TW200835712A - Process for preparing soluble polymers with low conversion of acid from aromatic epoxy resins and diacids and process for preparing crosslinked coatings therefrom - Google Patents

Abstract

A process for preparing an uncrosslinked, soluble, epoxy terminated high molecular weight epoxy ester resin having an acid number from about 5 to about 30 comprising reacting a low molecular weight aromatic epoxy resin and a dicarboxylic acid in the absence of solvent; and a process for producing a coating from the uncrosslinked, soluble, epoxy-terminated high molecular weight epoxy ester resin product.

Description

200835712 IX. Description of the Invention [Technical Field of the Invention]: The invention relates to a method for dissolving a soluble high molecular weight epoxy resin which is a low molecular weight aromatic epoxy resin and a diweiric acid hexafluorene. Such soluble high molecular weight epoxy ester resins are advantageously provided as crosslinked coatings. Tian /, clothing [prior art] / protective coating on metal is one of the first applications of epoxy resin, and ^ find: the use of internal coatings for metal food and beverage containers for them = 2 ': - Typically, it is made from an internal high molecular weight epoxy resin used in metal food and beverage containers. And typically, the

The % oxygen resin is prepared by using a low molecular weight epoxy resin such as diglycidyl ether of bisphenol A and a compound containing a double base: a double body. Further, the cyclic reaction product of A-螂 propyl propyl ether, also known as ring-nine-incorporate, often mixes the solution (4) from the coating, causing contamination of the processing equipment and accompanied by loss of productivity and waste generation. Food and Drink Search for methods that can be used to make epoxy heat (iv) internal container coatings ^ Technology that eliminates these problems. "Relief" represents a broad range of materials that are potentially effective for reacting with low molecular weight epoxy resins, with the same knife oxime ester resin. However, according to a known method for preparing a high molecular weight epoxy resin, a monocarboxylic acid guides the formation of a crosslinked insoluble polymer. Industrially, it is desirable to use a dicarboxylic acid as a method for reacting a sulphonic acid with an epoxy resin monomer, and a non-parental soluble epoxy functional polymer. 6 200835712, a known method of not using a dicarboxylic acid and an epoxy resin, such as U.S. Patent No. 4,722,981, U.S. Patent Publication No. 2Gm428Ai, and European Patent Publication No. G5q1575A2. However, U.S. Pat. Thus, the method taught in the above prior art does not produce an epoxy-terminated uncrosslinked soluble high molecular weight epoxy ester resin. The method known to him teaches diepoxides and dicarboxylic acids. The methods disclosed in U.S. Patent Nos. 5,962,621, 5,852,163, and 5,058, the disclosures of which are hereby incorporated herein by reference. Literature such as Suzuki, Akira; Kameyama, Atsushi; Nishikubo, Tadatomi, Kobunshi Ronbunshu (1996) 5 53(9), 522-529, Alvey, Francis B.5 Journal of Polymer Science, K? Matejka, L5 Advances in Chemistry Series 1984? 2085 15 teaches the synthesis of high molecular weight polyesters from epoxy resins and dicarboxylic acids. However, the methods disclosed in these documents use equimolar amounts of epoxy and dicarboxylic acid, thus The resin product obtained by these known methods does not have an epoxy functionality '(2) includes a large amount of unreacted dicarboxylic acid, or (3) undergoes gelation. U.S. Patent No. 4,829,141 No. 4,3,02,574; and Canadian Patent No. 1,091,690 disclose the use of epoxy resins and carboxylic acids, but these documents do not teach epoxy-terminated uncrosslinked soluble high scores 7 200835712 sub-rings Oxygen ester resin. The literature can be used to disclose the use of a few acids, but it has not been taught to use a few acids as a comonomer. A _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The method for the uncrosslinking of the soluble ancient eight ^ yang que d ~ sex knives bismuth resin. For example, U.S. Patent No. 3,864,316 铗 笙/f /f~, , 4,935 discloses the use of oxidative hydrogenation, ie A method for the non-aromatic epoxy resin to be implanted by one m, the patent of the Japanese Patent No. 5, 171, 820: = a method for preparing a chewy vinegar containing (4), and a composition of W〇έ, ^9Α1, Among them, the epoxy-poly-guar fork/hard object has acid functionality.矣 庳 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — The high-end lacquer vinegar resin, which is a terminal end, can then react with a crosslinking agent to form a coating. SUMMARY OF THE INVENTION The invention relates to a method for preparing an uncrosslinked soluble high molecular weight epoxy resin such as a resin, which comprises the steps of: (1) (a) low molecular weight epoxy bismuth acid as needed In another difunctional monomer, such as double-president ▲ + in the next reaction 'the reaction system in the absence of a solvent and in the presence of a catalyst at a specific reaction temperature „ ^ order, and (11) before gelation, will The reaction mixture is quenched to form a soluble high molecular weight epoxy-resin. The method of the invention has provided a novel composition comprising a product having an epoxy end and a low rate of conversion of a slow acid group. 铖夺萨+^ 本明The method of preparing the non-flat peppers ^ my t 礼 0 树 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖 新颖The molecular weight epoxy ester resin is formed by the reaction of the fish (four) agent. One of the main purposes of the vinegar coating is to use the mouth or the 饫枓% and/or the inside of the can lid. Specific examples provide a close Target epoxy equivalent of resin, the reaction was quenched at this time, to avoid gelling.

Further, another specific example includes a soluble cyclic emulsion-derived high molecular weight epoxy ester resin prepared by reacting a low molecular weight epoxy resin with a j acid and optionally a difunctional monomer. Due to their epoxy properties, the resin can be used as a precursor for epoxy thermosets, including by cross-linking with cross-linking agents such as soluble ages, iM. Llc res〇les) crosslinked coating. Soil [Embodiment], the present invention includes - (1) reacting (4) a low molecular weight epoxy resin with (b) a diterpenic acid as needed in the presence of another difunctional monomer, such as a bis-A The reaction is carried out in the absence of a solvent and in the presence of a catalyst at a reaction temperature of, for example, up to about 3 GG ° C; and (u) prior to gelation, the reaction mixture is formed to form a valence high molecular weight epoxy ester resin. Method 0 The process of the present invention produces a composition comprising a product having an epoxy terminal and a low carboxylic acid group conversion or a high acid value. The present invention produces an uncrosslinked soluble epoxy-terminated high molecular weight epoxy ester resin prepared by reacting a low molecular weight epoxy resin with a diterpenic acid, which, due to their epoxy functionality, The resin is used as a precursor to an epoxy thermoset, including a coating that is crosslinked with a resol resin. The uncrosslinked high-molecular weight epoxy ester resin composition of the present invention which is uncrosslinked can be referred to herein as a solid epoxy ester resin "or, 'SEER" Epoxy resins of the invention and well-known, solid epoxy resins derived from low molecular weight epoxy resins and bisphenol A, or 'SER,. Uncrosslinked// means that the composition has a defined viscosity and no objectile gel-like reaction product. Coulomb means that the composition is dissolved in a suitable organic solvent. ', high molecular weight" means that the composition has a molecular weight of at least about 2 times that of the starting epoxy resin, preferably at least about 3 times. x, acid value means the amount of KOH in milligrams necessary for neutralizing 1 gram of sample according to the procedure described in ASTM D 1639-83., low carboxylic acid group conversion 〃 means dicarboxylic acid The carboxylic acid moiety and the intermediate are not completely reacted, as measured by the acid value of the composition, such that the acid value is greater than about 5. The reaction of the dicarboxylic acid with the epoxy resin component can be carried out neatly, ie without It is carried out in the presence of a diluent or a solvent. If the resulting product is used for the purpose of coating, any well-known solvent can be used in the composition to form a coating solution which is applied to the substrate in a well-known manner. Examples of the solvent include pyridine, triethylamine or a mixture thereof; n-methylpyrrolidone (NMP), methyl benzoate, ethyl benzoate, butyl benzoate, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctane Ketones, cyclohexyl pyrrolidone, and ethers or hydroxy ethers, such as dioxane, diglyme, triglyme, diethylene glycol diethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether , dipropylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether Ester, propylene 2 10 200835712 alcohol methyl ether and tripropylene glycol methyl ether; toluene, mesitylene, xylene, benzene, dipropylene glycol monoterpene ether acetate, halogenated solvent, such as dichlorobenzene, propylene carbonate, naphthalene, Diphenyl ether, butane vinegar, dimethylacetic acid amine, dimethylformamide, esters such as ethyl acetate or butyl acetate and mixtures thereof. Other suitable diluents are those which react to the reactants at the reaction temperature. An inert organic compound, for example, various glycol ethers such as ethylene glycol ether, ethylene glycol or propylene glycol monomethyl ether and esters thereof, such as ethylene glycol monoethyl ether acetate; ketones such as methyl Isobutyl ketone, methyl ethyl ketone (MEK) and acetone; and aromatic hydrocarbons such as toluene, xylene, cyclohexane or mixtures thereof. The low molecular weight epoxy resin used in the present invention includes polyepoxy a compound having more than one adjacent epoxy group per molecule, i.e., having more than one 1,2-epoxy group per molecule. The polyepoxides are saturated or unsaturated aromatic poly Epoxide; if necessary, it is replaced by a non-interfering substituent, Substituted by a halogen atom, a hydroxyl group, an ether group, and the like. The low molecular weight / / epoxy resin means having a number average molecular weight () of less than about 10,000, preferably less than about 8, fluorene, and more preferably less than about 4 An aromatic epoxy resin precursor of yttrium. Typically, the low molecular weight 5 oxirane precursor useful in the present invention has from about 200 to about 1 Torr, preferably from about A preferred average molecular weight of from 200 to about 8,000, and more preferably from about 25 to about 4. The preferred low molecular weight epoxy resin is a liquid polyepoxide comprising, for example, a liquid epoxy of more than 7 L of phenol. More preferred are propyl polyethers. More preferred are 2,2-bis(4-hydroxyphenyl groups) having an average molecular weight of between about 340 and about 900 and an epoxide equivalent of between about 17 Å and about 500 Å. ) Epoxypropyl polyethers of propane. 11 200835712 particularly preferably having an average molecular weight of between about 340 and about 900, an epoxide equivalent of between about 17 angstroms and about 5 angstroms and containing from about 1% by weight to about 1. % by weight or more of saponifiable chlorine, 2,2 bishydroxyphenyl) propyl oxypropyl polyether. The term, epoxide equivalent, and weight per epoxide, as used herein, refers to the average molecular weight of a polyepoxide molecule divided by the average number of oxirane groups present in the molecule. The diepoxides useful in the practice of the present invention include di-epoxypropyl ethers of dihydric phenols, such as those in U.S. Patent Nos. 5,246,751, 5,115, 5, 5,089,588, 4,480,082, and U.S. Patent No. 4,438,254, the entire disclosure of which is incorporated herein by reference in its entirety, in its entirety, in its entirety, in U.S. Pat. Diepoxy = commercially available as der® 300 and 600 series epoxy resins and commercially available from

The Dow Chemical Company is an epoxy resin based on α,ω_diepoxypropoxyisopropylidene-bisphenol. Preferred diepoxides are those having an epoxy equivalent weight of from about 100 to about 4,000. The most preferred diepoxides are bisphenolphthalein diepoxypropyl ethers, 4,4,-sulfonyl diphenol, 4,4-oxydiphenol, 4,4,-dihydroxydiphenylhydrazine. Ketone, resorcinol, hydroquinone, 9,9,-diphenyl), 4,4'-dihydroxybiphenyl or 4,4,-dihydroxy-α-methyldiphenylethylene and previously described Di-epoxypropyl alcohols of dicarboxylic acids. These bis-epoxides are more reactive toward dicarboxylic acids than non-aromatic diepoxides and are therefore more prone to cross-linking or gelation. In the towel of the present invention, it is said that the unmarried soluble resin product is prepared by using the aromatic diepoxides. 12 200835712 The amount of epoxy resin used is based on the molecular weight of the target and the epoxy functionality. The epoxy resin is used in an amount of from about 30% by weight to about 85% by weight based on the weight of the reactant. More preferably, from about 4% by weight to about 75% by weight 'and optimally from about 45% by weight to about 7% by weight. The carboxylic acid used in the present invention may be, for example, a saturated, unsaturated, ruthenium, an aliphatic, an aromatic or a heterocyclic group. Examples of such acids include, in particular, butyl ketone, glutaric acid, adipic acid (aa), pimelic acid, suberic acid, hydrazine, oxalic acid, rosin acid, cis-butyl succinic acid. , aconitic acid, hexachloro-nonenyl-tetrahydro succinic acid (chl〇rendic acid), phthalic acid (PA), terephthalic acid (TPA), isophthalic acid (IPA), 2 ,6_ 不一k 3,4 _Liandi dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, malonic acid, 14· 裒: ": 兀一carboxy 驮, 1,1 〇 癸 癸Carboxylic acid, hydrazine, dodecacinated dicarboxylic acid, 1,) cyclohexanedicarboxylic acid (UCHDA), M_cyclohexanedicarboxylic acid (CHDA), tartaric acid, citramalic acid and hydroxyglutaric acid. More preferred carboxylic acids include p-benzoic acid, isophthalic acid, adipic acid, and mixtures thereof. The amount of the carboxylic acid used in the present invention can be varied in a wide range. Generally, the amount of carboxylic acid used in the present invention is from about 1% by weight to about 50% by weight, more preferably from about 5% by weight to about 45% by weight, based on the weight of the reactants, and most preferably from From about 10% by weight to about 4% by weight. The reaction mixture of the low molecular weight epoxide and the carboxylic acid can be carried out as needed in the presence of a secondary monomer such as a compound containing a thiol group or a thiol group, such as a quinone or a porphin. A preferred optionally hydroxyl group-containing compound is a phenol having at least one radical attached to an aromatic core. The phenols may be units or polyphenols, sub-substituted or unsubstituted. The polymeric polyhydric phenols can be obtained by a condensation unit or 13 200835712 polyphenols and furfural. Preferred phenols as desired are polyhydric phenols containing from 2 to 6 hydrazine H groups and up to 30 carbon atoms, including those represented by:

Wherein X is a multivalent member or group, and each R is independently selected from the group consisting of hydrogen, dentate and leuco. Preferred groups represented by X are oxygen, sulfur, _s〇·, _s〇2_, a divalent hydrocarbon group having at most 1 carbon atom, and a hydrocarbon group containing oxygen, hydrazine, sulfur or nitrogen. A preferred phenol is 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) wherein each R is hydrazine and X is an isopropylidene group. The relatively simple one-aged class used in the preparation of the resin of the present invention which can be used in the practice of the present invention includes 4,4'-isopropylidene double (double test a), 4,4'-dihydroxydiphenyl b. Methane, 3,3 dihydroxydiphenyldiethylmethane, 3,4,-di-diphenyl-methylpropyl-methyl, double-aged, 4,4,-di-diyl-diphenyl Ether, 4,4 _ a base of a phenyl ketone, 4,4'-di-biphenyl, 4,4'-di-benzophenone, 4,4, dihydroxydiphenyl sulphide , 4,4, dihydroxydiphenyl hydrazine, 2,6-dihydroxynaphthalene, 1,4 '-dihydroxynaphthalene, phenol, resorcinol, o-xylenol, m-dimethyl-n-pair Cresol, chlorophenol, nitrophenol, hydroquinone, 2,2_bis(4-hydroxyphenyl)propene: 2,2-bis(4-phenylphenyl)pentane, catechu, halogenated For example, tetrabromo-based A-age A and other dihydric phenols listed in U.S. Patent Nos. 3,395,118, 4,43,254, and 4,480,082 are incorporated herein by reference. In addition, a mixture of different binary species can be used. 14 200835712 and other A ® 7 categories, the best of the two, A, 1 Kun and their mixture. The amount of phenol used in this specification depends on the molecular weight of the phenol, the molecular setting of the epoxy, the target equivalent of SEER, and the level of branching. Generally, it is used from about i% by weight to about (9)% by weight, based on the weight of the reactants, more preferably from about 5% by weight to about 5% by weight, and most preferably from about 20% by weight. About 45% by weight. 'Reaction of epoxy resin with dicarboxylic acid in low knife requires catalyst

: Any material that catalyzes the reaction. In the preparation of the epoxy resin of the present invention, the diterpene acid and the epoxy resin component are used in the presence of the (4) reaction of the dicarboxylic acid group and the epoxy group of the dicarboxylic acid. Contacted under conditions sufficient to form the desired resin. Catalysts useful in the present invention include, but are not limited to, phosphines, amines, quaternary ammonium salts, and scale salts, such as tetraethylammonium chloride, desert tetraethylammonium, tetraethylammonium, a oxidation Tetraethylammonium, tetrakis(n-butyl) chloride, desertified tetrakis(n-butyl)m (TBAB), hardened tetrakis(n-butyl)ammonium, tetra(n-butyl)ammonium hydroxide, chlorinated tetra (n-octyl)ammonium, desertified tetrakis(n-octyl)ammonium, tetrakis(n-octyl)ammonium iodide, tetrakis(n-octyl)ammonium hydroxide, methylglycol (n-octyl)ammonium chloride, chlorine Bis(tetraphenylphosphinoalkyl)ammonium, ethyl acetate acesulfame toluene scales/acetic acid malformer: ethyl acetate triphenyl scale/acetic acid complex, N-methylmorpholine, 2-benzene The imidazoles or compositions thereof and the analogs as described in U.S. Patent Nos. 5,208,317, 5,1,9,9, and 4,981,926 are incorporated herein by reference. The most preferred catalysts include tetrabutyl bromide (TBPB), tetraethylammonium bromide, tetraethylammonium hydroxide, ethyl acetate triphenyl phenyl scale, ethyl acetate triphenyl scale and N-methyl Morpholine, 2_phenylimi = 15 200835712 (2-Phlm). Although any material capable of catalyzing the reaction can be used, the preferred reminder is (4). Preferred rust salt catalysts include scale or ammonium salt catalysts. More preferred rust salt catalysts include the evolution of tetrabutylammonium, desertified tetrabutyl squamous (ΤΒΡΒ) 4-ethylidene diphenyl scales, desertified tetraphenyl hydrazine and desertified hydrazine (n-butyl) ammonium and corresponding Chloride, moth, desert, acetate, formic acid, difluoroacetate, oxalate and bicarbonate, preferably tetrabutyl bromide. The amount of catalyst used depends on the molecular weight of the catalyst, the activity of the catalyst, and the rate at which polymerization is desired. The amount of the catalyst used in the process of the present invention can be varied within a wide range as long as a catalytic amount is present. Generally, the amount of catalyst used in the present invention falls within a range from about 1% to about 1%, preferably from about 0.001% to about 5%, based on the total reactant weight s. More preferably from about 2% to about 2%, and most preferably from about 0.03% to about 1% by weight of the reactants. Generally, the epoxy resin composition of the present invention can be formed by a low molecular weight aromatic epoxy resin and a dicarboxylic acid in the presence of a catalyst and in the presence of a solvent in an amount sufficient to form an uncrosslinked soluble high molecular weight epoxy ester resin. Prepared by reaction under the conditions. The reaction can be carried out using a batch or continuous process carried out in a reaction extruder, as described in European Patent No. 0,193,809. The invention can be carried out in an open vessel or in an extruder or in an injection molding machine. The conditions most favorable for carrying out the polymerization are determined according to various factors, and 16 200835712 includes the specific reactants used and the catalyst used. Typically, the reaction is carried out under a non-oxidizing gas such as nitrogen or another inert gas layer.

The reaction conditions used in the process of the invention may vary. The time and temperature most advantageous for use will vary depending upon the particular monomers employed, particularly their reactivity and particular oligomers. However, a convenient rate for the reaction to form a polycondensation is generally obtained at a reaction temperature ranging from about 50 ° C to about 300 ° C and at atmospheric pressure, low atmospheric pressure or superatmospheric pressure. Typically, the reaction pressure ranges from about atmospheric pressure to about 150 psig, and the reaction time is from about 3 minutes to about 24 hours. The reaction of the epoxy resin with the carboxylic acid is advantageously carried out at elevated temperatures. The reaction temperature is preferably from about 6 (TC to about 22 (TC, more preferably from about 10 {rc to about 15 ° C, and most preferably from about i2 ° C to about 14 Torr. 反应. Reaction time) Preferably from about ! hours to about 24 hours, and optimally from about 2 hours to about 8 hours. Continuous reaction until the desired conversion is achieved, as measured by acid number (AN) titration The acid conversion of the resin is determined and the target molecular weight of the resin is reached or _ day [the reaction is effectively terminated at this point. In one embodiment, the reaction is usually carried out by a polyepoxide ruthenium dicarboxylic acid reactant The reaction is carried out at a temperature of about "(^ to oxime, the reaction is carried out at a temperature of about i hr to about 2, +/- 2), and the temperature is allowed to proceed to about 2, C. The time is exothermed to about 160. The relative amounts of the materials depend on the molecular weight, and are preferably V-based, particularly depending on the desired product, and the coating oxide equivalent is between about 600 and about 4,000 17 200835712. For the polyester resin product, about 0.60 to 〇_95 moles of dicarboxylic acid and each mole have an epoxide when The reaction of bisphenol-A diglycidyl ether is between about 170 and about 500. The reaction of the present invention can be carried out in one step, wherein a liquid aromatic epoxy resin (LER), a dicarboxylic acid and a catalyst are reacted. And, before gelation, terminate the reaction at the point at which the targeted epoxy reaction product is obtained. Alternatively, if a difunctional monomer, such as a binary, is used as desired, the liquid aromatic ring can be used. The oxygen resin is reacted with the dihydric phenol first and then the dicarboxylic acid can be added to the reaction mixture; or the LER can be reacted with the dicarboxylic acid first and then the dihydric phenol can be added to the reaction mixture; and before the gelation, in the reaction The point at which the product comprises the target epoxide equivalent terminates the reaction. The termination of the reaction at the point when the reaction product comprises at most the target epoxide equivalent is referred to as a quenching step prior to gelation. The quenching step can be effected by effective inhibition. Any method of achieving a desired degree of conversion is carried out. When the rate of reaction of the carboxyl group with the epoxy group is sufficiently reduced, further reactions, if any, do not significantly and detrimentally affect the product. When the characteristics are treated, the reaction is effectively inhibited. Preferably, the reaction is sufficiently inhibited so that the viscosity of the solution of the uncrosslinked resin remains substantially unchanged or only minimally increases with time. Once the desired degree of conversion is achieved, the reaction mixture can be quenched to stop the reaction. However, rapid quenching of the reaction mixture must be carried out carefully to avoid coagulation or agglomeration of the uncrosslinked resin and to avoid The crosslinked resin forms a bulk solid which is used for subsequent use. 18 200835712 A convenient method for quenching the reaction mixture involves adding a solvent to the mixture to thereby dilute the mixture and reduce its temperature. The reaction temperature and the effective termination of the reaction of the warm sound 6 / dish 7 and impotence. When the uncrosslinked resin is subsequently coated from a solution, it is particularly preferred to add the organic solvent to the reaction mixture. The solvent which can be used for quenching can be one of the solvents described above. The best method for inhibiting the reaction involves adding the material to the reaction mixture.

It effectively inhibits further reactions, such as by deactivating the catalyst or interrupting the reaction mechanism, thereby inhibiting further reaction between the polyol and the polyepoxide. It has been found that strong inorganic and organic acids and anhydrides and esters of the acid (including semi-sodium and partial esters) are particularly effective as reaction inhibitors. The term "strong" means an organic acid having a PKa value of less than about 4, preferably less than about 2.5. Representative reaction inhibitors include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; inorganic acid anhydrides such as phosphoric anhydride; inorganic acid esters such as dimethyl sulfate; and organic acids such as alkyl, aryl and aromatic Alkyl and substituted alkyl, aryl and aryl sulfonic acids, such as p-toluenesulfonic acid and phenyl sulfonic acid, and stronger organic carboxylic acids such as trichloroacetic acid, alkyl with the acid Esters, such as alkyl esters of p-methyl sulphate, for example, methyl p-toluenesulfonate and p-toluene κ & L ethyl acetonate, methyl methanesulfonate and mixtures thereof. An example of an organic anhydride that can be used herein is p-toluenesulfonic anhydride. Among the reaction inhibitors, the employer uses an alkyl ester of sulfuric acid, an aryl or an aralkyl acid, and an alkyl ester of the acid. Most preferably, the alkyl s oxime of p-toluenesulfonic acid, especially methyl or ethyl-p-toluenesulfonic acid, is used as the reaction of the present invention. The amount of the reaction inhibitor added to the reaction mixture depends on the particular inhibitor used and the catalyst used in the preparation of the uncrosslinked resin. The inhibitor is added in an amount sufficient to overcome the catalytic activity of the catalyst, preferably at least about 0.9 equivalents of inhibitor, more preferably at least about 2 equivalents, per equivalent of catalyst used. Although the maximum amount of inhibitor added to the reaction mixture is based on the nature of the desired resin and the cost of adding an excess of hydrazine d, the inhibitor is preferably no more than about 5 per equivalent of catalyst in the reaction mixture. The equivalent amount is added. During the polymer synthesis,? The fear compound is self-reacted by a conventional method. For example, a reaction containing a polymer that is a sink can be used to remove a solid polymer. The solid monomer can then be water, oxime ether or non-solvent as far as the polymer is concerned, but is good for impurities: 2:: Saline rinse. The polymer can also be isolated by pouring the reaction mixture into a non-solvent for the wide range and collecting the precipitated product. Also press to remove the solvent (if any) and divide it. Scratch film "hair removal or devolatilization The resin of the present invention can be cured with various epoxy curing agents, = y = road resin and liver, and via a trans- or epoxy group. Carboxyl group: 1 scoop tree 1 is intended to be a hardener such as an amine-terminated polymer, a polymer with a few acids or ages, a (4) terminal, a polyfunctional amine, a planthopper, or a resol resin. The polymer can be used in various applications or in other epoxy-bonded hard-bonded layers. The industrial coating is a surface-protected coating (paint coating) applied to the substrate 20 200835712, and is typically cured or crosslinked to form a continuous film and protective substrate for decorative purposes. The protective coating generally comprises an organic ♦ a binder, a pigment and various paint additives, wherein the polymerized knot 2 acts as a fluid vehicle for the pigment and the rheological shell of the fluid paint coating is applied to the polymerized combination when cured or crosslinked. The agent will harden and function as a chelating agent for the binder and provide adhesion of the dried paint film to the substrate. The pigments may be organic or inorganic and provide opacity and color in addition to durability and degree of functionality. The manufacture of protective coatings involves the preparation of polymeric binders, mixed component materials, pigments milled in polymeric binders, and thinness that becomes a commercial standard. The coating of the present invention using a sieve prepared as described herein was prepared under the conditions described in ASTM 4M7-99. - polymeric binders may include a wide variety of other additives, such as hardening: dyes, pigments and flow modifiers, flame retardants, auto-extinguishing agents, dry agents, and used herein for their known purposes. All of the ways of adding = examples of flame retardants include: monoammonium phosphate, diammonium phosphate and trihydrate. The additives may have a liquid or fg 4 颗 pull form, as long as the binder is still solid: having the desired particle size and without any adverse effect of the binder, obtaining the resin of the invention and suitable pigments, A liquid coating composition of a catalyst additive. A combination of unexpectedly good properties derived therefrom. According to the object, :: has received two degrees of attention to the company's L-based agent, catalyst and properties, Γ:: choice and quantity, for example, good chemical resistance with good flow drop, high夯: Bodhisattva, ancient; u Θ 泽 度 度 耐 耐 、 、 、 、 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 3 The water-dispersible coating composition of the resin of the present invention is highly desirable for can and coil coating compositions. In order to provide a further understanding of the present invention, including its advantages, the following embodiments are presented. The various terms, shrinkages, and nomenclature used in the materials used in the following examples are explained as follows: Φ 'EEW〃 represents an epoxy equivalent. AN" stands for acid value. D.E.R.tm331 (EEW:= 188) and D E R. 383 (eew= 18〇) are liquid aromatic epoxy resins (LER). D.E.R. 669E (EEW = 3290) is a solid epoxy resin (SER). These products are commercially available from The Dow Chemical Company. A-1 is a catalyst from Morton Chemical Company (70% by weight of n-Bu4P〇Ac / HOAc in methanol). TBPB, 4-methylmorpholine (4-MMP), 2-phenylimidazole (Phlm), hexamidine (AA), PA, monoglycol, cyclohexanone, DowanolTM PM (PM) and The PTBP is a commercially available chemical from Aldrich. Xingben Yijia® (IPA) is a commercially available acid from Aldrich or MB Biomecidals, Inc. KOH is a commercial item available from J. T. Baker Chemical Co. Methylon 75108 is a methylphenyl dimethyl ether commercially available from Occidental Chemical Co. 22 200835712. Superphosphoric acid (105%), methyl ethyl I (MEK), lactic acid, 2-butoxyethanol (DowanolTM EB) and methyl isobutyl ketone (MIBK) are commercially available chemicals from Aldrich Chemical Co. . Vv HPLC 〃 stands for high pressure liquid chromatography. HPLC grade water, acetonitrile (ACN) and tetrahydrofuran (THF) are commercially available chemicals from EMD.

The various standard test methods and procedures for measuring certain properties in the examples are as follows: • The number average molecular weight (?n) is determined by using the GPC-LS of the viscotek Gpc analysis system. Epoxide equivalent (EEW) titration was accomplished according to the procedure corresponding to ASTM D-1652-97. The acid value (AN) analysis was carried out according to the procedure equivalent to ASTM D 1639_83. The following examples are for illustrative purposes and are not intended to limit the scope of the invention. All parts and percentages are by weight unless otherwise indicated. Step 1 Solvent preparation of resin 4 〇ο·ο ag (g) DER· 331 epoxy resin and g of bisphenol A were added to a mechanical stirrer, condenser, heating jacket and thermocouple connected to the programmable controller 1 八A r τ, & Α (L) resin pot. The mixture was heated to 13 (TC, to form a homogeneous, six, six, & Ί, gluten, and then added 0. 48 grams of A-1 catalyst (benzaldehyde acetate 二 2 7 苴 G base scale /acetic acid complex, 70% by weight in methanol, based on solids > σ tens of millions of 750 parts (ppm). 23 200835712 ” The reaction is heated to 18 ° C and the reaction is allowed until The target EEW is reached. Then the final actual EEW is measured.

Comparative Example A Comparative Example A was carried out as described in the general procedure above using 26.7 grams of bisphenol a, 32.7 grams of adipic acid, 150.0 grams of DER. 331 epoxy resin and 0 at the reaction temperature. • 16 grams of A_i catalyst, no solvent used, as shown in Table I. Example 1 - Matter of Resin Product - Example 1 was carried out as described in Comparative Example A above, except that the reaction product was quenched by rapid cooling before gelation.

Comparative Example B Comparative Example B was carried out as described in Comparative Example A above, except that 165.3 grams of D.E.R. 331 epoxy resin was used 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 before gelation. Example 3 - Resin product - Example 3 was carried out as described in Comparative Example A above, except that 18.0 g of PTBP was added and the reaction product was quenched by rapid cooling before gelation. outer. In this embodiment, the target EEW is calculated without the resin composition of ptbp.

Comparative Example C Comparative Example C was carried out as described in Example 1 above, with 24 200835712 using 33.3 grams of adipic acid, 150 gram of DER 331 epoxy resin and 0.14 at the reaction temperature. The grams of A-1 catalyst did not use a solvent' as shown in Table I.

ΚΑΑExample D Comparative Example D, Part 1 was carried out as described in Example 1 above, using 33.3 grams of adipic acid, 15 〇 〇 gram DER 331 epoxy resin and hydrazine at the reaction temperature. • 14 g Α-1 catalyst without solvent, as shown in Table I. Part 2 was prepared using the product from Part 1 and 26.1 g of bisphenolphthalein and 0.16 g of rhodium-1 catalyst at the reaction temperature as shown in Table I. Or SER and AA reaction examples ^_Reaction catalyst conditions target EEW actual EEW Example 1 LER+ BA + AA A-1 130-180〇C 18 00 1537 Comparative real LER+ BA + AA A-1 130-180 〇C 1800 Gel Example 2 ~-_ LER+ BA + AA A-1 130-1 80〇C 1150 1050 Comparative Real B LER + BA + AA A-1 130-1 80〇C 1150 Gel Example Reactant Catalyst Condition Target EEW Actual EEW Example 3 - ^_ LER + BA + AA + PTBP A-1 140-155 〇 C 1800 1782 Comparative Real C LER + AA A-1 160 ° C 530 Gel Comparative Example D - ^Part 1 LER+ AA A-1 130°C 530 533 25 200835712 Comparatively Comparative Example Α-1 Square Example D _ D-Part 1 + ΒΑ Part 2 Example 4-11 16〇t 1800 Gel In this process, a non-uniform system is produced at the beginning of the reaction and a clear solution is formed when the dicarboxylic acid (DCA) used is completely dissolved by heating. The solution was sampled periodically to track changes in EEW and an. When the progressing reaction is completed, the SEEIU# liquid is allowed to cool to below 9 generations and the transfer is quickly transferred to the glass jar.

LER, DC A, solvent and catalyst 恭 味 剜 戟 戟 戟 戟 配备 配备 配备 配备 配备 配备 配备 配备 配备 配备 配备 配备 配备 配备 N N N N N N N N N N N N N N N N N N N N N N N N N 空气 空气Even with a heating sleeve of 500 ml of people ^, Mao Kai glass 螭 secret fat pot. The reaction was mixed until the target π _ : degree and then the strange temperature was maintained, and it was shipped to the EER. In the square n sl^ r: /, the desired solution temperature time is reached between the desired EEW彳纟# _. Between the durations of the period as a reaction

The reaction conditions for preparing the resin are shown in the table, and the analysis results are shown in Table Ιπ. Η中, and the resin 26 200835712 table ιι· used to prepare the resin reaction conditions Example a LER DCA solvent reminder 4 temperature (°C) DERe (g) acid (g) catalyst (g) 4 383 179.76 IPA 90.01 Alcohol TBPB 1.8999 110 Dimethyl ether - 5 383 199.99 IPA 84.93 Cyclohexanone Phlm ------^ 0j996_ 140 6 383 200.06 IPA 84.92 Cyclohexanone 4-MMP _^---^ 0J 986_ 140 —7 383 99.98 IPA 42.40 Cyclohexanone KOH _____— 0J022_ 140 __8 383 200.03 IPA 84.90 Cyclohexanone A-1 --------- 〇^〇08^_ 140 9 383 200.08 IPA 84.90 PM TBPB 9 0080 125 10 383 199.99 IPA 84.89 Cyclohexane with TBPB 0.2004 140 ----- / HOAC —11 383 200.16 IPA 84.89 Cyclohexanone A-1 ------- ^0,2022^- 140 a Method A and 50% by weight Solvent, unless otherwise stated. b The weight % of the catalyst is based on the amount of LER, DCA and catalyst. The weight % of the solution is based on the total amount of the reaction system, i.e., LER, DC A, catalyst, and solvent. • Type of epoxy resin. d true catalytic dose (amount of non-catalyst solution). EEW, AN and Mn of SEER in Example a '-- Time (minutes) LER Acid Ε] EW mn AN Μη Target Actual 4 ---- 520 383 ΙΡΑ 3,200 Not measured 24.1 _5 ^_6 — 383 ΙΡΑ 3,200 3,252 12.8 2,442 _208 383 ΙΡΑ 3,200 3,276 11.8 2,338 27 200835712 7 296 383 PA 3,200 617 11.2 8 272 383 IPA 3,200 3,277 15.7 2,404 9 177 383 IPA 3,200 3,847 8.4 10 270 383 IPA 3,200 3,240 15.4 2,436 11 272 383 IPA 3,200 3,026 16.5 2,352 aEEW and The AN is measured after the overall resin solution has cooled to ambient temperature unless otherwise noted. Examples 12-19 and Comparative Example E - Coated steel sheets were prepared from Weirton Steel Corporation's commercially available L-type, T4CA, surface 50 tin-free steel (TFS - coated with a single reduced electrolyte chromium) The sheet) is used as the metal substrate in this embodiment. The coating formulation was not taken onto the TFS plate and cured according to the procedure described in ASTM 4147-99 to give a coating thickness of 〇2〇 + / - 〇 2 mil. The coated panels were tested for tamper resistance according to ASTM D 5402-93, the maximum double wear (DR) number test prior to poor coating, and the wedge bending flexibility test according to astm D 3281-84. The pasteurization against lactic acid was carried out by inserting a vial containing 2% by weight of lactic acid and a wedge-shaped curved plate sample (approx. 170° of coating tension bending) heated for 12 minutes in 12 TC pressurized dad. Finishing. Use the grading system described in Table a below to describe the coating properties. Table A. Grading system for lactic acid-resistant pasteurization test Grading observation 5 纟 Bending or flat sections without any red stains or bubbles 28 200835712 4 There are no red stains or bubbles on the flat section. 3 There is red stain on the flat section, but there are no bubbles. 2 There are some small bubbles on the flat section. 1 There are many red bubbles on the flat section. All coating failures were repeated for all test runs, and are reported here as the average of the results.

The results of this example are shown in the following list iv. Table IV. Resole phenolic resin hardener and H3p〇4 catalyst at 2〇5£)(:下下 D.E.R. 669E 树月 I

15 0.75 Example Comparative Example

E

Comparative Example F

D.E.R. 669E 10 12 DER 331 - BA-AA (EEW-1050) 2.5 10

AA EEW-1050 DER 331 — BA AA — PTBP (EEW= 1782 R 33 AA-PTBP (EEW= 1782 2.: 20 100 33 75 75 25 29 2 37 26 2 2 15 25 30 16 DER 331 - BA-AA- PTBP (EEW= 1782 2.5 10

125 42 2 29 200835712 1 η Γ> FP ^ ^ 1 R Δ —— --- 1 / U LJ SS^ DJ i JO r\ AA-PTBP (EEW- 1782 ) 5 2.5 To 18 DER 331 - BA-AA- PTBP (EEW= 1782 ) .. 2.5 -- 10 19 DER 331 - BA — AA-PTBP (EEW= 1782 ) 50 31 2 50 44 2 50 61 2 Ming, but those who are in the technical know-how and § brother The invention itself will guide you not to say 3=pass: the knowledge will understand the changes in this a. For this reason, reference should be made only to the "patent model" for the purpose of determining the true scope of the present invention.

Ml [Main component symbol description]

30

Claims (1)

200835712 X. Applying for a patented solid for the preparation of uncrosslinked aromatic epoxy resin and (b) bis-acid in the reaction:: step::) (4) in the presence of a low molecular agent; and (8) Gelation = in the presence of a phase and in the absence of dissolved acid values from about 5 to about 3, the reaction is in the form of an uncontained 虱 虱 虱 EE (EEW) about 600 or more, work, soluble Quenching under conditions of high fat separation. It is known that the epoxy is a terminal epoxy ester tree. 2. According to the patent application, the first aromatic epoxy tree (IV) is used in an amount of the reactant, and the amount of the low molecular weight is used. The amount of the reference is about 30 to about 85 Α Α 应 “ “ “ ... ... ... ... ... ... 约 约 约 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围 范围By adding a solvent to the reaction mixture, thereby diluting the mixture and lowering the temperature of the mixture. Step 5: The method of the first aspect of the patent, wherein the reaction is carried out in the process of Activating or interrupting the reaction to inhibit further reaction between the polyol and the polyepoxide. The method of claim 1 wherein the reaction is quenched in (11), By adding a reaction inhibitor to a reaction mixture. 7. A method comprising the strong mineral acid or the organic compound according to the patent application, wherein the reaction inhibits the acid or the anhydride or the acid of the acid. 31 200835712 8· In the method of claim 7 of the patent scope, the agent contains hydrochloric acid, sulfuric acid, phosphoric acid, etc., inhibits the bovine yoke, phenyl sulphate, phenyl decanoic acid, dichloroacetic acid, phosphonium anhydride, and sulphuric acid. ',二# Τ本石页酸酯,对·甲本Ethyl acetate, methanesulfonate or a mixture thereof. 9. According to the patent application scope iM1 million, wherein the catalyst is a foot, a female, a quaternary ammonium salt or a quaternary salt. ..., 10 Patent application No. 9顼^ 固乐y, wherein the catalyst is vaporized tetraethylammonium, tetraamethylene bromide*', Ethyl hydrazine tetraethylammonium iodide, tetraethylammonium hydroxide, tetrakis(n-butyl) chloride, evolution of tetrakis (n-butyl), Ai Te four (n-butyl ammonium, hydrogen tetraoxide) Butyl) money, tetrakis(n-octyl) chloride, filled tetrakis (n-octyl), iodized tetra(n-octyl), hydrogenated tetra(n-octyl), ruthenium chloride Refractory (n-octyl) ammonium, gasified bis(tetraphenylphosphorus) ammonium, acetic acid tri-p-tolyl scale/acetic acid complex, acetic acid g-based triphenyl scale/acetic acid 11. The method of claim 1, wherein the catalyst is tetraethylammonium bromide, tetraethylammonium hydroxide, ethyl acetate trimethylbenzene or ethyl acetate triphenyl 12. The method of claim 3, wherein the catalyst is used in an amount of from 0.001 to about 5% by weight based on the weight of the reactants. The method of the invention wherein the reaction between components (a) and (b) is carried out at a reaction temperature of up to about 30 (rc). 14. According to claim 13 The method wherein the reaction between components (a) and (b) is carried out at a temperature of from about 60 to about 220 ° C at a temperature of 32 200835712 degrees. According to claim 14 The method wherein the reaction temperature is from about 100 Torr to about 15 (rc. = · according to the method of claim 15 wherein the reaction temperature is from about 12 (TC to about 14 Torr). The method of claim 1, wherein the reaction between the components (a) / is carried out in the presence of a mononuclear monomer different from the components (a) and m.) and (1) - Lu Appeal 18. According to the scope of the patent application, the sex monomer contains (4) A. 19 · According to the scope of the patent application 篦丨j, the method of the first eve, the dry kiln, including the dihydric phenol Di-epoxypropyl ether. 20. According to the method of claim 19, wherein the dihydric phenolphthalein is 4,4,-isopropylidene, 4,4, di-diphenyl乙乙甲院, 3 3, _ ΐ: base: phenyl di, ethyl, oxime, 3, di-diphenyldimethyl-methyl propyl, 4'4-di- phenyl diphenyl 4 4'·Di-based triphenyl aryl group = di-based biphenyl, 4,4, di(tetra)benzophenone, 4,4, _ 经 土 苯 苯 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 , 2,6-di-naphthalene, 1,4,-dihydroxynaphthalene, catechol, resorcinol, hydroquinone or tetrabromobisphenol A. Ding 21. According to the method of claim 20, Wherein the bis-epoxy=dimethicone-containing diepoxypropyl group-hydrogenated diepoxypropyl group or di-epoxypropyl ether of m-diphenol. 22. According to the method of claim μ , wherein the diterpenoid contains succinic acid, sputum S#, F7-deficient, sputum, scorpion scorpion-acid (ΑΑ), pimelic acid, suberic acid, 壬33 200835712 广力一皈, oxalic acid, Rosin acid, maleic acid, aconitic acid, hexa-quot; chlorendic acid, phthalic acid =, p-benzene: acid (TPA), isophthalic acid 3,4 bismuth Acid, 4,4, _biphenyldicarboxylic acid, propylene dicyclohexanone ruthenium, u〇_癸烧二绕一十二【, 环己烧二赖(1)-CHDA), M.环己烧二钱(i, _ C_), tartaric acid, transacid and perylene diacid or mixtures thereof. (1,4. The method according to claim 22, wherein the dicarboxylic acid W is a p-dicarboxylic acid, an isophthalic acid, an adipic acid or a mixture thereof. 2. The method according to claim 1 , wherein the uncrosslinked "ΙΓ^ molecular weight epoxy (tetra) lipid comprises having an epoxy group end, having a clothing oxygen S is greater than 丨, having an acid value of from about 5 to about 3 equivalents. a larger tree wax. There are 4 kinds of methods for preparing a binder composition, which comprises the epoxy resin of claim 1 of the main patent scope and the 25th item of the patent scope of claim 25, Wherein the hardener is an amine-terminated polymer, a carboxyl-terminated polymer, a terminally-ended polymer, a polyfunctional amine, a carboxylic acid or a phenol. 27. The method according to claim 26 Wherein the binder composition further comprises a pigment, a filler or a flow modifier. 28. A method for preparing a coated substrate comprising mixing and at least a portion of the binder composition of the scope of item 2! The binder composition is applied to the substrate. Μ 29.- The method of making the coating "comprising as the patent application 34200835712 range around a race of soluble noncrosslinked prepared in item 1 of high molecular weight epoxy ester resin is reacted with a crosslinker ^ •, drawings:. Μ 35