US2866763A - Process of preparing aqueous dispersion of an acrylonitrile interpolymer and a thermosetting resin and product obtained - Google Patents

Process of preparing aqueous dispersion of an acrylonitrile interpolymer and a thermosetting resin and product obtained Download PDF

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US2866763A
US2866763A US578405A US57840556A US2866763A US 2866763 A US2866763 A US 2866763A US 578405 A US578405 A US 578405A US 57840556 A US57840556 A US 57840556A US 2866763 A US2866763 A US 2866763A
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interpolymer
aqueous dispersion
weight
acidic
acid
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Philip F Sanders
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to NL105265D priority patent/NL105265C/xx
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Priority to US578405A priority patent/US2866763A/en
Priority to GB9275/57A priority patent/GB826455A/en
Priority to DK134457AA priority patent/DK104260C/da
Priority to DEP18353A priority patent/DE1208023B/de
Priority to FR71477D priority patent/FR71477E/fr
Priority to CH4509857A priority patent/CH368567A/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C09D133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only

Definitions

  • the invention relates to stabilized aqueous dispersion compositions comprising ammonium salts of certain acidic acrylonitrile interpolymers characterized by package-stability and resistance to gelation and to a method of preparing these ammoniacal aqueous dispersions.
  • aqueous dispersion For many coating purposes, it was found desirable to modify the acidic interpolymer in the form of an aqueous dispersion with a water-dilutable, heat-reactive phenol/formaldehyde resin.
  • aqueous dispersion compositions to metal substrates, such as in the case of wire-coating, best results ordinarily are obtained when the coating composition at the time of use is adjusted to a pH value in the range of about 9.0 to 10.0 with ammonium hydroxide or a volatile amine.
  • aqueous dispersions of acidic interpolymers can be satisfactorily applied to a wide variety of substrates to provide useful coated or impregnated articles, these dispersions have certain undesirable deficiencies pertinent to packaging and storage.
  • the acidic dispersions ordinarily cannot be packaged in conventional metal containers and must be stored in glass or in metal containers interiorly protected with a coating inert toward the aqueous dispersion in order to prevent contamination with corrosion products. Even when packaged in an appropriate container, the acidic dispersions are not as storage-stable as is ordinarily desired for commercial use.
  • ammoniacally adjusted dispersions can be stored and subjected to pumping and agitation without development of coagulum or polymer grit, but these dispersions are lacking in viscosity-stability and resistance to gelation.
  • the primary object of this invention is to overcome the described deficiencies of the aqueous dispersions of the aforementioned interpolymers.
  • An important object of this invention is to provide improved aqueous dispersion interpolymer compositions of the aforementioned class of interpolymers characterized by superior viscosity-stability,
  • Another object is to provide an aqueous dispersion interpolymer composition of the described class stably advanced in viscosity.
  • a further object is to provide a method of preparing ammoniacal aqueous dispersion interpolymers of a monomer mixture consisting of acrylonitrile, an alpha olefinic monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid, and,
  • an aqueous dispersion of an ammonium salt of an acidic interpolymer by initially preforming the acidic interpolymer by emulsion polymerization in water of a consisting of (A) 30% to by weight of acrylonitrile, (B) 1.5% to 15% by weight of at least one alpha-olefinic mo-nocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid, and (C) 15 to 65% by weight of at least one ester of an acid of (B) with a saturated aliphatic monohydric alcohol having from 1 to 12 carbon atoms,
  • the drawing is a flow-sheet of a of the process of the invention.
  • the sodium meta bisulfite (Na S O had an assay of 97.5% and a corresponding content of at least 65.58% 80;.
  • the sodium lauryl sulfate was the commercial available DuponoP C having an assay of at least 90%, the remainder being 1.5% to 3.5% of unsulfated fatty alcohol and not more than 8% of a mixture of sodium chloride and sodium sulfate.
  • the acrylonitrile monomer as purchased contained 250 to 300 parts per million of organic amines as a polymerization inhibitor. These amine inhibitors were removed by passing the inhibited acrylonitrile through a column of Amberlite IR-120 ion exchange resin in its acid form.
  • the methacrylic acid monomer was the commercially available glacial grade which contained hydroquinone at a concentration of about 1000 parts per million as an inhibitor. This monomer was used without removal of the inhibitor.
  • the butyl acrylate monomer as purchased contained hydroquinone at a concentration of about 100 parts per million as an inhibitor. This monomer was also used without removal of the inhibitor.
  • the resultingaqueous dispersion of, the acidic interpolymer had a pH value of 3.8 and was characterized by an average particle size of..22 micron. .
  • the interpolymer separated from the aqueous dispersion was characterized by a relative viscosity of 6.6 as determined with an A. E. T. M. #200 ostwald-Cannon-Fenske viscosimeter at 25 C. using dimethyl formamide as the solvent for preparing the viscosity test solutionat 0.5% by weight of the interpolymer.
  • This unstabilized aqueous dispersion interpolymer product of Example 1 was filtered through felt and divided into aliquot portions which were treated respectively as follows with the final composition in eachinstance 4 adjusted with distilled water to a non-volatile content of 30% by weight.
  • Sample B The aqueous dispersion product neutralized to a pH value of 9.0 with ammonium hydroxide and diluted.
  • Sample C.Diluted with distilled water heated to C. in about 5 minutes, held at this temperature for 15 minutes and immediately cooled to room temperature.
  • Sample G initially neutralized to a pH value of 7.5 with ammonium hydroxide, heat-treated as described for sample D and thereafter ammoniacally neutralized to a pH value of 9.0.
  • the viscosity of these respective samples was determined at 25 C. using a Broolifield viscosimeter operating at 6 R. P. M. with a #2 spindle.
  • the samples were then stored in an oven at 50 C., periodically removed from the storage oven, cooled to 25 C. and measured for viscosity to determine the effect of storage at 50 C. on viscosity stability.
  • other standard spindles were used with the Brookfield viscosimeter.
  • Sample B exhibited a desirable initial viscosity, but the product was unstable in viscosity and bodied during 28 days of storage to a viscosity impractical for use.
  • Sample E equivalent to sample B but heat-treated, was advanced to a high initial viscosity impractical for use and gelled more rapidly than sample B.
  • salt-form is subsequently ammoriiacally adjusted to ,a pH value of 9.0, the products were unstable in viscoslty.
  • the aqueous dispersion interpolymer composition is desirably modified with a water-dilutable, heat-reactive aldehyde condensation resin, such as phenol/formaldehyde Since this preferred modifier is heat-reactive, another series of the following samples was prepared from the filtered aqueous dispersion product of Example 1 to ascertain the effect of ammoniacal neutralization and heat-treatment of the aqueous interpolymer dispersion in admixture with the heat-reactive resin.
  • a water-dilutable, heat-reactive aldehyde condensation resin such as phenol/formaldehyde Since this preferred modifier is heat-reactive, another series of the following samples was prepared from the filtered aqueous dispersion product of Example 1 to ascertain the effect of ammoniacal neutralization and heat-treatment of the aqueous interpolymer dispersion in admixture with the heat-reactive resin.
  • the phenol/formaldehyde resin identified as Bakelite BR-15100 resin containing 66% non-volatile resin dispersed in water, was used in the proportion of 11 parts dry weight per 100 'parts dry weight of the interpolymer.
  • Sample H The mixture of the aqueous dispersion product of Example 1 and BR-15100 resin was neutralized to a pH value of 7.5 with ammonium hydroxide, heated in 5 minutes to 75 C., held at this temperature for 15 minutes and immediately cooled to room temperature.
  • Sample I This sample was prepared as described for sample H and thereafter adjusted to a final pH value of 9.0 with ammonium hydroxide.
  • Sample J This sample was prepared as described for sample H except that the heat-treatment at 75 C. was extended to 30 minutes.
  • Sample K.-The acidic aqueous dispersion product of Example 1 was ammoniacally neutralized to a pH value of 7.5, heated to 75 C. in 5 minutes, held at this temperature for 15 minutes, the BR-15100 resin was blended therein and the resulting composition immediately cooled to room temperature.
  • Sample M This sample was the same as sample L except that it was ammoniacally adjusted to a final pH value of 9.0.
  • Sample N The process of preparing this sample was the same as that used for sample H except the mixture of the acidic aqueous dispersion of Example 1 and BR-15100 resin was ammoniacally neutralized to a pH value of 9.0 prior to the heat-treament.
  • the data show that the phenolic resin can be blended with the aqueous dispersion interpolymer composition either before or after the heat-efiected ammoniacal reaction without altering the stability of the product.
  • a comparison of the data for samples H and I show that the heat-reactive phenol/formaldehyde resin is advantageously blended with the aqueous dispersion interpolymer composition prior to the ammoniacal neutralization when it is desirable to provide the composition with an advanced viscosity which is stable.
  • the unstabilized aqueous dispersion interpolymer composition was prepared as described in Example 1 using the same relative proportions of the respective monomers, that is, acrylonitrile 63%, butyl acrylate 32% and methacrylic acid 5%.
  • the polymerizable mixture consisted of the following composition:
  • the emulsion polymerization was carried out at 60 C.
  • the monomer conversion was 98.8% and the aqueous dispersion product had a polymer content of 41.0%.
  • the pH value of the aqueous dispersion was 3.7 at 25 C. and the average particle size of the interpolymer in the dispersion was ;25 micron.
  • the interpolymer had a relative viscosity of 6.3 using dimethyl formamide as the solvent.
  • the unstabilized acidic aqueous interpolymer dispersion was filtered through felt before it was used in' the preparation of the product of Example 2.
  • ammonium hydroxide cor-' responds to the approximate amount added to raise the pH value of the acidic aqueous dispersion at 3.7 to an ammoniacal alkalinity of 7.65.
  • Example 2 The component of the composition of Example 2 were blended at room temperature until uniform.
  • the result ing mixture was heat processed as follows: (a) heated in 5 minutes to 45 C., (b) heated in another 5 minutes to 65 C., (c) heated in another 5 minutes to C. and thereafter held at this latter temperature for.120 minutes. Samples were taken at 45 'C., 65 C., 85 C. and at intervals while the temperature was held at 85 C.
  • the viscosity data reported in centipoises for these samples measured at 25 C. using the Brookfield viscosim eter at 6 R. .P. Maare shown in Table 3.
  • Viscosity 3 Original 30 (a) Afterheating to 45 C. in 5 minutes 65 (b) After heating to 65 C. in minutes 110 (0) After heating to 85 0m minutes 210 (d) Thereafter holding at 85 C. for 10 minutes 245 (e) Thereafter holding at 85 C. for
  • Part 2 Ammonium hydroxide 29% NH;, to pH value 5.5 to 6.5 0.15
  • Part 3 Ammonium hydroxide 29% NH;, to pH value 5.5 to 6.5 0.15
  • Part 3 Ammonium hydroxide 29% NH;, to pH value 5.5 to 6.5 0.15
  • 'Part 1 representing the unstabilized aqueous dispersion interpolymer composition was prepared following the process described for thepreparation of the aqueous dispersion product of Example 1, carrying out the emulsion polymerization at about 60 C.
  • the resulting aqueous dispersion product had a pH value of 3.8, an average particle diameter of about 0.20 micron, and an interpolymer content of 37.5% by weight.
  • the polymer had a relative viscosity of 6.5 using dimethyl formamide as the solvent.
  • the resulting acidic aqueous dispersion interpolymer composition while at the temperature of about 60 C. was neutralized with the ammonium hydroxide of part 2 to a pH value in the range of 5.5 to 6.5.
  • the added amount of ammonium hydroxide was sufficient to neutralize at least 10% by Weight of the methacrylic acid component of the interpolymer.
  • the combined parts 1 and 2 were filtered through felt, transferred to a storage tank as an intermediate product for subsequent use and allowed to cool to room temperature. In the ammoniacal neutralization stage, the combined parts 1 and 2 ordinarily are exposed to an elevated temperature in the range of 45 C. to 60 C. for about 30 minutes or longer.
  • This intermediate ammoniacal product consisting of combined parts 1 and 2 represents a preferred and convenient point of interruption in the commercial manufacturing process.
  • This intermediate product is viscosity-stable and storage-stable. It is adequately low in viscosity for convenient filtering and it can be reheated, cooled and subjected to mechanical operations, such as agitation and pumping, after filtration without introducing fine-grit formation or coagulation.
  • part 3 was blended with the intermediate product; that is, the combined parts 1 and 2 which had been filtered and stored, combined parts 1, 2 and 3 were heated to 87 C. with agitation and part 4 was added thereto as a second stage ammoniacal neutralization to adjust the composition to a pH value of 7.2.
  • the total amount of ammonium hydroxide of parts 2 and 4 was sufiicient to neutralize approximately 90% by weight of the methacrylic acid component of the interpolymer.
  • the resulting mixture was agitated at 120 R. P. M. for 70 minutes Without either supplying heat or accelerating the cooling. Thereafter the product was cooled to room temperature and filtered to remove any coarse foreign matter, such as polymer skins.
  • the drawing showing a diagrammatic flow-sheet of the invention process is representative of the steps in the process described above for the preparation of the product of Example 3.
  • the flow sheet indicates the operative optional single stage am'moniacal neutralization which can be used in place of the preferred two stages of ammoniacal neutralization.
  • the flow-sheet also indicates the optional second stage of addition of sodium lauryl sulfate dispersing agent which is described in the preparation of the product of Example 4.
  • the process for preparing the product of Example 3 can consist of the indicated steps without cooling and storing the intermediate product.
  • the filtered product of the first-stage ammoniacal neutralization can be transferred warm or hot to the final product mixer for blending with the heat-reactive phenol/formaldehyde resin, second-stage ammoniacal neutralization and heattreatment for stably advancing the viscosity.
  • the resulting stabilized product exhibited excellent package-stability and viscosity-stability while stored at 45 C. (40 F.) and 25 C. respectively for one year and stability for at least 8 months when stored at 50 C.
  • Example 3 For use as a wire coating, the resulting product of Example 3 having a non-volatile content of 32.5% by weight as determined by weighing the residue after heating a 1 gram sample for two hours at C., was adjusted to a pH of 9.3, and diluted with deionized water to a non-volatile content of 21% by weight.
  • This ammoniaeal aqueous dispersion wire enamel composition was applied to No. 18 A. W. G. copper wire in six coats at a coating speed of 1.4 feet per minute using a conventional vertical dip-coating bath for the aqueous enamel.
  • the coated wire Prior to each immersion of the wire into the coating bath, it was pre-wet by immersion in a 1% aqueous solution of sodium lauryl sulfate serving as a wetting agent to facilitate wetting of the copper wire with the aqueous dispersion wire enamel.
  • the coated wire was heated by passing it through an oven having an average air temperature of about 221 C. (425 F.).
  • the path of the coated wire through the oven was 12 feet in length; hence each successive coat of enamel was subjected to about 51 seconds exposure to the oven temperature.
  • the six coats of enamel increased the diameter of the wire by '9 3 mils, that is, the thickness of the coating on the copper substrate was 1.5 mils.
  • Another sample of the same No. 18 copper wire was coated at a coating speed of 26 feet per minute using the same aqueous dispersion wire enamel composition adjusted to a pH value of 9.3 with ammonium hydroxide and diluted with deionized water to a non-volatile content of 13% by weight.
  • the successive coats of applied enamel were cured by passage through an oven having an average air temperature of 315 C. (600 F.) and a heating path of 12 feet. Each successive coat was exposed for about 28 seconds to the oven temperature.
  • the 6 coats of cured wire enamel increased the diameter of the wire by 3 mils.
  • a sample of No. 25 A. W. G. copper wire was also coated with 4 coats of the product of Example 3 similarly adjusted to a pH value of 9.3 and diluted to a nonvolatile content of 15% by weight with deionized water.
  • This aqueous composition was applied at a coating speed of 35 feet per minute and the successive coats were each cured by passage through a path of 4 feet in an oven having an average air temperature of 455 C. (850 B). Each successive coat was exposed for about 7 seconds to this oven temperature.
  • the four coats of wire enamel increased the diameter of the wire by 2 mils.
  • Example 3 The product of Example 3 was also satisfactorily applied to square and rectangular cross-section copper wire as well as to the conventional wire of circular crosssection.
  • the components of this composition were the same as those used in the preceding examples.
  • the mixture of monomers corresponded to 35% acrylonitrile, 5% methacrylic acid and 60% butyl acrylate for a total of 100% by weight of the mixture of monomers.
  • the resulting aqueous dispersion interpolymer product had an average particle diameter of about 0.11 micron.
  • the polymer had a relative viscosity of about 3.8 This product was viscosity-stable and storage-stable over a period of at least 9 months at room temperature.
  • Example 4 The product of Example 4 was successfully used to impregnate mats of non-woven fibers of Orlon acrylic fiber laid down as a waterleaf by paper-making methods.
  • the resulting dry web impregnated with 26% by weight of the interpolymer derived from the aqueous dispersion and weighing 3.8 grams total for an 8" x 8" square was found to provide almost greater bursting strength and 60% greater tear strength than conventional kraft paper of the same weight, when tested by Tappi Standard Methods T-403 M53 and T-414 M-49.
  • This product was also used to impregnate a mat of nonwoven glass fibers which initially weighed 4 ounces per square foot.
  • the weight ratio of fiber to the interpolymer binder was 1.6 to 1.0 of binder.
  • the resulting impregnated mass was dried for 30 minutes at 107 C. (225 F.) and thereafter pressed at p. s. i. for 10 minutes at 205 C. (400 F.).
  • the resulting product was a rigid panel about .045 inch thick. This rigid structure exhibited high dielectric strength and was useful as slot-liners for motors and generators. The rigid structure was also useful as structural panelling where resistance to solvents and vapors were required.
  • Solvent resistance was enhanced for these impregnated structural units where the aqueous dispersion composition of Example 4 included 5% to 10% of a Water-dilutable heat-reactive phenol/formaldehyde resin such as BR-15100 based on the weight of the interpolymer.
  • a Water-dilutable heat-reactive phenol/formaldehyde resin such as BR-15100 based on the weight of the interpolymer.
  • the acidic monomer component of the interpolymer can be any alpha olefinic monocarboxylic acid selected from the group consisting of methacrylic acid, acrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid or mixtures thereof.
  • any of these acidic monomers can be substituted on an equal weight basis for the methacrylic acid monomer used in the preparation of the described interpolymers in the examples.
  • the acidic monomer component can be present in any amount ranging from about 1.5% to 15%, preferably about 2% to about 10% by weight based on the total weight of the mixture of monomers.
  • methacrylic acid is particularly preferred.
  • ester monomer component of the acidic interpolymer is butyl acrylate
  • other esters of acrylic acid with a saturated aliphatic monohydric alcohol having from 1 to 12 carbon atoms can be substituted wholly or in part for the indicated amount of butyl acrylate monomer in the preparation of the interpolymers described in the examples.
  • acidic interpolymers operative in the practice of this invention can also be prepared from monomer mixtures in which the ester monomer component, present in an amount ranging from 15% to 65% by weight of the monomer mixture, is at least one ester of a saturated aliphatic monohydric alcohol having from 1 to 12 carbon atoms with an alpha olefinic monocarboxylic acid selected fro-m the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid.
  • Representative 1 to 12 carbon atom alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isobutyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol and lauryl alcohol.
  • the acrylonitrile monomer content of the monomer mixture used in the preparation of the acidic acrylonitrile interpolymer can range from 30% to 80% by weight.
  • the emulsion polymerization in the preparation of the interpolymers can be carried out by any conventional emulsion methods, using a redox initiator.
  • the bisulfite/ persulfate redox initiator mixture is particularly preferred. While the weight ratio of potassium persulfate to sodium meta bisulfite can range from 1:1 to 10:1, optimum results are obtained when the ratio is about 2 to 5 parts of the persulfate per part of the bisulfite.
  • the preferred proportion of this redox initiator is in the range of about 25% to 50% based on the weight of the mixture of monomers although a proportion as high as 1.0% on said basis can be satisfactorily used.
  • the presence of traces of iron contamination in the polymerizable charge is desirable for activation of the redox initiator.
  • a trace of iron concentration in the range of about 0.5 part to about 10.0 parts per million of the charge is preferred.
  • Trace copper contamination functions similarly.
  • Raw materials used ordinarily provide total amounts of iron and copper within thi preferred range.
  • At iron and copper trace concentrations lower than 0.5 p. p. m. the exothermic reaction time of polymerization is significantly extended and at concentrations higher than 10.0 p. p. m., activa' tion becomes too accelerated to be practical at 60 C. However, this accelerated activation of the redox initiator can be used to advantage when the polymerization is carried out at lower temperatures.
  • temperatures in the range of 50 C. to 70 C. are ordinarily most suitable.
  • the polymerization can be carried out at room temperature and at temperatures as low as about 0 0, above the freezing temperature. Temperatures higher than 70 C. can be used, but operations must be carried out under pressure when the temperature exceeds the boiling point of any one of the monomers. The reactions are difiicult to control at these higher temperatures.
  • the dispersing agent used in the emulsion polymerization is preferably sodium lauryl sulfate and it is preferably used in the proportions of 0.30% to 1.50% based on the weight of the mixture of monomers. However, a proportion in the range of 0.2% to 4.0% on said basis is operative. ()ther alkali m etal salts of fatty alcohol sulfates, non-ionicdispersing agents and mixtures thereof can be used in place of the sodium lauryl sulfate.
  • the emulsion polymerization was carried out in the presence of the amount of hydroquinone inhibitor ordinarily present in the monomers as purchased,that is, the total hydroquinone content was in the range of about 25, to 40 p. p. m. based on the total polymerization charge.
  • polymerization is operative over the rangeof 0 to 100 parts of hydroquinone per million of charge.
  • Inhibitor-free monomers of butyl acrylate and methacrylic acid can be obtained by vacuum distillation. .A concentration of the inhibitor greater than 40 p. p. m. causes a lengthening of the exothermic reaction timeand a decrease in the relative viscosity of the interpolymer.
  • Monomethyl ether of hydroquinone is occasionally used in place of hydroquinone as a polymerization inhibitor. No distinction is observed between the use of this inhibitor and hydroquinone.
  • Beta, beta-imino-dipropionitrile was the major component of the organic amine mixture used to inhibit one commercial grade of acrylonitrile monomer in an amount ranging from 250 to 300 p. p. m. based on the monomer. This inhibitor significantly retarded the redox initiated polymerization. While the polymerization is operable in the presence of this amount of amine inhibitors contributed by the inhibited acrylonitrile monomer, complete removal of this inhibitor is preferred. Removal of the inhibitors i best accomplished by passage of this amine-inhibited acrylonitrile monomer through a column of ion-exchange resin Amberlite IR- regenerated to H-form (acid-form). Alternatively, the amine inhibitors can be removed by adding 1% of orthophosphoric acid to the acrylonitrile monomer to react with the amine and thereafter distilling the acrylonitrile at atmospheric pressure.
  • the monomer concentration in the aqueous polymerizable charge is preferably in the range of 25% to 45% by weight. While higher concentrations up to 70% are operative, coagulation losses make operations at concentrations above 50% impractical or prohibitive.
  • the water specified in the examples is preferably of distilled, deionized or demineralized quality. This is to eliminate or minimize the effect of chemical compounds normally present in tap water on the polymerization reaction. Tap water having a low content of such compounds can be used.
  • Agitation during emulsion polymerization is preferably carried out within the range of to 300 R. P. M., but any speed which provides adequate heat transfer and maintains uniform dispersion of the monomers in the aqueous emulsion is operative. Ordinarily this requires agitation at a speed within the range of 50 to 400 R. P. M. Higher speeds are undesirable because many interpolymer dispersions coagulate or coalesce under mechanical shear.
  • the polymerization charge is preferably emulsified as a homogeneous premix prior to charging into the polymerization reactor.
  • a particularly suitable homogenizer for premixing is the Eppenbach homo-mixer.
  • the model of this mixer used was comprised of a multi-bladed rotor having a rotor/ stator clearance in the range of about .030 to about .0625 inch and rotated with a peripheral speed of about 60 feet per second.
  • the homogenized premix ordinarily is stable against phase separation for at least about 60 minutes at 60 C.
  • agitator speed in the polymerization reactor is less critical and serves primarily to provide good heat transfer when the process includes the step of high speed homogeneous premixing.
  • the polymerization reaction period is preferably in the range of 75 to 150 minutes, as measured by the duration of the exothermic reaction, to assure adequate heat-trans fer. Rate of heat dissipation ordinarily provided in commercial operations practically limits the exothermic period to at least 60 minutes in commercial operations. Exothermic reaction periods beyond about 6 hours are con sidered to be impractically long.
  • Aqueous dispersion interpolymers as represented by Examples 1, 2 and 3 prepared by emulsion polymerization under the aforementioned preferred operating conditions, ordinarily have a particle size in the range of about .10 to .30 micron and the interpolymer is characterized by a weight average molecular weight, as deter mined by light scattering, in the range of about 300,000 to 800,000.
  • the relative viscosity of these interpolymers based on a 0.5% solution in dimethylformamide ordinarily ranges from about 4.0 to 10.0.
  • Emulsion polymerized interpolymers derived from monomer mixtures in which the weight proportion of the acrylic ester predominates over the acrylonitrile, as
  • Example 4 ordinarily are characterized by a relative viscosity in the range of 2.5 to 5.0 in dimethylformamide and the average particle size of the interpolymer in the aqueous dispersion is in the range of about .05 to .15 micro
  • a suflicient amount of ammonium hydroxide is added to the acidic aqueous dispersion, which ordinarily is at a pH value no greater than about 4.0, to increase the pH value to at least about 5.5.
  • ammonium hydroxide ordinarily added to reach this pH value is sufiicient to convert at least by weight of the acidic component of the interpolymer to its ammonium salt.
  • a pH value in the range of 5.5 to 6.5 the ammoniacal aqueous dispersion composition is not highly advanced in viscosity over the unneutralized acidic aqueous dispersion and it is most convenient to separate undesirable coagulum and fineparticle-size polymer grit from the dispersion at this ammoniacal stage, such as by filtration.
  • the ammoniacal neutralization is carried out to a pH value of 5.5 to 6.5 and in the second stage the ammoniacal neutralization is advanced to a pH value in the range greater than that of the first stage up to 8.0, preferably in the range of 6.7 to 7.5.
  • the total amount of ammonium hydroxide ordinarily added is sufiicient to convert from 50% to about 100% by weight of the acidic component of the interpolymer to its ammonium salt.
  • ammonium hydroxide can be made as a single stage, separating the coagulum and polymer grit from the acidic composition prior to the ammoniacal neutralization.
  • the temperature can range from about 45 C. to about 95 C.
  • the heating period can range from about 5 minutes to about '4 hours.
  • the preferred heat-treatment ranges from about 15 minutes to about 120 minutes at a temperature ranging from about 65 C. to about 90 C. Heating for a period as short as 5 minutes within these temperature ranges ordinar'ily provides viscosity-advancement of at least 50% over that of the untreated aqueous dispersion.
  • ammoniacal neutralization When ammoniacal neutralization is in two stages, heating in the initial neutralization stage is not critical as viscosity-advancement is not'the primary object of the initial stage.
  • the ammonium hydroxide can be added at the temperature existing after-completion of the emulsion polymerization, this temperature being in the range of room temperature to about 70 C. and ordinarily at least about 45 C.
  • the second stage ammoniacal neutralization to a pH value in the range of 6.7 to 8.0 accompanied with further heating represents the pertinent viscosity-advancing stage.
  • the modifier can be blended with the interpolymer dispersion either before or after the ammoniacal heat-treatmentor between the first and second stage of ammoniacal neutralization. Blending prior to the heat-treatment is preferred as the entire composition is thereby stabilized rather than just the component interpolymer dispersion.
  • the particularly preferred method of preparing the final enamel from the acidic aqueous dispersion interpolymer composition and the heat-reactive aldehyde con densation resin includes the steps of first stage ammoniacal neutralization of the acidic dispersion at a temperature in the range of 45 C. to 65 C. to a pH value of 5.5 to 6.5, filtering, blending the partially neutralized aqueous dispersion with the heat-reactive aldehyde condensation resin, second stage ammoniacal neutralization to a pH value in the range of 6.7 to'7.5, heating at a temperature in the range of 65 C. to C. to viscosityadvance the composition and cooling to room temperature. Ordinarily the final product is filtered to remove any coarse coagulum formed by drying out of interpolymer dispersion on parts of the heat-treating equipment.
  • Water-soluble coalescing agents are desirable components of the aqueous dispersion compositions when applied at room temperature as an air-drying coating or impregnant.
  • the presence of a coalescing agent ordinarily is not required where the applied coating is baked at high temperatures sufiicient to bring about coalescence.
  • the content of acrylonitrile in the interpolymer has a pertinent eitect on the need for a coalescing agent. When the acrylonitrile content is low, ordinarily there is no need for the coalescing agent, but when the acrylonitrile content is high, suchas 65% to 80% by weight of the interpolymer, a coalescing agent is required in applications where the dry coating is not baked.
  • Cyclic ethylene carbonate, tetramethylene sulfone, ethylene glycol monoethers of 1 to 4 carbon atom saturated aliphatic monohydric alcohols, diethylene glycol monoethers of l to 4 carbon atom saturated aliphatic monohydric alcohols, diacetone alcohol, dimethylformamide and dimethylacetamide are representative water-soluble coalescing agents which can be included in the aqueous dispersion interpolymer composition.
  • the amount of water-soluble coalescing agent can be present in amounts up to based on the weight of the dispersed interpolymer in the final composition, but ordinarily the presence of the coalescing agent is avoided during the ammoniacal heattreating step.
  • the stabilized aqueous dispersion interpolymer com positions can be further modified with pigments, fillers, extenders; finely-divided water-swellable hydrous silicates such as bentonite and montmorillonite clays, dyes and compatible film-forming resins and plasticizers.
  • the compositions of this invention can be adjusted at the time of use to a higher ammoniacal pH value in the range of 8.0 to 10.0 with ammonium-hydroxide or volatile amines. In some applications, this higher alkalinity provides improved Wetting of the sub- 'strate.
  • aqueous dispersion compositions of this invention can contain as much as 50% by weight of dispersed ammonium salt of the acidic interpolymer and as little as Ordinarily the practical content of ammoniacal interpolymer is-in the range of to 45% by weight.
  • aqueous dispersion interpolymer compositions can be applied by any of the conventional methods ordinarily used in coating or impregnating with aqueous dispersion products.
  • the applied coatings or impregnants can be dried or cured at temperatures ranging from room temperature to baking temperatures as high as 500 C.
  • the stabilized aqueous dispersion interpolymer compositions have wide utility in the coating and impregnating fields. They provide excellent baking finishes for electrical wire insulation. They provide excellent airdrawing finishes for wood, such as on bowling alleys and bowling pins. They can be applied to metallic and nonmetallic substrates either as baking or air-drying finishes. They are particularly useful as impregnants for fabrics and non-woven webs prepared from synthetic fibers such as derived from polyacrylonitrile, ethylene terephthalate polyester polymers, nylon, viscose rayon, polyurethane, polytetrafluoroethylene and polyvinylidene chloride.
  • the proportion of dry weight impregnant to fiber can be varied to provide useful products ranging in properties from those of thin paper-like sheets or leather-like products to thick rigid panels.
  • This invention otters a significant advance in the art in providing commercially acceptable ammoniacal aqueous dispersion interpolymer salt compositions which are characterized by package-stability, gelation-resistance and viscosity-stability.
  • This invention also provides for the preparation of stable aqueous dispersion interpolymer compositions desirably advanced in viscosity.
  • a process for preparing a package-stable and gelation-resistant aqeuous dispersion interpolymer composition which process comprises preforming, by emulsion polymerization in water, an acidic interpolymer of a mixture of monomers consisting of (A) to 80% by weight of acrylonitrile, (B) 1.5% to 15% by weight of at least one alpha olefinic monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid, and (C) 15% to 65% by weight of at least one ester of an acid of (B) with a saturated aliphatic monohydric alcohol having from 1 to 12 carbon atoms, forming an ammonium salt of said interpolymer byreacting the acidic (B) component of the interpolymer with arm monium hydroxide at a temperature in the range of about C.
  • ammoniacal reaction is carried out in two stages with a separation step between the initial stage and the second stage, to remove coagulum and polymer grit, the reaction in said initial stage being at a pH value in the range of 5.5 to about 6.5, the second stage reaction subsequent to said separation step being carried out at a temperature in the range of 45 C. to 95 C. with sufficient ammonium hydroxide being present to provide the aqueous dispersion with a pH value in the range of greater than that of the first stage up to 8.0.
  • a process for preparing a gelation resistant, viscosity-stable and package-stable aqueous dispersion interpolymer composition which process comprises the steps of forming a homogeneous premix composition comprising water, sodium lauryl sulfate, sodium meta bisulfite and a mixture of monomers consisting of (A) 30% to by weight of acrylonitrile, (B) 1.5% to 15% by weight of methacrylic acid, and (C) 15% to 65% by weight of butyl acrylate, emulsion-polymerizing said homogeneous premix in the presence of potassium persulfate added to complete in combination with the bisulfite a redox initiator, forming an ammonium salt of the acidic interpolymer by adding ammonium hydroxide to the resulting aqueous dispersion of the acidic interpolymer to a pH value in the range of-5.5 to 6.5 as a first stage ammoniacal reaction, filtering the resulting ammoniacal aque
  • the process of preparing a package-stable, gelation-resistant, heat-bodied aqueous dispersion interpolymer composition comprising the steps of: (a) preforming an aqueous acidic interpolymer dispersion composition by initially preparing an aqueous dispersion polymerization charge consisting essentially of water, a mixture of polymerizable monomers consisting of (A) 30% to 80% acrylonitrile, (B) 1.5% to of at least one alpha olefinic monocarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, phenyl acrylic acid and crotonic acid, and (C) 15% to 65% of at least one ester of an acid of (B) with a saturated aliphatic monohydric alcohol having from 1 to 12 carbon atoms per molecule, and from .2% to 4% of an alkali metal salt of an acidic fatty alcohol sulfate ester based on the weight of said polymerizable monomers
  • step (b) forming an ammonium salt of said dispersed acidic interpolymer resulting from step (a) by adding ammonium hydroxide thereto in an amount sufiicient to adjust said aqueous interpolymer dispersion to a pH value of 5.5 to 6.5 and reacting the resulting mixture at a temperature from about 45 C.
  • step (c) filtering the product of step (b), the aqueous dispersion of said interpolymer ammonium salt being the filtrate, (d) further adding ammonium hydroxide to said filtered dispersion in an amount suflicient to adjust said aqueous dispersion to a pH value of 6.7 to 8, (e) heating the product aqueous dispersion of the resulting interpolymer ammonium salt at a temperature from 65 C. to C. for a period of about 15 to minutes, and (f) cooling the product dispersion to room temperature below 30 C.

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US578405A 1953-07-23 1956-04-16 Process of preparing aqueous dispersion of an acrylonitrile interpolymer and a thermosetting resin and product obtained Expired - Lifetime US2866763A (en)

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NL216362D NL216362A (enrdf_load_stackoverflow) 1956-04-16
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US578405A US2866763A (en) 1956-04-16 1956-04-16 Process of preparing aqueous dispersion of an acrylonitrile interpolymer and a thermosetting resin and product obtained
GB9275/57A GB826455A (en) 1956-04-16 1957-03-21 Stabilized, non-gelling aqueous dispersion compositions and process of making same
DK134457AA DK104260C (da) 1956-04-16 1957-04-12 Stabil, vandig acrylsyrenitrilblandingspolymerdispersions og fremgangsmåde til dens fremstilling.
DEP18353A DE1208023B (de) 1956-04-16 1957-04-15 Verfahren zur Herstellung von lagerungs- und gelierungsbestaendigen UEberzugsmitteln auf der Grundlage von waessrigen Polyacrylatdispersionen
FR71477D FR71477E (fr) 1953-07-23 1957-04-16 Interpolymères acryliques, leur procédé de préparation et compositions de revêtement à base de ces interpolymères
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037881A (en) * 1958-07-21 1962-06-05 Du Pont Aqueous dispersion paint compositions
US3206421A (en) * 1962-05-22 1965-09-14 Du Pont Interpolymer latex compositions and process
US3316123A (en) * 1964-01-28 1967-04-25 American Cyanamid Co Paper carrying non-blocking flexible grease-proof vinyl polymer coating
US3386939A (en) * 1964-11-27 1968-06-04 Du Pont Acrylic dispersions for wire enamels
US3388189A (en) * 1963-04-08 1968-06-11 Monsanto Co Copolymers for acrylic fibers having improved basic dyeing properties comprising acrylonitrile, a cinnamic acid and vinylacetate or vinylidene chloride
US3492252A (en) * 1963-10-07 1970-01-27 Scm Corp Emulsion coating comprising neutralized latex of acidic polymer and an epoxy component
US3505045A (en) * 1968-03-19 1970-04-07 Minnesota Mining & Mfg Abrasive backings saturated with copolymers of acrylic ester and nitrile monomers
DE2634868A1 (de) * 1975-08-04 1977-02-17 Ici Ltd Beschichteter verbundfilm
DE2634834A1 (de) * 1975-08-04 1977-02-24 Ici Ltd Beschichtete verbundfilme
US4129544A (en) * 1976-04-29 1978-12-12 E. I. Du Pont De Nemours And Company Aqueous acrylic coating composition for electrical conductors
US4278579A (en) * 1979-08-06 1981-07-14 Desoto, Inc. Aqueous coating systems containing bisphenol-formaldehyde ethers
US4321175A (en) * 1978-12-16 1982-03-23 Bayer Aktiengesellschaft Copolymer dispersions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1265113B (de) * 1964-03-07 1968-04-04 Bayer Ag Verfahren zur Veredlung von Textilmaterialien aus natuerlicher oder regenerierter Cellulose

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1981102A (en) * 1932-08-10 1934-11-20 Agfa Ansco Corp Photographic material and process of making the same
US2557266A (en) * 1944-05-20 1951-06-19 Du Pont Reaction product of an acrylic acid resin and a resin containing hydroxyl groups
US2582303A (en) * 1947-10-16 1952-01-15 American Cyanamid Co Hot-moldable compositions comprising melamine-formaldehyde resin and acrylonitrile copolymer
US2772166A (en) * 1953-02-11 1956-11-27 Eastman Kodak Co Hydrophilic compositions and their preparation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1105357A (fr) * 1953-07-23 1955-11-30 Du Pont Interpolymères acryliques, leur procédé de préparation et compositions de revêtement à base de ces interpolymères

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1981102A (en) * 1932-08-10 1934-11-20 Agfa Ansco Corp Photographic material and process of making the same
US2557266A (en) * 1944-05-20 1951-06-19 Du Pont Reaction product of an acrylic acid resin and a resin containing hydroxyl groups
US2582303A (en) * 1947-10-16 1952-01-15 American Cyanamid Co Hot-moldable compositions comprising melamine-formaldehyde resin and acrylonitrile copolymer
US2772166A (en) * 1953-02-11 1956-11-27 Eastman Kodak Co Hydrophilic compositions and their preparation

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037881A (en) * 1958-07-21 1962-06-05 Du Pont Aqueous dispersion paint compositions
US3206421A (en) * 1962-05-22 1965-09-14 Du Pont Interpolymer latex compositions and process
US3388189A (en) * 1963-04-08 1968-06-11 Monsanto Co Copolymers for acrylic fibers having improved basic dyeing properties comprising acrylonitrile, a cinnamic acid and vinylacetate or vinylidene chloride
US3492252A (en) * 1963-10-07 1970-01-27 Scm Corp Emulsion coating comprising neutralized latex of acidic polymer and an epoxy component
US3316123A (en) * 1964-01-28 1967-04-25 American Cyanamid Co Paper carrying non-blocking flexible grease-proof vinyl polymer coating
US3386939A (en) * 1964-11-27 1968-06-04 Du Pont Acrylic dispersions for wire enamels
US3505045A (en) * 1968-03-19 1970-04-07 Minnesota Mining & Mfg Abrasive backings saturated with copolymers of acrylic ester and nitrile monomers
DE2634868A1 (de) * 1975-08-04 1977-02-17 Ici Ltd Beschichteter verbundfilm
DE2634834A1 (de) * 1975-08-04 1977-02-24 Ici Ltd Beschichtete verbundfilme
US4129544A (en) * 1976-04-29 1978-12-12 E. I. Du Pont De Nemours And Company Aqueous acrylic coating composition for electrical conductors
US4159364A (en) * 1976-04-29 1979-06-26 E. I. Du Pont De Nemours And Company Aqueous acrylic coating composition for electrical conductors
US4321175A (en) * 1978-12-16 1982-03-23 Bayer Aktiengesellschaft Copolymer dispersions
US4278579A (en) * 1979-08-06 1981-07-14 Desoto, Inc. Aqueous coating systems containing bisphenol-formaldehyde ethers

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NL216362A (enrdf_load_stackoverflow)
GB826455A (en) 1960-01-06
DE1208023B (de) 1965-12-30
DK104260C (da) 1966-04-25
NL105265C (enrdf_load_stackoverflow)

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