328 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 180.6, and 228.70 grams (1.002 moles, 2.004 OH equiv.) of bisphenol A, then heated with stirring under a nitrogen purge of 200 ml/min to about 85°C before adding 0.93 grams of a 70 percent by weight solution of
  • advanced epoxy resin was 2349. Samples were removed 15 minutes and thi ⁇ t minutes after the peak temperature was reached to determine extent of reaction by measuring the EEW's which were 2118 and 2150 respectively. The final EEW was 2183.
  • b x ((2xEEW)-340.4)/Formula Weight of repeating unit.
  • DSC differential scanning calorimetry
  • An aluminum pan was charged with 6.38 grams (0.0268 epoxide equivalents) of the diglycidyl ether from example 6 and 3-60 grams (0.011 moles) of 1,8- Bis(4-hydroxyphenoxy)octane from example 4. The pan was then heated on a hot plate at 130 to 140°C to effect a homogeneous melt of the reactants.
  • Four drops of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate.acetic acid complex catalyst in methanol was added with stirring and the temperature of the hot plate was increased to 195°C to 205°C. The viscosity increases and the aluminum pan was removed from the hot plate 15 minutes after the addition of catalyst.
  • the opaque, tan colored, brittle solid product was insoluble in methylene chloride, and soluble in hot (100°C) 2- butoxyethanol and hot (100°C) cyclohexanone.
  • An aluminum pan was charged with 5.06 grams (0.028 epoxide equivalents) of the diglycidyl ether of bisphenol A having an EEW of 180.6 and 3-60 grams (0.011 moles) of 1,8- Bis(4-hydroxyphenoxy)octane from example 4. The pan was then heated on a hot plate at 130°C to 140°C to effect a homogeneous melt of the reactants.
  • An aluminum pan was charged with 6.76 grams (0.028 epoxide equivalents) of the diglycidyl ether of 1,8-bis(4-hydroxyphenoxy)octane from example 6 and 3.01 grams (0.011 moles) 1,4-Bis(3-hydroxyphenoxy)butane from example 2.
  • the pan was then heated on a hot plate at 1300°C to 140°C to effect a homogeneous melt of the reactants.
  • One drop of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate.acetic acid complex catalyst in methanol was added with stirring and the temperature of the hot plate was increased to 200°C to 220°C.
  • An aluminum pan was charged with 6.76 grams (0.028 epoxide equivalents) of the diglycidyl ether of 1,8-bis(4-hydroxyphenoxy)octane from example 6 and 3.63 grams (0.011 moles) 1,8-Bis(3-hydroxyphenoxy)octane from example 5.
  • the pan was then heated on a hot plate at 130°C to 140°C to effect a homogeneous melt of the reactants.
  • One drop of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate «acetic acid complex catalyst in methanol was added with stirring and the temperature of the hot plate was increased to 200°C to 220°C.
  • the opaque, brittle solid product was slightly soluble in methylene chloride and soluble in hot (100°C) 2-butoxyethanol. It was also soluble in cyclohexanone at room temperature and a warm (50°C) 40/60 mixture by weight of cyclohexanone/2- butoxyethanol, but only slightly soluble in the latter solvent mix at room temperature.
  • the hot plate was increased to 195°C to 205°C.
  • the moderately opaque, tan colored, brittle solid product was swelled by methylene chloride, and soluble in hot (100°C) 2-butoxyethanol and warm cyclohexanone. It was slightly soluble in warm (50°C)
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 70.25 grams of the diglycidyl ether of 1,8-Bis(3-hydroxyphenoxy)octane having an EEW of 234.75 prepared in example 9 . and 29.61 grams 1,2- Bis(3-hydroxyphenoxy)ethane from example 1.
  • the mixture was heated with stirring to about 85°C before adding 0.0700 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol under a nitrogen purge of 200 ml/min. The temperature was increased over a thirty minute period to 120°C then over a seven minute period to 140°C.
  • reaction mixture was cooked for another forty-six minutes at 135 to 140°C before pouring out the contents on a sheet of aluminum foil to cool. Samples were removed when the temperature reaches 120°C and at zero, 15, 30, and 46 minutes after the peak temperature of 140°C was reached to determine extent of reaction by measuring the EEW's which were 448, 991, 1706, 1838, and 1902 respectively.
  • EXAMPLE 45 PREPARATION OF EPOXY RESIN FROM 1,2-BIS(3-
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 64.74 grams of the diglycidyl ether of 1,2-Bis(3-hydroxyphenoxy)ethane having an EEW of 186.3 prepared in example 8, and 35.11 grams 1,2- Bis(3-hydroxyphenoxy)ethane from example 1.
  • the mixture was heated with stirring to about 85°C before adding 0.0700 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol under a nitrogen purge of 200 ml/min. The temperature was increased over a fifteen minute period to 120°C then over a six minute period to 135°C.
  • the reaction mixture was cooked for another thirty minutes at 135°C before pouring out the contents on a sheet of aluminum foil to cool.
  • Samples Mere removed when the temperature reaches 120°C and at zero, 15, and 30 minutes after the peak temperature of 135°C was reached to determine extent of reaction by measuring the EEW's which were 341, 435, 840, and 1784
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 50.815 grams (0.281 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 180.6, and 49.042 grams (0.1158 moles, 0.2316 OH equiv., 8.0266 percent OH) of poly(bisphenol A) ether of ethylene glycol prepared in example 10, then heated with stirring under a nitrogen purge of 200 ml/min to about 80°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • the temperature was increased over a twenty-nine minute period to 185°C and held at that temperature for one hour before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • a sample was removed when the peak temperature of 185°C was reached to determine extent of reaction by measuring the EEW which was 2905.
  • An aluminum pan was charged with 7.559 grams (0.0444 epoxy equiv.) of a diglycidyl ether of bisphenol A having an EEW of 180.6, and 7.420 grams (0.0172 moles, 0.0344 OH equiv., 7.878 percent OH) of poly(bisphenol A) ether of ethylene glycol prepared in example 10.
  • the pan was then heated on a hotplate at 130 to 140°C to effect a homogeneous melt of the reactants.
  • Four drops of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol was added with stirring and the temperature of the hotplate was increased to 200°C. The viscosity increases and the aluminum pan was removed from the hot plate 30 minutes after the addition of catalyst.
  • the EEW of the resultant advanced epoxy resin was 2299.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 71.16 grams (0.3013 epoxide equiv.) of a diglycidyl ether of poly(bisphenol A) ether of ethylene glycol prepared in example 11 having an EEW of 236.173, and 28.70 grams (0.1433 moles, 0.2867 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to about 65°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol. The temperature was increased over a thirty minute period to 130°C and held at that temperature four minutes before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • the EEW of the resultant advanced epoxy resin was 3872.
  • An aluminum pan was charged with 11.06 grams (0.0638 epoxide equivalents) of the diglycidyl ether of Bisphenol F and 8.88 grams (0.0269 moles) 1,8-Bis(3- hydroxyphenoxy)octane from example 5. The pan was then heated on a hotplate to about 130 to 140°C to effect a homogeneous melt of the reactants. Six drops of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol was added with stirring and the temperature of the hotplate was increased to 190 to 210°C. The viscosity increases and the aluminum pan was removed from the hotplate 17 minutes after the addition of catalyst.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 113-17 grams (0.627 epoxide equiv.) of a diglycidyl ether of bisphenol A having an EEW of 180.6, and 54.06 grams (0.270 moles, 0.540 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to 85°C before adding 0.25 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol. The temperature was increased over a thirty-seven minute period to 190°C.
  • reaction exotherms up to a peak temperature of 195°C, so the heating mantle was removed and a stream of cooling air was directed at the flask.
  • the reaction mixture was cooked at 185°C until one hour after the reaction temperature first reaches 190°C, then it was quickly heated to 210°C before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • the EEW of the resultant advanced epoxy resin was 2205.
  • the final EEW was 2038.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 65.98 grams (0.352 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 187.31, and 33.88 grams (0.1484 moles, 0.297 OH equiv.) of bisphenol A, then heated with stirring under a nitrogen purge of 200 ml/min to about 8 ⁇ °C before adding 0.143 grams of a 70 percent by weight solution of
  • ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • the temperature was increased over a twenty-seven minute period to 175°C, then cooked an additional thirty minutes at 175°C and quickly heated to 210°C before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • Samples were removed when the peak temperature of 175°C was reached and 15 minutes after the peak temperature was reached to determine extent of reaction by measuring the EEW's which were 1748 and 1830 respectively. The final EEW was 1861.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 66.472 grams (0.383 equiv.) of a diglycidyl ether of bisphenol F having an EEW of 173.39, and 33-385 grams (0.1667 moles, 0.3334 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to 85°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • the temperature was increased over a fourteen minute period to 200°C, then cooked one hour at 185°C before quickly pouring out the contents on a sheet of aluminum foil to cool. A sample was removed when the peak temperature of 200°C was reached to determine extent of reaction by measuring the EEW which was 1741. The final EEW was 2139.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 66.472 grams (0.383 equiv.) of a diglycidyl ether of bisphenol F having an EEW of 173.39, and 33-385 grams (0.1667 moles, 0.3334 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to 80°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 66.472 grams (0.383 equiv.) of a diglycidyl ether of bisphenol F having an EEW of 173.39, and 33.385 grams (0.1667 moles, 0.3334 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to 70°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • the temperature was increased over a fourteen minute period to 79°C, then increased again over a ten minute period to 123°C, and cooked another fifteen minutes at 120°C before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • the EEW of the resultant advanced epoxy resin was 1937.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 63.65 grams (0.367 equiv.) of a diglycidyl ether of bisphenol F having an EEW of 173-39, and 36.21 grams. (0.1586 moles, 0.317 OH equiv.) of bisphenol A, then heated with stirring under a nitrogen purge of 200 ml/min to 65°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol.
  • the temperature was increased over a twenty- three minute period to 85°C, then increased again over a twenty-one minute period to 130°C, and cooked another seventeen minutes at 130°C before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • the EEW of the resultant advanced epoxy resin was 1955.
  • a three-neck 250 ml round bottom flask equipped with a thermocouple and an air driven steel stirrer shaft was charged with 66.18 grams (0.382 equiv.) of a diglycidyl ether of bisphenol F having an EEW of 173.39, and 33-67 grams (0.168 moles, 0.336 OH equiv.) of bisphenol F, then heated with stirring under a nitrogen purge of 200 ml/min to 61°C before adding 0.143 grams of a 70 percent by weight solution of ethyltriphenyl phosphonium acetate/acetic acid complex catalyst in methanol. The temperature was increased over a twenty- five minute period to 125°C, and cooked another five minutes at 135°C before quickly pouring out the contents on a sheet of aluminum foil to cool.
  • the EEW of the resultant advanced epoxy resin was 1762.
  • the advanced epoxy resins of Examples 29 to 56 were represented by Formula B. The characteristics of these resin are provided in Table II.
  • a ODDP (octylenedioxy)diphenol.
  • Polybisphenol A was poly(bisphenol A) ether of
  • METHYLONTM 75108 a mixture of the allyl ethers of mono-, di-, and tri- methylol phenols commercially available from BTL
  • curing agent was adjusted to comprise 2.5, 5.0, 10.0 and 20.0 weight percent based on total solids.
  • BYKTM 361 a proprietary acrylic copolymer flow modifier available from BYK Chemie USA
  • 85 percent phosphoric acid sufficient to comprise 0.05 and 0.30 weight
  • each stock solution was then shaken at least 24 hours at room temperature before applying to a tin free steel substrate with a #16 wire wound drawdown bar and baking at 400°F (204.4°C) for 10 or 20 minutes.
  • the properties of the cured coatings are given in Table III.
  • each stock solution was added an amount of BYKTM361 flow modifier and 85 percent phosphoric acid sufficient to comprise 0.05 and 0.50 weight percent, respectively, based on total solids.
  • an amount of BYKTM361 flow modifier and 85 percent phosphoric acid sufficient to comprise 0.05 and 0.75 weight percent, respectively, based on total solids.
  • an amount of BYKTM361 flow modifier and 85 percent phosphoric acid sufficient to comprise 0.05 and 1.00 weight percent, respectively, based on total solids.
  • the portions were then shaken at least 24 hours at room temperature before applying to tin free steel with a wire wound drawdown bar and baking at 400°F (204.4°C) for 10 or 20 minutes in a Blue M forced air electric oven.
  • the properties of the cured coatings are given in Table III.
  • the advanced epoxy resin and METHYLONTM 75108 (a mixture of the allyl ethers of mono-, di-, and tri- methylol phenols commercially available from BTL
  • the advanced resins prepared in Examples 21 and 27 and the advanced resin D.E.R.TM 667 (an advanced resin having an EEW of 1767 prepared by reacting a diglycidyl ether of bisphenol A with bisphenol A) were formulated into coating compositions employing the following procedure.
  • the advanced epoxy resin and METHYLONTM 75108 (a mixture of the allyl ethers of mono-, di-, and tri- methylol phenols commercially available from BTL
  • the acidified solution was then shaken at least 24 hours at room temperature before applying to tin free steel with a wire wound drawdown bar and baking at 400°F (204.4°C) for 10 minutes in a Blue M forced air electric oven to give a cured coating thickness of 0.2 mils.
  • the properties are given in Table III.
  • the advanced epoxy resin and METHYLONTM 75108 (a mixture of the allyl ethers of mono-, di-, and tri- methylol phenols commercially available from BTL
  • the acidified solution was then shaken at least 24 hours at room temperature before applying to tin free steel with a wire wound drawdown bar and baking at 400°F (204.4°C) for 10 minutes in a Blue M forced air electric oven to give a cured coating thickness of 0.2 mils.
  • the properties are given in Table III.
  • the advanced epoxy resin and METHYLONTM 75108 (a mixture of the allyl ethers of mono-, di-, and trimethylol phenols commercially available from BTL
  • the advanced epoxy resin was dissolved in an 80/20 blend by weight of 2-butoxyethanol and cyclohexanone respectively and the percent by weight solids were adjusted over a range of 25.5 to 32 percent to give a solution with viscosity of Gardner G at 25°C.
  • To a portion of the solution was added an amount of METHYLONTM 75108 (a mixture of the allyl ethers of mono-, di-, and tri-methylol phenols commercially available from BTL Specialty Resins Corp.) curing agent to comprise 2.5, 5, 10, 15, or 20.0 percent by weight based on the total solids.
  • BYKTM 361 (a proprietary acrylic, copolymer flow modifier available from BYK Chemie USA) sufficient to comprise 0.05 percent by weight based on total solids and an amount of 85 percent phosphoric acid sufficient to comprise 0.5 or 0.75 percent by weight based on total solids.
  • the solutions were then shaken at least 24 hours at room temperature before applying to tin free steel with a wire wound drawdown bar and baking at 400°F (204.4°C) for 10 minutes in a Blue M forced air electric oven to give a cured coating thickness of 0.2 mils.
  • Table III The properties are given in Table III.
  • the advanced epoxy resin was dissolved in an
  • METHYLONTM 75108 a mixture of the allyl ethers of mono-, di-, and tri-methylol phenols
  • the advanced epoxy resin was dissolved in a
  • METHYLONTM 75108 a mixture of the allyl ethers of mono-, di-, and trimethylol phenols commercially available from BTL
  • BYKTM 361 a proprietary acrylic copolymer flow modifier
  • BYKTM 361 (a proprietary acrylic copolymer flow modifier available from BYK Chemie USA) sufficient to comprise 0.05 percent by weight based on total solids and an amount of 85 percent phosphoric acid sufficient to comprise 0.30, 0.50, 0.75, 1.00, or 1.50 percent by weight based on total solids.
  • thermomechanical analysis TMA
  • the advanced epoxy resin from Example 22 with an epoxide equivalent weight of 2087 (97.4 grams, 0.0468 equivalents) and 25.00 grams (0.212 moles) of 2- butoxyethanol were added to a four neck 500 milliliter round bottom flask equipped with a means for temperature control, stirring by means of a steel stirrer shaft, condensing and reactant addition under a nitrogen purge of 96 milliliters per minute.
  • the epoxy resin was slowly dissolved by heating between 123°C and 138°C for a period of 34 minutes. During this time period, the nitrogen adapter which had no dip leg was replaced with one having a three inch dip leg. Then the resin was cooled to 85°C.
  • the white aqueous dispersion with a non-volatile content of 30 percent by weight and charge density of 0.33 milliequivalent/gram resin was allowed to cool to ambient temperature with stirring.
  • the pH of the stable aqueous dispersion was 4.4.
  • the viscosity which was measured with a No. 4 Ford Cup was 25.5 seconds.
  • the volatile organic content of the dispersion was 1.80 pounds per gallon (216
  • Coatings were prepared by blending 46.53 grams of the aqueous dispersion prepared in Example 58, with 0.761 grams of CYMELTM 325 (a highly methylated
  • melamine-formaldehyde resin having a Gardner-Holdt viscosity at 25oC of X-Z 1 commercially available from the American Cyanamid Co.
  • CYMELTM 325 The formulation was applied to degreased 24 gauge x 4 inches x 12 inches (0.66 mm x 101.6 mm x 304.8 mm) unpolished clean-treated cold rolled steel panels and degreased 7.5 mils x 4.5 inches x 9.0 inches (0.19 mm x 114.3 mm x 228.6 mm) tin free steel panels with a No. 16 wire wound rod according to ASTM D 4147-82. The panels were degreased by washing the panels with Aromatic 100 (a light aromatic solvent containing primarily C ⁇ -io aromatic hydrocarbons
  • Coatings were prepared by blending 51.26 grams of the aqueous dispersion prepared in Example 58, with 1.58 grams of CYMELTM 325 as a curing agent to give a formulation containing 10.2 phr CYMELTM 325. The formulation was applied and cured as described in
  • Example 59 The thickness of the coating was between 0.20 and 0.23 mils (0.0051 mm and 0.0058 mm).
  • Coatings were prepared by blending 51.48 grams of the aqueous solution prepared in Example 58, with 2.32 grams of CYMELTM 325 as a curing agent to give a formulation containing 15.0 phr CYMELTM 325, The formulation was applied and cured as described in
  • Example 59 The thickness of the coating was between 0.23 and 0.27 mils (0.0058 mm and 0.0068 mm). The results are given in Table IV.
  • EXAMPLE 62 PREPARATION OF COATING
  • Coatings were prepared by blending 49.62 grams of the aqueous solution prepared in Example 58, with 2.98 grams of CYMELTM 325 as a curing agent to give a formulation containing 20.1 phr CYMELTM 325. The formulation was applied and cured as described in Example 59. The thickness of the coating was between 0.20 and 0.25 mils (0.0051 mm and 0.0064 mm). The results are given in Table IV.
  • Coatings were prepared by blending 47.02 grams of the aqueous dispersion prepared in Example 58, with 3.53 grams of CYMELTM 325 as a curing agent to give a formulation containing 25.3 phr CYMELTM 325. The formulation was applied and cured as described in Example 59. The thickness of the coating was between 0.22 and 0.26 mils (0.0056 mm and 0.0066 mm). The results are given in Table IV.
  • Coatings were prepared by blending 46.42 grams of the aqueous dispersion prepared in Example 58, with 1.16 grams of CYMELTM 325 as a curing agent to give a formulation containing 10.0 phr CYMELTM 325.
  • the formulation was applied as described in Example 59. However, the coated panels were baked in an oven at 400°F (204.4°C) for 20 minutes. The thickness of the coating was between 0.26 mils and 0.31 mils (0.0066 mm and 0.0079 mm). The results are given in Table IV. COMPARATIVE EXPERIMENT Q
  • a bisphenol A based epoxy resin having an epoxide equivalent weight of 1755 (100.0 grams, 0.0570 equivalents) and 25.66 grams (0.217 moles) of ethylene glycol n-butyl ether were added to a reactor of the type described in Example 58.
  • the epoxy resin was slowly dissolved by heating between 122°C and 139°C for thirty- seven minutes under a nitrogen purge of 96 milliliters per minute. During this time period, the nitrogen adapter having no dip leg was replaced with one having a three inch dip leg. Then the resin was cooled to 70°C.
  • Coatings were prepared by blending 21.02 grams of the aqueous dispersion prepared in Example 58, 18.798 grams of the aqueous dispersion prepared in Comparative Experiment Q, with 1.10 grams of CYMELTM 325 as a curing agent to give a formulation containing 10.5 phr CYMELTM 325.
  • the formulation was applied and cured as described in Example 59.
  • the thickness of the coating was between 0.18 mils and 0.21 mils (0.0046 mm and 0.0053 mm). The results are given in Table IV.
  • the mixture was heated to 85°C and 0.23g of a 70 percent solution of ethyltriphenyl phosphonium phosphate in methanol was added as a catalyst.
  • the mixture was heated to 175°C and allowed to exotherm to 185°C. The temperature was maintained at 175°C for an additional hour.
  • the epoxide equivalent weight of the advanced resin was 1125.
  • the resin was cooled to 100°C and
  • An aqueous dispersion was prepared by combining 285 grams of the above resin solution, 165g of
  • Crosslinker A 70 percent non-volatile
  • 14.0g of propylene glycol phenyl ether, 4.2g of Surfactant A, and 12.8g of lactic acid solution (73.5 percent) into a suitable reaction vessel.
  • the mixture was stirred very rapidly as 537 grams of D.I. water was added in a dropwise fashion over a 90 minute period.
  • the resultant aqueous dispersion was then stripped of methyl isobutyl ketone solvent to yield a dispersion of about 32 percent solids.
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25.
  • the final .bath had a non-volatile content of 20 percent.
  • MIBK methyl isobutyl ketone
  • An aqueous dispersion was prepared by combining 285g of the above resin solution, 165g of Crosslinker A (70 percent non-volatile), 13.1g of propylene glycol phenyl ether, 4.2g of Surfactant A, and 13.1g of lactic acid solution (73.5 percent) into a suitable reaction vessel. The mixture was stirred very rapidly as 540.7g of D.I. water was added in a dropwise fashion over a period of 90 minutes. The resultant aqueous dispersion was then stripped of methyl isobutyl ketone solvent to yield a dispersion of about 32 percent solids.
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25.
  • the final bath had a non-volatile content of 20 percent.
  • Table V contains physical properties of the coatings from Example 66 and
  • An aqueous dispersion was prepared by combining 275 grams of the above resin solution, 167.1g of Crosslinker A, 13.2g of propylene glycol phenyl ether, 4.3g of
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25/1.
  • the final bath had a non-volatile content of 20 percent.
  • phosphonium phosphate was added as a catalyst. The mixture was heated to 150°C and allowed to exotherm to 194°C. The temperature was then maintained at 175°C for an additional 40 minutes at which time the percent epoxy was at 3-55 percent. The solution was cooled and 223.5g of methyl isobutyl ketone was added. At 95°C, 41.6g (0.4 equiv) of
  • An aqueous dispersion was prepared by combining 300g of the above resin solution, 165.2g of Crosslinker A, 13.0g of propylene glycol phenyl ether, 4.2g of Surfactant A, and 12.4g of lactic acid solution (73.5 percent) into a reaction vessel. The mixture was stirred very rapidly as 524g of D.I. water was added in a dropwise fashion over a period of 90 minutes. The resultant aqueous dispersion was then stripped of methyl isobutyl ketone solvent to yield a dispersion of about 32 percent solids.
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25/1.
  • the final bath had a non-volatile content of 20 percent.
  • Table VI contains physical properties of the coatings from Example 66 and
  • the mixture was heated to 150deg C and allowed to exotherm. The temperature was maintained at 165-170°C for an additional 40 minutes and the epoxide equivalent weight was analyzed to be 1115. The mixture was cooled to 110°C and 179.1g of methyl isobutyl ketone was added. At 85°C, 46.2g of 2-(methylamino)ethanol was added and allowed to react with the epoxy for 60 minutes. The resin solution was then cooled to room temperature and the non-volatile content was measured at 76.0 percent.
  • aqueous dispersion was prepared by combining 280 grams of the above resin solution, 167.2 grams of Crosslinker A, 13-2g of propylene glycol phenyl ether, 4.3g of Surfactant A, and 13.0 grams of lactic acid (73.5 percent non-volatile) in a suitable reaction vessel. The mixture was stirred very rapidly as 553 grams of D.I. water was added dropwise over a period of 90 minutes. The resulting aqueous dispersion was then stripped of methyl isobutyl ketone solvent to yield a dispersion of about 32 percent solids.
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25.
  • the final bath had a non-volatile content of 20 percent. The results are given in Table VII.
  • An aqueous dispersion was prepared by combining 280 grams of the above resin solution, 165.9g of Crosslinker A, 13.1g of propylene glycol phenyl ether, 4.2g of
  • the dispersion was then pigmented with a commercial ED-4 pigment paste to a pigment/binder ratio of 0.25/1.
  • the final bath had a non-volatile content of 20 percent.
  • the epoxide equivalent weight was determined by titration with perchloric acid and tetramethyl ammonium bromide by the procedure of ASTM D-1652-87.
  • the glass transition temperature of the resins were determined on a DuPont 912 Differential Scanning Calorimeter (DSC).
  • the glass transition temperature of the cured coatings was determined on a DuPont 943
  • Thermomechanical Analyzer (TMA). The glass transition temperature of the cured coatings prepared in Examples 66-69 and comparative experiments S and R were
  • Wedge bend was determined according to a modified ASTM D3281-84 procedure, where the diameter of the bend at the less stressed end was either 1/8 inch (3.175 mm) or 1/16 inch (1.5875 mm). The bend was taped and pulled with Scotch brand 610 tape and treated with acidic copper sulfate solution to highlight the exposed metal. The results are reported as millimeters of coating failure.
  • the resistance of the cured coating on a cold rolled steel panel to removal with methyl ethyl ketone was determined by rubbing across the baked panels a two pound ball pein hammer with the ball end covered with eight layers of cheesecloth which had been saturated with methyl ethyl ketone (MEK). No force was applied to the hammer other than that necessary to guide the hammer back and forth over the same area. A twelve inch ruler clamped into place was used to guide the hammer in the same path.
  • the coated panels after rubbed were dipped into a mixture of 20 percent CuSO4 5H2O and 10 percent concentrated hydrochloric acid in water for 30 seconds and then dipped into deionized water to determine breakthrough. A forward and reverse stroke returning to the starting point was considered as being one MEK double rub.
  • T-bend was used as a measure of the flexibility of the coating on the panel at a slow rate of
  • the purpose of this step was to oxidize any resulting bare metal in order to more accurately observe adhesion failures.
  • the specimen was examined under a magnifying glass to determine failure.
  • the first bend was noted as TO (T zero) because there was no panel sandwiched between the bend.
  • the process of bending the panel by using the fingerbrake and vice was continued until there was no sign of cracking or adhesion loss.
  • Each successive bend was noted as T1, T2, T3, T4, etc. because of the number of layers of panel sandwiched between plys. The lower the number of T-bends, the better the flexibility.
  • Impact resistance was a measure of the formability of a coating on a panel at a rapid rate of deformation.
  • Coated cold rolled steel panels were subjected to the impact of a falling weight from a Gardner Impact Tester at different calibrated heights ranging from 0 to 160 inch-pounds.
  • the impacted area was then tested for adhesion by taping with Scotch 610 tape.
  • the tape was applied in such a manner that no air bubbles were trapped under the tape.
  • the tape was then pulled with a rapid and forceful fashion at a 90 degree angle in an attempt to pull the coating away from the substrate.
  • Water pasteurization resistance was performed on a single specimen for each coating to determine the permeability of the coating to water with pressure and heat.
  • the coating substrate was tin free steel.
  • the width of each specimen was about 12 centimeters while the length was about 6 centimeters.
  • Gardner Impacter Tester were used to form a semicircular bend in each specimen.
  • the semi-circular bend was used to simulate a stressed area.
  • the dart impacter rod was dropped from 56 inch-pounds for all the
  • specimens when forming the bend were then placed in a Model 8100-TD NORCO Autoclave with deionized water for 90 minutes at 121°C (250°F) and 1 bar (15 psi) pressure. The clock was only started after both the desired temperature and pressure were reached. After the specimens were pasteurized for the prescribed conditions, the heat was turned off, the pressure bled off and the panels removed for testing. The coated specimens were submerged in deionized water after removal from the autoclave. The specimens were blotted dry after removal from the water with a paper towel.
  • the tested coatings were rated for blush and adhesion.
  • the tested coatings were rated for blush by placing the specimens next to the panels from which the specimens were cut.
  • the coatings were rated for blush according to the following scale:
  • Adhesion was determined by using the tape test described in method A of ASTM 3359-87.
  • the tape was Scotch 610 tape. X-cuts were made in the stressed and non-stressed areas of each specimen. The adhesion of the non-stressed specimen was listed first while the adhesion in the stressed area was listed second. The coatings were listed for adhesion according to the following scale.
  • the coatings were tested for wet and dry.
  • test panels performed on test panels by first immersing the test panels in 90oC water for four days and then carrning out the T-peel test. A dry adhesion test was carried out on test panels without immersing the test panels in 90°C water.
  • Chip Resistance was determined by the procedure of ASTM D3170-87 and the results were quantified using a Que-2 Image analyzer. The number recorded represnts the number of chips in an 80 cm 2 area multiplied by the average area of each chip. The smaller the number, the better the chip resistance.
  • This test was a cyclic test where the panels were scribed and subjected to 20 corrosion cycles.
  • One cycle consists of a 24 hour period which the panels were immersed in ambient temperature 5 percent salt solution for 15 minutes followed by a room temperature drying period for one hour and 15 minutes and then placed in a humidity cabinet (60°C and 85 percent relative humidity) for 22 hours and 30 minutes.
  • cycles 1, 6, 11 and 16 the panels were additionally exposed to hot and cold by placing them in an oven at 60°C for 1 hour followed by a freezer at -10°F (-23.9°C) for 30 minutes.
  • the total time the panels were in the humidity cabinet was 22 hours and 30 minutes.
  • the panels were scraped to remove any loose coatings.
  • the width of the scribe was measured in millimeters at ten different positions. The results are reported as the average width of the total creep. A lower number represents better corrosion resistance.

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Abstract

Résines traditionnelles et résines époxy non traditionnelles dans lesquelles le composé non traditionnel et au moins une partie de la résine époxy traditionnelle contiennent au moins un groupe -O-R1-O- ou (O-CH2-CHR2)n-O- utilisé comme pont entre deux groupes choisis indépendamment dans le groupe composé de (1) un groupe cycloaliphatique saturé ou insaturé, (2) un groupe aromatique, (3) un groupe représenté par la formule (I), ou (4) un groupe représenté par la formule (II). L'invention concerne également leurs dérivés nucléophiles ainsi que des compositions polymérisables et des compositions de revêtement contenant les résines traditionnelles ou les résines époxy non traditionnelles ou des résines traditionnelles ou époxy non traditionnelles modifiées nucléophiles. Ces résines traditionnelles et ces résines époxy non traditionnelles permettent d'obtenir des revêtements présentant une bonne flexibilité ou une bonne aptitude au formage démontrées par de bonnes propriétés de flexion ou de formage déterminées par des essais de détachement brusque, de flexion T et de flexion en coin, une résistance à l'écaillage ainsi qu'une bonne résistance à la corrosion et un bon pouvoir de pénétration.
EP91912798A 1990-05-15 1991-05-15 Compositions de resine epoxy traditionnelles et non traditionnelles, leurs derives nucleophiles et leurs compositions polymerisables et de revetement Ceased EP0483352A1 (fr)

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US52361390A 1990-05-15 1990-05-15
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US07/691,881 US5147905A (en) 1991-05-01 1991-05-01 Advanced and unadvanced compositions, nucleophilic derivatives thereof and curable and coating compositions thereof

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DE3108073C2 (de) * 1981-03-04 1983-10-06 Basf Farben + Fasern Ag, 2000 Hamburg Wasserdispergierbare Bindemittel für kationische Elektrotauchlacke
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BR9105755A (pt) 1992-08-18
JPH06501969A (ja) 1994-03-03
AU646482B2 (en) 1994-02-24
MY106546A (en) 1995-06-30
CA2063581A1 (fr) 1991-11-16
PT97670A (pt) 1992-05-29
AU8204291A (en) 1991-12-10
WO1991018034A1 (fr) 1991-11-28

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