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WO2017135925A1 - Additifs d'amines polyglycidyliques linéaires pour la réticulation contrôlée de polymères de latex - Google Patents

Additifs d'amines polyglycidyliques linéaires pour la réticulation contrôlée de polymères de latex Download PDF

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Publication number
WO2017135925A1
WO2017135925A1 PCT/US2016/016067 US2016016067W WO2017135925A1 WO 2017135925 A1 WO2017135925 A1 WO 2017135925A1 US 2016016067 W US2016016067 W US 2016016067W WO 2017135925 A1 WO2017135925 A1 WO 2017135925A1
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Prior art keywords
paint
amine
latex
diamine
pgam
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Inventor
Jiali Cai
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Ennis Flint Inc
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Ennis Paint Inc
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    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C09D171/03—Polyepihalohydrins
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C08G65/3255—Ammonia
    • 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
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)

Definitions

  • This process serves as a trigger for controlled crosslinking of the latex (binder) as it interacts with the polyfunctional amines of the present disclosure during application and drying.
  • the pursuit of fast drying aqueous traffic paints requires there be strong and effective interactions between the latex binder and water-soluble polyfunctional amine crosslinkers, to ensure fast hardening at proper high build (in a single coat thick application) translating into corresponding scrub resistance.
  • aqueous coating compositions continue to replace traditional organic solvent-based coating compositions. Paints, inks, sealants, and adhesives, for example, previously formulated with organic solvents are now formulated as aqueous compositions. This reduces potentially harmful exposure to volatile organic compounds (VOC's) commonly found in solvent-based compositions.
  • VOC's volatile organic compounds
  • aqueous coating compositions must meet or exceed the performance standards expected from solvent- based compositions.
  • the need to meet or exceed the organic solvent based performance standards places a premium on the characteristics and properties of waterborne polymer compositions used in aqueous coating compositions.
  • the latex industry and specifically the latex-based traffic paint products have historically held a long established goal of developing effective "one-pack" (proper high build -in a single coat thick application) - or single step crosslinking systems.
  • the ideal system allows for film formation prior to substantial crosslinking as the latex is applied to surfaces.
  • the nature of this coating technology requires that it is stable when being stored and fast drying only when being applied.
  • the structural make-up of these aqueous systems must be unreactive in the wet state, but very capable of ionic bonding (in ambient conditions) in the dry state; referred to hereinafter as latent crosslinking.
  • latent crosslinking The result of latent crosslinking would be a good film- forming latex with excellent hardness that is very durable and scrub resistant.
  • non-aqueous compositions examples are disclosed in U.S. Pat. No. 4,772,680. Even though improved stability may be achieved by specific aromatic aldimines, volatile by-products are still formed and the compositions have no application in waterborne coatings and are restricted to coatings using organic solvents as the carrier.
  • WO 95/09209 describes a crosslinkable coating composition
  • a crosslinkable coating composition comprising an aqueous film forming dispersion of addition polymer comprising acetoacetate functional groups and an essentially non-volatile polyamine having at least two primary amine groups and wherein the mole ratio of acetoacetate to primary amine groups is between 1 :4 to 40: 1.
  • EP 555,774 and WO 96/16998 describe the use of carboxylated acetoacetoxy ethyl methacrylate latexes mixed with multifunctional amines (such as diethylene triamine) for a shelf-stable, one-component system.
  • multifunctional amines such as diethylene triamine
  • the system is stabilized by using vinyl acid polymerized with AAEM and the latex is "neutralized" with a polyamine.
  • the patent teaches that the carboxyl groups should be 70 to 96 mol percent relative to the acetoacetoxy groups.
  • WO 96/16998 similarly describes a polymerization process with the vinyl acid and AAEM being polymerized in the first stage.
  • EP 744,450 describes aqueous coating compositions containing acetoacetate functional polymers with a weight-average molecular weight of 100,000 or greater and which contain acetoacetate functional groups and acidic functional groups, and multifunctional amine.
  • EP 778,317 describes an aqueous self-crosslinkable polymeric dispersion comprising a polymeric component (a relatively hydrophobic polymer having a Hansen number >1.5, at least 5% of a carbonyl functional group capable of reacting with a nitrogen moiety, and at least 1 % of a non-acidic functional group having hydrogen-bondable moieties); and a crosslinking agent comprising a nitrogen-containing compound having at least two nitrogen functional groups capable of reacting with a carbonyl functional moiety. Again it is reported that no gelation has taken place after ten days at 60° C.
  • U. S. Pat. No. 5,498,659 discloses a single-package aqueous polymeric formulation consisting essentially of an evaporable aqueous carrier, at least one polymeric ingredient having acid- functional pendant moieties able to form stable enamine structures, a non-polymeric polyfunctional amine having at least two amine functional moieties, and an effective amount of base for inhibiting gelation. It is stated in the patent that at least some of the crosslinking of the composition may take place in the liquid phase, possibly within one to four hours of adding the non-polymeric polyfunctional amine.
  • 5,405,701 provides a resin composition for an aqueous coating having as its main components (A) a resin having hydroxyl and cationic groups, (B) at least two glycidyl groups each in a glycidylamino group.
  • the resulting resin can be used for electro-coating and can be cured at lower temperatures of 70-160°C.
  • the curing agent (C) of the final resin composition is selected from the group consisting of lead, zirconium, cobalt, aluminum, manganese, copper, zinc, iron, bismuth, and nickel compounds.
  • This paper presents the synthesis of new adducts from glycidyl methacrylate and the following amines: aniline, »-phenylenediamine, 4,4-oxydianiline, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenyl sulfone, 4,4- thiodiaxiiline, and 4,4-diaminodicyclohexylmethane,
  • the exemplar synthesis of the adduct of 4,4-oxydianiline and glycidyl methacrylate provides that the amounts of reagents were chosen in such a way that 2 mol of glycidyl compound reacted with 1 mol of amine. In the case of diamines 4 mol of glycidyl methacrylate was used.
  • Non-linear glycidyl amine adducts are discussed which present high crosslinking degrees, high thermal stabilities, and extreme hardness.
  • the methyl and ethyl alkyl groups of A may be substituted with lower alkyl groups.
  • These amines are useful as coupling agents for polymer formation and are particularly useful as curing agents in polyurea coatings, for example, sprayed polyurea coatings.
  • the curing agents provided are linear curing agents for polyurethane spray coatings.
  • the usable pot life of the latex formulations is demonstrated by lack of sedimentation. It is quite possible, however, that crosslinking is taking place within each particle, without causing the latex to coagulate or gel (e.g. loss of colloidal stability). This type of intra-particle crosslinking (before drying) limits the ability of the latex to form a film upon drying.
  • a need exists for truly latent linking or "crosslinking” systems— those in which intraparticle crosslinking is inhibited until after film formation.
  • a "one pack system” refers to a single packaged system that provides the necessary premixed formulations that have adequate shelf life so that they can be applied where and when needed.
  • the application for using such formulations further includes decorative and protective coatings, adhesives, non-woven binders, textiles, paper coatings, traffic markings, inks, etc.
  • further advantages include the development of "soft" ductile polymers that convert to harder, more resistant latex films upon drying.
  • the following acronyms are used throughout the body this specification and provide information regarding chemical compounds and structures as follows;
  • ADS ammonium dodecyl sulfate
  • GAm glycidyl amine
  • GAz glycidyl azide
  • MAA methacrylic acid
  • MMA methyl methacrylate
  • M n number average molecular weight
  • Ph 3 PO triphenylphosphine oxide
  • SDS sodium dodecyl sulfate
  • ZBU3AI triisobutylaluminium
  • SUMMARY Amine linkers are water soluble polyfunctional amines establishing interactions with anionic latex particles when the pH and solid content of the dispersion media changes. Often this chemical phenomenon is commonly referred to as "crosslinking", which is a more general terminology that is not entirely accurate.
  • crosslinking which is a more general terminology that is not entirely accurate.
  • the polyglycidyl amines (pGAm) exhibit high water solubility due to an ethoxylated backbone and pendant moieties containing primary amines dispersed along the molecular chain.
  • compositions of primary, secondary, and tertiary groups can be achieved through direct reaction of primary amine groups with other reactive groups.
  • Linearity of the polyfunctional polyglycidyl amine crosslinkers has been found to surprisingly provide increased rheology control by allowing tailoring of viscosity and molecular weight in an efficient manner. Due to the presence of ethylene oxide moieties in the final composition, hydrophilicity is maintained provided the size of the R-substituent moieties do not cause significant steric hindrance or increase the bulkiness of the overall composition.
  • a coating composition comprising;
  • R and c) at least one volatile base, wherein;. wherein the substituent Ri is -H; and wherein the substituent R2 is selected from group consisting of: -NH 2 , methyl amine, ethyl amine, 1 -propyl amine, ethanol amine, 2-propyl amine, 1 -butyl amine, 2-butyl amine, 2- methyl-2-propyl amine, piperazine, ⁇ , ⁇ -dimethyl-ethyl diamine, ⁇ , ⁇ -diethyl-ethyl diamine, ⁇ , ⁇ -dimethyl propyl diamine, ⁇ , ⁇ -diethyl-propyl diamine, ⁇ , ⁇ -dimethyl amino propylamine, N,N-dimethyl ethylene amine, ⁇ , ⁇ -diethyl amino propylene amine, N,N- diethylamino ethylene amine, amino ethyl-piperazine, N-methyl-l,2-ethane
  • the coating composition is one or more polyfunctional amines that are homopolymers, and/or homo-oligomers designated as pGAm-1, wherein pGAm-1 is a chemical structure represented as;
  • the coating composition may be one or more polyfunctional amines that more copolymers wherein pG-co-GAm-1 is a chemical structure represented as;
  • n may or may not equal n and wherein m and n are numbers greater than 10 and less than 300 .
  • the coating composition is one or more polyfunctional oligomeric/polymeric amines that provide cationic charge and a molecular weight that when placed in solution with a latex binder yields an aqueous based crosslinked polymer latex coating that forms better films, quicker drying times and increased scrub resistance in comparison with polymer latex coatings that do not contain these specific polyfunctional amines.
  • an aqueous latex paint is described as comprising:
  • substituent Ri is -H
  • substituent R2 is selected from group consisting of: -NH 2 , methyl amine, ethyl amine, 1 -propyl amine, ethanol amine, 2-propyl amine, 1 -butyl amine, 2-butyl amine, 2- methyl-2-propyl amine, piperazine, ⁇ , ⁇ -dimethyl-ethyl diamine, ⁇ , ⁇ -diethyl-ethyl diamine, ⁇ , ⁇ -dimethyl propyl diamine, ⁇ , ⁇ -diethyl-propyl diamine, ⁇ , ⁇ -dimethyl amino propylamine, N,N-dimethyl ethylene amine, ⁇ , ⁇ -diethyl amino propylene amine, N,N- diethylamino ethylene amine, amino ethyl-piperazine, N-methyl-l,2-ethane diamine, N-methyl-piperazine, N-methyl-l,2-ethane
  • the aqueous latex paint includes or more polyfunctional amines are homopolymers, and/or homo-oligomers designated as pGAm-1, wherein pGAm-1 is a chemical structure represented as;
  • n may or may not equal n and wherein m and n are a number greater than 10 and less than 300 .
  • latex paint formulations are both a latex and one or more polyfunctional amines that are combined.
  • the latex paint one or more polyfunctional oligomeric/polymeric amines provide cationic charge and molecular weight that when placed in solution with a latex binder yields an aqueous based crosslinked polymer latex coating that forms better films, quicker drying times and increased scrub resistance in comparison with polymer latex coatings that do not contain said polyfunctional amines.
  • These latex paints provides for dry times on paved surfaces in an atmosphere that is characterized as possessing at least 50% relative humidity with a final AKU value of no greater than 10.0, as measured using ASTM D711.
  • the latex paints provides for dry times on paved surfaces, in an atmosphere that is characterized as possessing at least 75% relative humidity, with a final AKU value of no greater than 10.0, as measured using ASTM D711.
  • the latex paints provide for improved scrub resistance as compared to aqueous latex paint by at least 10% using ASTM D2486.
  • the latex paint wherein the paint contains only white pigment contains only white pigment.
  • the latex paint wherein the paint contains only yellow pigment.
  • the latex paint wherein the polyfunctional amine has a weight average molecular weight of 500 to 5,000,000 Daltons; more preferably from 1,000 to 50,000 and most preferably from 2000 to 20,000.
  • the latex paint wherein the polyfunctional amine has a number average molecular weight of between 1,000 and 30,000 Daltons.
  • the latex paints further include additional pigments, fillers, dispersants, coalescents, pH modifying agents, plasticizers, defoamers, surfactants, thickeners, biocides, co-solvents, and combinations thereof.
  • the latex paints additionally include additives integrated into the paint including rheology modifiers, wetting and spreading agents, leveling agents, conductivity additives, adhesion promoters, anti-blocking agents, anti-cratering agents and anti-crawling agents, anti-freezing agents, corrosion inhibitors, anti-static agents, flame retardants and intumescent additives, dyes, optical brighteners and fluorescent additives, UV absorbers and light stabilizers, chelating agents, cleanability additives, crosslinking agents, flatting agents, flocculants, humectants, insecticides, lubricants, odorants, oils, waxes and slip aids, soil repellants, stain resisting agents, and combinations thereof.
  • the latex paint also includes aqueous dispersions having a volume solids content of between 45 and 65% by weight of a total paint formulation.
  • the latex paint further includes aqueous dispersions having a volume solids content of between 60 and 77% by weight of a total paint formulation.
  • the latex paint is often applied to a surface selected from the group consisting of metal, asphalt, concrete, stone, ceramic, wood, plastic, polyurethane foam, glass, and combinations thereof.
  • the coating compositions may also be applied to a surface selected from the group consisting of metal, asphalt, concrete, stone, ceramic, wood, plastic, polyurethane foam, glass, and combinations thereof.
  • the latex paints which exist as a coating have dry thickness of between 10 mils and 100 mils.
  • a method for preparing one of the pGAm-x structures obtaining pGAm-1 comprises a specific three-step synthesis reaction including;
  • I includes ⁇ 3 ⁇ 4 ⁇ 1/ ⁇ BuNH 4 Cl in toluene at 0° C in a nitrogen atmosphere' (ii) preparation of pGAz as follows;
  • III includes adding DMF and Ph 3 P with water at room temperature to convert the pGAz to pGAm-1.
  • the polyfunctional polyglycidyl amines of the present disclosure are the result of a three step substitution reaction process to provide, in this particular example, pGAm-1.
  • the resulting polyfunctional amines using similar reaction conditions comprise at least two separate primary amino groups which are pH responsive and will accept or release proton(s) in response to a change in pH.
  • pGAm-x structures and more specifically pGAm-1, shown above, are representative of one group of linear polyfunctional oligomeric/polymeric amines which possess the necessary cationic charge at lower pH values and molecular weight so that when placed in solution with the latex binder allows for providing a final aqueous based crosslinked polymer latex coating that forms proper films, is quick drying, and exhibits increased scrub resistance.
  • the linear polyfunctional polyglycidyl amines, as described herein, can be used in latex paint formulations to function as crosslinkers. Complete paint formulations utilizing both a latex and one or more polyfunctional polyglycidyl amines, or a combination of several
  • polyfunctional polyglycidyl amines as described, and provided herein, are also subjects of the present disclosure.
  • the paint formulations may additionally include at least one member of the group consisting of; dispersants, defoamers, surfactants, biocides, ammonia, rheology agents, pigments, solvents, coalescents, and water.
  • the paint formulations may be used as traffic paint on various pavement surfaces.
  • the paint formulations provide for paint that is applied to pavement surfaces such that crosslinking of the paint occurs and the paint dries within 15 minutes.
  • the paint formulations using the polyfunctional polyglycidyl amines of the present disclosure impart substantially increased scrub resistance when compared with previously prepared latex paint formulations not using the linear polyfunctional amines disclosed herewith.
  • Substantially increased scrub resistance is possibly due to the formation of a significant number of hydrogen bonds between the hydrogen of the amine groups and the oxygen of the carboxylates and/or oxygen from the ethoxylated backbone of the polyfunctional polyglycidyl amine, strengthening the connections between latex particles.
  • the contribution of ionic bonding between the carboxylic acid anions and cationic polyfunctional polyglycidyl amines also plays a role in increasing scrub resistance of paints.
  • the mostly or completely linear polyfunctional polyglycidyl amine homopolymer/oligomer structures of the present disclosure provide the ability to more easily tailor the crosslinking capability, final molecular weight, and overall product viscosity of latexes.
  • the present invention provides special linear polyfunctional polyglycidyl amine
  • the latex polymer emulsion compositions of the present invention typically include, but are not limited to, latexes, dispersions, microemulsions, and/or suspensions.
  • the latex polymer compositions of the present invention may be stored at room temperature or moderately above room temperature (e.g., about 50 to 60° C) thereby providing the desired, acceptable shelf life. Subsequently they provide adhesion and crosslinking upon film formation when applied to a substrate.
  • a film or coating using with polymers of the present disclosure may be formed at room temperature or elevated temperatures
  • the latex polymer binders used in the present disclosure are generally prepared as particles.
  • the particles may be structured or unstructured. Structured particles include, but are not limited to, core/shell particles and gradient particles.
  • the average polymer particle size may range from about 100 to about 300 nm.
  • the present disclosure includes compositions and methods for the preparation of water soluble polyfunctional polyglycidyl amine homopolymers/homo-oligomers along with the possibility of implementing copolymers, for use as crosslinking agents in solutions of latex emulsions, which have been shown to provide greatly enhanced scrub resistance upon drying.
  • the oligomeric/polymeric polyglycidyl amine is synthesized in the previously detailed three- step synthesis process by first reacting an organohalogen epoxide, such as epichlorhydrin, with an initiator and catalyst producing polyepichlorhydrin (pECH).
  • the resulting pECH polymer product shown by the Step 1 reaction, is reacted with an ionic solid salt, such as sodium azide. Conversion of chloromethyl groups to azidomethyl groups is confirmed by the FTIR spectrum [100] of pECH in comparison with pGAz.
  • the byproduct of this reaction is only sodium chloride (NaCl).
  • the conversion of pGAz to pGAm-x is achieved via a reduction reaction using a suitable reducing agent.
  • pGAz is dissolved in Step 3 into DMF with the addition of Ph 3 P (triphenyl phosphine).
  • Ph 3 P triphenyl phosphine
  • a corresponding phosphine-imine is formed that is easily hydrolyzed by the addition of water to release the amine with byproducts of only gaseous nitrogen and hydrophobic Ph 3 PO (triphenylphosphine oxide).
  • the resulting water soluble polyfunctional polyglycidyl amines of the general structure pGAm-x serve to provide useful crosslinkers for latex paints.
  • the determination of whether the resulting chemical compound structures are an oligomer or polymer depends on the final number and weight average molecular weights (as determined primarily by the number and molecular weight) of the repeating monomeric chains.
  • the three-step reaction schema provides GRAS (generally regarded as safe) byproducts comprising; NaCl, gaseous nitrogen, and Ph 3 PO, the products provided using these reactants/reactions are considered environmentally friendly. More specifically, running this reaction and obtaining the linear polyfunctional polyglycidyl amine polymer/oligomers, as well as any wastes generated during production, will not cause any known ecological harm to the environment. This issue has become an increasingly important consideration due to continued development of government regulations in most of the western industrial locations where these products will be manufactured and sold.
  • GRAS generally regarded as safe
  • substantially increased scrub resistance is possibly due to the formation of a significant numbers of hydrogen bonds between the hydrogen of the amine groups and the oxygen atoms contained in the carboxylates and/or oxygen from the ethoxylated backbone of the polyfunctional polyglycidyl amine resulting in the strengthening of bonding with the latex particles.
  • the contribution of ionic bonding between the carboxylic acid anions and cationic polyfunctional polyglycidyl amines also plays a role in increasing scrub resistance of paints.
  • the waterbome scrub resistant paint serves as road and pavement marking paint which can be used to mark lines or symbols on roads, parking lots, and walkways etc.
  • the synthesis of the polyfunctional amine crosslinkers of the present disclosure can be completed utilizing the three-step synthesis process described. Possibilities exist in optimizing the compositions contained herein through reaction of the primary amine(s) of the pGAm-x compound with various reactive moieties.
  • polyfunctional polyglycidyl Amines (pGAm-x)
  • polyfunctional polyglycidyl amine crosslinkers comprising recurring units derived from a three-step synthesis reaction process beginning with one glycidyl moiety and resulting in a polyfunctional polyglycidyl amine of the general formula (pGAm-x):
  • the pGAm-X homopolymer/oligomer includes the structural repeating unit (n) and wherein the substituent Ri is -H
  • the substituent R2 is selected from group consisting of: -NH 2 , methyl amine, ethyl amine, 1 -propyl amine, ethanol amine, 2-propyl amine, 1 -butyl amine, 2-butyl amine, 2- methyl-2-propyl amine, piperazine, ⁇ , ⁇ -dimethyl-ethyl diamine, ⁇ , ⁇ -diethyl-ethyl diamine, N,N-dimethyl propyl diamine, ⁇ , ⁇ -diethyl-propyl diamine, N,N-dimethyl amino propylamine, N,N-dimethyl ethylene amine, ⁇ , ⁇ -diethyl amino propylene amine, N,N- diethylamino ethylene amine, amino ethyl-piperazine, N-
  • the molecular weights were determined using the following GPC methodology for amine testing in aqueous solutions.
  • the detectors for this equipment included a Waters 410 Differential Refractometer (RI) with a Viscotek Dual Detector 270 - (RALS, DP, IP, LALS).
  • the running solvent used was deionized water with 0.2% ethylenediamine (EDA).
  • the polyglycidyl amine crosslinker samples were diluted in DI water and filtered through 0.22 um PTFE filters into 1.5mL vials and run through the GPC system at a flow rate of l .OmL/min. Each vial had a run time of 30 minutes to allow samples to be entirely flushed out before the next run.
  • a set of polyethylene glycol (Oxide) (PEO) samples were run to provide a calibration curve ranging from 232 to over one million Daltons. Omnisec software was used to create a method to fit the molecular weight distributions of the amine samples to the calibration curve of the standardized PEG samples.
  • the present disclosure involves the use of crosslinkers for the preparation of final latex polymer compositions containing at least one polyglycidyl amine primarily acting as a component for ionic bonding.
  • An example of a homopolymer or homo-oligomer (depending on the number and size of the repeating units) resulting in a polyglycidyl amine of the present disclosure has been designated as pGAm-1 and is schematically represented again below;
  • a general method for achieving the reaction leading to the linear polyglycidyl amine, pGAm- 1, as represented above is as follows;
  • a solution of a quaternary ammonium salt and an organochlorine epoxide was dissolved in toluene under a nitrogen atmosphere.
  • the polymerization was started by adding an anhydrous toluene solution (25 wt.%) of an organoaluminum compound at a constant temperature of 0°C. The reaction mixture was kept overnight at this temperature. After polymerization (complete monomer conversion) toluene was removed under reduced pressure. The poly(organochloride epoxide) was dissolved in dimethylformamide and ionic sodium azide was added to the solution. The reaction mixture was stirred at 1 10°C for 18 h and then the reaction was stopped. The precipitate was filtered off and then
  • equation (1) describes how the wt.% of the polyamine is determined:
  • weight % polyamine weight of reactants / total weight (w/ water)
  • the crosslinkers made from the substitution chemistry of the present disclosure should include at least two primary amino group sites that are responsive to change in pH and will accept or release proton(s) in response to such a change in pH .
  • the polymerization was started by adding an anhydrous toluene solution (25 wt.%) of triisobutylaluminium ( ⁇ ' ⁇ 3 ⁇ 4 ⁇ 1), 125.0 ml, at a constant temperature of 0°C. The reaction mixture was kept overnight at this temperature. After polymerization (complete monomer conversion) toluene was removed under reduced pressure. l OO.Og pECH was dissolved in 350 ml dimethylformamide (DMF) and 98.2g sodium azide was added to the solution. The reaction mixture was stirred at 110°C for 18 h and then the reaction was stopped.
  • DMF dimethylformamide
  • Examples 2 and 3 Example 2 - pGAm-2 & Example 3- pGAm-3
  • the latex polymer compositions of the present invention will have various properties, often depending on end-use applications.
  • the polymer components have glass transition temperatures (Tg) of 15 to 40° C and more preferably 20 to 30° C.
  • the weight average molecular weight of the latex polymer compositions may vary from about 5,000 to 5,000,000 Daltons; more preferably from 20,000 to 2,000,000 and most preferably from 40,000 to 100,000.
  • Particle size of the latex compositions has been determined to be 224.8nm with a ⁇ -potential of 55.9 mV. Solids content of the latex compositions have been determined to be 50.1%.
  • a waterborne polymer composition may be prepared using the latex polymer composition of the present invention along with other known additives and may also employ other emulsion polymerization methodologies.
  • a 2 liter reactor was charged with 210.9 g SDS solution (14% of the total solution), (sodium dodecyl sulfate), 4.6 g NaHC0 3, 503.3 g water, 158.0 g BA, 189.5 g MMA, 6.8 g MAA and 16.2 g APS.
  • the solution was mechanically stirred and heated to 65 C. Radical polymerization occurred immediately and caused the temperature to rise quickly.
  • the exotherm was controlled using 410.1 g water which was added gradually over a period of four minutes.
  • the seed solution was allowed to react for another 130 minutes to ensure the reaction proceeded to completion.
  • the latex particle size obtained was determined to be 51 nm.
  • Latexes or other waterborne compositions containing small particle sized seed polymers range from about 25 to about 700 nm, preferably from about 50 to about 500 nm and more preferably from about 75 to about 300 nm and represent one embodiment of latexes used in the present invention.
  • the pre-emulsion mixture (1293.8g) and initiator (0.9g) in DI water (39.4g) were concurrently added into kettle at a constant rate over a period of 3h.
  • the temperature of the kettle was held at 81°C for additional lh to digest the residual monomers.
  • the latex was then filtered through a 300 mesh screen to remove any coagulum.
  • Table 2 provides the process steps and corresponding weights of each constituent required to complete the synthesis of the latex - Example 4 - for the paints described below.
  • the polyfunctional amine of Example 1 (pGAm-1) was added to the latex binder (Example 4) to make traffic paint, Paint 1.
  • Addition of the polyfunctional polyglycidyl amine of Example 2 (pGAm-2) to the latex binder of Example 4 provided the traffic paint, Paint 2.
  • the polyfunctional polyglycidyl amine of Example 1 (pGAm-3) was added to the latex binder (Example 4) to make traffic paint, Paint 3.
  • the traffic paint from the polymer binder Example 4 without polyfunctional polyglycidyl amine addition was formulated as the control.
  • the final traffic paint formulations were drawn down over 10cm x 30cm glass test panels to form a layer of the traffic paint composition thereon.
  • the thickness of the layer was controlled to approximately 380 microns.
  • the test panels were promptly placed in a test chamber and maintained at a desired relative humidity of 75 percent with wind speed of 2 miles per hour at 75° F.
  • the test chamber was equipped with a certified hygrometer and a certified temperature indicator, both of which were fastened to the center of the rear wall of the test chamber to ensure balanced measurement.
  • a pan at the bottom of the test chamber was filled with 2 cm of water and all the ports and doors were closed. The test chamber was allowed to equilibrate overnight.
  • the relative humidity within the test chamber reached 100 percent. By carefully opening and closing the various chamber ports, the relative humidity within the chamber was brought to the desired relative humidity of 75 percent.
  • the dry -to no pick up time was determined in accordance with ASTM D-711 by rolling a traffic paint drying wheel over the wet film. The end point for the dry-to-no-pickup time is defined as the point in time where no paint adheres to the rubber rings of the test wheel.
  • the traffic paints were tested for consistency in accordance with ASTM D562-10 by using Brookfield KU-2 Viscometer.
  • the traffic paint composition samples were placed in sealed 0.25 L containers and stored in a sealed circulation oven at 60°C for two weeks. The containers were then removed from the oven and allowed to cool to room temperature for 24 hours. The containers were opened, mixed for 3 minutes on a mechanical mixer and immediately tested again for consistency under ASTM D562-10.
  • the stored traffic paint was rated to have passed the storage stability test if the traffic paint composition consistency, as measured in Krebs units (KU), did not increase by more than ⁇ 10 KU from measurement before storage in the oven.
  • test paint and reference paint were thoroughly stirred, and then drawdown panels of the test and reference paints were prepared side by side, perpendicular to the length of the panel following procedures outlined:
  • Test panels were carefully wiped and placed on top of the shimmed plate with the painted side up. It was observed that there were no defects in the film above the shims and that the test areas were level. The gasket was placed over the painted surface and clamped in place. The brush was removed and shaken vigorously to remove any excess water. Before testing, the brush was conditioned for 400 cycles. The brush was again removed and shaken vigorously to remove any excess water. The abrasive scrub medium was stirred and 10 g of the medium was spread uniformly over the brush bristles. The brush was placed at one end of the path. The panel moistened with 5 mL of water in the path of the brush and the test was started.
  • the brush was removed without rinsing and 10 g of stirred abrasive scrub medium was added to the brash. Next, 5 mL of water was placed on the path of the brush before continuing. It is recommended that the first two panels to be tested are prepared by altering the position of the reference paint, that is, one panel has the reference paint on the right, and the second panel has the reference paint on the left. The number of cycles to remove one continuous thin line of paint film from both the test and reference paints across the 12.7-mm (1/2 -in.) width of each of the shims was recorded. The machine was stopped and the shim areas were wiped off to determine, if necessary, if each end point was achieved. Two of the drawdowns were tested. If the two results displayed a difference of more than 30 %, the third drawdown was tested. If one of the three results is obviously discrepant, it was discarded the results from the remaining drawdowns were averaged.
  • Paint 2 has lower dry time relative to the control. Paint 1 almost passed the storage stability test limit of 10 KU by recording a 10.7 KU value. Paints 2 and 3 pass the storage stability test as control. For scrub resistance, Paint 1 provided the highest (best) values.
  • anionic surfactant was used for latex synthesis.
  • the type of anionic surfactants provided are not limited to: sodium dodecyl sulfate (SDS), ammonium dodecylsulfate (ADS), disodium salt of ethoxylated lauryl sulfosuccinate and sodium benzyl dodecyl sulfate.
  • compositions of the present disclosure may be incorporated in those coating formulations in the same manner as with other known latexes and used with conventional components and/ or additives of such compositions. These coating formulations may be clear or pigmented. With their crosslinking ability, adhesion and resistance properties, the water-based latexes of the present invention impart new and/or improved properties to various coating formulations. Upon formulation, the coating/paint formulations containing the compositions of the present disclosure may then be applied to a variety of surfaces, substrates, or articles, e.g., paper, plastic, steel, aluminum, wood, gypsum board, concrete, brick, masonry, or galvanized sheeting (either primed or unprimed).
  • surfaces, substrates, or articles e.g., paper, plastic, steel, aluminum, wood, gypsum board, concrete, brick, masonry, or galvanized sheeting (either primed or unprimed).
  • the type of surface, substrate, or article to be coated generally determines the type of coating formulation used.
  • the coating formulation may be applied using means known in the art.
  • a coating formulation may be applied by spraying or by coating a substrate.
  • the coating may be dried by heating but preferably would be allowed to air dry.
  • the present disclosure relates to a shaped or formed article which has been coated with coating formulations described in detail above. .
  • Additives or fillers used in formulating coatings include, but are not limited to, leveling, rheology, and flow control agents such as silicones, fluorocarbons, urethanes, or cellulosics; extenders; curing agents such as multifunctional isocyanates, multifunctional carbonates, multifunctional epoxides, or multifunctional acrylates; reactive coalescing aids such as those described in U. S. Pat. No.

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Abstract

La présente invention concerne des structures oligomères et/ou polymères d'amines polyglycidyliques polyfonctionnelles linéaires présentant au moins deux amines primaires, lesquelles fournissent des capacités de réticulation à des compositions de peinture au latex. Ces agents de réticulation présentent non seulement des propriétés de réticulation latentes, mais aussi une résistance à l'abrasion améliorée comparativement à des formulations de latex existantes. Une fois le latex déposé sur un substrat, la base volatile s'évapore et les groupes réagissent pour former un revêtement réticulé présentant de meilleures propriétés de résistance à l'abrasion.
PCT/US2016/016067 2016-02-02 2016-02-02 Additifs d'amines polyglycidyliques linéaires pour la réticulation contrôlée de polymères de latex Ceased WO2017135925A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061254A (zh) * 2021-03-18 2021-07-02 浙江工业大学 一种阳离子聚合物基因载体及其制备方法
CN113307963A (zh) * 2021-06-08 2021-08-27 华南理工大学 一种合成缩水甘油基线形聚合物的方法
IT202200010901A1 (it) * 2022-05-25 2023-11-25 Team Segnal S R L Sistema verniciante multicomponente a base acquosa

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5534111A (en) * 1978-08-31 1980-03-10 Toray Ind Inc Semipermeable membrane
JP2005298646A (ja) * 2004-04-09 2005-10-27 Showa Highpolymer Co Ltd 速乾性水性樹脂組成物、これを用いた速乾性塗料用樹脂、及びこれを用いた塗料
EP1627903A1 (fr) * 2004-08-19 2006-02-22 Rohm and Haas Company Compositions de revêtement et procédé de revêtements de substrats
US20070173576A1 (en) * 2003-11-04 2007-07-26 Basf Aktiengesellschaft Method for the anionic polymerization of oxirans

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5534111A (en) * 1978-08-31 1980-03-10 Toray Ind Inc Semipermeable membrane
US20070173576A1 (en) * 2003-11-04 2007-07-26 Basf Aktiengesellschaft Method for the anionic polymerization of oxirans
JP2005298646A (ja) * 2004-04-09 2005-10-27 Showa Highpolymer Co Ltd 速乾性水性樹脂組成物、これを用いた速乾性塗料用樹脂、及びこれを用いた塗料
EP1627903A1 (fr) * 2004-08-19 2006-02-22 Rohm and Haas Company Compositions de revêtement et procédé de revêtements de substrats

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061254A (zh) * 2021-03-18 2021-07-02 浙江工业大学 一种阳离子聚合物基因载体及其制备方法
CN113061254B (zh) * 2021-03-18 2023-02-28 浙江工业大学 一种阳离子聚合物基因载体及其制备方法
CN113307963A (zh) * 2021-06-08 2021-08-27 华南理工大学 一种合成缩水甘油基线形聚合物的方法
IT202200010901A1 (it) * 2022-05-25 2023-11-25 Team Segnal S R L Sistema verniciante multicomponente a base acquosa
WO2023228097A1 (fr) * 2022-05-25 2023-11-30 Team Segnal S.R.L. Système de peinture à composants multiples à base d'eau

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