Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/36—Oxygen or sulfur atoms
  • C07D207/40—2,5-Pyrrolidine-diones
  • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
  • C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
  • C07C275/48—Y being a hydrogen or a carbon atom
  • C07C275/50—Y being a hydrogen or an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
  • C07C275/48—Y being a hydrogen or a carbon atom
  • C07C275/52—Y being a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
  • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
  • C07D207/456—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/32—One oxygen atom
• • 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
  • C08F22/00—Homopolymers and 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/36—Amides or imides
  • C08F22/38—Amides
• • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/22—Esters containing nitrogen
• • 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
  • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
  • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

• This invention relates to ethylenically unsaturated polymerizable monomers which are particularly suitable for use as wet adhesion promoters and in the preparation of self- crosslinking polymers More specifically, the polymerizable monomers of the present invention are useful to promote adhesion in polymers and copolymers, and especially in aqueous emulsion copolymer latices which are used to prepare latex paints, as well as in the preparation of self-crosslinking polymers for coating systems
• wet adhesion is used in the paint industry to describe the ability of a paint to retain its adhesive bond to a substrate under wet or high humidity conditions While oil-based systems are known to retain their adhesive properties under wet or humid conditions, the tendency of many water based coatings (i.e., latices) to lose their adhesive properties when wet has limited the usefulness of such coatings.
• the wet adhesion deficiency of latex paints also makes surfaces painted with such paints less scrub resistant than those surfaces painted with organic solvent based paints See S M Kabanis and G Chip, “Polymer and Paint Properties Affecting Wet Adhesion," Journal of Coatings Technology. 53(682), 57-64 (November 1981 )
• Latex-containing surface coatings and coating compositions having superior wet adhesion properties may therefore be produced by including in the monomer system one or a mixture of these new functional monomers
• the monomers of this invention have been found to be especially useful in water-based latex-containing paints
• Self-crosslinking polymers are distinguished from crosslmkable polymers in that the latter contain functionality such as a carboxyl group which can only be crosslmkable by the addition of an external crosslinker to the polymer emulsion or solution
• a typical crosslmkable system is a poly(carboxyl functional) polymer crosslinked with a polyepoxy crosslinker
• self-crosslinking polymers contain reactive functionalities which allow these polymers to self-crosslink without the need for an external crosslmking agent.
• Certain self-crosslmkable polymerizable monomers are generally described, for example, in U.S Patents 4577031 , 4596850, 4622374 and 5235016, and EP-A-0629672, all of which are incorporated by reference herein for all purposes as if fuly set forth
• the advantages of the self-crosslinking polymer systems include their simplicity, economy, and particularly their efficiency.
• a further disadvantage is that if the monomers are based on formaldehyde, the resulting polymers release formaldehyde during curing of the polymer and coatings derived therefrom
• monomers which can be used to form self-crosslinking polymers which polymers can be employed either in solution or emulsion form, for example, as coatings, binders or adhesives
• Self-crosslinking properties can be imparted to latex-based polymers and coatings produced from such polymers by incorporating into the monomer system, from which the polymers are produced, one or more of the present invention's self- crosslmking monomers
• a unique advantage of the present invention's monomers is that they can be made from inexpensive and readily obtainable raw materials including urea, common dicarboxylic acids and anhydrides, and appropriate hydroxy and ammo functional coreactants
• each R 1 is individually an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms
• each R 2 is individually hydrogen or an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms
• each R 3 is individually an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms
• each R 4 is individually hydrogen or a methyl group wherein m is an integer of from 1 to 4 wherein ml is 0 or an integer of from 1 to 4 wherein n is an integer of from 1 to 8 wherein p is 1 or 2, and wherein q is an integer of from 1 to 4, with the proviso that, when Y is -CH 2 -CH 2 -, then A is a group as defined above which contains ethylenic unsaturation.
• novel polymerizable monomers of the present invention are capable of polymeriza ⁇ tion through their double bond(s).
• novel monomers of the invention are useful as components of monomer systems, particularly free-radically polymerizable monomer systems, especially those used in forming aqueous emulsion polymers and self-crosslinking polymers for paint, coatings and adhesives.
• the invention includes polymers prepared from ethylenically unsaturated monomers, at least one of which is a compound of the Formula (I), and compositions comprising such polymers, especially acrylic, vinyl, vinyl-acrylic, and styrene-acryhc latex paints comprising polymers made from the novel polymerizable monomers of this invention.
• the present invention provides a method of enhancing the adhesion/wet adhesion of aqueous polymer systems by incorporating the novel urea functional monomers of the present invention in the precursor monomer mixtures. More specifically, the present invention provides a method for enhancing the wet adhesion properties of a latex polymer dervied from the addition polymerization of an ethylencially unsaturated monomer system, by incorporating into the ethylenically unsaturated monomer system, prior to polymerization, one or more compounds of the formula (I).
• the present invention further provides a method for enhancing the wet adhesion properties of a latex polymer system by mixing into such latex polymer system a polymer of one or more ethylenically unsaturated monomers, wherein at least one of the ethylenically unsaturated monomers is a compound of the formula (I).
• the present invention also provides a method for incorporating self-crosslinking functionality into polymers derived from the addition polymerization of an ethylencially unsaturated monomer system, by incorporating into the ethylenically unsaturated monomer system, prior to polymerization, one or more compounds of the formula (I).
• the present invention relates most broadly to urea/ureido functional monomers of the general Formula (I) shown above
• the presence of the non-cyclic ureas adjacent to the carbonyl groups additionally alters the reactivity profile of these monomers.
• Suitable cyclhc imides include N-carbamylmaleimide (NCMI), N-carbamylsuccmimide (NCSI), N-carbamylcitraconimide (NCCI), N-carbamylitaconimide (NCII), N- carbamyltetrahydrophthalimide (NC-THPI), N-carbamyl-endo/exo-norbornene dicarboximide (NC-NDI) and N-carbamyl-endo/exo-3,6-epoxy-tetrahydrophthal ⁇ m ⁇ de (NC-ETHPI), which compounds have the formulae indicated below
• the monomers of the present invention are prepared by reacting NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI with hydroxyfunctional and/or aminofunctional compounds
• the acrylated monomers are prepared by reacting NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI with hydroxyalkyl acrylates or methacrylates, preferably in essentially stoichiometric quantities, at a temperature ranging from about 20 C to 150 r C Preferably, the temperature ranges from about 25°C to about 100°C
• suitable hydroxyalkyl acrylates and methacrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and ethoxylated and propoxylated acrylic and methacrylic acid, and the like.
• a non-reactive solvent may be employed.
• suitable non-reactive solvents include acetonitrile, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, aromatic hydrocarbons such as toluene and xylene, and carboxylic acids such as acetic acid, propnonic acid, and the like
• the reaction may optionally be carried out in the presence of other ethylenically unsaturated comonomers such as methyl methacrylate, methacrylic acid, styrene and mixtures thereof.
• ethylenically unsaturated comonomers such as methyl methacrylate, methacrylic acid, styrene and mixtures thereof.
• a catalyst is not necessary for the reaction but, if desired, a catalyst may be added to accelerate the reaction.
• Suitable catalysts include ZnCI 2 , Zn(OCOCH 3 ) 2 , FeCI 3 , cobalt acetate, chelates of transition metal ions with ⁇ , ⁇ -d ⁇ ketones and ketoesters, tin salts such as SnCI 2 , SnCI 4 , Sn0 2 and tin based urethane catalysts such as dibutyltin dilaurate, tetrabutyldiacetoxy- stannoxane, dimethyltm dilaurate, stannous octoate and dibutyltin oxide
• the preferred catalysts are the zinc and tin compounds.
• the amount of catalyst generally used is 5.0 mole percent or less based on NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI
• the range of catalyst when used, is from about 0.1 to 1.0 mole%
• suitable inhibitors include hydroquinone, the methyl ether of hydroquinone, di-tert-butyl catechol, di-tert-butyl phenol, phenothiazene, etc
• the total inhibitor concentration is typically in the range from about 100 to 2000 ppm.
• the preferred range of radical inhibitor is from about 200 to 250 ppm.
• the preferred inhibitors are methyl ether of hydroquinone and hydroquinone
• the cyclic urea derivatives of hydroxyalkylethyleneurea, hydroxyalkylpropyleneurea, aminoalkylethyleneurea, aminoalkylpropyleneurea, ethylene urea and propylene urea are prepared by reacting NCMI, NCSI, NCCI, NCII, NC-THPI. NC-NDI or NC-ETHPI with hydroxyalkylethyleneurea, hydroxyalkylpropyleneurea, aminoalkylethyleneurea, aminoalkyl- propyleneurea, ethylene urea or propylene urea, preferably in essentially stoichiometric amounts.
• the reaction with the various N-carbamyl imides can produce varying amounts of ring-opened products resulting from the attack of the ureido NH on the imide carbonyl. These products are also effective as monomers hereunder.
• the reaction is preferably carried out in the temperature range of 20°C to 150°C, more preferably in the range of 25°C to 100°C.
• the reaction with aminoalkylethyleneurea is best carried out in the 20°-50°C range to avoid by-product formation.
• the reaction is preferably carried out in the presence of one or more of the solvents and catalysts disclosed above for the acrylated monomers.
• Suitable hydroxyalkylalkyleneureas and aminoalkylalkyleneureas include hydroxyethyl- ethyleneurea, hydroxyethylpropyleneurea, aminoethylethyleneurea and ammoethylpropylene- urea Depending on the reaction conditions and the catalyst employed, a mixture of cis and trans derivatives can be obtained.
• a solvent is not necessary for the reaction, but if desired, nonreactive inert solvents such as toluene, xylene, and the like may be employed.
• the allyl and methallyl derivatives are prepared by reacting NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI with the corresponding allylic alcohols or amines under conditions described above for the acrylic and methacrylic derivatives.
• suitable allylic alcohols and amines include allyl alcohol, methallyl alcohol, allylamme, methallylamine, diallylamme and dimethallylamme. Again, the reaction of amines should be conducted at lower temperatures to avoid by-product formation.
• the vinyl ether and vinyl ester derivatives are similarly prepared by reacting NCMI, NCSI, NCCI , NCII. NC-THPI, NC-NDI or NC-ETHPI with vinyl alcohols or vinyl ester alcohols.
• suitable vinyl alcohols include ethylene glycol monovinyl ether, propylene glycol monovinyl ether, polyethylene glycol monovinyl ether and the like.
• suitable vinyl ester alcohols include vinyl esters of lactic acid and 3-hydroxyprop ⁇ onic acid.
• the alkyl ester and amide derivatives are likewise prepared by reacting NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI with alcohols such as methanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, phenol, octanol, octadecanol and dodecanol; or various primary or secondary amines.
• alcohols such as methanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, phenol, octanol, octadecanol and dodecanol; or various primary or secondary amines.
• alcohols such as methanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, phenol, octano
• the trans isomers of the monomers of this invention can also be prepared by isome ⁇ zing the corresponding cis isomers by heating in the presence of catalysts including, for example, hydrochloric acid, sulfu ⁇ c acid, aluminum chloride and pyridine, preferably in a polar organic solvent such as acetonitrile, 1 ,2-d ⁇ methoxyethane, and the like.
• catalysts including, for example, hydrochloric acid, sulfu ⁇ c acid, aluminum chloride and pyridine, preferably in a polar organic solvent such as acetonitrile, 1 ,2-d ⁇ methoxyethane, and the like.
• a preferred method for preparing the maleurate monomers is a one-pot procedure, wherein urea and maleic anhydride are reacted in a non-reactive polar organic solvent including, for example, acetonitrile, methyl ethylketone, acetic acid and acetone.
• the preferable non-reactive polar organic solvents are acetonitrile and acetic acid, more preferably acetic acid
• the reaction of urea and maleic anhydride in the non-reactive polar organic solvent, acetic acid is conducted at 50°-100°C, preferably 60°-80°C, to form the maleunc acid intermediate.
• the reaction is typically complete in about 4-10 hours depending on the reaction temperature employed
• a dehydrating agent is then added to the reaction mixture which is heated at 50 ⁇ -100°C, preferably 60 - 80°C, for another 2 to 4 hours to cyclize the maleunc acid to NCMI
• Suitable dehydrating agents include, for example, acetic anhydride, propnonic anhydride and butyric anhydride
• the resulting solution of NCMI is then reacted in the same pot with an appropriate hydroxyl coreactant, such as hydroxyethyl methacrylate (HEMA), at the same temperature ranges indicated above to form the monomers as solutions in the non-reactive polar organic solvent (i.e , acetic acid)
• HEMA hydroxyethyl methacrylate
• the reaction of NCMI with an hydroxyl compound may be accelerated by incorporating into the reaction mixture suitable catalysts as, for example, zinc acetate.
• the monomers may be used without isolation.
• the non-reactive solvent i.e., acetic acid
• the reaction mixture may be diluted with water to precipitate the monomers which can be dried and dissolved in other suitable solvents or comonomers such as methyl methacrylate, methacrylic acid and/or acrylic acid
• the monomers may be dissolved in aqueous methacrylic and/or acrylic acid
• the maleurate esters and amides of hydroxyalkylalkylene ureas can also be obtained by the same one- pot process described above
• hydroxyalkylalkylene ureas such as hydroxyethylethyleneurea (HEEU)
• aminoalkylalkylene ureas such as ammoethylethyleneurea (AEEU)
• cyclic ureas such as ethylene urea (EU)
• HEEU hydroxyethylethyleneurea
• AEEU ammoethylethyleneurea
• EU cyclic ureas
• NCMI ethylene urea
• the resulting reaction mixtures can contain varying amounts of isome ⁇ c products derived from ring opening of the imides with the ring NH of HEEU and AEEU, in addition to the usual trans isomers.
• These monomers are water soluble and thus cannot be precipitated by adding water to the non-reactive polar organic solvent (i.e., acetic acid) solution. Instead, they can be used in the solution of the non-reactive polar organic solvent (i.e., acetic acid) solution or the non- reactive polar organic solvent can be removed by vaccum stripping and the resulting monomers may be dissolved in water and/or methyacrylic acid and its mixtures with other comonomers.
• the non-reactive polar organic solvent i.e., acetic acid
• Additional preferred embodiments are dervied from the reaction of the cyclic imides with hydroxyalkyl acrylates, allyl alcohol, hydroxyethylethylene urea and monoalcohols as described above.
• R 1 is an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl, ethylhexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl.
• m is 1 and q is an integer of from 1 to 4.
• n 2 or 3, and more preferably 2, p is 1 and R is H.
• R is H or -(C q H 2q -0) m -R 2 , m is 1 , q is 2 or 3 (and preferably 2), and R 2 is
• novel functional monomers represented by the Formula (I), above find use, for example in the preparation of polymers for adhesives, caulks, sealants, coatings, wood coatings, automotive coatings, binders, wet/dry strength resins for paper, paper coatings, textiles, lubricants, intermediates for surfactants, intercoat adhesion promoters, polymer compatibilizers, primers, surface modifiers, corrosion inhibitors and formaldehyde scavengers, pressure sensitive adhesives, nonwovens, can coatings, marine coatings, architectural coatings, and modifiers for cement, concrete, mortar and the like
• novel monomers of the present invention are polymerizable or copolymenzable through the unsaturation in the compounds. They may be used as comonomers in monomeric systems for forming aqueous emulsion polymers, including in compositions comprising monomers such as acrylics, vinyls, vinyl aromatics, ⁇ , ⁇ -unsatu rated carboxylic acids and their esters, as well as other known specialty monomers.
• acrylic monomers examples include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2- hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2- hydroxypropyl acrylate, pipe ⁇ dmoethyl methacrylate, morpholinoethyl methacrylate, and the like.
• Suitable vinyl monomers include ethylene, propylene, butylene, isobutylene, hexene, vinyl acetate, vinyl esters of versatic acids (e.g., VEOVA-9 and VEOVA-10), vinyl chloride, acrylonitnle, acrylamide, methacrylamide, vinylidene chloride, oleic acid, linoleic acid, 1 ,3-butad ⁇ ene, isoprene, norbornene, cyclopentadiene and the like.
• VEOVA-9 and VEOVA-10 vinyl chloride
• acrylonitnle acrylamide
• methacrylamide vinylidene chloride
• oleic acid linoleic acid
• 1 ,3-butad ⁇ ene isoprene
• norbornene cyclopentadiene and the like.
• Examples of useful unsaturated carboxylic acids include itaconic acid, citraconic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like; ⁇ , ⁇ -unsaturated dicarboxylic acid esters of the dicarboxylic acids described above including aromatic esters, cycloalkyl esters, alkyl esters, hydroxyalkyl esters, alkoxy alkyl esters, and the like.
• Suitable vinyl aromatic monomers include styrene, ⁇ -methylstyrene, vinyltoluene, ethylstyrene, isopropylstyrene, p-hydroxystyrene, p-acetoxystyrene, and p-chlorostyrene.
• the monomers of this invention may be incorporated in effective amounts in aqueous polymer systems to enhance the adhesion/wet adhesion of paints made from the polymers.
• the emulsion polymers used in formulating latex paints usually are all acrylic copolymers comprising alkyl esters of acrylic and methacrylic acid with minor amounts of acrylic and methacrylic acid, or they are vinyl/acrylic polymers comprising vinyl containing monomers or polymers in combination with softer acrylic monomers
• the commonly used ethylenically unsaturated monomers in making acrylic paints are butyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof.
• acrylic paint compositions at least 50% of the polymer formed is comprised of an ester of acrylic or methacrylic acid
• the vinyl-acrylic paints usually include ethylenically unsaturated monomers such as vinyl acetate and butyl acrylate or 2- ethylhexyl acrylate.
• vinyl acrylic paint compositions at least 50% of the polymer formed is comprised of vinyl acetate, with the remainder being selected from the esters of acrylic or methacrylic acid.
• the monomers of this invention may be added to a monomer composition from which acrylic or vinyl acrylic polymers are formed in a concentration which may vary over a wide range.
• concentration is at least sufficient to improve the wet adhesion of paints made from the polymer composition.
• Concentrations may range from about 0.05% to about 20%, by weight, based on the total weight of monomers.
• concentration is in the range of from about 0.1 % to about 5.0%, and more preferably from about 0.5% to about 3.0%
• the monomer composition may be used in conjunction with other ingredients, such as various free radical catalysts to initiate polymerization, emulsifying agents to protect particles from agglomeration, and buffers to maintain a desired pH during polymerization, as is generally well-known to those of ordinary skill in the art of polymerization.
• ingredients such as various free radical catalysts to initiate polymerization, emulsifying agents to protect particles from agglomeration, and buffers to maintain a desired pH during polymerization, as is generally well-known to those of ordinary skill in the art of polymerization.
• suitable free radical polymerization catalysts are the catalysts known to promote emulsion polymerization and include water-soluble oxidizing agents such as organic peroxides (e.g., t-butyl hydroperoxide, cumene hydroperoxide, etc.), inorganic oxidizing agents (e.g., hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc.) and those catalysts that are activated in the water phase by a water-soluble reducing agent
• water-soluble oxidizing agents such as organic peroxides (e.g., t-butyl hydroperoxide, cumene hydroperoxide, etc.), inorganic oxidizing agents (e.g., hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc.) and those catalysts that are activated in the water phase by a water-soluble reducing agent
• Such catalysts are employed in a catalytic amount
• Suitable emulsifying agents include anionic, cationic, and nonionic emulsifiers customarily used in emulsion polymerization Usually, at least one anionic emulsifier is utilized and one or more nonionic emulsifiers may also be utilized.
• Representative anionic emulsifiers are the esters of sulfosuccinic acid, amides of sulfosuccinic acid, the alkyl aryl sulfonates, alkali metal alkyl sulfates, the sulfonated alkyl esters and fatty acid soaps.
• the emulsifying agents are employed in amounts to achieve adequate emulsification and to provide desired particle size and particle size distribution.
• suitable buffers used to maintain a desired pH during polymerization include ingredients such as acids, salts, chain transfer agents and chelatmg agents
• the polymerization constituents include a monoethylenically unsaturated carboxylic acid comonomer, polymerization under acidic conditions (pH 2-7, preferably 2-5) is preferred.
• the aqueous medium can include those known weak acids and their salts that are commonly used to provide a buffered system at the desired pH range.
• the manner of combining the polymerization ingredients can be various known monomer feed methods, such as, continuous monomer addition, incremental monomer addition, or addition in a single charge of the entire amount of monomers.
• the entire amount of the aqueous medium with polymerization additives can be present on the polymerization vessel before introduction of the monomer, or alternatively, the aqueous medium, or a portion of it, can be added continuously or incrementally during the course of the polymerization.
• the polymerization of the monomer system which includes ethylenically unsaturated monomers and either one or more of the novel monomers of the present invention can be accomplished by known procedures for polymerization in aqueous emulsions, as disclosed, for example, in US3366613, US4104220, US2881 171 , US4219452 and EP-A-0626672, which are incorporated by reference herein for all purposes as if fully set forth
• Pre-polymer monomeric starting materials used to form polymeric pre-emulsion compositions using the monomers of the present invention are typically dissolved or suspended in the aqueous medium to a desired concentration.
• the polymerization of the invention is performed at a concentration range of about 10 we ⁇ ght-% to about 70 we ⁇ ght-% of the monomers in the aqueous medium, although somewhat higher or lower concentrations may be employed in some cases
• polymerization is initiated by heating the emulsified mixture with continued agitation to a temperature usually between about 50°C to about 110°C, preferably between 60°C to about 100°C. Heating of the emulsified mixture is also preferably conducted in an inert atmosphere (e.g., purging with nitrogen, argon, etc.). Polymerization is continued by maintaining the emulsified mixture at the desired temperature until conversion of the monomer or monomers to polymer has been reached.
• an inert atmosphere e.g., purging with nitrogen, argon, etc.
• the polymer may contain anywhere from about 0.05 we ⁇ ght-% to about 20.0 we ⁇ ght-% of the monomer of the present invention (based on the concentration of the monomer), preferably from about 0.1 % to about 5.0 we ⁇ ght-% of the present monomer, and more preferably from about 0.5% to about 3.0 we ⁇ ght-% of the monomer of the present invention.
• blends of latices modified with the addition monomers of the present invention include acrylic, vinyl acrylic, styrene acrylic, styrene butadiene, styrene butadiene-acrylic as well as latices derived from esters of versatic acid (e.g., VEOVA-9 and
• VEOVA-10 VEOVA-10
• These concentrates may contain polymers prepared from higher amounts of the monomers of the present invention (for example, 20-50 % by weight based on the monomer mixture), and are added to the unmodified latices in amounts so as to result in an overall wet adhesion monomer content within the ranges earlier mentioned.
• the monounsaturated monomers of the present invention be used to form solution copolymers
• Polymerization towards the formulation of solution polymers may be completed under substantially similar circumstances as described above for emulsion polymerization except that the medium of polymerization in a solution polymerization reaction is organic instead of aqueous.
• the solution polymerization reaction is carried out with the monomers in solution in an inert organic solvent such as tetrahydrofuran, methyl ethyl ketone, acetone, ethyl acetate, or other suitable organic solvents such as hexane, heptane, octane, toluene, xylene and mixtures thereof
• an inert organic solvent such as tetrahydrofuran, methyl ethyl ketone, acetone, ethyl acetate, or other suitable organic solvents such as hexane, heptane, octane, toluene, xylene and mixtures thereof
• inverse emulsions may also be prepared Inverse emulsion being defined as a water-soluble polymer system dispersed in an organic solvent
• Preferred solvents are non-toxic and odorless Self-Crosslinking Curable Compositions
• the functional monomers of the present invention may be used to form self-crosslinking polymers for curable compositions.
• a number of different potential uses for such curable compositions are mentioned above, and the person of ordinary skill in the art can generally formulate the appropriate curable composition for the desired end use.
• the present polymers may be formulated into coating compositions employing a liquid medium such as water, or it may employ solid ingredients as in powder coatings which typically contain no liquids.
• a liquid medium such as water
• solid ingredients as in powder coatings which typically contain no liquids.
• Low melting solids M.P.: 70°-110°C
• the use of a liquid medium may permit formation of a dispersion, emulsion, inverse emulsion, or solution of the ingredients of the curable composition.
• a liquid medium which is a solvent for the curable composition ingredients.
• Suitable solvents include aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, amides, alcohols, water, compounds having a plurality of functional groups such as those having an ether and an ester group, and a mixture thereof.
• the curable composition may also contain other optional ingredients for the desired end use, such as fillers, light stabilizers, pigments, flow control agents, plasticizers, mold release agents, corrosion inhibitors, and the like.
• the liquid or powder coating compositions and a substrate to be coated are contacted by applying the curable composition to the substrate by a suitable method, for example, by spraying in the case of the liquid compositions and by electrostatic spraying in the case of the powder compositions.
• the substrate covered with the powder composition is heated to at least the fusion temperature of the curable composition forcing it to melt and flow out and form a uniform coating on the substrate. It is thereafter fully cured by further application of heat, typically at a temperature in the range of about 120X to about
• the solvent is allowed to partially evaporate to produce a uniform coating on the substrate. Thereafter, the coated substrate is heated in an oven at a temperature up to about 250°C, for a period of time in the range of about 20 seconds to about 14 days and preferably for a period of time in the range of 10 to 45 minutes to obtain a fully cured film.
• the heat cured compositions of this invention may be employed as coatings in the general areas of coatings such as original equipment manufacturing (OEM) including automotive coatings, general industrial coatings, including industrial maintenance coatings, architectural coatings, powder coatings, coil coatings, can coatings, wood coatings, and low temperature cure automotive refinish coatings. They are usable as coatings for wire, appliances, automotive parts, furniture, pipes machinery, and the like. Suitable surfaces include metals such as steel and aluminum, plastics, wood, and glass
• the polyfunctional crosslinkers of the present invention are also well suited for use in compositions used to refinish automotive parts and to coat sensitive substrates such as wood.
• the polymers containing the novel monomers of the present invention may also be used in compositions as binders for nonwovens, as textile treatment agents for permanent press textiles, as coating insolubilizers for gellation of starch in paper and as colloidal wet and dry strength agents in paper manufacture.
• curable compositions containing the crosslinkers of the present invention may be used in adhesives, paper, textile, decorative laminated boards and crosslinked molded articles. They may also be used as corrosion inhibitors, formaldehyde scavengers and as additives to primer formulations.
• Maleuric acid was prepared according to the procedure of US2717908. A mixture of 500 g of maleic anhydride (5.1 moles) and 300 g of urea (5 moles) in 1000 mL of acetic acid was heated to 50 °C The mixture was a homogeneous solution until maleuric acid began to precipitate out. After 12 hours, the mixture was cooled to room temperature overnight. The maleunc acid was filtered and washed with acetic acid to afford 530 g (67% yield). Additional maleunc acid precipitated from the mother liquor over time to afford nearly a quantitative yield.
• N-Carbamylmaleimide was prepared according to the procedure of US2788349. 500 g of maleunc acid was added to 1.5 L of acetic anhydride heated to 85 °C After 30 minutes, the mixture became homogeneous After an additional 1 hour, the solution was cooled to room temperature The precipitated N-carbamylmaleimide was filtered and washed with acetone to afford 405 g (90% yield).
• the maleurate ester of 2-hydroxypropyl acrylate was prepared in 95% yield according to the procedure in example 9
• the hydroxypropyl derivative was a mixture of isomers and therefore not crystalline.
• the acetonitrile was evaporated from the crude reaction mixture and no further purification was done.
• 1 H NMR (CDCI 3 ): d 10.5, 8.2, 6.0-6.4, 5.8, 5.3, 4.0-4.4, 1.3; HPLC (10% CH 3 CN/H 2 0, C 18 ): R t 12 and 13.9 min.
• the maleurate ester of 2-hydroxypropyl methacrylate was prepared in 95% yield according to the procedure in example 9.
• the hydroxypropyl derivative was a mixture of isomers and therefore not crystalline.
• the acetonitrile was evaporated from the crude reaction mixture and no further purification was done.
• Monomer M12B A mixture of 7 g of N-carbamylmaleimide (0.05 moles), 6.5 g of 2-hydroxyethyl methacrylate (0.05 moles) and 320 mg of dibutyltin dilaurate (0.0005 moles) in 12 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and the product precipitated from H 2 0 to afford 10.3 g (76%).
• Example 12E Maleurate Ester of 2-Hydroxyethyl Methacrylate Zinc Acetate Catalyst in Acetic Acid
• Monomer M12F A mixture of 14 g of N-carbamylmaleimide (0.1 mole), 14.3 g of 2-hydroxyethyl methacrylate (0.11 moles), 136 mg of zinc chloride (0.001 moles) and 30 g of methyl methacrylate was heated to 85 ' C. After 6 hours the mixture was cooled to room temperature to afford 56.7 g of mixture (97 % of theory).
• NMR analysis of the product indicated the purity of the methacrylate maleurate ester to be around 90%.
• Citraconuric acid was prepared according to the procedure of US2717908. A mixture of 286 g of citraconic anhydride (2.55 moles) and 150 g of urea (2.5 moles) in 500 mL of acetic acid was heated to 50°C. After 12 hours, the mixture was cooled to room temperature overnight. Most of the acetic acid was evaporated. The citraconuric acid was filtered and washed with acetic acid to afford 215 g (50% yield).
• N-Carbamylcitracommide was prepared according to the procedure of US2788349. 167 g of citraconuric acid (0.97 moles) was added to 500 mL of acetic anhydride heated to 85 °C After 30 minutes, the mixture became homogeneous. After an additional 1 hour, the solution was cooled to room temperature. The precipitated N-carbamylcitraconimide was filtered and washed with acetone to afford 105 g (70% yield).
• Itaconuric acid was prepared according to the procedure of US2717908 A mixture of 123 g of itaconic anhydride (1 1 moles) and 60 g of urea (1 moles) in 200 mL of acetic acid was heated to 50 °C. After 12 hours, the mixture was cooled to room temperature overnight. Most of the acetic acid was evaporated. The itaconuric acid was filtered and washed with acetic acid to afford 51 g (30% yield)
• N-Carbamylitacommide was prepared according to the procedure of US2788349. 30 g of itaconuric acid (0.17 moles) was added to 100 mL of acetic anhydride heated to 85°C. After
• Monomer M25 A mixture of 9.7 g (0.05 moles) of N-carbamylnadicmaleimide, 6.5 g of 2-hydroxyethyl methacrylate (0.05 moles) and 110 mg of zinc acetate dihydrate (0.0005 moles) in 12 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and the product precipitated from H 2 0.
• N-carbamylsucc ⁇ n ⁇ c acid was prepared according to the procedure in US2788349. A mixture of 20.4 g of succmic acid (0.203 mol) and 12 g of urea (0.2 mol) in 50 mL of acetic acid was heated to 60°C. After 12 hours, the mixture was allowed to cool to room temperature and filtered. The solid was washed with hexanes and dried to afford 16.4 g of N-carbamylsucc ⁇ n ⁇ c acid.
• N-Carbamylsuccinimide was also prepared according to the procedure in US2788349. 12 g of N-carbamylsuccmic acid (0.075 mol) in 40 mL of acetic anhydride was heated to 90°C. After 1 hour, the mixture was concentrated until precipitation occured. The solid was filtered, washed with hexane and dried to afford 10.1 g of N-carbamylsuccinimide.
• Example 29 N-Carbamylsuccinimide
• the wet adhesion monomer (WAM) used in the preparation of the acrylic latexes was either a monomer of the present invention or, alternatively, a commerically available wet adhesion monomer.
• a 1 liter glass jacketed resin reactor with a bottom discharge valve was used.
• the reactor was equipped with thermometer, a circulating constant temperature heating bath, N 2 purge, a Teflon turbm agitator, a monomer emulsion feed pump calibrated for 4.59 grams/mm and an initiator feed pump calibrated for 0.5 g/mm.
• the following charge is used:
• the monomer emulsion was prepared by.
• reaction mixture was heated to 85X for 30 minutes.
• the emulsion was then cooled to 23°-25X and the pH adjusted to 9.0 ⁇ 0.2 with 28% NH 4 OH
• the resulting emulsion was filtered through a cheesecloth paint filter
• the typical yield was -955 grams, with a viscosity of 20-28 cps and solids of -50%
• Table III identifies the various ingredients used in the paint formulation. The ingredients were added in the order listed to a high speed paint disperser. TABLE
• the wet adhesion test utilized was a version of the scrub resistance test described in the ASTM procedure #D2486 Using a 7 mil Dow bar, a film of Glidden Ghd-Guard ® 4554 gloss alkyd was cast on a
• Leneta scrub panel The panels were aged for a minimum of 21 days, but not more than 6 weeks prior to use The test paint was applied with a 7 mil Dow blade over the aged alkyd and air dried 4 hours, 24 hours and seven days. The test paint was cross-hatched in a 10 x 10 grid of 3 mm squares using a razor knife and template The panels were then soaked in room temperature distilled water for 35 minutes, and any blistering or edge lift was recorded If there was no blistering or edge lift from the water soak, the panel was placed on the scrub machine (described in ASTM procedure D2486). 25 ml of water was applied to the panel, and the scored area was scrubbed. During the scrubbing, more water was applied if the panel became dry. The percentage of the squares removed after 1000 cycles was recorded.
• Example 39 Following the test procedure of Example 37, when M8 was used in place of M12 and tested in accordance therewith, substantially equivalent results were obtained
• Example 41 Following the test procedure of Example 37, when M14 was used in place of M12, and tested in accordance therewith, substantially equivalent results were obtained
• Example 44 Following the test procedure of Example 37, when M12 was replaced with M23, and tested in accordance therewith, substantially equivalent results were obtained

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