Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
• • 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
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

• This invention is directed to a stable aqueous dispersion of a curable resinous composition
• a curable resinous composition comprising a half ester of a dicarboxylic acid with the secondary hydroxyl of a vinyl ester resin.
• the carboxylic acid group of said half ester being at least partially neutralized with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine.
• the dispersions have an o average particle size of less than 2500 A (250 nm) and are curable through the vinyl groups of the vinyl ester resin.
• the vinyl ester resins useful herein are the reaction products of a polyepoxide with an ethylenically unsaturated monocarboxylic acid which are further reacted with a dicarboxylic acid or anhydride to form a half ester.
• Such vinyl ester resins are disclosed in U.S. Patent No. 3,564,074.
• polyepoxides Any of the known polyepoxides can be employed in the preparation of the vinyl ester resins.
• Useful polyepoxides are glycidyl polyethers of both polyhydric alcohols and polyhydric phenols, epoxy novolacs or mixtures thereof.
• polyepoxide modifications can be readily made. It is possible to increase the molecular weight of the polyepoxide by polyfunctional reactants, such as bisphenols, dicarboxylic acids or carboxyl terminated polydiene rubbers, which react with the epoxide group and serve to link two or more polyepoxide molecules in such a manner so as to join those diepoxide molecules and still retain terminal epoxide groups. Where polyhydric phenols are selected to prepare the polyepoxide, many structural embodiments are possible. Polyepoxides prepared from polyhydric phenols may contain the structural group
• R- is a divalent hydrocarbon radical such as, for example,
• novolac resins leads to a separate, well recognized class of epoxy novolac resins. Other modifications are well known to those skilled in the art.
• poly ⁇ epoxides While the invention is applicable to poly ⁇ epoxides generally, a most advantageous class of poly ⁇ epoxides are those glycidyl polyethers of polyhydric alcohols or polyhydric phenols having weights per epoxide group of 150 to 2000 (i.e., epoxy equivalent weight). These polyepoxides are usually made by react ⁇ ing at least about two moles of an epihalohydrin or glycerol dihalohydrin with one mole of the polyhydric alcohol or polyhydric phenol, and a sufficient amount of an alkali metal to combine hydroxide with the halogen of the halohydrin. The products are characterized by the presence of more than one epoxide group, i.e., a 1,2-epoxy equivalency greater than one.
• a preferred class of polyepoxides are those derived from a methylene bisphenol or a 2,2'-isopropy- li ene bisphenol.
• Suitable ⁇ , ⁇ -ethylenically unsaturated monocar- boxylic acids include, for example, acrylic, methacrylic, crotonic, and cinnamic.
• the above reactants are incorporated in the compositions to provide essentially a stoichiometric equivalency of carboxyl function with the oxirane groups present.
• the esterification reaction is preferably catalyzed with known catalysts for the esterification of carboxyl groups with oxirane groups.
• catalysts include tertiary amines, such as tris(dimethylamino- methyl) phenol, and also include chromium salts.
• the composition is used to prepare a curable product by mixing the mentioned ingredients and reacting the mixture preferably between 80° to 120°C under catalytic inducement. If temperatures lower than 80°C are used, the reaction is very slow. If reaction temperature exceeds 120°C, side reactions are promoted decreasing the yield of the desired product and the possibility of a difficult controllable exother is presented.
• the ethylenically unsaturated monocarboxylic acid-polyepoxide reaction product containing secondary hydroxyl groups is further reacted with 0.1 to 1.2 mole proportions of dicarboxylic acid anhydride per equiva ⁇ lent of epoxide in a manner as disclosed in U.S. Patent No. 3,564,074.
• the dicarboxylic acid anhydride may be selected from either saturated or unsaturated dicarboxy ⁇ lic acid anhydrides or mixtures thereof as disclosed in that patent.
• a vinyl polymerization inhibitor such as, for example, the methyl ether of hydroquinqne or hydro- quinone may be added.
• the reaction mixture is cooled and the polym- erizable monomer may be blended therewith.
• Representative species are the vinyl aromatic compounds which include such monomers as styrene, vinyl toluene, halogenated styrenes, and divinylbenzene.
• Other valuable monomers include, for example, the methyl, ethyl, isopropyl, octyl, etc., esters of acrylic or methacrylic acid, vinyl acetate, diallyl maleate, dimethallyl fumarate, acidic monomers such as acrylic acid, methacrylic acid, crotonic acid and amide monomers such as acrylamide and N-alkyl acrylamides and mixtures thereof.
• a nonreactive solvent can be used to replace all or a part of the reactive solvent.
• Such nonreactive solvents include glycol ethers; alcohols, such as butanol; ketones and methylene chloride.
• the resulting acid functionalized vinyl ester resin is next reacted with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine in an amount to provide water dispersibility to that resin.
• alkali metal hydroxides While all of the alkali metal hydroxides are useful, sodium hydroxide and potassium hydroxide are preferred.
• Suitable tertiary amines include, for example, trimethylamine, triethylamine, triethanolamine, dimethyl- ethanolamine and methyldiethanolamine.
• the neutralization is carried out at a tempera ⁇ ture preferably between 20° to 80°C, most preferably between 20° and 75°C_
• the resin can be dispersed in water to the desired solids content and viscosity.
• the dispersions of this invention contain from 1 to 13 weight percent carboxyl, preferably 1.5 to 7 percent.
• the dispersions advantageously have an average particle size of less than 2500 Angstrom units.
• the polymer of the particles is curable by free radical catalytic inducement generally at somewhat elevated temperatures and/or may be cured through the pendant carboxyls.
• the dispersions are useful as such or may be blended with aminoplasts, such as melamines or urea-formaldehyde or phenolplasts. Because the disper ⁇ sion can be water based, the problems associated with organic solvents in coatings can be eliminated or minimized.
• the dispersion may be formulated with color ⁇ ants, fillers, waxes or other conventional additives used for its expected effect.
• the dispersions find utility in adhesives and coatings. For example, they are useful as tire cord adhesives, glass sizings and adhesives for wood products. As coatings, they are metal decorative primers and finishes, interior and exterior can coatings, drum linings and other industrial and commercial coatings.
• Suitable tire cord adhesives for bonding the cord fiber to rubber are made by curing a blend of the dispersions of this invention with a suitable latex such as, for example, a styrene/butadiene/vinyl pyridine (15/70/15 weight percent) latex with a free radical initiator.
• Suitable free radical initiators include, for example, tertiary-butyl perbenzoate.
• the blend of a dispersion of this invention with a latex may also be cured with a p * henolplast or an aminoplast resin which is catalyzed by an acid.
• Suitable coating compositions are made from dispersions of this invention and aminoplast or phenol- plast resins with an acid catalyst.
• Suitable aminoplast resins include hexamethoxy- methyl melamine and methylated melamine formaldehyde resins.
• Suitable acids as catalysts include carboxylic or sulfonic acids such as, for example, para-toluene ⁇ sulfonic acid or the amine salt of para-toluenesulfonic acid. The inventive concept is more apparent in the following nonlimiting examples which illustrate the best mode for preparing and utilizing the dispersions.
• Example 1 To a 1-liter, 5-neck, round-bottom flask equipped with a condenser, thermometer, air sparge tube and a stirrer, there was charged 273 g of the reaction product of methacrylic acid and a polyepoxide having an epoxy equivalent weight (EEW) of 361 and which was the diglycidyl ether resulting from reaction of the digly ⁇ cidyl ether of bisphenol-A with bisphenol-A.
• the vinyl ester base resin was heated to 110°C and 26.80 g of maleic anhydride and 0.03 g of hydroquinone were added. The mix was reacted 1 to 2 hours or until the acid content was 4.0 percent.
• the rubber mat was cut exactly 1/4 inch (6.35 mm) from the point of insertion of the tire cord just deep enough to cut the cord.
• the mat was placed into an 110°C oven for 30 minutes and then the load necessary to pull the cord out of the rubber was measured for each individual cord. Adhesion was measured at 38.4 lbs/in (6720 N/m); adhesion for the control is 40.32 lbs/in (7061 N/m).
• a vinyl ester base resin which was the reaction product of a 208 EEW resin (mixture of bisphenol-A epoxy resin and epoxy novolac), methacrylic acid, and maleic anhydride to 4.7 percent acid. That was heated to 70°C and 0.12 g of phenothiazine and 53 g of styrene were added. The mix was stirred for 1 hour and cooled to 40°C. Then 48.9 g of triethanolamine and 5.89 g of monobutyl ether of diethylene glycol were added and mixed well for 30 minutes.
• a vinyl ester base resin which was the reaction product of a 208 EEW resin (mixture of bisphenol-A epoxy resin and epoxy novolac), methacrylic acid, and maleic anhydride to 4.7 percent acid. That was heated to 70°C and 0.12 g of phenothiazine and 53 g of styrene were added. The mix was stirred for 1 hour and cooled to 40°C. Then 48.9
• the dispersion contained 30 percent solids with a viscosity of 27,500 cps (27.5 Pa-s) at 25°C and had a particle size o of 685 A (68.5 nm).
• a 77°F (25°C) gel time was measured for this dispersion following the procedure in Example 2. The gel time was 7 minutes.
• a tire cord adhesive was prepared from this dispersion following the procedure in Example-2_; .
• the adhesion was measured at 34.6 lbs/in (6059 N/m) compared with 32.4 lbs/in (5674 N/m) for the control.
• Example 2 To a 2-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 500 g of vinyl ester base resin of that example. The resin was heated to 110°C and 27.9 g of maleic anhydride and 0.04 g of hydroquinone were added. Reaction was con ⁇ tinued for 1 hour to an acid level of 3.25 percent and 75.57 g of styrene added and the mix was cooled to 70°C. Then 0.15 g of monomethyl ether of hydroquinone and 0.12 g of phenothiazine were added, stirred for 1 hour and then cooled to 40°C.
• Example 2 To a 1-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 273 g of the dimethacrylate of a 361 EEW bisphenol-A epoxy base resin of that example. The resin was heated to 110°C and 11.9 g of maleic anhydride and 0.03 g of hydroquinone were added and reaction continued for 1 hour to an acid level of 2.2 percent. Then 0.06 g of oxalic acid dihydrate and 42.74 g of styrene were added. The mix was cooled to 70°C and 0.06 g of phenothiazine was added. After cooling to 50°C, dimethylethanolamine (15.02 g) was added and mixed well for 30 minutes. With stirring, 472 g of water was added at a rate of 15-20 ml/minute. The dispersion had a solids content of 35 percent and a particle size of 2240 A (224 nm).
• a cord was first dipped into water to. ' saturate and then into the adhesive mixture described above. The cord was then placed into an oven to set the adhesive to the cord. Cure times and temperature are as shown in Table I. The pickup of adhesive onto the cord was
• the commercial adhesive is a two-stage cure of 45 seconds at 300°F (149°C) and 60 seconds at 475°F (246°C).
• Example 7 Using the same procedure as Example 7, a dispersion having the following composition was synthe ⁇ sized: the diglycidyl ether of that example (350 g, 1.8460 eq), hydroquinone (0.12 g), glacial methacrylic acid (158.76 g, 1.8460 eq), DMP-30 (0.53 g), maleic anhydride (48.62 g, 0.4961 eq) to give a percent COOH equal to 4.58, phenothiazine (0.08 g), 4-chloro-2- nitrophenol (0.11 g) dimethylethanolamine (60.61 g, 0.681 eq), and water (1150.5 g).
• the percent solids was 29.0. Brookfield viscosity at 25°C was 1600 cps (1.6 Pa-s).
• Example 9 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 2 (228.6 g, 1.2057 eq), bisphenol-A (23.9 g, 0.2095 eq), Hycar* 1300 X 18 (67 g, 0.0944 eq), tetrabutylphosphonium acetate (0.44 g) hydroquinone (0.13 g), glacial methacrylic acid (79.22 g, 0.9212 eq), DMP-30 (0.36 g), maleic anhydride (38.13 g, 0.3891 mole), to give a percent COOH equal to 4.80, phenothiazine (0.05 g), styrene (77.3 g), dimethylethanolamine (49.88 g, 0.5604 eq) and deionized water (1186 g).
• the final product contained o
• Example 11 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 7 (254 g, 1.3417 eq), bisphenol-A (55 g, 0.4822 eq), tetrabutylphosphonium acetate (0.22 g), hydroquinone (0.09 g), glacial methacrylic acid (72.44 g, 0.8423 eg), DMP-30 (0.46 g), maleic anhydride (17.43 g, 0.1778 mole) to give a percent COOH egual to 2.5, phenothiazine (0.07 g), 4-chloro-2-nitrophenol (0.09 g), styrene (70.6 g), dimethlethanolamine (23.73 g, 0.2666 eg), and water (1486 g). At 20.2 percent solids this product had a Brookfield viscosity at 25°C of o
• Example 9 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 7 (254 g, 1.3417 ⁇ eg), bisphenol-A (55 g, 0.4822 eg), tetrabutylphosphonium acetate (0.22 g), hydroguinone (0.09 g), glacial methacrylic acid (72.44 g, 0.8423 eq), DMP-30 (0.46 g), maleic anhydride (17.43 g, 0.1778 mole) to give a percent COOH egual to 2.5, phenothiazine (0.07 g), 4-chloro-2-nitrophenol (0.09 g), styrene
• Example 7 epoxy resin of Example 7 (413.9 g, 2.183 eg), bisphenol-A (89.4 g, 0.784 eg), tetrabutyl- phosphonium acetate (0.35 g), hydroguinone (0.14 g), glacial methacrylic acid (119.98 g, 1.3951 eg), DMP-30 (0.75 g), maleic anhydride (59.61 g, 0.6083 mole) to give a percent COOH equal to 4.57, phenothiazine (0.11 g), 4-chloro-2-nitrophenol (0.15 g), styrene (76.0 g), dimethylethanolamine (71.67 g, 0.8053 eg), and water
• the dispersion had a Brookfield viscosity at 25°C of 3040 cps (3.04 Pa-s) at 15 percent solids.
• Example 2 Using the same procedure as in Example 1, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (26.8 g) to give a percent COOH of 4.55, styrene (44.97 g), monoethyl ether of hydroguinone (0.11 g), phenothiazine (0.08 g), dimethylethanolamine (32.4 g) and water (480 g).
• Example 6 Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (21.15 g); Cymel 303 (1.11 g); deionized water (32.92 g); and styrene/- butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.02 g). A polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F (191°C) for 60 seconds. The resulting adhesion was 42.0 lbs/in (7360 N/m).
• Example 6 Using the same procedure as in Example 6, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (41.0 g), oxalic acid dihydrate (0.06 g), phenothiazine (0.06 g), dimethylethanolamine (43.47 g) and water (678 g).
• Example 6 Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (27.57 g), Cymel 303 (1.2 g), deionized water (30.8 g), and styrene/butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.93 g) .
• a polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F _(191°C) for 60 seconds. The resulting adhesion was 48.3 lbs/in (8460 N/m). ' , " ' ⁇ ⁇
• a polyester cord was coated and tested by the method of Example 6. Adhesive pickup was 5 percent. The adhesive was cured at 175°C for 10 minutes. The resulting adhesion was 40 lbs./m (7000 N/m).

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• 1983
  • 1983-06-28 EP EP19830902388 patent/EP0112391A4/de not_active Withdrawn
  • 1983-06-28 WO PCT/US1983/000979 patent/WO1984000170A1/en not_active Application Discontinuation

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