WO1995001387A1 - Self-dispersing curable epoxy resins and coatings - Google Patents

Self-dispersing curable epoxy resins and coatings Download PDF

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Publication number
WO1995001387A1
WO1995001387A1 PCT/US1994/006770 US9406770W WO9501387A1 WO 1995001387 A1 WO1995001387 A1 WO 1995001387A1 US 9406770 W US9406770 W US 9406770W WO 9501387 A1 WO9501387 A1 WO 9501387A1
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WO
WIPO (PCT)
Prior art keywords
epoxy
amine
self
adduct
epoxy resin
Prior art date
Application number
PCT/US1994/006770
Other languages
English (en)
French (fr)
Inventor
John G. Papalos
Reuben H. Grinstein
Shailesh Shah
Joseph L. Mulvey
Brian G. Jewell
Original Assignee
Henkel Corporation
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Filing date
Publication date
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to DE69433207T priority Critical patent/DE69433207T2/de
Priority to EP94923202A priority patent/EP0707610B1/en
Priority to JP7503528A priority patent/JPH08512080A/ja
Priority to AU73142/94A priority patent/AU7314294A/en
Priority to CA002166414A priority patent/CA2166414A1/en
Publication of WO1995001387A1 publication Critical patent/WO1995001387A1/en

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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds

Definitions

  • the present invention relates to coating compositions made from aqueous epoxy dispersions. More specifically, this invention relates to self-
  • Epoxy resins have come into widespread use as components in coating compositions. Coatings which comprise cured epoxy resins are valued for their durability, chemical resistance, and excellent adhesion to a
  • aqueous dispersions employs one or more additives, also known as dispersants or emulsifiers or surfactants, which are necessary to stabilize the epoxy resin in the dispersion or emulsion form.
  • additives also known as dispersants or emulsifiers or surfactants, which are necessary to stabilize the epoxy resin in the dispersion or emulsion form.
  • Representative examples include an aqueous epoxy dispersion as described in U.S. Patent No.
  • PROX-E-141 a diglycidyl ether of Pluronic (Reg. TM) F88 diol (an ethylene oxide - propylene oxide - ethylene oxide block copolymer available from BASF Performance Chemicals, Parsippany, New Jersey) as a reactive dispersant for epoxy resins.
  • PROX-E-141 can act as a dispersant for epoxy resin in water, but then will react along with the epoxy resin when exposed to an amine functional curing agent.
  • U.S. Patent No. 4,315,044 describes a stable epoxy dispersion composition comprising (1) an aqueous medium; and (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the molecular weight of the epoxy resin is in the range between about 500-20,000.
  • the dispersion can also contain 1-25 weight percent based on resin solids of a water-immiscible C 8 -C 20 aliphatic monoepoxide
  • U.S. Patent No. 4,608,406 describes stable aqueous epoxy resin dispersions comprised of (1) an aqueous medium; and (2) between about 50 to about 70 weight percent of self-emulsifying epoxy resin which is the addition reaction product of (a) 40-90 parts by weight of a diglycidyl ether of a dihydric phenol; (b) 5-35 parts of a dihydric phenol; (c) 2-15 parts by weight of a diglycidyl ether of a polyoxyalkylene glycol; and (d) 2 to 15 parts by weight of an alkyl phenol-formaldehyde novolac resin wherein the molecular weight of the epoxy resin is in the range of about 1000 to about 20,000.
  • the stable dispersions can be modified by the addition of about 1 to about 25 weight percent of an aliphatic monoepoxide reactive diluent.
  • the stable aqueous epoxy resin dispersions can be modified by the addition of about 5-20 weight percent, based on resin solids weight, of a water-miscible solvent which, preferably, is a 2 to 8 carbon glycol or glycol ether.
  • a primary object of this invention to provide a self- dispersing curable epoxy resin which may be dispersed in water without the necessity for an additive to stabilize the epoxy dispersion.
  • Another object of this invention is to provide aqueous dispersions of self-dispersing curable epoxy resins which exhibit long term stability under ambient storage conditions.
  • Yet another object of this invention is to provide coating compositions incorporating a self-dispersing curable epoxy resin, where the coating
  • composition exhibits excellent properties when cured.
  • the self-dispersing curable epoxy resin of the invention forms an aqueous dispersion upon mixing with water.
  • films of the self- dispersing curable epoxy resin are useful as a coating composition.
  • the self-dispersing curable epoxy resin formulation of the invention is
  • amine-epoxy adduct is formed upon contacting 1.0 equivalents of an aliphatic polyepoxide and from about 0.3 to 0.9 reactive equivalents, preferably from about 0.6 and 0.8 reactive equivalents of a polyoxyalkyleneamine.
  • the polyoxyalkyleneamine reactant comprises one or more amino- compounds where the amino-compound comprises both an amine group and a substantially water-soluble polyether chain.
  • the polyoxyalkyleneamine reactant is soluble or at least partially soluble in water.
  • Techniques to prepare suitable polyoxyalkyleneamine reactants are known in the art, and include reacting a hydroxyl group containing initiator with ethylene oxide and/or propylene oxide, followed by conversion of the resulting terminal hydroxyl group(s) to amine(s).
  • Illustrative of the polyoxyalkyleneamine reactants employed in the invention are the Jeffamine (Reg. TM) brand of polyoxyalkyleneamines available from Texaco Chemical Company, Bellaire, Texas.
  • polyoxyalkyleneamines of this invention have the structural formula
  • R-i designates a monovalent organic radical selected from the group consisting of C, to C 12 aliphatic, alicyclic or aromatic hydrocarbons, and
  • R 2 represents a polyoxyalkylene chain having the structural formula: (CH 2 -CH 2 -0) a -(CH 2 -CH(R 4 )-0) b wherein
  • R 4 is a monovalent organic radical selected from the group consisting of C 1 to C 4 aliphatic hydrocarbons,
  • 'a' designates a number of ethoxy groups (CH 2 -CH 2 -0)
  • 'b' designates a number of monosubstituted ethoxy groups (CH 2 -CH(R 4 )-0) where the substitution of one monosubstituted ethoxy group is independent from the substitution of any other monosubstituted ethoxy group in the polyoxyalkylene chain, the sum of 'a' and 'b' is equal to or greater than 10 but less than or equal to 200, and where the sequence of ethoxy and monosubstituted ethoxy groups within a polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or monosubstituted ethoxy groups, and
  • R 3 designates H or a monovalent organic radical selected from the group consisting of C, to C 4 aliphatic hydrocarbons.
  • Preferred polyoxyalkyleneamines have R 1( R 3 and R 4 each equal to methyl, and either (i) a ratio of 'a' and 'b' of about 4:1 , wherein the ethoxy and iso-propoxy groups are arranged in random blocks and the molecular weight of the polyoxyalkyleneamine is less than about 4,000, or (ii) a block of 5 ethoxy groups joined to a random sequence of ethoxy and iso-propoxy groups wherein the ratio of 'a' and 'b' in the random sequence is about 7:3 and the molecular weight of the polyoxyalkyleneamine is less than about 4,000, or (iii) a ratio of 'a' and 'b' of about 95:5, wherein the ethoxy and iso-
  • propoxy groups are arranged substantially in two blocks and the molecular weight of the polyoxyalkyleneamine is less than about 6,000, or (iv) a ratio of
  • polyoxyalkyleneamine is less than about 4,000, or (v) a ratio of 'a' and 'b' of about 4:1 , wherein the ethoxy and iso-propoxy groups are present in random
  • sequence and the molecular weight of the polyoxyalkyleneamine is less than about 4,000.
  • the most preferred polyoxyalkyleneamine is Jeffamine (Reg. TM) M- 2070 from Texaco Chemical Company, Bellaire Texas. According to Texaco, this polyoxyalkyleneamine is prepared by reacting methanol with ethylene oxide and propylene oxide followed by conversion of the resulting terminal hydroxyl group to an amine.
  • the most preferred polyoxyalkyleneamine has
  • the aliphatic polyepoxide reactant comprises one or more compounds each having a plurality of epoxide functional groups.
  • polyepoxide reactant has at least 2 epoxide groups present in the molecule
  • Suitable polyepoxide compounds include reacting compounds having a plurality of hydroxyl groups with
  • Suitable aliphatic polyepoxide compounds are commercially available from Henkel Corporation, Ambler Pennsylvania under the trademarks "Capcures Reg. TM" or
  • Rs designates a linear, branched or cyclic aliphatic or alicyclic organic
  • R 5 designates a linear, branched or cyclic aliphatic
  • Rg designates a linear, branched or cyclic aliphatic or alicyclic trivalent organic radical having from 3 to 14 carbon atoms, and specifically includes the hydrocarbon portions of the trihydric alcohols glycerol, 1 ,1,1-tris(hydroxymethyl)ethane, and 2-ethyl-2- (hydroxymethyl)-1,3-propanediol which remain after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals four (4), R 5 designates a linear, branched or cyclic aliphatic or alicyclic tetravalent organic radical
  • R 5 designates a linear, branched or cyclic aliphatic or alicyclic pentavalent organic radical having from 6 to 30 carbon atoms, and when the sum of 'c' and 'd' equals six (6)
  • Rg designates a linear, branched or cyclic aliphatic or alicyclic hexavalent organic radical having from 8 to 30 carbon atoms, and specifically includes the hydrocarbon portion of the hexahydric alcohol dipentaerythritol which remains after the hydroxyl groups have been removed
  • Re represents a divalent polyoxyalkylene chain having the structural formula:
  • R 7 is a monovalent organic radical selected from the group consisting of C, to C 4 aliphatic hydrocarbons,
  • 'e' designates a number of ethoxy groups (CH 2 -CH 2 -0), designates a number of monosubstituted ethoxy groups (CH 2 - CH(R 7 )-0) where the substitution of one monosubstituted ethoxy group is independent from the substitution of any other monosubstituted ethoxy group in the polyoxyalkylene chain, the sum of 'e' and 'f is equal to or greater than 0 but less than or equal to 10, and where the sequence of ethoxy and monosubstituted ethoxy groups within a
  • polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or monosubstituted ethoxy groups.
  • the most preferred aliphatic polyepoxide compound is the reaction product of pentaerythritol, propylene oxide and epichlorohydrin, having an epoxide equivalent weight (EEW) of about 230.
  • the EPOXV Resin used in the practice of this invention comprises one or more polyglycidyl ethers of polyhydric phenols having two (2) or more epoxide groups and one (1 ) or more six-carbon aromatized rings present in the molecule, as represented by the structural formula:
  • R 8 represents a 'g' valent C ⁇ -Cso organic radical comprising at least one six-carbon aromatized ring (e.g. when g is 2, Rs can be -CH 2 - O -0- C(CH 3 ) 2 - ⁇ -0-CH 2 - or Rg can be -CH 2 - O - ⁇ -CH 2 - ⁇ -0-CH 2 - wherein 0
  • 'g' is equal to or greater than 2 but less than
  • EPON (Reg. TM) epoxy resins from Shell Chemical Company, Houston, Texas, and DER
  • Suitable epoxy resins are:
  • Polyglycidyl and poly(beta-methylglycidyl) esters obtainable by reacting a compound having at least two carboxy groups in the molecule with epichlorohydrin or beta-methyl-epichlorohydrin, respectively.
  • the reaction is advantageously carried out in the presence of bases.
  • aromatic polycarboxylic acids which may be used include, for example, phthalic acid, isophthalic acid or terephthalic acid.
  • Polyglycidyl or poly(beta-methylglycidyl) ethers obtainable by reacting a compound having at least two free phenolic hydroxy groups with epichlorohydrin or beta-methyl-epichlorohydrin, respectively, under alkaline conditions, or in the presence of an acid catalyst and with subsequent alkali treatment.
  • the epoxy compounds of this type may be derived from mononuclear phenols, such as, for example, resorcinol or hydroquinone; or they are based on polynuclear phenols, such as, for example, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, 1 ,1 ,2,2-tetrakis(4- hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5- dibromo-4-hydroxyphenyl) propane, and from novolacs obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols that are substituted in the nucleus by halide atoms or 0,-0, 8 (preferably C r C 9 ) alkyl groups
  • epoxy resins are polyglycidyl ethers of bisphenols, such as, for example, of 2,2-bis(4- hydroxyphenyl)propane (bisphenol A) or bis(4-hydroxyphenyl)methane (bisphenol F), or novolacs formed by reacting formaldehyde with a phenol.
  • bisphenol A 2,2-bis(4- hydroxyphenyl)propane
  • bisphenol F bis(4-hydroxyphenyl)methane
  • Preferred epoxy resins have an epoxide equivalent weight of less than about 400 grams/equivalent, e.g. from about 100 grams/equivalent to about 350 grams/equivalent, more preferably from about 150 grams/equivalent to about 225 grams/equivalent, e.g. DER 331 available from Dow Chemical at about 182 grams/equivalent.
  • the polyhydric phenol reactant comprises one or more compounds each having a plurality of hydroxyl groups covalently bonded to one or more six-carbon aromatized rings.
  • the polyhydric phenol reactant may contain substituents such as alkyl, aryl, sulfido, sulfonyl, halo, and the like.
  • the polyhydric phenol is represented by the structural formula:
  • R 9 represents an 'h' valent C 6 -Cso organic radical comprising at least
  • 'h' represents a number of phenolic hydroxyl groups where 'h' is equal to or greater than 2 but less than or equal to 6.
  • Techniques to prepare suitable polyhydric phenol compounds are known in the art. Suitable polyhydric phenol compounds are commercially available from Dow Chemical Company, Midland Michigan, and Shell Chemical Company, Houston, Texas.
  • Suitable polyhydric phenols are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)-
  • hydroxyphenyl)sulfone bis(4-hydroxyphenyl)sulfide, resorcinol, hydroquinone, phenol-formaldehyde novolac resins, and the like.
  • dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol
  • the preparation of the self-dispersing curable epoxy resins of the invention may proceed through an amine-epoxy adduct, where the amine- epoxy adduct is subsequently reacted with a polyhydric phenol and an epoxy resin.
  • the structure of the amine-epoxy adduct is dependant on the structures of the polyoxyalkyleneamine and the aliphatic polyepoxide used in the preparation of the amine-epoxy adduct, as well as the relative ratio of the reactants.
  • a representative amine-epoxy adduct has the structural formula: ((CH 2 -CH-R 6 ) (d . 1) (H-R 6 ) c R 5 R 6 -CH(OH)CH 2 -N-
  • T indicates a number of repetitive units where ⁇ is equal to or greater than zero (0) but less than or equal to about fifty.
  • the self-dispersing curable epoxy resins of the invention may be prepared by reacting an amine-epoxy adduct with a polyhydric phenol and an epoxy resin.
  • the structure and composition of the self-dispersing curable epoxy resin will depend on the identity of the amine-epoxy adduct, the
  • the products of the above reaction are envisioned to be an extremely complex mixture of polymeric materials comprising two distinct groups.
  • a simplified structure for each group of reaction products can be shown if it is
  • 'j' indicates a number of repeating units, and is equal to or greater than zero (0) but less than or equal to twenty (20). Structure fill
  • the self-dispersing curable epoxy resin of the present invention may be combined with a non-reactive, water-miscible, organic cosolvent.
  • the cosolvent serves to reduce the viscosity of the self-dispersing curable epoxy resin.
  • Preferred organic cosolvents include the alkyl ethers of monohydric and dihydric alcohols, where the alkyl group comprises C ⁇ C ⁇ linear or branched aliphatic or alicyclic chains. The choice of cosolvent can affect the pot-life of the self-dispersing curable epoxy resin.
  • a cosolvent such as Ektasolve EP (Eastman Chemicals) with one of the following cosolvents (the greater increase being obtained in order): 1-methoxy-2-propyl acetate, methyl n-amyl ketone, or dipropylene glycol n-butyl ether.
  • the preferred stable aqueous epoxy resin dispersions of the present invention are those which contain a water-immiscible C 8 -C 20 aliphatic monoepoxide reactive diluent.
  • the said monoepoxide component can contain alicyclic and aromatic structures, as well as halogen, sulfur,
  • Suitable reactive diluents are
  • monoepoxide reactive diluents are epoxidized unsaturated hydrocarbons such as decene and cyclohexene; glycidyl ethers of monohydric alcohols such as 2-ethylhexanol, dodecanoi and eicosanol; glycidyl esters of monocarboxylic acids such as hexanoic acid; acetals of glycidaldehyde; and the like.
  • the preferred reactive diluent is glycidyl ether of
  • a water-immiscible C 8 -C 20 aliphatic monoepoxide reactive diluent in an aqueous epoxy resin dispersion has significant beneficial effects in addition to modifying the viscosity of the dispersion.
  • the said water-immiscible reactive diluent appears to coat the particles of epoxy resin solids and thereby provide the aqueous dispersion with improved shear, freeze-thaw resistance, shelf viscosity stability, and
  • the reactive diluent is epoxy functional, it becomes chemically bonded into the film which is formed during the subsequent room temperature curing of the aqueous dispersion composition after it has been blended with a curing agent and coated on a surface.
  • an amine-epoxy adduct is first prepared by combining the polyoxyalkyleneamine reactant and the aliphatic polyepoxide reactant, heating the mixture slowly to about 130 °C, holding the mixture at
  • the self-dispersing epoxy resin is prepared by combining the amine-epoxy adduct, the polyhydric phenol and the epoxy
  • the mixture is maintained at about 160 °C for about one hour subsequent to the conclusion of the exothermic reaction, followed by heating to 190 °C.
  • the reaction is maintained at 190 °C for about 15 minutes in order to drive the reaction to completion, then cooled to about 160 °C whereupon a
  • the aqueous epoxy dispersion of the invention is prepared by
  • the particle size of the oil phase in the aqueous dispersion can be modified by physical techniques to reduce the particle size.
  • the particle size reduction is preferably accomplished by subjecting an aqueous dispersion of the precipitate to high shear, e.g. in a homogenizer such as that disclosed in U.S. Patent No. 4,533,254 (Cook et al.), the disclosure of which is incorporated herein be reference, and commercially available as MICROFLUIDIZERTM from Microfluidics Corporation, Newton, Massachusetts. Homogenizers are discussed in W. C. Griffin, "Emulsions", Encyclopedia of Chemical Technology. Vol. 8, pp. 900-930 (Kirk-Othmer, eds., John Wiley & Sons, Inc., New York, New York, 3d ed., 1979), the disclosure of which is incorporated herein by reference.
  • the aqueous dispersion of self-dispersing resin will typically exhibit excellent chemical and physical stability over an extended shelf-life, e.g. of from five to six months.
  • the epoxide equivalent weight (EEW) of the aqueous dispersion of self-dispersing resin should remain essentially constant, e.g. should show no trend of increasing molecular weight, over a period of at least one month from the preparation of the aqueous dispersion.
  • Epoxide equivalent weight can be determined by differential titration
  • the resin should not display layer formation for a period of at least one month from the preparation of the aqueous dispersion, i.e. there should be no formation of a macro-observable
  • Coating Compositions Comprising an Agueous Dispersion of the Self- Dispersing Curable EPOXV Resin
  • the coating composition of the invention is prepared by combining the
  • epoxy resin paint composition of the present invention may further contain additives conventionally employed in coating technology, such as organic pigments, inorganic pigments, surfactants, thickeners, and the like.
  • a room temperature curable water-borne coating composition is
  • Suitable polyamine curing agents are those which are soluble or dispersible in water and which contain more than 2 active hydrogen atoms per molecule. Examples of such curing agents are alkylene polyamines represented by the formula:
  • T is an alkylene radical containing 2 to 6 carbon atoms and 'u' is equal to or greater than zero (0) but less than or equal to five (5).
  • alkylene polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene diamine, dibutylene triamine, hexamethylene diamine, and the like.
  • polyamido amines which are reaction products of alkylene polyamines and fatty acids.
  • polyamidoamines are well known in the art and are described in U.S. Pat. Nos. 2,705,223, 2,811 ,495 and
  • polyamine curing agents are the adducts of polyamines and epoxy compounds such as those described in U.S. Pat. Nos. 2,651,589, 2,864,775 and 4,116,900, which patents are hereby incorporated by reference.
  • useful curing agents also include those disclosed in U.S. patent application Serial No. 08/085,861, filed June 30, 1993, entitled “Curing Agents for Aqueous Epoxy Resins", by Jason Chou et al., the disclosure of
  • reaction product consisting essentially of an alkylene polyamine having less than about 12 carbon atoms, an aromatic mono-glycidyl ether having less than, about 18 carbon atoms, and a diglycidyl
  • a curing accelerator in addition to the amine curing agent, can be any curing accelerator.
  • Such an accelerator will serve to reduce
  • Useful accelerators for amine curing agents include tertiary amines, e.g. N,N'-bis(dimethyl-amino-propyl) urea.
  • Suitable aminoplast resins are the reaction products of ureas and melamines with aldehydes further etherified in some cases with an alcohol.
  • Examples of aminoplast resin components are urea, ethylene urea, thiourea, melamine, benzoguanamine and acetoguanamine.
  • resins can be used in the alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a monohydric alcohol containing from 1 to 8 carbon atoms.
  • suitable aminoplast resins are methylol urea, dimethoxymethylol urea, butylated polymeric urea-formaldehyde resins,
  • Phenolplast resins are the reaction products of phenols and aldehydes which contain reactive methylol groups. These compositions can be monomeric or polymeric in nature depending on the molar ratio of phenol to aldehyde used in the initial condensation reaction. Examples of suitable phenols are phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol, cardanol, p-tert-butyl phenol, and the like.
  • Useful aldehydes are formaldehyde, acetaldehyde and propionaldehyde. Particularly useful
  • phenolplast resins are polymethylol phenols wherein the phenolic group is etherified with an alkyl, e.g., methyl or ethyl, group.
  • epoxy resin curing agents may also be useful, e.g. catalytic curing agents: Lewis bases (such as tertiary amines), Lewis acids (such as
  • boron trifluoride boron trifluoride
  • cationic curing agents such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Via elements, especially sulfur
  • cationic curing agents such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Via elements, especially sulfur
  • the product amine polyepoxide adduct has 0.4 meq./gm of total amine and 0.33 meq./gm of epoxide which indicates that about 66% of the initial free epoxide groups have been reacted with the amine.
  • Example 1A Amihe-epoxide adduct (50% capped. Example 1 was repeated except 75.0 gm (0.063 equivalent) of
  • Example 1 was repeated except 75 gm (0.063 equivalent) of polyethoxy amine* and 23.6 gm (0.083 equivalent) polyepoxide of
  • Example 1 was repeated except 50.0 gm polyethoxy amine* (0.0831 equivalent) and 35.0 gm (0.1245 equivalent) polyepoxide of propoxylated (5PO) pentaerythritol were reacted.
  • the resulting adduct contained 0.61 me/gm of total amine and 0.37 me/gm of epoxide which represents about
  • Example 1 D Example 1 was repeated except 150.0 gm (0.102 equivalent) of polyethoxy amine* and 41.6 gm (0.153 equivalent) polyepoxide of
  • the resulting adduct contained 0.32 me/gm of total amine and 0.31 me/gm of epoxide which represents about 66% of the initial epoxide capped with the amine.
  • reaction mixture is heated slowly to 150°C with stirring whereupon an exothermic reaction is observed. Cooling is immediately applied to maintain the reaction temperature between 150°C and 160°C. After the exothermic reaction subsides, the reaction mixture is maintained at 160°C for an
  • reaction mixture is then cooled to 160°C and 14 grams of propyl cellosolve is added
  • the reaction mixture is cooled to 100°C and analyzed.
  • the resultant self-dispersing resin present at 87.5% solids in propyl cellosolve, has 0.07 meq./gm total amine and an epoxide equivalent weight of 552 based on resin solids.
  • Example 2A Example of a Larger Scale Preparation of Self-Dispersing Resin.
  • Example 3 Preparation of Water-Borne Dispersion.
  • SDR self-dispersing resin
  • the resin is heated to 60 °C to 65 °C and 130.3 grams of water is added over one hour. The temperature is then lowered to 50 °C over about 30 minutes whereupon the water in oil emulsion formed inverted to an oil in water emulsion. After inversion is complete, 8.8 grams of C ⁇ -C 10 alcohol mono-glycidyl ether is added. After mixing for 10 minutes, 159.3 grams of water was added at 50 °C over one hour. The resulting water borne dispersion contains 56% resin solids.
  • Example 3B Example 3 was repeated except the SDR contained the amine epoxide
  • Example 3C Example 3 was repeated except the SDR contained the amine epoxide
  • Example 3D Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1C.
  • Example 3E Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1 D.
  • Example 3 was repeated except the amine-epoxide adduct of Example
  • Example 3 was repeated except the amine-epoxide adduct from Example 1 B was post-added after the reaction of the diglycidyl ether of Bis-phenol A and Bis-phenol A.
  • 3B produced an unstable dispersion and large particle size because the amine-epoxy adduct at 50% capping was ineffective.
  • 3F and 3G produced unstable dispersions and large particle size because the amine-epoxy adduct was post added to the resin. Film properties were acceptable for the dispersions tested.
  • the epoxy dispersion/curing agent blend is aged for 10 minutes then a film casting is produced by drawing the blend down on pre-sanded TRU COLD cold rolled steel panel (3 x 6 x 0.32 inches) using a #34 wire wound steel rod. The film was tack free after 45 minutes. The physical properties of the coating composition were measured after the film had air dried at room temperature for 28 days.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
PCT/US1994/006770 1993-06-30 1994-06-22 Self-dispersing curable epoxy resins and coatings WO1995001387A1 (en)

Priority Applications (5)

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DE69433207T DE69433207T2 (de) 1993-06-30 1994-06-22 Selbstdispergierbare härtbare epoxidharze und beschichtungen
EP94923202A EP0707610B1 (en) 1993-06-30 1994-06-22 Self-dispersing curable epoxy resins and coatings
JP7503528A JPH08512080A (ja) 1993-06-30 1994-06-22 自己分散型硬化性エポキシ樹脂、それからなるディスパージョンおよびそれからなる塗料組成物
AU73142/94A AU7314294A (en) 1993-06-30 1994-06-22 Self-dispersing curable epoxy resins and coatings
CA002166414A CA2166414A1 (en) 1993-06-30 1994-06-22 Self-dispersing curable epoxy resins and coatings

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US8628893A 1993-06-30 1993-06-30
US08/255,732 US5565505A (en) 1993-06-30 1994-06-14 Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US08/086,288 1994-06-14
US08/255,732 1994-06-14

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EP0857188A4 (en) * 1995-10-27 1999-02-03 Henkel Corp SELF-DISPERSING CURABLE EPOXY RESIN ESTER
US6225376B1 (en) * 1996-02-29 2001-05-01 The Dow Chemical Company In-situ emulsified reactive epoxy polymer compositions
US6245835B1 (en) 1996-02-29 2001-06-12 The Dow Chemical Company Polymeric amines and reactive epoxy polymer compositions
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EP0748341A4 (en) * 1994-03-01 1997-11-26 Henkel Corp SELF-DISPERSING AND HARDENING EPOXIDE RESINS, DISPERSIONS AND COATINGS MADE THEREFROM
EP0778856A4 (en) * 1994-09-01 1997-11-19 Henkel Corp SELF-DISPERSIBLE EPOXY RESIN COMPOSITIONS AND COATINGS THEREOF
EP0857188A4 (en) * 1995-10-27 1999-02-03 Henkel Corp SELF-DISPERSING CURABLE EPOXY RESIN ESTER
WO1997031962A1 (en) * 1996-02-29 1997-09-04 The Dow Chemical Company In situ emulsified reactive epoxy polymer compositions
US6225376B1 (en) * 1996-02-29 2001-05-01 The Dow Chemical Company In-situ emulsified reactive epoxy polymer compositions
US6245835B1 (en) 1996-02-29 2001-06-12 The Dow Chemical Company Polymeric amines and reactive epoxy polymer compositions
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US5652323A (en) 1997-07-29
CA2166414A1 (en) 1995-01-12
AU7314294A (en) 1995-01-24
PH31436A (en) 1998-11-03
DE69433207D1 (de) 2003-11-06
US5763506A (en) 1998-06-09
SG54235A1 (en) 1998-11-16
US5565505A (en) 1996-10-15
EP0707610A1 (en) 1996-04-24
EP0707610A4 (en) 1997-11-26
TW254963B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1995-08-21
DE69433207T2 (de) 2004-07-29
JPH08512080A (ja) 1996-12-17
EP0707610B1 (en) 2003-10-01

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