WO1997045468A1 - Surfactant-containing acetoacetoxy-functional and enamine-functional polymers - Google Patents
Surfactant-containing acetoacetoxy-functional and enamine-functional polymers Download PDFInfo
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- WO1997045468A1 WO1997045468A1 PCT/US1997/008808 US9708808W WO9745468A1 WO 1997045468 A1 WO1997045468 A1 WO 1997045468A1 US 9708808 W US9708808 W US 9708808W WO 9745468 A1 WO9745468 A1 WO 9745468A1
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- 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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- 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
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- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
Definitions
- This invention belongs to the field of emulsion chemistry. In particular, it relates to acetoacetoxy-functional polymers which are useful in a variety of coating formulations.
- Background of the Invention In an increasing number of industries, 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. While the move from organic solvent-based to aqueous compositions brings health and safety benefits, the aqueous coating compositions must meet or exceed the performance standards expected from solvent-based compositions. The need to meet or exceed such performance standards places a premium on the characteristics and properties of waterbome polymer compositions used in aqueous coating compositions.
- Waterbome polymer having various functional groups have been used to impart and achieve desired properties to a particular coating composition.
- a coating composition should exhibit good film formation, print and block resistance, as well as adhesion and tensile properties.
- Polymers having acetoacetoxy- and enamine-functional groups represent one example of waterbome polymers which have such properties, may carry different functional groups, and are useful in aqueous coating compositions.
- U.S. Patent 5,296,530 discloses a quick-curing coating prepared from a polymer having acetoacetyl groups, in which substantially all of the acetoacetyl groups have been converted to enamine functional groups. This conversion occurs, for example, by treatment with ammonia or a primary amine. Coatings so prepared cure more quickly under sunlight or ultraviolet light than coatings which contain the acetoacetyl functional polymer but which have not been converted to an enamine form.
- U.S. Patents 5,484,975 and 5,525,662 describe the preparation of polymers containing functional acetoacetate groups and then, following the polymerization, reacting the acetoacetate group with a functional amine to form an enamine.
- the resulting polymers are reported to have a variety of uses including coatings, sealants, adhesives, and saturant applications.
- U.S. Patent 5,498,659 discloses polymeric formulations comprising an aqueous carrier, at least one polymeric ingredient, a non-polymeric polyfimctional amine, and a base.
- the polymeric ingredient has both acid-functional and acetoacetoxy-type functional moieties.
- the aqueous polymeric formulations produce crosslinked polymeric surface coatings on a substrate.
- Japanese Patent 61-21171 describes a fast-curing adhesive consisting of two separate liquids.
- the first liquid is an aqueous solution and/or aqueous emulsion of a polymer compound containing an acetoacetyl group.
- the second liquid consists of polyethylenimine.
- the acetoacetoxy-functional polymer is a surfactant-containing enamine-functional polymer and more preferably a surfactant- containing, polymeric (polyamino)enamine (PPAE).
- the PPAE is the reaction product of a surfactant-containing acetoacetoxy-functional polymer (SAAP) and a poly(alkylenimine).
- the polymers of the invention may be prepared as waterbome polymer compositions, such as latexes.
- the waterbome polymer compositions can be prepared with high solids content while maintaining low viscosity.
- Waterbome polymer compositions containing the polymers of the invention are useful in a variety of coating formulations such as, for example, paints, inks, sealants, and adhesives.
- coating formulations such as, for example, paints, inks, sealants, and adhesives.
- the polymers of the invention provide adhesion and crosslinking in the final film or coating.
- the film or coating may be cured at ambient temperatures or may be thermally cured.
- Figure 1 depicts the affect of polymer particle size and percent solids on the viscosity of a latex of the invention. Detailed Description of the Invention
- the present invention provides polymers which may be used in a waterbome polymer composition, that is a composition containing a polymer and water.
- Waterbome polymer compositions include, but are not limited to, latexes, dispersions, microemulsions, or suspensions. Waterbome polymer compositions are stable when stored at room temperature or moderately above room temperature (e.g., about 50 to 60°C) and provide adhesion and crosslinking upon film formation when applied to a substrate. Yet, a film or coating formed with polymers of the invention may be cured at room temperature (ambient cure) or at elevated temperatures (thermal cure).
- the polymers of the invention are generally prepared as particles, particularly in a waterbome composition. 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 25 to about 500 nm. Preferred average polymer particle sizes for small particles range from about 25 to about 100 nm and more preferably from about 45 to about 80 nm. For large particles, preferred average polymer particle sizes range from about 110 to about 450 nm.
- the polymer particles generally have a spherical shape.
- the generally spherical polymeric particle may have a core portion and a shell portion.
- the core/shell polymer particles may also be prepared in a multilobe form, a peanut shell form, an acom form, or a raspberry form. It is further preferred in such particles that the core portion comprises about 20 to about 80% of the total weight of said particle and the shell portion comprises about 80 to about 20% of the total weight of the particle.
- a surfactant-containing acetoacetoxy-functional polymer (SAAP) with ammonia, a primary or secondary amine yields a surfactant-containing enamine- functional polymer of the invention.
- a polymeric (polyamino)enamine (PPAE) results from the reaction of a SAAP with a poly(alkylenimine).
- Polymeric (polyamino)enamines represent a particularly preferred group of amino-functional polymers for use in a waterbome polymer composition according to the invention.
- the SAAP may be prepared by free radical emulsion polymerization of a non- acid vinyl monomer having an acetoacetoxy functionality such as those of Formula (1 ) below with at least one non-self-polymerizing, surface-active vinyl monomer and other non-acid vinyl monomers. This affords water-based dispersion of surfactant- containing polymer particles with the polymer having pendant acetoacetoxy groups.
- a non-acid vinyl monomer is an ethylenically-unsaturated, non- carboxylic acid-containing monomer.
- a pendant acetoacetoxy group is not strictly limited to those at the termini of the polymer.
- Pendant acetoacetoxy groups also include groups attached to the polymer's backbone and available for further reaction.
- the SAAP preferably contains about 1 to about 40 weight percent acetoacetoxy-functional monomers such as those of Formula (1) below, about 0.05 to about 20 weight percent of at least one non-self-polymerizing, surface-active vinyl monomer and about 60 to about 90 weight percent of other non-acid vinyl monomers. The weight percentage is based on the total amount of monomer. More preferably, the SAAP has about 10 to about 25 weight percent acetoacetoxy monomers, about 0.1 to about 10 weight percent of at least one non-self-polymerizing, surface-active vinyl monomer and about 75 to about 90 weight percent of other vinyl monomers.
- the water-based emulsion polymerization to prepare the SAAP preferably occurs in the presence of a nonionic surfactant and an anionic surfactant.
- the nonionic surfactant may be present in amounts ranging from about 0.25 to about 5 phr, and the anionic surfactant in amounts ranging from about 0.1 to 1 phr.
- the unit "phr” defines the grams dry weight of the recited component, for example the surfactant, per 100 grams dry weight of the resin, where the "resin” includes all polymerization components excluding water. Aspects of this emulsion polymerization and preferred embodiments are discussed below.
- Any non-acid vinyl monomer having acetoacetoxy-type functionality may be used to prepare a polymer of the invention.
- preferred monomers are those of Formula (1).
- R l -CH C(R 2 )C(0)-X l -X 2 -X 3 -C(0)-CH r C(0)-R 3 (1 )
- R 1 is a hydrogen or halogen.
- R 2 is a hydrogen, halogen, C,-C 6 alkylthio group, or C,-C 6 alkyl group.
- R 3 is a C,-C 6 alkyl group.
- X 1 and X 3 are independently O, S, or a group of the formula - N(R')-, where R' is a C,-C 6 alkyl group.
- X 2 is a C 2 -C, 2 alkylene group or C 3 -C, 2 cycloalkylene group.
- the alkyl and alkylene groups described here and throughout the specification may be straight or branched groups.
- Preferred monomers of Formula (1 ) are acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoaceloxy(methyl)ethyl acrylate, acetoacetoxypropyl acrylate, allyl acetoacetate, acetoacetamidoethyl (meth)acrylate, and acetoacetoxybutyl acrylate.
- Acetoacetoxyethyl methacrylate (AAEM) represents a particularly preferred monomer of Formula (1).
- Suitable non-acid vinyl monomers which may be used, for example, include, but are not limited to, methyl acrylate; methyl methacrylate; ethyl acrylate; ethyl methacrylate; butyl acrylate; butyl methacrylate; isobutyl acrylate; isobutyl methacrylate; ethylhexyl acrylate; 2-ethylhexyl methacrylate; octyl acrylate; octyl methacrylate; iso-octyl acrylate; iso-octyl methacrylate; trimethylolpropyl triacrylate; styrene; ⁇ -methyl styrene; glycidyl methacrylate; carbodiimide methacrylate; C,-C 18 alkyl crotonates; di-n-butyl maleate; di-octylmaleate; allyl methacryl
- (meth)acrylate acrylonitrile, vinyl chloride; ethylene; vinyl ethylene carbonate; epoxy butene; 3,4-dihydroxybutene; hydroxyethyl (meth)acrylate; methacrylamide; acrylamide; butyl acrylamide; ethyl acrylamide; vinyl (mefh)acrylate; isopropenyl (meth)acrylate; cycloaliphaticepoxy (meth)acrylates; and ethylformamide.
- monomers are described in "The Brandon Worldwide Monomer Reference Guide and
- AMPS sodium 2- acrylam ⁇ do-2-methylpropane sulfonate
- other stabilizing monomers may be incorporated into the SAAP. Adding such stabilizing monomers to the polymer shell, for example, aids in preventing flocculation upon the addition of a polyalkylenimine to form a PPAE. High levels of such stabilizing monomers may create water membrane layers between polymer particles in the latex or disrupt film formation.
- AMPS is available from Pcnnwalt Corporation under the LUBRIZOL 2405 Trade name.
- Vinyl esters of the general Formula (2) represent further examples of non-acid vinyl monomers:
- R is independently hydrogen or an alkyl group of up to 12 carbon atoms.
- Vinyl ester monomers also include vinyl esters of vinyl alcohol such as the VEOVA series available from Shell Chemical Company as VEOVA 5, VEOVA 9, VEOVA 10, and VEOVA 11 products. See O.W. Smith, M.J.
- the SAAP may also incorporate nitrogen- containing, non-acid vinyl monomers known to promote wet adhesion.
- exemplary wet adhesion monomers include, for example, t-butylaminoethyl methacrylate; dimethylaminoefhyl methacrylate; diethylaminoethyl methacrylate; N,N- dimethylaminopropyl methacrylamide; 2-t-butylaminoethyl methacrylate; N,N- dimethylaminoethyl acrylate; N-(2-methacrylamido-ethyl)ethylene urea; and N-(2- methacryloyloxy-ethyl)ethylene urea.
- N-(2-methacryloyloxyethyl)ethylene urea is available from RohmTech as 50%> solution in water under the Rohamere 6852-0 trade name and as a 25% solution in water under the Rohamere 6844 trade name.
- N-(2- methacrylamido-ethyl)ethylene urea is available from Rhone-Poulenc under the WAM trade name.
- Small amounts of acid vinyl monomers may also be used to prepare an SAAP according to the invention.
- Such acid vinyl monomers include, for example, acrylic acid, mefhacrylic acid, itaconic acid, crotonic acid, and monovinyl adipate.
- Incorporating acid vinyl monomers into the SAAP may increase the viscosity of the resulting latex and may have a detrimental effect on the formation of an enamine- functional polymer according to the invention.
- these monomers are used in small amounts.
- the amount of acid vinyl monomers may range, for example, from 0 to 5 phr. Greater amounts may be used to achieve a desired effect, such as increased viscosity.
- Preparation of the SAAP reacts non-acid vinyl monomers, such as described above, with at least one non-self-polymerizable, surface-active vinyl monomer (also known as a non-self-polymerizable ethylenically-unsaturated surfactant or a reactive surfactant).
- a non-self-polymerizable surfactant monomer rather than polymerizing with itself to form a separate polymeric surfactant, is substantially (preferably completely) incorporated into the polymer of the invention.
- the surfactant becomes part of the polymer.
- Non-self-polymerizing surfactants possessing, for example, propenylphenyl or allyl groups are preferred.
- Examples include surface active monomers sold by PPG Industries, Inc., as MAZON® SAM 181 , 183, 184, 21 1 surfactants which are anionic sulfates or sulfonates and MAZON® SAM 185-187 surfactants which are nonionic surfactants.
- Other non-self-polymerizing, surface- active vinyl monomers include the macro monomers sold by Daiichi Kogyo Seiyaku under the names NIOGEN RN, AQUARON or HITENOL surfactants. These include polyoxyethylene alkyl phenyl ether compounds of the general formulae (3), (4), and (5):
- R is nonyl or octyl and n and m are preferably integers of from 15 to 50 and 15 to 40, respectively. More preferably, n ranges from 20 to 40, and m from 15 to 25.
- HITENOL RN, HITENOL HS-20 and HITENOL A- 10 products are particularly preferred non-self-polymerizing, surface-active monomers.
- Other such polymerizable surfactants include the sodium alkyl allyl sulfosuccinate sold by Henkel, under the trade name TREM LF-40 surfactant.
- the SAAP (as well as other polymers useful in the invention) may be prepared using emulsion polymerization techniques known in the art.
- the polymer may, as is known in the art, be prepared using free radical emulsion polymerization techniques which yield structured or unstructured particles.
- structured particles include, for example, core/shell particles, raspberry particles, and gradient particles.
- Chain transfer agents, initiators, reducing agents, buffers, and catalysts, known in the art of emulsion polymerization may be used to prepare the polymers.
- Exemplary chain transfer agents are butyl mercaptan, dodecyl mercaptan mercaptopropionic acid, 2-efhylhexyl 3-mercaptopropionate, n-butyl 3- mercaptopropionate, octyl mercaptan, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate, and the reactive chain transfer agents taught in U.S. Patent No. 5,247,040, incorporated here by reference.
- 2-efhylhexyl 3-mercaptopropionate represents a preferred chain transfer agent.
- Typical initiators include hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, ditertiary butyl peroxide, 2,2'- azobisisobutyronitrile, t-butyl hydroperoxide, benzoyl peroxide, and the like.
- Suitable reducing agents are those which increase the rate of polymerization and include for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof.
- Polymerization catalysts are those compounds which increase the rate of polymerization and which, in combination with the above described reducing agents, may promote decomposition of the polymerization initiator under the reaction conditions.
- Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.
- the emulsion polymerization to prepare the SAAP preferably occurs in water and in the presence of a nonionic surfactant and/or an anionic surfactant.
- Suitable nonionic surfactants include surfactants such as alkyl polyglycol ethers such as ethoxylation products of lauryl, oleyl, and stearyl alcohols; alkyl phenol polyglycol ethers such as ethoxylation products of octyl- or nonylphenol, diisopropyl phenol, and triisopropyl phenol.
- Preferred nonionic surfactants are the TERGITOL 15-S-40 and TERGITOL NP-40 surfactants available from Union Carbide.
- TERGITOL 15-S-40 surfactant (CAS # 68131-40-8) is a reaction product of a mixture of 1 1 -15 carbon, linear secondary alcohols and ethylene oxide.
- TERGITOL NP-40 surfactant is the reaction product of a nonylphenol and about 40 moles of ethylene oxide.
- Another preferred nonionic surfactant is SURFYNOL 485 surfactant available from Air Products.
- Anionic surfactants which may be used in the invention include surfactants such as alkali metal or ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulfates, phosphates, and the like.
- anionic surfactants include, for example, sodium lauryl sulfate, sodium octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, and ammonium tritertiarybutyl phenol and penta- and octa-glycol sulfonates, sulfosuccinate salts such as disodium ethoxylated nonylphenol half ester of sulfosuccinic acid, disodium n-octyldecyl sulfosuccinate, sodium dioctyl sulfosuccinate, and the like.
- AEROSOL 18 surfactant a 35% solution of N-octyldecyl sulfosuccinimate in water and AEROSOL OT-75 surfactant, a 75% solution of sodium dioctyl sulfosuccinate in water, from Cytech are preferred anionic surfactants.
- Water-dispersible and water-soluble polymers may also be employed as surfactants/stabilizers in the water-based latexes of the invention.
- Examples of such polymeric stabilizers include water-dispersible polyesters as described in U.S. Patent
- acetoacetoxy functionality in the SAAP may be present as free acetoacetoxy groups or as derivatives of those groups such as, for example, an enamine group or acetoacetamide group.
- the acetoacetoxy-functional polymer may contain both free acetoacetoxy groups and acetoacetoxy derivatives.
- Surfactant- containing enamine-functional polymers according to the invention may be prepared by reacting a SAAP with ammonia or a primary or secondary amine. Typically, the reaction stoichiometry uses at least one molar equivalent of amino hydrogen (N-H) groups to acetoacetoxy groups.
- Surfactant-containing enamine-functional polymers represent a preferred derivative of polymers of the invention.
- Enamine-functional polymers may be used as the acetoacetoxy-functional polymer in the water-based latex of the invention. In water-based latexes, the enamine functionality serves to further stabilize the acetoacetoxy-groups and protect them from hydrolysis.
- Enamine-functional polymers have been described in Moszner et al., Polymer Bulletin 32, 419-426
- Enamine-functional polymers may be prepared by reacting a polymer having acetoacetoxy groups with ammonia or a p ⁇ mary or secondary amine.
- the primary or secondary amine may be a monoamine compound or a polyamine compound.
- Preferred amines include, for example, triaminononane
- a SAAP is reacted with a poly(alkylenimine).
- a poly(alkylenimine) contains primary, secondary, and tertiary amine groups. At least a portion of the primary and secondary amine groups of the poly(alkylenimine) react with the pendant acetoacetoxy groups on the SAAP to form enamine linkages yielding a crosslinked polymeric (polyamino)enamine or PPAE.
- Poly(alkylenimines), particularly poly(ethylenimine), are known to flocculate latexes, and are actually sold for that purpose.
- the PPAE of the present invention does not flocculate, but provides a stable, waterbome polymer composition.
- a poly(alkylenimine) for use in the invention may have a weight average molecular weight of about 400 to about 750,000.
- the poly(alkylenimine) is preferably a poly(ethylenimine) (PEI) and more preferably PEI having a weight average molecular weight of about 800 to about 25,000.
- PEI compounds are commercially available from many sources and include POLYMIN poly(ethylenimine) and LUPASOL poly(ethylenimine) available from BASF
- BASF polyethylenimine product literature reports the ratio of p ⁇ mary:secondary:tertiary amine groups to be about 1 :2: 1.
- a preferred PEI, LUPASOL G35 poly(ethylenimine) has a molecular wight of 2,000 and a ratio of primary:secondary:tertiary amine groups of about 1.5: 1.4: 1.
- the reaction to form the PPAE may be accomplished by adding, with stirring, the appropriate poly(alkylenimine) to an emulsion of the SAAP.
- Sufficient poly(alkylenimine) should be used to achieve a molar ratio of amino hydrogen (N-H) groups to acetoacetoxy groups of about 0.1 to about 35, preferably a molar ratio from about 0.5 to about 20, and more preferably, from about 1 to about 5.
- the amount of poly(alkylenimine) added to the polymer having pendant acetoacetoxy groups may range from about 1 phr (grams dry weight poly(alkylenimine) to 100 grams dry weight resin) to about 30 phr and preferably from about 7 phr to about 25 phr.
- a water-based solution of the poly(alkylenimine) is preferably combined with a SAAP emulsion over about 15-30 minutes at ambient temperature.
- the reaction mixture containing the SAAP may need to be cooled before adding the poly(alkylenimine).
- the acetoacetoxy-functional, or enamine-functional polymers, (preferably a PPAE) may be present from about 5 to about 60 weight percent solids, based on the polymer's dry resin weight. More preferably, from about 25 to about 55 weight percent of the water-based composition.
- the examples below illustrate the polymer preparation and water-based compositions of the invention.
- Latexes or other water-based compositions containing small particle size polymers represent one preferred embodiment of the invention.
- latex compositions containing these small particle enamine- functional polymers have a high solids content, preferably about 25 to about 55, and more preferably, about 35 to about 55, percent solids, as well as low viscosity, preferably about 10 to about 1000 cps, and more preferably about 10 to about 200 cps.
- the reactions used to prepare the polymers and corresponding latexes of the invention produce low levels of coagulum.
- Figure 1 depicts the relationship between polymer particle size, percent solids, and viscosity of a latex of the invention. As Figure 1 shows, even with a particle size of nearly 60 nm and a 50% solids level, the latex viscosity is still less than 200 cps.
- the invention provides waterbome polymer compositions which are stable, have high solids content, but low viscosity.
- the polymer particles within the composition may be present as essentially monodispersed particles. Such compositions are particularly well-suited for coating formulations.
- the pH of a waterbome polymer composition of the invention may be adjusted and/or buffered using, for example, buffers such as sodium bicarbonate, ammonium bicarbonate, ammonium dihydrogenphosphate, an ammonium poly(mefh)acrylate, or a mixture of such buffers.
- the buffer such as ammonium bicarbonate, may generally be added to the waterbome polymer composition to adjust and/or buffer the pH of the composition.
- Waterbome polymer compositions having pH values in the range of about 7.0 to 9.2, preferably 8.4 to 9.2, may be achieved using ammonium buffers.
- Buffered compositions of the invention are particularly useful in coating formulations.
- the enamine-fucntional polymers of the invention may be used to prepare stable cationic latexes having an acidic pH from an anionic stabilized latex without precipitation or coagulation of the latex.
- a latex of the invention containing an enamine-functional polymer, such as a PPAE has a pH of about 10 or above. Adding a Bronsted acid to such a latex lowers the pH and below neutral pH forms a stable cationic latex. A wide range pH values may be achieved, even pH values as low as 0.5.
- the acid is generally added to a cooled latex. Any Bronsted acid may be used.
- mineral acids such as sulfuric acid, phosphoric acid, hydrochloric acid, etc.
- organic acids such as p-toluene sulfuric acid, acetic acid, etc.
- Cationic latexes such as these are particularly useful in coating compostions for hard to adhere to substrates (for example rusty metal surfaces).
- Exemplary coating compositions include laminate coatings, inks, textile coatings, coatings for plastic and primer coatings.
- a waterbome polymer composition of the invention may also contain other additives known in those compositions and may use other emulsion polymerization methodology.
- U.S. Patent No. 5,371,148 describes such additives and is incorporated here by reference.
- the polymers and waterbome polymer compositions of the invention are useful in a variety of coating formulations such as metal coatings, wood coatings, plastic coatings, textile coatings, cementitious coatings, paper coatings, inks, and adhesives.
- coating formulations adapted for particular uses include, but are not limited to, corrosion inhibitors, architectural coatings, concrete coatings, maintenance coatings, latex paints, industrial coatings, automotive coatings, textile back coatings, laminating inks and surface printing inks.
- the present invention relates to such coating formulations containing a waterbome polymer composition of the invention, preferably a water-based latex.
- the polymers and waterbome polymer compositions of the invention may be incorporated in those coating formulations in the same manner as known polymer latexes and used with the conventional components and or additives of such compositions.
- the coating formulations may be clear or pigmented. With their crosslinking ability, adhesion properties, and resistance properties, the water-based latexes of the invention impart new and/or improved properties to the various coating formulations.
- a coating formulation containing a polymer or waterbome polymer composition of the invention 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).
- 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 is allowed to air dry.
- a coating employing a polymer of the invention may be thermally or ambiently cured.
- the present invention relates to a shaped or formed article which has been coated with a coating formulations of the present invention.
- a coating formulation according to the invention may comprise a polymer or waterbome polymer composition of the invention, water, a solvent, a pigment (organic or inorganic) and/or other additives and fillers known in the art.
- a latex paint composition of the invention may comprise a waterbome polymer composition of the invention, a pigment and one or more additives or fillers used in latex paints.
- additives or fillers 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.
- Patent No. 5,349,026 flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; extenders; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-ski ⁇ ning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; drying agents; catalysts; crosslinking agents; or coalescing agents.
- UV absorbers ultraviolet (UV) absorbers
- UV light stabilizers tinting pigments
- extenders defoaming and antifoaming agents
- anti-settling, anti-sag and bodying agents anti-ski ⁇ ning agents
- anti-flooding and anti-floating agents fungicides and mildewcides
- corrosion inhibitors corrosion inhibitors
- thickening agents plasticizers
- reactive plasticizers drying agents
- the preferred PPAE polymer or waterbome PPAE polymer composition of the invention may be used in many of the same industries and applications where poly(alkylenimines) such as PEI are now used.
- a PPAE of the invention may be used as an adhesion promoter for binding proteins and enzymes to inert substrates, a shampoo additive to improve hair substantivity, as a dye fixative for textiles, a pigment dispersion for coatings, or a flocculant in water treatment.
- a polymer or waterbome polymer composition of the invention can be utilized alone or in conjunction with other waterbome polymers.
- Such polymers include, but are not limited to, water dispersible polymers such as polyesters, polyester-amides, cellulose esters, alkyds, polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers, polymers having pendant allyl groups such as described in U.S. Patent No. 5,539,073, styrene-butadiene polymers, vinylacetate-ethylene copolymers, and the like.
- the PPAE polymers of the invention bring a unique advantage to the final composition, in addition to their crosslinking ability, adhesion properties, and resistance properties.
- the PPAE has the ability to scavenge, via a Michael Reaction, ⁇ , ⁇ -unsaturated carbonyl-containing monomer or ⁇ , ⁇ -unsaturated electron withdrawing group- containing monomer remaining in the polymer latex.
- the PPAE scavenges residual monomers or contaminants such as ketones, aldehydes, ⁇ , ⁇ - unsaturated acids, ⁇ , ⁇ -unsaturated esters, ⁇ , ⁇ -unsaturated amides, and ⁇ , ⁇ - unsaturated nitriles. Removing these monomers can, not only eliminate the odors associated with them, but also improve health and safety when using the composition.
- the following examples are intended to illustrate, not limit, the invention.
- the examples and various coating formulations of the invention use one or more of the following materials:
- LUPASOL G35 poly(ethylenimine), 2,000 MW, sold by BASF as a 50% solution in water.
- TAMOL 1124 dispersant sold by Rohm & Haas Company sold by Rohm & Haas Company.
- SURFYNOL 104 and 104DPM products (50% Solids), sold by Air Products and Chemicals, Inc., Allentown, Pennsylvania.
- DOWICIL 75 preservative sold by Dow Chemical Company, Midland,
- OMYACARB UP a calcium carbonate extender, sold by Omya Inc., Proctor,
- EASTMAN EB and EASTMAN DB solvents sold by Eastman Chemical
- TAFIGEL PUR 45 thickener sold by King Industries, Norwalk, Connecticut.
- RHEOVIS CR2 thickener sold by Allied Colloids, Suffolk, Virginia.
- t-butylhydroperoxide was used as a 70% solution in water.
- Film gel fraction is obtained by determining the insoluble weight fraction of polymer in a dry film sample.
- Film swell ratio is obtained by determining the ratio of the insoluble polymer weight fraction swollen in the selected solvent (by weight) to dry weight of the insoluble weight fraction in a dry film sample. Average values are determined from quadruplicate measurements with acetone as the solvent.
- the procedure used was as follows: for each sample determination, a 4"x 4" 325-mesh steel screen and a metal weighing boat are baked in a vacuum oven at 120°C for 90 minutes, cooled 30 minutes over P 2 0 5 and weighed (WI and W2, respectively). After the latex film is dried the required number of days under constant temperature and humidity or baked in the oven at the specified time and temperature, a piece of the film is cut, weighed (W3), placed in the aluminum pan, and put aside. Another film sample is cut, weighed (W4), and placed in a screw cap jar with excess solvent on a shaker bath for 16 hours at constant temperature.
- the film gel is recovered by pouring the solution plus wet solids from the jar through the screen and then weighing the screen plus retained wet solids (W5). At this point, the screen plus solids and the film sample in the aluminum boat are dried in a forced air oven at 80°C overnight and then in a vacuum oven at 120°C for 3 hours and cooled for 30 minutes in a desiccator over P 2 0 5 . The samples are weighed and the vacuum portion of the baking procedure is repeated until reproducible weights are obtained for the screen plus dry solids (W6) and the film sample in the aluminum boat (W7). Calculations were made by the equations shown below:
- FGF (W6-W1)/[(W4)*[(W7-W2)/W3]]
- FSR (W5-W1)/(W6-W1)
- Model STM-l-PC which is a constant rate of elongation machine.
- Film samples are obtained by casting the sample on release paper with a 7 mil bird bar, drying the film for the desired time at the stated conditions, and cutting a dogbone-shaped thin-film sample with a 1 " wide die. The film is measured for film thickness, mounted in the tensile tester grips and tested at a crosshead speed of 1 "/minute using a 5 lb-force load cell. Ten samples are run and the five samples with the greater breaking stress are averaged for all tensile values reported according to ASTM D2370. Tensile values were calculated using Datum software from United Testing Systems, Inc., Flint, Michigan. Glass Transition:
- Blocking resistance was determined using 6 mil (wet) films on Leneta 2B opacity paper according to ASTM 4946 Test Method for Blocking Resistance of Architectural Paints using 1 psi pressure after film dried to designated times. Heated block resistance was determined in a forced air oven at 120°F with the painted surfaces face-to-face under 1 psi pressure for 30 minutes. The tests were numerically rated where a rating of 1 represents 100% pass where painted surfaces lift apart with no noise, a rating of 2 represents noise when painted surfaces are separated but no film degradation occurs, a rating of 3 represents some destruction of the painted surfaces when the two surfaces are separated and a rating of 4 represents 100% fail where the painted surfaces flow completely together and complete destruction of the films occurs upon separation.
- Print Resistance :
- Print resistance was determined using 6 mil (wet) films on Leneta 2B opacity paper according to ASTM D 2064 - 91 Test Method for Print Resistance of Architectural Paints using a 4 psi pressure placed on top of a #6 black rubber stopper which was placed on four layers of cheesecloth after film dried to designated times. Heated print resistance was determined in a forced air oven at 120°F with folded cheesecloth (as above) under 4 psi pressure for 30 minutes. The tests were numerically rated where a rating of 1 represents 100% pass with no demarcation (cloth lifts off with no print left behind), a rating of 2 represents demarcations (some impression is observed), a rating of 3 represents 100% fail (the cheesecloth impregnates the film). Scrub Resistance:
- Scrub resistance was determined following ASTM D2486 Test Method for scrub resistance of architectural coatings. The coating is applied at 7 mil wet on Scrub Test Charts Form PI 21-1 ON and allowed to dry for the specified period of time. The panel is placed in a Gardco Scrub Machine, Model D-10V, 10 g of Standardized
- Scrub Medium (abrasive type) for ASTM D2486 and D3450 is placed on the scrub brush, the panel is wet with 5 ml DI water, the test machine counter is zeroed, and the test is run at the maximum test speed on the machine. After each 400 cycles before failure, the brush is removed and 10 more g of scrub medium is added evenly on the bristles, the brush is replaced, 5 ml of DI water is placed on the panel and the test is continued. The test is stopped at 1000 cycles or failure, whichever comes first. Failure is defined as the number of cycles to remove the paint film fully in one continuous line across the width of the shim.
- Wet Adhesion Test This procedure tests the coatings adhesion to an aged, alkyd substrate under wet, scrubbing conditions.
- a ten-mil drawdown of a commercial gloss alkyd paint is made on a "Leneta" scrub panel (adhesion varies from alkyd to alkyd - a Glidden Industrial Enamel was used.)
- the alkyd film is allowed to age one week at ambient conditions, then baked at 110°F for 24 hours, and then aged at least one more week at ambient conditions.
- a seven-mil drawdown of the test paint is then made over the aged alkyd and allowed to air dry three days. (In order to differentiate between samples that pass this test, dry times may be shortened. Seven days is a common period, and occasionally 5 hours dry time is used.
- Constant temperature/humidity conditions 72°F/50%, are normally used for drying.
- the test paint is then cross-hatched with a razor and submerged in water for 30 minutes.
- the paint film is inspected for blistering and scratched with the fingernail to gauge the adhesion. While still wet, the panel is placed on a "Gardner" scrub machine.
- Ten ml of five percent "LAVATM” soap slurry are added to the film, and the nylon scrub brush (WG 2000NB) is passed over the scored paint film area. Water is added as needed to keep the paint film wet (flooded). The number of brushing cycles for initial peel and ten percent peel are noted. The number of cycles for complete removal of the film is often noted also.
- Example 1 Preparation of a Large Particle Size, Core/Shell Enamine-Containing
- an initiator charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor.
- An emulsion feed composed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOL NP- 40 (70%), 271.78 g of methyl methacrylate, 50.72 g of styrene, 350.63 g of 2- ethylhexyl acrylate, and 1.55 g of trimethylolpropane triacrylate was begun at 8.38 g/min.
- an initiator solution composed of 4.36 g of sodium persulfate dissolved in 1 12 g of water was fed at 0.466 g/min.
- a second emulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40
- this latex was similar to the latex preparation described in Example 1 except that 316.S6 g of poly(ethylenimine) (50% in water) was added in place of the ammonium hydroxide solution. Mole ratio of N-H group to acetoacetoxy group was 5.47.
- the latex was then filtered through 100 mesh wire screen. Solids level, 46.5; pH, 10; amount of dried material (100 mesh screen), 4.1 1 g; particle size (Dw), 225 nm, latex gel fraction/swell ratio 76/5.7.
- a second emulsion feed composed of 147 g of water, 12.15 g of AEROSOL 18, 12.5 g of TERGITOL NP-40 (70%), 180.88 g of styrene, 90.0 g of 2-ethylhexyl acrylate, 143.92g of acetoacetoxyethyl methacrylate, and 1.68g of the sodium 2-acrylamido-2- methylpropanesulfonate (50% in water) was fed at 8.38 g/min.
- this latex was similar to the latex preparation described in Example 1 except that 247.35 g of poly(ethylenimine) (50% in water) was added in place of the ammonium hydroxide solution. Mole ratio of N-H group to acetoacetoxy group was 4.27. The latex was then filtered through 100 mesh wire screen. Solids level, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g; particle size (Dw), 58 nm, latex gel fraction/swell ratio 62/5.6.
- poly(ethylenimine) 50% in water
- Mole ratio of N-H group to acetoacetoxy group was 4.27.
- the latex was then filtered through 100 mesh wire screen. Solids level, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g; particle size (Dw), 58 nm, latex gel fraction/swell ratio 62/5.6.
- this latex was similar to the latex preparation described in Example 1 except that 314.45g of poly(ethylenimine) (50% in water) was added in place of the ammonium hydroxide solution. Mole ratio of N-H group to acetoacetoxy group was 4.27. The latex was then filtered through 100 mesh wire screen. Solids level, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g; particle size (Dw), 70 nm, latex gel fraction/swell ratio 61/6.5.
- poly(ethylenimine) 50% in water
- Mole ratio of N-H group to acetoacetoxy group was 4.27.
- the latex was then filtered through 100 mesh wire screen. Solids level, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g; particle size (Dw), 70 nm, latex gel fraction/swell ratio 61/6.5.
- an initiator charge composed of 7.70 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor.
- An emulsion feed composed of 355 g of water, 1 1.7 g of TREM LF-40, 10.21 g of TERGITOL NP-40 (70%), 271.78 g of methyl methacrylate, 50.72 g of styrene, 350.63 g of 2-ethylhexyl acrylate, and 1.55 g of trimethylolpropane triacrylate was begun at 8.38 g/min.
- an initiator solution composed of 4.36 g of sodium persulfate dissolved in 1 12 g of water was fed at 0.5.36 g/min.
- a second emulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40 (70%), 21 1.03 g of styrene, 80.0 g of 2-ethylhexyl acrylate, 123.77g of acetoacetoxyethyl methacrylate, and 1.68g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 8.38 g/min.
- Example 8 Preparation of a Small Particle Size, Unstructured Enamine-Containing Waterbome Polymer
- an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water was fed at 0.536 g/min.
- TERGITOL NP-40 (70%), 7.1 g of sodium carbonate, 5.01 g of methyl methacrylate, 28.95 g of styrene, 17.54 g of methyl methacrylate, 33.78 g of 2-ethylhexyl acrylate, and 0.16 g of trimethylolpropane triacrylate.
- a nitrogen purge was begun, then the contents of the reactor brought up to 80°C at 400 rpm. After reaching 80 C C, an initiator solution composed of 5.28 g of sodium persulfate dissolved in 20.88 g of water was added to the reactor.
- a second emulsion feed composed of 205 g of water, 15.73 g of AEROSOL 18, 6.12 g of TERGITOL NP-40 (70%), 251.8 g of styrene, 175.1 g of 2- ethylhexyl acrylate, 94.94 g of acetoacetoxyethyl methacrylate, 47.92 g of allyl methacrylate, 23.99 g of dimethylaminoethyl methacrylate, and 4.79 g of 2-ethylhexyl 3-mercaptopropionate was started at 8 g/minute.
- an initiator solution composed of 7.05 g of sodium persulfate dissolved in 43.55 g of water was added to the reactor.
- An initiator solution composed of 4.36 g of sodium persulfate dissolved in 112 g of water was started at 0.466 g/min.
- an emulsion feed composed of 355 g of water, 19.65 g of AEROSOL 18, 20.19 g of TERGITOL NP-40 (70%), 224.84 g of methyl methacrylate, 221.95 g of styrene, 224.4 g of 2-ethylhexyl acrylate, and 2.06 g of trimethylolpropane triacrylate was begun at 5.24 g/min.
- a second emulsion feed composed of 147 g of water, 12.15 g of AEROSOL 18, 12.48 g of
- TERGITOL NP-40 (70%), 168.6 g of styrene, 80 g of 2-ethylhexyl acrylate, and 167.9 g of acetoacetoxyethyl methacrylate was fed at 8.4 g/min.
- an initiator solution composed of 1.34 g of sodium formaldehyde sulfoxylate and 1.34 g of t-butylhydroperoxide dissolved in 40.2 g of water was charged to the reactor and heating continued for 30 minutes.
- the emulsion was cooled to less than 35°C, and 283.84 g of polyethylenimine (50%) were pumped in over 15 minutes.
- Example 12 Preparation of a Large Particle Size, Unstructured Acetoacetoxy- Containing Waterbome Polymer
- an initiator solution composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water was added to the reactor.
- An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water was fed into the reactor at 0.16 g/min.
- TERGITOL NP-40 (100%), 186.6 g of styrene, 115.63 g of 2-ethylhexyl acrylate, 40.8 lg of acetoacetoxyethyl methacrylate, and 0.52g of sodium 2-acrylamido-2- methylpropanesulfonate (50% in water) was fed into the reactor at 1.72 g/min. Five minutes after the feeds were completed, then an initiator solution composed of 0.4 g of sodium persulfate and 0.4g of sodium metabisulfite dissolved in 12 g of water was added to the reactor and heating continued for 30 minutes. The latex was then filtered through 100 mesh wire screen.
- Example 13 Preparation of a Large Particle Size, Unstructured Acetoacetoxy- Containing Waterbome Polymer To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, and subsurface feed tube were added 351 g of water, 0.76 g of AEROSOL OT, 5.11 g of TERGITOL NP-40 (100%), 2.05 g of sodium carbonate, 3.58 g of styrene, 1 1.63 g of 2-ethylhexyl acrylate, and 2.68g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water).
- a nitrogen purge was begun, then the contents of the reactor brought up to 80°C at 400 rpm. After reaching 80°C, an initiator solution composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water was added to the reactor. An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water was fed into the reactor at 0.16 g/min. Ten minutes after the initiator feed was started, a monomer feed composed of 4.10 g of AEROSOL OT (75%), 88.02 g of styrene, 221.06 g of 2-ethylhexyl acrylate, 51.01g of acetoacetoxyethyl methacrylate, and
- Solids level 47.6; amount of dried material (100 mesh screen), 0.10 g; particle size (Dw), 122 nm; Tg of Polymer, -28 °C.
- Example 14 Preparation of a Large Particle Size, Unstructured Acetoacetoxy- Containing Waterbome Polymer
- a 1000 mL resin kettle equipped with a condenser, nitrogen purge, and subsurface feed tube were added 294 g of water, 1.34 g of TREM LF-40, 1.79 g of TERGITOL NP-40 (100%), 2.044 g of sodium carbonate, 12.71 g of styrene, 3.84 g of isooctyl acrylate, and 0.014 g of sodium 2-acrylamido-2-methylpropanesulfonate (50%) in water).
- a nitrogen purge was begun, then the contents of the reactor brought up to 80°C at 400 rpm.
- an initiator solution composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water was added to the reactor.
- An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water was fed into the reactor at 0.16 g/min.
- an emulsion feed composed of 120 g of water, 9.94 g of AEROSOL 18, 7.16 g of TERGITOL NP-40 (100%), 241.47 g of styrene, 73.02 g of isooctyl acrylate, 25.61 g of acetoacetoxyethyl methacrylate, and 0.52g of sodium 2-acrylamido-2- methylpropanesulfonate (50% in water) was fed into the reactor at 1.72 g/min.
- an initiator solution of 0.72 g of sodium formaldehyde sulfoxylate and 1.03 g of t-butylhydroperoxide dissolved in 12 g of water was added to the reactor.
- the latex was then filtered through 100 mesh wire screen. Solids level, 43.8; amount of dried material (100 mesh screen); 3.3 g; pH, 7.4; particle size (Dw), 151 nm; Tg of Polymer, 16°C.
- Example 15 Preparation of a Large Particle Size, Core/Shell Amine-Containing Waterbome Polymer
- an initiator solution composed of 2.31 g of sodium persulfate dissolved in 13.06 g of water was added to the reactor.
- An initiator solution composed of 1.31 g of sodium persulfate dissolved in 34 g of water was started at 0.54 g/min.
- an emulsion feed composed of 106 g of water, 3.51 g of TREM LF-40, 3.06 g of TERGITOL NP-40 (70%), 83.23 g of methyl methacrylate, 7.44 g of styrene, 105.91 g of 2-ethylhexyl acrylate, and 0.619 g of trimethylolpropane triacrylate was begun at 8.38 g/min. After the first emulsion feed was completed, the feed lines were washed with 80 g of water, and the temperature held at 80°C for 30 minutes.
- an initiator solution of 0.40 g of sodium formaldehyde sulfoxylate and 0.40 g of t- butylhydroperoxide dissolved in 12.1 g of water was added to the reactor. .
- the emulsion was cooled to less than 35 °C, and 69.51 g of polyethylenimine (50%) were pumped in over 15 minutes.
- the latex was then filtered through 100 mesh wire screen. Solids level, 46.6; amount of dried material (100 mesh screen), 0.15 g; particle size (Dw), 167 nm; Tg, 5 °C.
- Example 16 Preparation of a Large Particle Size, Core/Shell Amine-Containing Waterbome Polymer
- an initiator solution composed of 7.0 g of sodium 5 persulfate dissolved in 43.6 g of water was added to the reactor.
- An initiator solution composed of 4.36 g of sodium persulfate dissolved in 122 g of water was started at 0.54 g/min.
- an emulsion feed composed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOL NP-40 (70%), 399.3 g of methyl methacrylate, 24.78 g of styrene, 291.2 g of 2-ethylhexyl acrylate, and 2.06 g of trimethylolpropane triacrylate was begun at 8.38 g/min. After the first emulsion feed was completed, the feed lines were washed with 80 g of water, and the temperature held at 80°C for 30 minutes.
- an initiator solution of 1.34 g of sodium formaldehyde sulfoxylate and 1.34 g of t- butylhydroperoxide dissolved in 40.2 g of water was added to the reactor. .
- the emulsion was cooled to less than 35°C, and 121 g of polyethylenimine (50%) were pumped in over 15 minutes.
- the latex was then filtered through 100 mesh wire screen. Solids level, 46.6; amount of dried material (100 mesh screen), 25 g; particle size (Dw), 450 nm; Tg, 14°C; pH, 10.4
- Example 17 Preparation of a Large Particle Size, Core/Shell Allyl- and Acetoacetoxy-Containing Waterbome Polymer
- an initiator solution composed of 6.16 g of sodium persulfate dissolved in 34.84 g of water was added to the reactor.
- An initiator solution composed of 3.48 g of sodium persulfate dissolved in 89.8 g of water was fed into the reactor at 0.336 g/min.
- an emulsion feed composed of 210.4 g of water, 2.75 g of AEROSOL OT, 5.72 g of TERGITOL 15-S-40 (100%), 95.21 g of methyl methacrylate, 157.23 g of styrene, 183.02 g of 2-ethylhexyl acrylate, and 1.31 g of trimethylolpropane triacrylate was begun at 5.25 g/min. After the first emulsion feed was completed, the lines were rinsed with 60g of water, and heating continued. After 25 minutes, a second emulsion feed composed of 138 g of water, 8.74 g of
- Example 18 Preparation of a Small Particle Size, Core/Shell Amine-Containing Waterbome
- an initiator solution composed of 6.16 g of sodium persulfate dissolved in 34.84 g of water was added to the reactor.
- An initiator solution composed of 2.08 g of sodium persulfate dissolved in 53.6 g of water was started at 0.336 g/min.
- an emulsion feed composed of 158.4 g of water, 15.72 g of AEROSOL 18, 11.00 g of TERGITOL 15-S-40 (100%), 110.4 g of methyl methacrylate, 148.7 g of styrene, 111.52 g of 2-ethylhexyl acrylate, and 1.12 g of trimethylolpropane triacrylate was begun at 5.24 g/min. After the first emulsion feed was completed, the feed lines were washed with 80 g of water, and the temperature held at 80°C for 30 minutes.
- the reactor was then cooled to 65 °C, and an initiator solution of 2.74 g of sodium formaldehyde sulfoxylate dissolved in 16 g of water, and 5.05 g of a catalyst solution composed of 0.5% iron (II) sulfate chelated with ethylenediamine tetracetic acid were added to the reactor.
- a pigment grind was prepared using a Premier disperser, as below, and a portion of the grind was used to letdown each specified paint.
- Example 20 Preparation of a Pigmented Coating Formulation using Latex from Example 17
- RHEOVIS CR2 thickener 24.26 (60% aqueous by weight)
- Example 21 Preparation of a Small Particle Size, Core/Shell Acetoacetoxy-Containing Waterbome Polymer
- an initiator solution composed of 6.16 g of ammonium persulfate dissolved in 34.84 g of water was added to the reactor.
- An initiator solution composed of 2.08 g of ammonium persulfate dissolved in 53.6 g of water was started at 0.336 g/min.
- an emulsion feed composed of 153.6 g of water, 15.72 g of AEROSOL 18, 15.72 g of TERGITOL NP-40 (70%), 110.4 g of methyl methacrylate, 148.7 g of styrene, 111.52 g of 2-ethylhexyl acrylate, and 1.12 g of trimethylolpropane triacrylate was begun at 5.24 g/min. After the first emulsion feed was completed; the feed lines were washed with 80 g of water, and the temperature held at 80 °C for 30 minutes.
- the reactor was then cooled to 65°C, and an initiator solution of 2.74 g of sodium formaldehyde sulfoxylate dissolved in 16 g of water, and 5.05 g of a catalyst solution composed of 0.5%» iron (II) sulfate chelated with ethylenediamine tetracetic acid were added to the reactor.
- a second emulsion feed composed of 138.4 g of water, 9.72 g of AEROSOL 18, 9.98 g of TERGITOL NP-40 (70%), 191.90 g of styrene, 45.6 g of methyl methacrylate,
- Example 22 Preparation of a Small Particle Size, Core/Shell Amine-Containing Waterbome Polymer
- a 400 mL resin kettle equipped with a condenser, nitrogen purge, and subsurface feed tube were added 900 g of water, 49 g of HITENOL HS-20, 1.93 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 32.67 g of methyl methacrylate, 44 g of styrene, 33 g of 2- ethylhexyl acrylate, and 0.33 g of trimethylolpropane triacrylate.
- a nitrogen purge was begun, then the contents of the reactor brought up to 80°C at 400 rpm.
- an initiator solution composed of 7.70 g of sodium persulfate dissolved in 43.55 g of water was added to the reactor.
- An initiator solution composed of 2.61 g of sodium persulfate dissolved in 67 g of water was started at 0.42 g/min.
- an emulsion feed composed of 192 g of water, 19.65 g of AEROSOL 18, 19.65 g of TERGITOL NP-40 (70%), 138.01 g of methyl methacrylate, 185.88 g of styrene, 139.41 g of 2-ethylhexyl acrylate, and 1.394 g of trimethylolpropane triacrylate was begun at 6.56 g/min. After the first emulsion feed was completed, the feed lines were washed with 80 g of water, and the temperature held at 80°C for 30 minutes.
- the reactor was then cooled to 65 °C, and an initiator solution of 3.42 g of sodium formaldehyde sulfoxylate dissolved in 20 g of water, and 6.31 g of a catalyst solution composed of 0.5% iron (II) sulfate chelated with ethylenediamine tetracetic acid were added to the reactor.
- an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water was fed at 0.536 g/min.
- Example 23 The monomer compositions were the same as described in Example 23.
- the process was similar to that described in Example 23 except for solid levels adjustments, surfactant changes, levels of poly(efhylenimine) and process changes described in Table 6.
- Figure 1 illustrates the relationship between polymer particle size, percent solids, and viscosity of these latexes.
- a latex according to the invention having a small polymer particle size of nearly 60 nm and a 50% solids level, still possesses a latex viscosity of less than 200 cps.
- PEI was added with stirring into the latex at 60 °C. b. Used 38.8g of TREM LF-40 as the reactive surfactant instead of HITENOL HS-20 c. Used 31.7g of ammonium hydroxide solution (28%> active in water) in place of PEI.
- Example 36 Preparation of a Small Particle Size, Unstructured Amine-Containing Waterbome Polymer
- an initiator solution composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water was fed at 0.536 g/min.
- the monomer compositions were the same as described in Example 36.
- the process was similar to that described in Example 36 except for solid levels adjustments, surfactant changes, levels of poly(ethylenimine) and process changes described in Table 7.
- Clear films were prepared using the latexes of Examples 24, 25, 27, and 28. Clear films were cast on release paper and cured ambiently for specified periods of time in the CTH room or cured for 30 minutes in a forced air oven at 120°C. The film tensile properties, film gel fraction (FGF), film swell ratio (FSR), and volatile content were determined. The results are shown in Table 8 below. The changes observed in ambient versus thermal (120°C) curving demonstrate the curing behavior of the films.
- Three AAEM acetoacetoxy-based latexes having average residual level of ethyl acrylate was 50 ppm, and the amount of acetone (from hydrolysis of AAEM during polymerization) detected in the latex was 0.13%.
- Samples were prepared by blending each latex with a PPAE latex (3 parts latex to 1 part PPAE latex).
- the PPAE latex contained no ethyl acrylate as a base monomer and 0.08% acetone.
- the amount of detectable ethyl acrylate and acetone in all three samples was 2 ppm (theoretical: 37 ppm) and the amount of detectable acetone, 0.006% (theoretical 0.1 1%), respectively.
- Example 47 Comparative: Preparation of latex described in European Patent Application, 0 634 425 Al, Example 10 Latex B (Composition: Core: Butyl Acrylate/Styrene/Di vinyl Benzene/Methacrylic Acid; 3/91.6/4.4/1 Shell: Butyl Acrylate/ Acetoacetoxyethyl Methacrylate/Methacrylic Acid; 83/10/7)
- an initiator solution composed of 1.278 g of sodium persulfate dissolved in 32.7 g of water was fed at 0.466 g/min.
- the reactor was cooled to 75 °C, and a second feed composed of 0.21 g of AEROSOL OT (75%), 0.21 g of TERGITOL 15-S-40 (70%), 149.32 g of butyl acrylate, 17.99 g of acetoacetoxyethyl methacrylate, and 12.59 of the methacrylic acid was fed at 2.0 g/min.
- the reactor was cooled to 65 °C, and 0.6 g of a 0.5% Fe(II) sulfate solution complexed with EDTA, and 0.39 g of isoascorbic acid dissolved in 6 g of water were charged to the reactor.
- Example 48 (Comparative'): Attempted Functionalization of Latex from Example 47 with Polyethylenimine using the process described in Example 10, Latex B, European Patent Application, 0 634 425 Al
- Example 46 To 104 g of the latex from Example 46 was successively added while stirring the latex at room temperature 8.93 g of butyl CELLOSOLVE, (available from Union Carbide, Houston, Texas), 2.98 g of butyl CARBITOL (available from Union Carbide, Houston, Texas), and 0.37 g of polyethylenimine (PEI, 50% in water). The latex began to coagulate. After adding a total of 0.97 g of polyethylenimine (PEI, 50% in water), the latex had completely coagulated forming a solid mass.
- butyl CELLOSOLVE available from Union Carbide, Houston, Texas
- butyl CARBITOL available from Union Carbide, Houston, Texas
- PEI polyethylenimine
- Example 49 Preparation of a Small Particle Size, Core/Shell Enamine-Containing Waterbome Polymer
- an initiator charge composed of 7.54 g of sodium persulfate dissolved in 43.6 g of water was added to the reactor.
- An emulsion feed composed of 198 g of water, 19.65 g of AEROSOL 18, 13.8 g of TERGITOL 15-S-40, 134.8 g of methyl methacrylate, 185.9 g of styrene, 139.4 g of 2-ethylhexyl acrylate, and 4.6 g of trimethylolpropane triacrylate was begun at 8.38 g/min.
- an initiator solution composed of 4.26 g of sodium persulfate dissolved in 109 g of water was fed at 0.466 g/min.
- a second emulsion feed composed of 173 g of water, 12.15 g of AEROSOL 18, 8.7 g of TERGITOL 15-S-40, 239.4 g of styrene, 54.1 g of methyl methacrylate, 179.9 g of 2-ethylhexyl acrylate, 119.9 g of acetoacetoxyethyl methacrylate, and 11.8 g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 8.38 g/min.
- Tafigel PUR 45 Solution 10.0 Adjust viscosity to approx 85 KU with the following CR2 Thickener 44.7 62.0
- Example 51 Preparation of Small Core/shell Amine- functional Particle.
- an initiator charge composed of 6.0 g of sodium persulfate dissolved in 34.84 g of water was added to the reactor.
- An emulsion feed composed of 197.2 g of water, 15.72 g of AEROSOL 18, 16.18 g of TERGITOL 15-S-40 (70% in water), 107.81 g of ethyl methacrylate, 148.70 g of styrene, 111.53 g of 2-ethylhexyl acrylate, and 3.72 of trimethylolpropane triacrylate was begun at 5.248 /min.
- an initiator solution composed of 3.41 g of sodium persulfate dissolved in 87.2 g of water was fed at 0.336 g/min. After the first emulsion feed as completed, the feed
- SUBSTITUTE SHEET (RULE 26 ⁇ line was washed with 20 g of water and the eaction was held at 80°C for 30 minutes. Then a second emulsion feed composed of 135.2 g of water, 9.72 g of AEROSOL 18, 10.28 g of TERGITOL 15-S-40 (68% in water), 191.90 g of styrene, 43.25 g of methyl methacrylate, 143.93 g of 2-ethylhexyl acrylate, 95.95 g of acetoacetoxyethyl methacrylate, and 9.45 g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 5.25 /min.
- Example 52 Addition of 10% Sulfuric Acid to Example 51 Latex to Make a Cationic System.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP54278897A JP3727663B2 (en) | 1996-05-28 | 1997-05-28 | Surfactant-containing acetoacetoxy functional and enamine functional polymers |
EP97927732A EP0902800B1 (en) | 1996-05-28 | 1997-05-28 | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
AU32122/97A AU729319B2 (en) | 1996-05-28 | 1997-05-28 | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
BR9709396A BR9709396A (en) | 1996-05-28 | 1997-05-28 | Polymer aqueous polymer composition coating formulation and process for preparing a polymer |
DE69715404T DE69715404T2 (en) | 1996-05-28 | 1997-05-28 | SURFACE-ACTIVE AGENT-CONTAINING ACETOACETOXY FUNCTIONAL AND ENAMINE FUNCTIONAL POLYMERS |
CA002255702A CA2255702C (en) | 1996-05-28 | 1997-05-28 | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1842496P | 1996-05-28 | 1996-05-28 | |
US1842396P | 1996-05-28 | 1996-05-28 | |
US60/018,423 | 1996-05-28 | ||
US60/018,424 | 1996-05-28 | ||
US2844496P | 1996-10-10 | 1996-10-10 | |
US60/028,444 | 1996-10-10 | ||
US08/861,433 | 1997-05-21 | ||
US08/861,433 US6028155A (en) | 1997-05-21 | 1997-05-21 | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
Publications (1)
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WO1997045468A1 true WO1997045468A1 (en) | 1997-12-04 |
Family
ID=27486751
Family Applications (1)
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---|---|---|---|
PCT/US1997/008808 WO1997045468A1 (en) | 1996-05-28 | 1997-05-28 | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
Country Status (9)
Country | Link |
---|---|
US (1) | US6297328B1 (en) |
EP (1) | EP0902800B1 (en) |
JP (1) | JP3727663B2 (en) |
CN (1) | CN1226260A (en) |
AU (1) | AU729319B2 (en) |
CA (1) | CA2255702C (en) |
DE (1) | DE69715404T2 (en) |
ES (1) | ES2179349T3 (en) |
WO (1) | WO1997045468A1 (en) |
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- 1997-05-28 WO PCT/US1997/008808 patent/WO1997045468A1/en not_active Application Discontinuation
- 1997-05-28 EP EP97927732A patent/EP0902800B1/en not_active Expired - Lifetime
- 1997-05-28 CA CA002255702A patent/CA2255702C/en not_active Expired - Fee Related
- 1997-05-28 ES ES97927732T patent/ES2179349T3/en not_active Expired - Lifetime
- 1997-05-28 DE DE69715404T patent/DE69715404T2/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
JP2002502442A (en) | 2002-01-22 |
AU729319B2 (en) | 2001-02-01 |
EP0902800A1 (en) | 1999-03-24 |
EP0902800B1 (en) | 2002-09-11 |
JP3727663B2 (en) | 2005-12-14 |
US6297328B1 (en) | 2001-10-02 |
CN1226260A (en) | 1999-08-18 |
CA2255702A1 (en) | 1997-12-04 |
ES2179349T3 (en) | 2003-01-16 |
DE69715404T2 (en) | 2003-01-09 |
CA2255702C (en) | 2003-06-17 |
DE69715404D1 (en) | 2002-10-17 |
AU3212297A (en) | 1998-01-05 |
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