EP0918749A1

EP0918749A1 - Urea/ureido functional polymerizable monomers

Info

Publication number: EP0918749A1
Application number: EP97932324A
Authority: EP
Inventors: Balwant Singh; Roland Ralph Dileone; Laurence W. Chang; David A. Siesel
Original assignee: Cytec Technology Corp
Current assignee: Cytec Technology Corp
Priority date: 1996-06-24
Filing date: 1997-06-24
Publication date: 1999-06-02
Also published as: BR9709981A; JP2000515129A; CA2258874A1; NO986107D0; KR20000022101A; AU3581297A; NO986107L; WO1997049676A1

Abstract

This invention relates to ethylenically unsaturated polymerizable monomers of formula (I) wherein Y is (a, b, c, d, e, f, g, h or i) wherein A is (j, k, l, m, n or o) wherein each R is individually H, -(-CqH2q-O-)m-R2, (p), etc., 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.

Description

UREA/UREIDO FUNCTIONAL POLYMERIZABLE MONOMERS

BACKGROUND OF THE INVENTION

Field of the Invention

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

Description of Related Art The term "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 )

Since the use of water-based emulsion polymer systems as protective and decorative coatings for many types of surfaces has become widespread, such systems being used by individuals in homes and in industry, there is a great need for improved wet adhesion of such systems. In recent years, the art has recognized the problem of loss of adhesive properties in latex paints and a variety of additives to latex systems to improve wet adhesion have been proposed. Incorporation of amine, amide and acetoacetate functionalities into latex polymers has been reported to improve the wet adhesion properties of latex paints A number of publications also describe the use of urea and ureido-functional monomers for such purpose See, for example, US2727016, US2727019, US2881 171 , US2980652, US3194792, US3356654, US3369008, US3509085, US4104220, US41 11877, US4219454, US4314067, US4319032, US4426503, US4596850, US4599417, US4617364, US4622374, US4730045, US4766221 , US4770668, US4777265, US4783539, US4883873, US5210199, US5498723, US5567826, US5610313 and WO91/12243, all of which are incorporated by reference herein for all purposes as if fully set forth

A number of these known urea/ureido functional monomers, however, have provided unsatisfactory wet adhesion results Many may also be very expensive and their inclusion into latex polymers results in a substantial increase in the cost of the vinyl, vinyl-acrylic and all- acrylic polymers used in latex-based paints

It has now been discovered that excellent wet adhesion properties can be imparted into aqueous emulsion systems used to make latex paints by incorporating into the monomer system, from which the polymer is produced, a new class of urea/ureido functional polymerizable monomers including acrylated maleurates; acrylated fumaurates; acrylated citraconurates; acrylated itaconurates; and the related vinylether, vinylester and cyclic urea derivatives of hydroxyalkylalkyleneureas, aminoalkylalkyleneureas and their Diels-Alder adducts with 1 ,3-dιenes

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 In particular the monomers of this invention have been found to be especially useful in water-based latex-containing paints

It has been further discovered that this new class of urea/ureido functional polymerizable monomers are also useful in the preparation of self-crosslinking polymers It is well-known in the art to employ self-crosslinking polymers, either in emulsion or solution form, as coatings, binders or adhesives for a variety of substrates. 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

In contrast, self-crosslinking polymers contain reactive functionalities which allow these polymers to self-crosslink without the need for an external crosslmking agent. A typical crosslinking polymer containing N-methylolated amide functionalities, incorporated via N- methylolacrylamide, undergoes thermosetting crosslmking by splitting out a mole of formaldehyde. 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. Such systems have been used in a variety of applications, including use as textile adhesives, nonwoven binders, pigment binders, fabric finishing agents, binders for paper and wood finishing applications. However, the self-crosslinking monomers of the above-described prior art may have the disadvantage that they are expensive and their inclusion into latex polymers results in substantial increase in the cost of the polymers. 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 We have now discovered 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

SUMMARY OF THE INVENTION

As indicated above, the present invention is directed to novel polymerizable monomers These compounds of the present invention may be represented by the following general Formula (I)

wherein Y is

- wherein A is

^X

^Jt

wherein each R is individually

wherein each R¹ is individually an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms

wherein each R² is individually hydrogen or an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms wherein each R³ is individually an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms wherein each R⁴ 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 -CH₂-CH₂-, then A is a group as defined above which contains ethylenic unsaturation.

Both the cis- and trans- stereoisomers of the above compouds, where appropriate (e.g., maleic and fumaric), are incuded within the above definition and the scope of the invention.

It is also within the scope of the invention to use mixtures of the novel compounds of Formula

(I) in aqueous emulsion polymer systems.

The novel polymerizable monomers of the present invention are capable of polymeriza¬ tion through their double bond(s). Thus, the 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.

Accordingly, 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.

In addition, 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).

These and other features and advantages of the present invention will be more readily understood by those skilled in the relevant art from a reading of the following detailed description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As indicated above, the present invention relates most broadly to urea/ureido functional monomers of the general Formula (I) shown above The novel compounds are characterized by the fact that the noncyclic urea nitrogens in the compounds of the present invention are attached directly to a carbonyl (C=0) group rendering these materials much more polar than the prior art urea/ureido compounds. The presence of the non-cyclic ureas adjacent to the carbonyl groups additionally alters the reactivity profile of these monomers. Preparation of the Novel Urea/Ureido Functional Monomers

The functional monomers of the Formula (I) indicated above may be derived by the ring opening reaction of "cyclic imides" with hydroxyfunctional and/or aminofunctional compounds 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-tetrahydrophthalιmιde (NC-ETHPI), which compounds have the formulae indicated below

As indicated above, 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 For example, 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^rC Preferably, the temperature ranges from about 25°C to about 100°C Examples of 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.

In order to lower the viscosity of the reaction mixture, a non-reactive solvent may be employed. Examples of 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. These optional comonomers do not enter into the above-described reaction and their sole function is to allow the final product to exist in solution form.

A catalyst is not necessary for the reaction but, if desired, a catalyst may be added to accelerate the reaction. Suitable catalysts include ZnCI₂, Zn(OCOCH₃)₂, FeCI₃, cobalt acetate, chelates of transition metal ions with α,β-dιketones and ketoesters, tin salts such as SnCI₂, SnCI₄, Sn0₂ 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 Preferably, the range of catalyst, when used, is from about 0.1 to 1.0 mole% To prevent polymerization of the reactants and/or the product, it is customary to use low levels of radical inhibitors Examples of 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. When a radical inhibitors is used, the preferred inhibitors are methyl ether of hydroquinone and hydroquinone

The above-described reaction of NCMI, NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC- ETHPI with hydroxyalkyl acrylates or methacrylates yields novel acrylated monomers. If it is desired to prepare the novel acrylated monomers so that they are not in solution form as a final product, the optional co-monomers described above are not added, and the acrylated monomers are isolated by removal, under reduced pressure, of the non-hydroxylic (non- reactive) solvent (i.e., acetonitrile, acetone) used, if any, followed by aqueous washing of the novel acrylated product with water, followed by drying

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. In the case of hydroxyalkylethyleneurea and hydroxyalkylpropyleneurea, 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. As in the case of the acrylic derivatives, 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. Examples of 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. Examples of suitable vinyl alcohols include ethylene glycol monovinyl ether, propylene glycol monovinyl ether, polyethylene glycol monovinyl ether and the like. Examples of suitable vinyl ester alcohols include vinyl esters of lactic acid and 3-hydroxypropιonic 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. As above, the reaction with amines should be conducted at lower temperatures to avoid by-product formation. The trans isomers of the monomers of this invention can also be prepared by isomeπzing the corresponding cis isomers by heating in the presence of catalysts including, for example, hydrochloric acid, sulfuπc acid, aluminum chloride and pyridine, preferably in a polar organic solvent such as acetonitrile, 1 ,2-dιmethoxyethane, 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, for example, 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^ϋ-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) As disclosed hereinabove, the reaction of NCMI with an hydroxyl compound may be accelerated by incorporating into the reaction mixture suitable catalysts as, for example, zinc acetate. For end use applications the monomers may be used without isolation. However, if desired, the non-reactive solvent, i.e., acetic acid, may be removed under vacuum or 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 Alternatively, the monomers may be dissolved in aqueous methacrylic and/or acrylic acid

The maleurate esters and amides of hydroxyalkylalkylene ureas, such as hydroxyethylethyleneurea (HEEU), aminoalkylalkylene ureas, such as ammoethylethyleneurea (AEEU), and cyclic ureas such as ethylene urea (EU), can also be obtained by the same one- pot process described above For example, following reaction of urea and maleic anhydride, as above, the resulting solution of NCMI is then reacted in the same pot with HEEU, AEEU and/or EU at the same temperature range of the one-pot procedure described above. The resulting reaction mixtures can contain varying amounts of isomeπc 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 same reaction conditions described above also apply to the use of NCSI, NCCI, NCII, NC-THPI, NC-NDI or NC-ETHPI, respectively, instead of NCMI.

Specific Preferred Embodiments In preferred embodiments, the monomers of the present invention are maleurates and fumaurates, that is, where Y is -CH=CH - (cis stereoisomer being maleurate, trans stereoisomer being fumaurate).

Additional preferred embodiments are dervied from the reaction of the cyclic imides with hydroxyalkyl acrylates, allyl alcohol, hydroxyethylethylene urea and monoalcohols as described above.

Certain preferred structures are provided below.

H₂N— ? C— NH— ? C — Y — ? C— OR ,

wherein R¹ 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.

wherein m is 1 and q is an integer of from 1 to 4.

wherein ml is 0.

wherein n is 2 or 3, and more preferably 2, p is 1 and R is H.

wherein p is 1 , and R is H or -(C_qH_2q-0)_m-R², m is 1 , q is 2 or 3 (and preferably 2), and R² is

H.

Uses of the Monomers of the Present Invention

The 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

The 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, α,β-unsatu rated carboxylic acids and their esters, as well as other known specialty monomers. Examples of suitable acrylic monomers 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, pipeπdmoethyl methacrylate, morpholinoethyl methacrylate, and the like. Examples of 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-butadιene, 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; α,β-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.

Examples of suitable vinyl aromatic monomers, with which the present invention's monomers can be polymerized, include styrene, α-methylstyrene, vinyltoluene, ethylstyrene, isopropylstyrene, p-hydroxystyrene, p-acetoxystyrene, and p-chlorostyrene.

In particular, 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. In 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. In 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. Preferably the 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. Preferably, the 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. For example, 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 Such catalysts are employed in a catalytic amount sufficient to cause polymerization. Generally, a catalytic amount ranges from about 0.01 to 5.0 parts per hundred parts of monomer. As alternatives to heat and catalytic compounds to activate polymerization, other free radical producing means, such as exposure to activating radiations, can be employed.

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.

Examples of suitable buffers used to maintain a desired pH during polymerization include ingredients such as acids, salts, chain transfer agents and chelatmg agents For example, if the polymerization constituents include a monoethylenically unsaturated carboxylic acid comonomer, polymerization under acidic conditions (pH 2-7, preferably 2-5) is preferred. In such instances, 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 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. Preferably, the polymerization of the invention is performed at a concentration range of about 10 weιght-% to about 70 weιght-% of the monomers in the aqueous medium, although somewhat higher or lower concentrations may be employed in some cases

By way of example, 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.

Generally, depending upon the final application of the polymeric composition, the polymer may contain anywhere from about 0.05 weιght-% to about 20.0 weιght-% of the monomer of the present invention (based on the concentration of the monomer), preferably from about 0.1 % to about 5.0 weιght-% of the present monomer, and more preferably from about 0.5% to about 3.0 weιght-% of the monomer of the present invention.

It is also within the scope of this invention to use blends of latices modified with the addition monomers of the present invention ("latex concentrates") with unmodified latices. The unmodified latices 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). 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. In addition to making emulsion polymers, it is contemplated that preferably 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. Generally, 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 In the case of water-soluble monomers, 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

As indicated above, 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.

For example, 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. Low melting solids (M.P.: 70°-110°C) are particularly preferred. The use of a liquid medium may permit formation of a dispersion, emulsion, inverse emulsion, or solution of the ingredients of the curable composition.

Particularly preferred is 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. In the case of powder coatings, 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

220°C for a period of time in the range of about 5 minutes to about 30 minutes and preferably for a period of time in the range of about 10 to about 20 minutes. In the case of the liquid compositions, 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. In addition to coatings, 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.

The invention will now be illustrated by the following examples The examples are not intended to be limiting of the scope of the present invention In conjunction with the general and detailed descriptions above, the examples provide further understanding of the present invention.

Example 1 Maleuric acid Monomer M1

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. Η NMR (DMSO-cQ- d 12.8 (br s, 1 H), 10.4 (br s, 1 H), 7.6 (br s, 1 H), 7.3 (br s, 1 H), 6.4 (s, 2 H)

Example A

N-Carbamylmaleimide

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). ¹H NMR (DMSO-d₆): d 7.8 (br s, 1 H), 7.4 (br s, 1 H), 7.1 (s, 2 H); ¹³C NMR (DMSO-d₆): d 169, 148, 135.

Example 2 Butyl Maleurate

Monomer M2

A mixture of 140 g of N-carbamylmaleimide (1 mole), 1.36 g of zinc chloride (0.01 moles) and 150 g of r>-butanol (2 moles) was heated to reflux. After 4 hours, the mixture was poured into 400 mL of water and cooled to room temperature. The butyl maleurate was filtered, washed with water and dried to afford 200 g (93% yield). M.P.: 97-9 °C; ¹H NMR (CDCI₃): d

10.6 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (AB, 2 H), 5.9 (br s, 1 H), 4.2 (t, 2 H), 1.6 (m, 2 H), 1.4 (m, 2 H), ).9 (t, 3 H); HPLC (20 to 40% CH₃CN/H₂O over 20 minutes, C_β): R_t= 9.4 minutes.

Example 3 Methyl Maleurate

Monomer M3

A mixture of 10 g of N-carbamylmaleimide (0.071 moles) in 40 mL of methanol was heated to reflux. After 6 hours, the excess methanol was evaporated to afford 1 1.5 g (93% yield) of methyl maleurate. M.P.: 1 12-14 °C; Η NMR (CDCLJ: d 10.4 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (m, 2 H), 5.6 (br s, 1 H), 3.8 (s, 3 H); HPLC (5% CH₃CN/H₂0, C_β): R,= 6.3 minutes.

Example 4

Isopropyl Maleurate

Monomer M4 The addition of isopropanol to N-carbamylmaleimide under the conditions of example 2 afforded a 95% yield of isopropyl maleurate. M.P.: 113-14 °C; ¹H NMR (CDCI₃): d 10.6 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (AB, 2 H), 5.8 (br s, 1 H), 5.2 (quintet, 1 H), 1.3 (d, 6 H); HPLC (20% CH₃CN/H₂0, C_B): R_t= 5.6 minutes.

Example 5

2-Ethylhexyl Maleurate

Monomer M5

The addition of 2-ethylhexanol to N-carbamylmateimide under the conditions of example 2 afforded a 95% yield of 2-ethylhexyl maleurate M.P.: 73-6 °C; 'H NMR (CDCI₃): d 10.6 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (m, 2 H), 5.8 (br s, 1 H), 4.2 (m, 2 H), 1.6 (m, 1 H), 1.3 (m, 8 H), 0.9 (t, 6 H); HPLC (40% CH₃CN/H₂0, C_β): R,= 14.2 minutes.

Example 6 Hexadecy I Maleurate

Monomer M6

A mixture of 49 g of hexadecanol (0.202 moles), 28 g of N-carbamylmaleimide (0.2 moles) and 270 mg of zinc chloride (0.002 moles) in 300 mL of p-dioxane was heated to reflux. After 24 hours, the mixture was cooled to room temperature and 200 mL of H₂0 was added. The resulting solid was filtered, washed with additional H₂0 and dried to afford 75 g (97% yield) of hexadecyl maleurate. M.P.- 106-09 °C (dec); ¹H NMR (CDCI₃)- d 10.5 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (m, 2 H), 5.4 (br s, 1 H), 4.2 (t, 2 H), 1.6 (m, 2 H), 1.2 (m, 26 H), 0.9 (t, 3 H); HPLC (80% CH₃CN/H,0, C₁₈): R,= 6.9 minutes

Example 7

Octadecyl Maleurate Monomer M7

The addition of octadecanol to N-carbamylmaleimide under the conditions of example 6 afforded a 97% yield of octadecyl maleurate. M.P.: 109-1 1 °C (dec); 'H NMR (CDCI₃): d 10 5 (br s, 1 H), 8.2 (br s, 1 H), 6.3 (m, 2 H), 5.4 (br s, 1 H), 4.2 (t, 2 H), 1 6 (m, 2 H), 1.2 (m, 30 H),

0.9 (t, 3 H); HPLC (80% CH₃CN/H₂0, C₁₈): R_t= 12.8 minutes.

Example 8

Allyl Maleurate

Monomer M8

A mixture of 2.96 g of allyl alcohol (0.051 moles), 7 g of N-carbamylmaleimide (0.05 moles) and 1 10 mg of zinc acetate dihydrate (0.0005 moles) in 20 mL of acetonitrile was heated to reflux. After 8 hours, the acetonitrile was evaporated. The solid was washed with H₂O and dried to afford 9.9 g (99% yield) of allyl maleurate. M.P.: 108-10 °C; ¹H NMR (DMSO- cQ: d 10.5 (br s, 1 H), 7.6 (br s, 1 H), 7.3 (br s, 1 H), 6.5 (AB, 2 H), 5.9 (m, 1 H), 5.3 (d of d, 1 H), 5.2 (d of d, 1 H), 4.6 (d, 2 H); HPLC (10% CH₃CN/H₂0, C_1θ): R,= 4.9 minutes.

Example 9

Maleurate Ester of 2-Hydroxyethyl Acrylate

Monomer M9

A mixture of 140 g of N-carbamylmaleimide (1 mole), 121.8 g of 2-hydroxyethyl acrylate (1.05 moles) and 1.36 g of zinc chloride (0.01 moles) in 200 mL of acetonitrile was heated to reflux. After 5 hours, the mixture was poured into 500 mL of water. The solid was filtered, washed with water and dried to afford 240.7 g (94% yield) of the maleurate ester of 2- hydroxyethyl acrylate. M.P.: 88-90 °C (dec); ¹H NMR (CDCI₃): d 10.4 (br s, 1 H), 8.2 (br s, 1 H), 6.4 (m, 3 H), 6.2 (d of d, 1 H), 5.9 (m, 2 H), 4.4 (A^, 4 H); ^,3C NMR (CDCy: d 165.9, 165.3, 165.2, 155.1 , 133.1 , 131.6, 129.5, 127.8, 63.2, 61.9; HPLC (10% CH₃CN/H₂0, C₁₈): R,=

5.7 minutes.

Example 10 Maleurate Ester of 2-Hydroxypropyl Acrylate Monomer M10

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. In this case, the acetonitrile was evaporated from the crude reaction mixture and no further purification was done. ¹H NMR (CDCI₃): d 10.5, 8.2, 6.0-6.4, 5.8, 5.3, 4.0-4.4, 1.3; HPLC (10% CH₃CN/H₂0, C₁₈): R_t= 12 and 13.9 min. Example 11

Maleurate Ester of 2-Hydroxypropyl Methacrylate

Monomer M11

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. In this case, the acetonitrile was evaporated from the crude reaction mixture and no further purification was done. ¹H NMR (CDCI₃): d 10.4, 8.2, 6.4,

6.2, 5.8, 5.6, 5.3, 4.0-4.4, 2.0, 1.3; HPLC (10% CH₃CN/H₂0, C₁₈): R_t= 5.9 and 6.8 min.

Example 12

Maleurate Ester of 2-Hydroxyethyl Methacrylate

Zinc Chloride Catalyst

Monomer M12

A mixture of 140 g of N-carbamylmaleimide (1 mole), 130 g of 2-hydroxyethyl methacrylate (1 mole) and 1.36 g of zinc chloride (0.01 moles) in 200 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and 500 mL of H₂O was added. The solid was filtered and dried to afford 200 g (74% yield) of 2-hydroxyethyl methacrylate maleurate. M.P.: 62°-4°C (dec); ¹H NMR (CDCI₃): d 10.5 (br s, 1 H), 8.2 (br s, 1 H), 6.4 (m, 2 H), 6.1 (m, 1 H), 5.8 (br s, 1 H), 5.6 (m, 1 H), 4.4 (A₂B₂, 4 H), 2.0 (m, 3 H); ¹³C (CDCI₃): d 167.1 , 165.24, 165.23, 155.1 , 135.8, 132.9, 129.6, 126.2, 63.2, 62.0, 18.2; HPLC

(20% CH₃CN/H₂O, C₁₈): R,= 3.5 minutes.

Example 12A Maleurate Ester of 2-Hydroxyethyl Methacrylate Zinc Acetate Catalyst

Monomer M12A

A mixture of 7 g of N-carbamylmaleimide (0.05 moles), 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 H₂0 to afford 9.7 g (72%). Example 12B

Maleurate Ester of 2-Hydroxyethyl Methacrylate

Dibutyltin Dilaurate Catalyst

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 H₂0 to afford 10.3 g (76%).

Example 12C

Maleurate Ester of 2-Hydroxyethyl Methacrylate

Diacetoxytetrabutyldistannoxane Catalyst

Monomer M12C

A mixture of 7 g of N-carbamylmaleimide (0.05 moles), 6.5 g of 2-hydroxyethyl methacrylate (0.05 moles) and 300 mg of diacetoxytetrabutyldistannoxane (0.0005 moles) in

12 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and the product precipitated from H₂0 to afford 10.3 g (76%).

Example 12D Maleurate Ester of 2-Hydroxyethyl Methacrylate

Titanium Isopropoxide Catalyst Monomer M12D

A mixture of 7 g of N-carbamylmaleimide (0.05 moles), 6.5 g of 2-hydroxyethyl methacrylate (0.05 moles) and 140 mg of titanium isopropoxide (0.0005 moles) in 12 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and the product precipitated from H₂0 to afford 10.2 g (75%).

Example 12E Maleurate Ester of 2-Hydroxyethyl Methacrylate Zinc Acetate Catalyst in Acetic Acid

Monomer M12E

A mixture of 7 g of N-carbamylmaleimide (0.05 moles), 6.5 g of 2-hydroxyethyl methacrylate (0.05 moles) and 110 mg of zinc acetate dihydrate (0.0005 moles) in 9 mL of acetic acid was heated to 85 C. After 6 hours, the acetic acid was evaporated and the product precipitated from H₂0 to afford 10 g (74%). Example 12F

Maleurate Ester of 2-Hydroxyethyl Methacrylate in Methyl Methacrylate

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).

Example 12G

Maleurate Ester of 2-Hydroxyethyl Methacrylate

One-Pot Procedure

Monomer M12G

A mixture of 59.8 g of maleic anhydride (0.61 moles) and 36 g of urea (0.6 moles) in 50.3 g of acetic acid was heated to 50°C. After 12 hours, 63.7 g of acetic anhydride (0.624 moles) was added and the temperature increased to 80°C. After 1 hour the mixture became homogeneous. After an additional hour, 67.6 g of 2-hydroxyethyl methacrylate (0.52 moles), 1.2 g of zinc acetate dihydrate (0.0055 moles) and 28 mg of MEHQ were added and the mixture was stirred at 80°C. After 6 hours, most (approximately 80% by weight) of the acetic acid was distilled off. NMR analysis of the product indicated the purity of the methacrylate maleurate ester to be around 90%. Identified impurities detected included N- carbamylmaleimide, maleimide, 2-acetoxyethyl methacrylate, acetic anhydride and acetic acid.

Example B Hydroxyethylethyleneurea

A mixture of 93.3 g of 2-(2-aminoethylamino)ethanol (0.9 moles) and 52.1 g of urea (0.87 moles) was heated slowly to 230 °C with stirring. The evolution of ammonia began when the temperature reached 130°C. The reaction mixture was heated at 230°C for 2 hours. The mixture solidified to a light-yellow solid after it had cooled to room temperature to afford 1 10.5 g of hydroxyethylethyleneurea. Recrystallized from acetone, M.P.: 55-57.5°C; ¹H NMR (DMSO-cQ: d 6.3 (s, 1 H), 4.6 (s, 1 H), 3.5-3.0 (m, 8 H). Example C Aminoethylethyleneurea

A mixture of 206.4 g of diethylenetπamine (2 moles) and 117.0 g of urea (1.95 moles) was slowly heated to 210°C. The evolution of ammonia began when the temperature of the reaction mixture reached 130°C. The reaction mixture was then held at 210°C for 3 hours before it was distilled under vacuum to afford 132 g of aminoethylethyleneurea. B.P.: 175°C

(1.5 mm); ¹H NMR (DMSO-c(₆): d 6.3 (s, 1 H), 3.4-2.5 (m, 8 H), 1.4 (s, 1 H).

Example 13 Maleurate Ester of Hydroxyethylethyleneurea

Monomer M13

A mixture of 3 g of hydroxyethylethyleneurea (0.023 moles), 3.2 g of N- carbamylmaleimide (0.023 moles) and 0.15 g of zinc acetate (0.0007 moles) was refluxed in 25 mL of acetonitrile After 6 hours, the reaction mixture was cooled to room temperature and the acetonitrile was evaporated to afford 6.2 g of hydroxyethylethyleneurea maleurate as a tan solid. Η NMR (DMSO-c/₆): d 10.5 (s, 1 H), 7.6 (s, 1 H), 7.3 (s, 1 H), 6.4 (s, 2 H), 6.3 (s, 1 H), 4.2 (t, 2 H), 3.4 (t, 3 H), 3 1-3.3 (m, 4 H).

Example 13A Maleurate ester of Hydroxyethylethyleneurea

One-Pot Procedure Monomer M13A

A mixture of 59.8 g of maleic anhydride (0 61 moles) and 36 g of urea (0.6 moles) in 50.3 g of acetic acid was heated to 50°C. After 12 hours, 63.7 g of acetic anhydride (0.624 moles) was added and the temperature increased to 80°C After 1 hour the mixture became homogeneous After an additional hour, 70.2 g of hydroxyethylethyleneurea (0.54 moles) and 1.2 g of zinc acetate dihydrate (0.0055 moles) were added and the mixture was stirred at 80°C. After 6 hours, most (approximately 80% by weight) of the acetic acid was distilled off. NMR analysis of the product indicated the purity of the hydroxyethylethyleneurea maleurate ester to be around 90%. Identified impurities detected include N-carbamylmaleimide, maleimide, acetoxyethylethyleneurea maleurate, acetic anhydride and acetic acid. Example 14

Maleuramide of Aminoethylethyleneurea

Monomer M14

To an aqueous solution of 3.0 g of aminoethylethyleneurea (0.023 moles) in 20 mL of H₂0 was added portionwise 3.26 g of N-carbamylmaleimide (0.025 moles) over 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. The H₂O was then evaporated to afford 6.3 g of crude aminoethylethyleneurea maleuramide.

Example 15 Isomerization of Maleurate Ester of 2-Hydroxyethyl Methacrylate to the Fumaurate Monomer M15

A mixture of 8.1 g of the maleurate ester of 2-hydroxyethyl methacrylate and 0.81 g of sulfuric acid in 45 mL of acetonitrile was heated to reflux. After 12 hours, the mixture was cooled to room temperature and H₂0 was added. The mixture was filtered, washed with H₂0 and dried to afford 7.1 g (87% yield) of the fumaurate. M.P.: 135-38°C; Η NMR (DMSO-c/₆): d 10.6 (br s, 1 H), 7.7 (br s, 1 H), 7.4 (br s, 1 H), 7.2 (d, 1 H), 6.8 (d, 1 H), 6.0 (m, 1 H), 5.7 (m, 1 H), 4.4 (A₂B₂, 4 H), 1.9 (m, 3 H); HPLC (20% CH ₃CN/H₂0, C,₈ ): P, = 7.7 minutes. HPLC analysis of the mother liquor indicated a mixture of the maleurate (R,= 3.7 minutes) and the fumaurate.

Example 16

Maleuramide of Allylamine

Monomer M16 2.8 g of N-carbamylmaleimide (0.02 moles) was reacted with 1.4 g of allyl amine (0.02 moles) in 10 mL of acetonitrile at room temperature. After 30 minutes, the acetonitrile was evaporated to afford a mixture which contains approximately 50% of the desired maleuramide.

Example 17

Citraconuric Acid

Monomer M17

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).

Example D

N-Carbamy I citracon i mide

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).

Example 18 Itaconuric Acid Monomer M18

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)

Example E N-Carbamylitaconimide

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

30 minutes, the mixture became homogeneous After an additional 1 hour, the solution was cooled to room temperature The precipitated N-carbamylitaconimide was filtered and washed with acetone to afford 16 g (60% yield) Example 19

Octadecyl Citraconurate

Monomer M19

A mixture of 27.6 g of octadecanol (0.101 moles), 15.4 g of N-carbamylcitraconimide (0.1 moles) and 135 mg of zinc chloride (0.001 moles) in 150 mL of p-dioxane was heated to reflux.

After 24 hours, the mixture was cooled to room temperature and 100 mL of H₂O was added.

The resulting solid was filtered, washed with additional H₂0 and dried to afford nearly a quantitative yield of octadecyl citraconurate.

Example 20

Octadecyl Itaconurate Monomer M20

A mixture of 5.47 g of octadecanol (0.02 moles), 3.08 g of N-carbamylitaconimide (0.02 moles) and 27.0 mg of zinc chloride (0.0002 moles) in 30 mL of p-dioxane was heated to reflux. After 24 hours, the mixture was cooled to room temperature and 20 mL of H₂0 was added. The resulting solid was filtered, washed with additional H₂0 and dried to afford nearly a quantitative yield of octadecyl itaconurate.

Example 21 Citraconurate Ester of 2-Hydroxyethyl Methacrylate

Monomer M21

A mixture of 15.4 g of N-carbamylcitraconimide (0.1 mole), 13.0 g of 2-hydroxyethyl methacrylate (0.1 mole) and 0.14 g of zinc chloride (0.001 moles) in 20 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and 50 mL of H₂O was added. The solid was filtered and dried to afford 19.8 g (70% yield) of 2-hydroxyethyl methacrylate citraconurate ester.

Example 22 Itaconurate ester 2-Hydroxyethyl Methacrylate Monomer M22

A mixture of 3.08 g of N-carbamylitaconimide (0.02 moles), 2.6 g of 2-hydroxyethyl methacrylate (0.02 moles) and 27.2 mg of zinc chloride (0.0002 moles) in 4 mL of acetonitrile was heated to reflux. After 6 hours, the acetonitrile was evaporated and 50 mL of H₂0 was added The solid was filtered and dried to afford 3.41 g (60% yield) of 2-hydroxyethyl methacrylate itaconurate ester Example 23

Ethylene Glycol Vinyl Ether Maleurate

Monomer M23

A mixture of 4.4 g (0.05 moles) of ethylene glycol vinyl ether and 7 g (0.05 moles) of NCMI in 10 mL of acetonitrile was refluxed for 8 hours. The mixture was filtered and the filtrate evaporated to afford a mixture containing the maleurate. ¹H NMR (CDCI₃): δ 10.45, 6.5, 6.4, 4.8, 4.4-4.2, 4.0-3.6.

Example 24 Lactic Acid Vinyl Ester Maleurate

Monomer M24

A mixture of 2.3 g (0.05 moles) lactic acid vinyl ester (made according to the procedure of US2384117) and 7 g (0.05 moles) of NCMI in 10 mL of acetonitrile was refluxed for 8 hours. The mixture was filtered and the filtrate evaporated to afford a mixture containing the maleurate.

Example 25

Reaction of HEMA with NCNDI

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 H₂0.

Example 26

Reaction of HEEU with NCNDI Monomer M26

A mixture of 9.7 g (0.05 moles) of NCNDI, 6.5 g of HEEU (0.05 moles) and 1 10 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 monomer M26 was obtained. Example 27 Reaction of Hydroxypropyl Methacrylate with Fumauric Acid

Monomer M27

A mixture of 1.44 g (0.01 moles) of hydroxypropyl methacrylate, 1.58 g (0.01 moles) of fumauric acid (transisomer of maleuric acid) and 50 mg of H₂SO₄ in 20 ml of toluene was heated to reflux. After 8 hours the mixture was filtered and the filtrate evaporated to afford a mixture of hydroxypropyl methacrylate and the trans- isomer of monomer M11.

Example 28 Reaction of Ethylene Urea with NCMI

Monomer M28

A mixture of 4.3 g (0.05 moles) of ethylene urea and 7.0g (0.05 moles) of NCMI in 10 mL AcOH was stirred at 50°C for 12 hours. After cooling to room temperature, the mixture was concentrated. The crude reaction product was a mixture by NMR analysis. Representative signals of the maleuramide were δ 10.4 and 6.4.

Example F

N-Carbamylsuccinic Acid

(Succinuric Acid) N-carbamylsuccιnιc 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-carbamylsuccιnιc acid. ¹H NMR (DMSO-cf₆): d 10.2 (br s, 1 H), 7.7 (br s, 1 H), 7.2 (br s, 1 H), 2.5 (m, 4 H)

Example G N-Carbamylsuccinimide 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. ¹H NMR (DMSO- d₆): d 7.9 (br s, 1 H), 7.7 (br s, 1 H), 2.9 (s, 4 H) Example 29

Succinurate Ester of 2-Hydroxyethyl Methacrylate

Monomer M29

A mixture of 4.26 g of N-carbamylsuccinimide (0.03 mole), 4.29 g of 2-hydroxyethyl methacrylate (0.033 moles) and 40 mg of zinc chloride (0.0003 moles) in 5 mL of acetonitrile was heated to reflux. After 6 hours the mixture was cooled to room temperature and the acetonitrile was evaporated to afford 8.2 g of 2-hydroxyethyl methacrylate succinurate as a viscous oil. Η NMR (CDCI₃): d 10.1 (br s), 8.3 (br s), 6.4 (br s), 6.2 (m, 1 H), 5.6 (m, 1 H), 4.4 (m, 4 H), 2.7 (m, 4 H), 1.9 (m, 3 H); HPLC (10% CH₃CN/H₂0, C_β): R,= 2.7 minutes.

Examples 30 - 52

These examples illustrate the utility of the monomers of the present invention in wet adhesion and self-crosslinking applications.

TEST PROCEDURE

A. Latex Preparation

The following general procedure was used in the synthesis of all acrylic latexes containing the monomers of the present invention. 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, N₂ 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:

Reactor Charge Wt, (g)

D.I. Water 192.1

Monomer Emulsion

D.I. Water 182.6 Rhodacal^® DS4 (Surfactant) 21.7

Wet Adhesion Monomer (WAM) 5.0

Methylmethacrylate 260.0

Butylacrylate 230.0

Methacrylic acid 2.7 Initiator Solution

Ammonium Persulfate^* 2.0

D.I. Water 98.0

^*23% solution in water; product of Rhόne-Poulenc Co.

The monomer emulsion was prepared by.

1 dissolving the surfactant in water;

2 if the WAM monomer was only water soluble, adding it to the water surfactant solution,

3 blending all the monomers together then, if the WAM monomer was soluble in the organic phase, dissolving it in the monomer blend; then

4 mixing the monomers with the water surfactant solution and keeping the mixture agitated to insure a homogeneous dispersion.

B. Polymerization Procedure The reactor water was heated to 80°C while the system was under a N₂ blanket At

80°C, 25 grams of initiator solution and 14.2 grams of monomer emulsion were added. The temperature was held at ~80°C for 15 minutes, then the the remainder of the monomer emulsion and initiator solutions were fed over a 2 5 hour period using the appropriate calibrated pumps. The polymerization temperature was maintained at 80 ± 1 X during the addition

After completion of the monomer and initiator addition, the 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% NH₄OH 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%

The physical properties of some of the latexes prepared using the monomers of the present invention are summarized in Table I, below Included for comparison are latices containing no urea/ureido functional monomer, which control is indicated as sample "L-C," and commercially available SIPOMER^® WAM II, indicated as sample "L-WII " The labels M1 , M3, etc., refer to monomers corresponding to the Examples described herein All monomers were tested at 1 wt % level based on the final latex polymer TABLE I

Physical Properties

Example Sample Monomer PH % Solids Particle Size (Microns)

30 L-C None 9.02 49.3 0.21 - 0.25

31 L-WII SIPOMER* ' 9.03 51.2 0.21 - 0.25 WAM II

32 L-M1 M1 9.11 50.5 0.21 - 0.25

33 L-M2 M2 9.01 50.5 0.21 - 0.25

34 L-M3 M3 9.06 49.9 0.21 - 0.25

35 L-M9 M9 9.06 49.1 0.21 - 0.25

36 L-M10 M10 9.03 49.7 0.21 - 0.25

35 L-M12 M12 9.02 50.6 0.21 - 0.25

36 L-M13 M13 9.01 50.0 0.21 - 0.25

C. Wet Adhesion Test

Certain of the above latices were formulated into semigloss latex exterior house paint for measurement of wet adhesion properties. The recipe used for the paint formulation is shown below in Table II. The results of the wet adhesion properties of the above-described monomers and other monomers of the present invention are shown in Table IV, below.

TABLE II

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

EXTERIOR TRIM HOUSE PAINT

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.

The wet adhesion test results obtained with latex paints containing the wet adhesion monomers of the present invention are shown in Table IV. Included for comparison are the paints containing no wet adhesion monomer ("P-L-0") and commerically available wet adhesion monomer SIPOMER^® WAM II ("P-L-WII"). As stated above, the labels M1 , M3, etc., refer to monomers corresponding to the Examples described herein.

TABLE IV WET ADHESION RESULT

The results in Table IV show that without the addition of the wet adhesion monomer, the paint films are completely removed regardless of the drying period and that the monomers of the present invention are at least equivalent to the commercially used monomer SIPOMER^® WAM II at the levels tested

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 40

Following the test procedure of Example 37, when M11 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 42

Following the test procedure of Example 37, when M21 was used in place of M12, and tested in accordance therewith, substantially equivalent results were obtained

Example 43

Following the test procedure of Example 37, when M12 was replaced with M22, 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

Example 45

Following the test procedure of Example 37, when M12 was replaced with M24, and tested in accordance therewith, substantially equivalent results were obtained Example 46

Following the test procedure of Example 37, when M12 was replaced with M25, and tested in accordance therewtih, substantially equivalent results were obtained.

D. Self-Crosslinking Test

Certain of the above latexes were cast into thin films, air-dried and cured at 120X for 1 hour in a forced-air oven. Air-dried films were found to be soluble in acetone except for acrylated maleurate and similar doubly unsaturated monomers which produced crosslinked insoluble films Cured films were insoluble in all cases. The results are shown in Table It, below.

TABLE II

Self-Crosslinking of All-Acrylic Latexes Using

Urea Functional Monomers of the Invention

The results in Table II, above, show that the functional monomers of the present invention provide self-crosslinking properties to the latex films

Examples 47-49

Following the test procedure of Example 33, when M2 was replaced with monomers M4, M5 and M13, substantially equivalent results were obtained.

Examples 50-52

Following the test procedure of Example 37, when M12 was replaced with monomers M1 1 , M15, M21 and M22, substantially equivalent results were obtained.

Although the present invention is described with reference to certain preferred embodiments, it is apparent that modifications thereof may be made by those skilled in the art without departing from the scope of this invention as defined by the appended claims

Claims

1 . A compound of the formula (I):

wherein Y is

wherein A is

^X

wherein each R is individually

T

wherein each R² is individually hydrogen or an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms wherein each R³ is individually an aliphatic, alicyclic or aromatic moiety having up to 24 carbon atoms wherein each R⁴ 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 -CH₂-CH₂-, then A is a group which contains ethylenic unsaturation.

2 A polymer of one or more ethylenically unsaturated monomers, characterized in that at least one of the ethylenically unsaturated monomers is a compound as set forth in claim 1

3 The polymer of claim 2, characterized in that the polymer is a copolymer of one or more compounds of the Formula (I) with one or more other ethylenically unsaturated monomers

4. A latex composition comprising a latex polymer of one or more ethylenically unsaturated monomers, characterized in that at least one of the ethylenically unsaturated monomers is a compound as set forth in claim 1

5 The latex composition of claim 4, characterized in that the latex polymer is a copolymer of one or more compounds of the formula (I) with one or more other ethylenically unsaturated monomers

6 A method for enhancing the wet adhesion properties of a latex polymer dervied from the addition polymerization an ethylencially unsaturated monomer system, by incorporating into the ethylenically unsaturated monomer system, prior to polymerization, one or more compounds as set forth in claim 1.

7. 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 as set forth in claim 1