WO2008045889A1 - Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères - Google Patents

Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères Download PDF

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WO2008045889A1
WO2008045889A1 PCT/US2007/080840 US2007080840W WO2008045889A1 WO 2008045889 A1 WO2008045889 A1 WO 2008045889A1 US 2007080840 W US2007080840 W US 2007080840W WO 2008045889 A1 WO2008045889 A1 WO 2008045889A1
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acid
reaction
epoxy
molecular weight
resin
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PCT/US2007/080840
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English (en)
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Maurice J. Marks
Susan K. Falcone-Potts
Xiuhua Cui
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Dow Global Technologies Inc.
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Publication of WO2008045889A1 publication Critical patent/WO2008045889A1/fr

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    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—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 using pre-adducts of epoxy compounds with curing agents with acids
    • 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 relates to process for preparing uncrosslinked, soluble, high molecular weight epoxy ester resins from low molecular weight aromatic epoxy resins and dicarboxylic acids. Such uncrosslinked, soluble, high molecular weight epoxy ester resins are advantageously used for preparing crosslinked coatings therefrom.
  • Dicarboxylic acids represent a broad class of potentially effective materials for use in the reaction with low molecular weight epoxy resins to prepare higher molecular weight epoxy ester resins.
  • dicarboxylic acids in accordance with known processes for preparing high molecular weight epoxy resins leads to the formation of crosslinked, insoluble polymers. What is needed in the industry is a process for reacting a dicarboxylic acid as a comonomer with an epoxy resin monomer which will lead to an uncrosslinked, soluble epoxy functional polymer.
  • U.S. Patent Nos. 4,829,141 and 4,302,574; and Canadian Patent No. 1091690 disclose reactions using epoxy resins and carboxylic acids; but these references do not teach an uncrosslinked, soluble, high molecular weight epoxy ester resin which is epoxy-terminated. Other references may disclose the use of carboxylic acids but do not teach a process for preparing an epoxy-terminated uncrosslinked, soluble, high molecular weight epoxy ester resin using a dicarboxylic acid as a comonomer with an aromatic diepoxide.
  • U.S. Patent Nos. 3,864,316 and 4,474,935 discloses processes for preparing hydrogenated, i.e. non-aromatic epoxy resins; U.S. Patent No.
  • 5,171,820 discloses a process for preparing hydroxyl-functional polyesters containing methylol groups
  • WO 0001779Al discloses coating compositions comprising epoxy-polyester block copolymers and crosslinker wherein the epoxy-polyester block copolymers are all acid functional.
  • the present invention is directed to a process for preparing an uncrosslinked, soluble, high molecular weight epoxy ester resin, the process comprising the steps of: (i) reacting (a) a low molecular weight epoxy resin and (b) a dicarboxylic acid, optionally in the presence of another difunctional monomer such as bisphenol A, conducted in the absence of a solvent and in the presence of a catalyst at a certain reaction temperature; and (ii) quenching the reaction mixture, prior to gelation, to form a soluble, high molecular weight epoxy ester resin.
  • the process of the present invention provides novel compositions comprising products having epoxy termination and low conversion of carboxylic acid groups.
  • the uncrosslinked, soluble, high molecular weight epoxy ester resins prepared by the process of the present invention are used to prepare novel epoxy ester coatings having an excellent balance of properties formed by reacting the above soluble, high molecular weight epoxy ester resins with assorted curing agents.
  • One primary purpose of the epoxy ester coatings prepared by the process of the present invention is for the interior of food or beverage cans and/or can ends.
  • One embodiment of the process of the present invention provides a resin close to its target epoxy equivalent weight at which the reaction is quenched to avoid gelation.
  • Another embodiment of the present invention includes soluble, epoxy terminated high molecular weight epoxy ester resins made by reaction of low molecular weight epoxy resins with dicarboxylic acids, and optionally difunctional monomers, which by virtue of their epoxy functionality can be used as precursors to epoxy thermosets, including coatings by crosslinking with hardeners such as phenolic resoles.
  • the present invention includes a process comprising (i) reacting (a) a low molecular weight epoxy resin and (b) a dicarboxylic acid, optionally in the presence of another difunctional monomer such as bisphenol A, conducted in the absence of a solvent and in the presence of a catalyst at a reaction temperature of, for example, up to about 300 0 C; and (ii) quenching the reaction mixture, prior to gelation, to form a soluble, high molecular weight epoxy ester resin.
  • the present invention process produces compositions comprising products having epoxy termination and a low conversion of carboxylic acid groups or high acid number.
  • the present invention produces an uncrosslinked, soluble, epoxy terminated high molecular weight epoxy ester resins made by the reaction of low molecular weight epoxy resins with dicarboxylic acids which by virtue of their epoxy functionality can be used as precursors to epoxy thermosets, including coatings by crosslinking with phenolic resoles.
  • solid epoxy ester resins solid epoxy ester resins
  • SEERs solid epoxy ester resins
  • uncrosslinked it is meant the composition has a finite viscosity and is free of observable gelatinous reaction products.
  • soluble it is meant the composition dissolves in suitable organic solvents.
  • high molecular weight it is meant the composition has a molecular weight of at least about 2 times that of the starting epoxy resin, preferably at least about 3 times.
  • acid number it is meant the amount in mg of KOH required to neutralize 1 g of sample in accordance with the procedure described in ASTM D 1639-83.
  • low conversion of carboxylic acid groups it is meant the substantially incomplete reaction of carboxylic acid moieties of the dicarboxylic acid and intermediates as measured by the acid number of the composition such that the acid number is greater than about 5.
  • the reaction of the dicarboxylic acid and epoxy resin components may be conducted neat, i.e., in the absence of a diluent or solvent. If the resulting product is to be used for coating purposes, any well known solvent may be used in the composition to form a coating solution for application to a substrate by well-known means.
  • Suitable solvents include, pyridine, triethylamine or mixtures thereof; N- methylpyrrolidinone (NMP), methyl benzoate, ethyl benzoate, butyl benzoate; cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclohexylpyrrolidinone; and ethers or hydroxy ethers such as dioxane, diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether acetate, propylene glycol methyl ether and tripropylene glycol methyl ether; toluene, mesitylene, xylene, benzene, dipropylene glycol monomethyl ether acetate,
  • Suitable diluents are those organic compounds which are inert to the reactants at the reaction temperature, for example, various glycol ethers such as ethylene glycol ethyl ether, ethylene or propylene glycol monomethylether and esters thereof such as ethylene glycol monoethylether acetate; ketones such as methylisobutylketone, methylethylketone (MEK) and acetone; and aromatic hydrocarbons such as toluene, xylene, cyclohexane or mixtures thereof.
  • various glycol ethers such as ethylene glycol ethyl ether, ethylene or propylene glycol monomethylether and esters thereof such as ethylene glycol monoethylether acetate
  • ketones such as methylisobutylketone, methylethylketone (MEK) and acetone
  • aromatic hydrocarbons such as toluene, xylene, cyclohexane or mixtures
  • the low molecular weight epoxy resin employed in the present invention include polyepoxides which are compounds possessing more than one vicinyl epoxy group per molecule, i.e. more than one 1,2-epoxy group per molecule. These polyepoxides are saturated or unsaturated, aromatic polyepoxides; and are substituted, if desired, with non-interfering substituents, such as halogen atoms, hydroxy groups, ether radicals, and the like.
  • low molecular weight epoxy resin an aromatic epoxy resin precursor that has a number average molecular weight (M n ) of less than about 10,000, preferably less than about 8,000, and more preferably less than about 4,000.
  • M n number average molecular weight
  • the "low molecular weight” epoxy resin precursors useful in the present invention have a number average molecular weight of from about 200 to about 10,000, preferably from about 200 to about 8,000, and more preferably from about 250 to about 4,000.
  • Preferred low molecular weight epoxy resins are liquid polyepoxides that include, for example, the liquid glycidyl polyethers of polyhydric phenols. More preferred are the glycidyl polyethers of 2,2-bis(4- hydroxyphenyl)propane having an average molecular weight between about 340 and about 900 and an epoxide equivalent weight of between about 170 and about 500. Especially preferred are the glycidyl polyethers of 2,2-bis(4-hydroxyphenyl) propane having an average molecular weight of between about 340 and about 900, an epoxide equivalent weight of between about 170 and about 500, and containing from about 0.01% to about 1.0% weight or higher of saponifiable chlorine. As used herein the terms "epoxide equivalent weight" and
  • weight per epoxide refer to the average molecular weight of the polyepoxide molecule divided by the average number of oxirane groups present in the molecule.
  • Diepoxides which can be employed in the practice of the present invention include the diglycidyl ethers of dihydric phenols, such as those described in U.S. Patent Nos. 5,246,751; 5,115,075; 5,089,588; 4,480, 082 and 4, 438,254, all of which are incorporated herein by reference, or the diglycidyl esters of dicarboxylic acids such as those described in U. S. Patent No. 5,171, 820 incorporated herein by reference.
  • Other suitable diepoxides include ⁇ - diglycidyloxyisopropylidene-bisphenol-based epoxy resins, commercially known as D.E.R.® 300 and 600 series epoxy resins, and commercially available from The Dow Chemical Company.
  • Preferred diepoxides are the epoxy resins having an epoxy equivalent weight of from about 100 to about 4000.
  • Most preferred diepoxides are the diglycidyl ethers of bisphenol A; 4,4'- sulfonyldiphenol; 4,4- oxydiphenol; 4,4'-dihydroxybenzophenone; resorcinol; hydroquinone; 9,9'- bis(4-hydroxyphenyl)fluorene; 4,4'-dihydroxybiphenyl or 4, 4'-dihydroxy- ⁇ -methylstilbene and the diglycidyl esters of the dicarboxylic acids mentioned previously.
  • aromatic diepoxides are much more reactive than non-aromatic diepoxides towards dicarboxylic acids and are thereby much more prone to crosslink or gel.
  • an uncrosslinked, soluble resin product is prepared using such aromatic diepoxides.
  • the amount of epoxy resins used depends on the targeted molecular weight and epoxy functionality. In general, the epoxy resin is used in an amount of from about 30 wt.% to about 85 wt.%, more preferably, from about 40 wt.% to about 75 wt.% and, most preferably, from about 45 wt.% to about 70 wt.%, based on the weight of reactants.
  • the carboxylic acids used in the present invention may be, for example, saturated, unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • examples of such acids include, among others, succinic acid, glutaric acid, adipic acid (AA), pimelic acid, suberic acid, azaleic acid, sebacic acid, oxalic acid, abietic acid, maleic acid, aconitic acid, chlorendic acid, phthalic acid (PA), terephthalic acid (TPA), isophthalic acid (IPA), 2,6- naphthalenedicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 4,4'- biphenyldicarboxylic acid, malonic acid, 1,4- cyclohexanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12- dodecanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid (1,
  • the amount of carboxylic acid used in the present invention is from about 1 wt.% to about 50 wt.%, more preferably, from about 5 wt.% to about 45 wt.% and, most preferably, from about 10 wt.% to about 40 wt.%, based on the weight of reactants.
  • the low molecular weight epoxide and carboxylic acid reaction mixture may optionally be carried out in the presence of a difunctional monomer such as a hydroxyl or thiol group- containing compound such as a phenol or thiophenol.
  • the preferred optional hydroxyl group- containing compounds are phenols having at least one hydroxyl group attached to an aromatic nucleus.
  • the phenols can be monohydric or polyhydric and can be substituted or unsubstituted.
  • Polymeric polyhydric phenols can be obtained by condensing monohydric or polyhydric phenols with formaldehyde.
  • Preferred optional phenols are the polyhydric phenols containing from 2 to 6 OH groups and up to 30 carbon atoms, including those represented by the formula:
  • X is a polyvalent element or radical and each R is independently selected from hydrogen, halogen and hydrocarbon radicals.
  • the preferred radicals represented by X are oxygen, sulfur, --SO--, -SO 2 — , divalent hydrocarbon radicals containing up to 10 carbon atoms and oxygen, silicon, sulfur or nitrogen containing hydrocarbon radicals.
  • the preferred phenol is 2,2- bis(4-hydrodxyphenyl)propane (bisphenol-A), in which each R is H and X is isopropylidene.
  • Preferred dihydric phenols which can be employed in the practice of the present invention for preparing the resin of the present invention include 4,4'-isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxydiphenylethylmethane, 3,3'-dihydroxy- diphenyldiethylmethane, 3,4'- dihydroxydiphenyl-methylpropylmethane, bisphenol, 4,4'-dihydroxy-diphenyloxide, 4,4'- dihydroxydiphenylcyanomethane, 4,4'- dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'- dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 2,6-dihydroxynaphthalene, 1,4'- dihydroxy- naphthalene, phenol, resorcinol, o-cresol, m- cresol, p-cresol, chlorophenol, nitro
  • Patent Nos. 3,395, 118; 4,438,254 and 4,480,082 which are hereby incorporated by reference.
  • mixtures of different dihydric phenols can be employed. Of these dihydric phenols, bisphenol A, hydroquinone and mixtures thereof are most preferred.
  • the amount of phenol used in the present invention depends on the molecular weight of the phenol, the molecular weight of the epoxy, as well as the target equivalent weight of the SEER and level of branching. In general, the phenol is used in an amount of from about 1 wt. % to about 60 wt. %, more preferably, from about 5 wt. % to about 50 wt. % and, most preferably, from about 20 wt.
  • the reaction of the low molecular weight epoxy resin with a dicarboxylic acid requires a catalyst or any material capable of catalyzing the reaction.
  • the dicarboxylic acid and the epoxy resin components are contacted in the presence of a catalyst for the reaction between the carboxylic groups of the dicarboxylic acid and the epoxy groups of the epoxy resin and at conditions sufficient to form the desired resin.
  • the catalysts useful in the present invention include, but are not limited to, phosphines, amines, quaternary ammonium and phosphonium salts, such as tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium hydroxide, tetra(n-butyl)ammonium chloride, tetra(n-butyl) ammonium bromide (TBAB), tetra(n- butyl)ammonium iodide, tetra(n-butyl) ammonium hydroxide, tetra (n-octyl) ammonium chloride, tetra(n-octyl) ammonium bromide, tetra(n-octyl)ammonium iodide, tetra(n- octy
  • Most preferred catalysts include tetrabutylphosphonium bromide (TBPB), tetraethylammonium bromide, tetraethylammonium hydroxide, ethyltritolylphosphonium acetate, ethyltriphenylphosphonium acetate, and N-methylmorpholine, 2-phenylimidazole (2-PhIm).
  • TBPB tetrabutylphosphonium bromide
  • tetraethylammonium bromide tetraethylammonium hydroxide
  • ethyltritolylphosphonium acetate ethyltriphenylphosphonium acetate
  • N-methylmorpholine 2-phenylimidazole
  • More preferred onium catalysts include tetrabutylammonium bromide, tetrabutylphosphonium bromide (TBPB), ethyltriphenylphosphonium iodide, tetraphenylphosphonium bromide and tetrakis(n-butyl)ammonium bromide and the corresponding chloride, iodide, bromide, acetate, formate, phosphate, borate, trifluoroacetate, oxalate and bicarbonate, with tetrabutylphosphonium bromide (TBPB) being most preferred.
  • TBPB tetrabutylphosphonium bromide
  • the amount of catalyst used depends on the molecular weight of the catalyst, the activity of the catalyst and the speed at which the polymerization is intended to proceed.
  • the amount of catalyst employed in the process of the present invention can vary over a wide range, so long as a catalytic amount is present. In general, the amount of catalyst used in the present invention will fall within the range of from about 0.001 percent (%) to about 10 percent, preferably from about
  • the epoxy resin compositions of the present invention can be prepared by reacting a low molecular weight aromatic epoxy resin and a dicarboxylic acid in the presence of a catalyst and in the absence of a solvent under conditions sufficient to form the uncrosslinked, soluble, high molecular weight epoxy ester resin.
  • the reaction can be done using a batch process or a continuous process conducted in a reactive extruder, such as that described in European Patent No. EP 0193809.
  • the process of the present invention can be conducted in an open container or in an extruder or in an injection molding machine.
  • the conditions at which the polymerization reaction is most advantageously conducted are dependent on a variety of factors, including the specific reactants employed, and catalyst employed. In general, the reaction is conducted under a non-oxidizing atmosphere such as a blanket of nitrogen or other inert gases.
  • reaction conditions employed in the process of the present invention may be varied.
  • the time and temperature most advantageously employed will vary depending on the specific monomers employed, particularly their reactivity and the specific oligomer. Generally, however, convenient rates of reaction to form the polyesters are obtained at reaction temperatures in the range of from about 50 0 C to about 300 0 C, at atmospheric, subatmospheric or superatmospheric pressure. Generally, the reaction pressures ranges from about atmospheric to about 150 psig, and the reaction times are from about 30 minutes to about 24 hours.
  • the reaction of the epoxy resin and carboxylic acid is advantageously carried out at an elevated temperature.
  • the reaction temperature is preferably from about 60 0 C to about 220 0 C and, more preferably, from about 100 0 C to about 150 0 C, and most preferably, from about 120 0 C to about 140 0 C.
  • the reaction time is preferably from about 1 hour to about 24 hours and, most preferably, from about 2 hours to about 8 hours.
  • the reaction is continued until the desired conversion, as determined by measuring the acid conversion of the resin by acid number (AN) titration and when the target molecular weight or EEW of the resin, is achieved, at which point, the reaction is effectively terminated.
  • AN acid number
  • the reaction is generally carried out by combining the polyepoxide and the dicarboxylic acid reactants at a starting temperature of about 100 0 C to about 120 0 C and allowing the reaction to exotherm to a temperature of about 160 0 C to about 200°C, for a time of about 1 hour to about 2 hours.
  • the relative amount of the reactants depends upon the characteristics, particularly the molecular weight, of the product desired.
  • the preferred high molecular weight epoxy- terminated polyester resin products having an epoxide equivalent weight of between about 600 and about 4,000, about 0.60 to 0.95 mole dicarboxylic acid will be reacted with each mole of a diglycidyl ether of bisphenol-A having an epoxide equivalent weight of between about 170 and about 500.
  • the present reaction can be done in one step wherein a liquid aromatic epoxy resin (LER), dicarboxylic acid, and catalyst are reacted and the reaction terminated at a point such that the targeted epoxy reaction product is obtained prior to gelation.
  • LER liquid aromatic epoxy resin
  • dicarboxylic acid dicarboxylic acid
  • catalyst catalyst
  • the liquid aromatic epoxy resin and the dihydric phenol may be reacted first and then the dicarboxylic acid may be added to the reaction mixture; or the LER and dicarboxylic acid may be reacted first, and then the dihydric phenol may be added to the reaction mixture; and the reaction terminated at a point when the reaction product contains the target epoxy equivalent weight prior to gelation.
  • an optional difunctional monomer such as a dihydric phenol
  • the quenching step (ii) can be carried out by any method which effectively inhibits the reaction upon reaching the desired degree of conversion.
  • the reaction is effectively inhibited when the rate of reaction of the carboxyl and epoxy group is sufficiently reduced such that further reaction, if any, does not significantly and deleteriously affect the product or its handling characteristics.
  • the reaction is sufficiently inhibited such that the solution viscosity of the uncrosslinked resin remains essentially constant or increases only marginally with time.
  • the reaction mixture can be quenched to stop the reaction.
  • the rapid quenching of the reaction mixture must be conducted carefully to prevent clotting or lumping of the uncrosslinked resin and to prevent the uncrosslinked resin from forming a large solid mass which cannot subsequently be used.
  • a convenient method for quenching the reaction mixture comprises the addition of a solvent to the mixture, thereby diluting the mixture and reducing its temperature.
  • the amount of organic solvent to be added is dependent on the reaction temperature and the temperature at which reaction is effectively terminated.
  • the addition of organic solvent to the reaction mixture is particularly preferred when the uncrosslinked resin is subsequently to be applied from solution.
  • the solvent useful for quenching may be any one of the solvents previously described above.
  • a most preferred method for inhibiting the reaction comprises adding a material to the reaction mixture which effectively inhibits further reaction such as by deactivating the catalyst, or by interrupting the reaction mechanism, thereby inhibiting further reactions between the polyol and the polyepoxide.
  • Strong inorganic and organic acids and the anhydrides and esters of said acids have been found to be particularly effective as reaction inhibitors.
  • strong acid it is meant an organic acid having a pKa value below about 4, preferably below about 2.5.
  • reaction inhibitors include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; inorganic acid anhydrides such as phosphoric acid anhydride; esters of inorganic acids such as dimethyl sulfate; the organic acids such as alkyl, aryl and aralkyl and substituted alkyl, aryl and aralkyl sulfonic acids such as p- toluene sulfonic acid and phenyl sulfonic acid and stronger organic carboxylic acids such as trichloroacetic acid and alkyl esters of said acids, such as the alkyl esters of p-toluene sulfonic acid, e.g., methyl-p- toluene sulfonate, and ethyl-p-toluenesulfonate, methanesulfonic acid methylester and mixtures thereof.
  • inorganic acids such as hydrochloric acid, sulfuric acid
  • an acid anhydride of a strong organic acid that can be employed herein is p-toluene sulfonic acid anhydride.
  • the alkyl esters of sulfuric acid the aryl or aralkyl sulfonic acids and the alkyl esters of said acids are preferably employed herein.
  • an alkyl ester of para-toluene sulfonic acid, particularly methyl or ethyl-p- toluene sulfonic acid is employed as the reaction inhibitor herein.
  • the amounts of reaction inhibitor added to the reaction mixture are dependent on the specific inhibitor employed and the catalyst employed in preparing the uncrosslinked resin.
  • the inhibitor is added in an amount sufficient to overcome the catalytic activity of the catalyst.
  • at least about 0.9, more preferably at least about 2, equivalents of the inhibitor are added for each equivalent of the catalyst employed.
  • the maximum amount of inhibitor added to the reaction mixture is dependent on the desired properties of the resin and the expense of adding excess inhibitor, the inhibitor is preferably added in an amount not exceeding about 5 equivalents for each equivalent of catalyst in the reaction mixture.
  • the polymers are recovered from the reaction mixture by conventional methods.
  • the reaction mixture containing the polymer as a precipitate can be filtered to remove the solid polymer.
  • the solid monomer can then be rinsed with water, methanol, and ether or other solvents which are non-solvents for the polymer, but good solvents for the impurities.
  • the polymer also can be isolated by pouring the reaction mixture into a non- solvent for the polymer and collecting the precipitated product.
  • the product polymer can be isolated by removal of the solvent, if any, by vacuum distillation, wiped-film evaporation or devolitilization extrusion.
  • the resin of the present invention can be cured with a variety of epoxy curing agents such as phenolics, amines, carboxylic acids, phenol formaldehyde resins, and anhydrides, as well as through the hydroxyl group or an epoxy group.
  • the resin of the present invention can be reacted with a hardener such as, for example, an amine-terminated polymer, a carboxy- terminated polymer, a phenol-terminated polymer, a multifunctional amine, carboxylic acid or phenol, or a phenolic resole polymer.
  • the SEER of the present invention can be used in a variety of industrial applications or other epoxy applications such as coatings, laminates and composites.
  • Industrial coatings are surface protective coatings (paint coatings) applied to substrates and typically cured or crosslinked to form continuous films for decorative purposes as well as to protect the substrate.
  • a protective coating ordinarily comprises an organic polymeric binder, pigments, and various paint additives, where the polymeric binder acts as a fluid vehicle for the pigments and imparts rheological properties to the fluid paint coating. Upon curing or crosslinking, the polymeric binder hardens and functions as a binder for the pigments and provides adhesion of the dried paint film to the substrate.
  • the pigments may be organic or inorganic and functionally contribute to opacity and color in addition to durability and hardness.
  • the manufacture of protective coatings involves the preparation of a polymeric binder, mixing of component materials, grinding of pigments in the polymeric binder, and thinning to commercial standards.
  • the coating of the present invention using the SEER prepared as described herein is prepared under the conditions described in accordance with ASTM 4147-99.
  • the polymeric binder can include a wide variety of other additives such as, for example, hardeners, dyes, pigments and flow modifiers, f ⁇ re-retardants, self extinguishing agents, desiccants and all manner of additives which are used herein for their known purposes.
  • fire retardants include: monoammonium phosphate, diamonium phosphate and aluminum trihydrate.
  • additives can be in the form of liquids or particles so long as the binder remains solid, has the desired particle size and imparts no adverse effects to the binder.
  • a liquid coating composition can be obtained which comprise the resin of the present invention, and suitable pigments, catalysts and additives.
  • the coatings therefrom have a surprisingly good combination of highly prized properties.
  • Water-dispersed coating compositions containing the resin of the present invention are highly desirable for can and coil coating compositions.
  • EW epoxy equivalent weight
  • AN acid number
  • A-I is a catalyst (70 wt. % «-Bu 4 POAc/HOAc in methanol) available from Morton Chemical Company.
  • TBPB 4-methylmorpholine (4-MMP), 2-phenylimidazole (PhIm), adipic acid (AA), PA, diglyme, cyclohexanone, Dowanol PM (PM), and /?-tert.-butylphenol (PTBP) are chemicals commercially available from Aldrich.
  • Isophthalic acid is an acid commercially available from Aldrich or MB Biomecidals, Inc.
  • KOH is commercially available from J. T. Baker Chemical Co.
  • Methylon 75108 is a methylolphenyl allyl ether commercially available from Occidental Chemical Co.
  • Super phosphoric acid (105 %), methyl ethyl ketone (MEK), lactic acid, 2-butoxyethanol (DowanolTM EB), and methyl isobutyl ketone (MIBK), are chemicals commercially available from Aldrich Chemical Co.
  • HPLC high pressure liquid chromatography
  • HPLC grade water, acetonitrile (ACN), and tetrahydrofuran (THF) are chemicals commercially available from EMD.
  • M n Number average molecular weight (M n ) was determined by GPC-LS analyses were done using a Viscotek GPC analysis system. Epoxide equivalent weight (EEW) titrations were done according to a procedure equivalent to ASTM D- 1652-97.
  • Acid number (AN) were done according to a procedure equivalent to ASTM D 1639-83.
  • Comparative Example A was carried as described in the General Procedure above using 26.7 g bisphenol A, 32.7 g adipic acid, 150.0 g D.E.R. 331 epoxy resin, and 0.16 g A-I catalyst and without solvent at the reaction temperature as shown in Table I.
  • Example 1 - Preparation of Resin Product Example 1 was carried as described in Comparative Example A above except that the reaction product was quenched by rapid cooling prior to gelation.
  • Comparative Example B was carried as described in Comparative Example A above except using, 165.3 g D.E.R. 331 epoxy resin, at the reaction temperature as shown in Table I.
  • Example 2 Preparation of Resin Product
  • Example 2 was carried out as described in Comparative Example B above except that the reaction product was quenched by rapid cooling prior to gelation.
  • Example 3 was carried out as described in Comparative Example A above except that 18.0 g PTBP was added and the reaction product was quenched by rapid cooling prior to gelation.
  • the target EEW is that calculated for the resin composition without PTBP.
  • Comparative Example C was carried as described in Example 1 above using 33.3 g. adipic acid, 150.0 g D.E.R. 331 epoxy resin, and 0.14 g A-I catalyst and without solvent at the reaction temperature as shown in Table I. Comparative Example D
  • Comparative Example D Part 1, was carried as described in Example 1 above using 33.3 g adipic acid, 150.0 g D.E.R. 331 epoxy resin, and 0.14 g A-I catalyst and without solvent at the reaction temperature as shown in Table I. Part 2 was done using the product from Part 1 and 26.1 g bisphenol A and 0.16 g A-I catalyst at the reaction temperature as shown in Table I. Table I. Reactions of LER or SER with AA.
  • LER, DCA, solvent and catalyst were loaded to a 500 mL glass resin kettle fitted with a reflux condenser, a N 2 inlet, a stirring rod connected to an air-driven motor, and a thermocouple and heating mantle connected to a temperature controller.
  • the reaction mixture was heated to the designated temperature in less than 1 hour and was then held isothermally until the target EEW was reached.
  • the reaction time was taken as the duration between the time at the desired solution temperature and the time after reaching the desired EEW.
  • Catalyst wt. % was based on amount of LER, DCA, and catalyst.
  • Solution wt. % was based on the amount of whole reaction system, i.e. LER, DCA, catalyst, and solvent.
  • Tin free steel TFS - single reduced electrolytic chromium coated sheet
  • type L Tin free steel
  • T4CA surface 50,obtained from Weirton Steel Corporation
  • Coating formulations were drawn down on TFS panels according to a procedure described in ASTM 4147-99 and cured to give 0.20 +/- 0.02 mil coating thickness.
  • the coated panels were tested for MEK resistance in accordance with ASTM D 5402-93, maximum number of double- rubs (DR) prior to coating failure; and for wedge bend flexibility in accordance with ASTM D 3281-84.
  • Lactic acid pasteurization resistance was done using wedge bend panel samples (about 170° bend with coating in tension) immersed in vials containing 2 wt. % lactic acid and heated in an autoclave at 120 0 C for 30 minutes.
  • the rating system described in Table A below, was used to describe the coating performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un procédé d'élaboration d'une résine soluble et non réticulée d'ester d'époxy de masse moléculaire élevée à terminaisons époxy et dont l'indice d'acide se situe entre environ 5 et environ 30. Ce procédé consiste à prendre une résine époxy aromatique de faible masse moléculaire et un acide dicarboxylique et à les faire réagir sans présence de solvant. L'invention concerne également un procédé de production d'un revêtement à partir de la résine soluble et non réticulée d'ester d'époxy de masse moléculaire élevée à terminaisons époxy obtenue.
PCT/US2007/080840 2006-10-10 2007-10-09 Procédé d'élaboration de polymères solubles avec faible taux de conversion de l'acide à partir de résines époxy et de diacides, et procédé d'élaboration de revêtements réticulés à partir de tels polymères WO2008045889A1 (fr)

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Cited By (9)

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WO2011071650A1 (fr) 2009-12-08 2011-06-16 Dow Global Technologies Llc Résines polyester à fonction hydroxyle
WO2012044490A1 (fr) 2010-09-30 2012-04-05 Dow Global Technologies Llc Compositions de revêtement
CN103255242A (zh) * 2013-05-23 2013-08-21 青岛联康油脂制品有限公司 一种砜桥型合成鞣剂的制备方法
US8962792B2 (en) 2010-09-30 2015-02-24 Dow Global Technologies Llc Process for preparing epoxy resins
US9068039B2 (en) 2010-09-30 2015-06-30 Dow Global Technologies Llc Thermosettable compositions and thermosets therefrom
US9080059B2 (en) 2010-09-30 2015-07-14 Blue Cube Ip Llc Coating compositions
US9284434B2 (en) 2010-09-30 2016-03-15 Blue Cube Ip Llc Epoxy resin compositions
US9371414B2 (en) 2010-09-30 2016-06-21 Blue Cube Ip Llc Epoxy resin adducts and thermosets thereof
CN113234214A (zh) * 2021-06-23 2021-08-10 中国科学院大连化学物理研究所 一种共聚酯及其制备方法

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* Cited by examiner, † Cited by third party
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US10982041B2 (en) 2016-02-25 2021-04-20 Swancor Advanced Materials Co., Ltd. Epoxy resin oligomer

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US5780582A (en) * 1996-12-31 1998-07-14 The Dow Chemical Company Hydroxy-functionalized polyester and poly(ester ether) oligomers
WO2000001779A1 (fr) * 1998-07-03 2000-01-13 Imperial Chemical Industries Plc Composition de revetement

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US4722981A (en) * 1986-02-14 1988-02-02 The Dow Chemical Company Epoxy resins of controlled conversion and a process for their preparation
US5780582A (en) * 1996-12-31 1998-07-14 The Dow Chemical Company Hydroxy-functionalized polyester and poly(ester ether) oligomers
WO2000001779A1 (fr) * 1998-07-03 2000-01-13 Imperial Chemical Industries Plc Composition de revetement

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071650A1 (fr) 2009-12-08 2011-06-16 Dow Global Technologies Llc Résines polyester à fonction hydroxyle
US8975343B2 (en) 2009-12-08 2015-03-10 Dow Global Technologies Llc Hydroxyl-functional polyester resins
WO2012044490A1 (fr) 2010-09-30 2012-04-05 Dow Global Technologies Llc Compositions de revêtement
US8962792B2 (en) 2010-09-30 2015-02-24 Dow Global Technologies Llc Process for preparing epoxy resins
US9068039B2 (en) 2010-09-30 2015-06-30 Dow Global Technologies Llc Thermosettable compositions and thermosets therefrom
US9080059B2 (en) 2010-09-30 2015-07-14 Blue Cube Ip Llc Coating compositions
US9284434B2 (en) 2010-09-30 2016-03-15 Blue Cube Ip Llc Epoxy resin compositions
US9371414B2 (en) 2010-09-30 2016-06-21 Blue Cube Ip Llc Epoxy resin adducts and thermosets thereof
CN103255242A (zh) * 2013-05-23 2013-08-21 青岛联康油脂制品有限公司 一种砜桥型合成鞣剂的制备方法
CN103255242B (zh) * 2013-05-23 2015-11-18 青岛联康油脂制品有限公司 一种砜桥型合成鞣剂的制备方法
CN113234214A (zh) * 2021-06-23 2021-08-10 中国科学院大连化学物理研究所 一种共聚酯及其制备方法
CN113234214B (zh) * 2021-06-23 2022-02-15 中国科学院大连化学物理研究所 一种共聚酯及其制备方法

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