WO1991012243A2

WO1991012243A2 - Copolymerizable imidazolidinone monomer

Info

Publication number: WO1991012243A2
Application number: PCT/US1991/000939
Authority: WO
Inventors: Thomas O. Murdock
Original assignee: H.B. Fuller Licensing & Financing Inc.
Priority date: 1990-02-14
Filing date: 1991-02-12
Publication date: 1991-08-22
Also published as: JPH05503941A; WO1991012243A3; EP0594596A1; CA2074098A1

Abstract

A monomer and polymers resulting therefrom, the monomer comprising (I), wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -alkyl, -aryl, -CH2(CH2)y-C = N, -CH2O alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; A = phenylene or alkylene; Y = -O-, -NH-, -NHNH, -O-M-, -NH-M-, or -NH-NH-M-; Z = -O- or -S-, and M = (a), (b), (c), and (d) wherein x = 2 - 5.

Description

COPOLYMERIZABLE IMIDAZOLIDINONE MONOMER Field of the Invention

This invention relates generally to polymer dispersions and solutions and to monomers used to prepare these dispersions and solutions. More specifically, the present invention relates to copolymerizable monomers which promote wet adhesion in any variety of polymeric compositions including sealants, coatings, paints, and adhesives among others.

Background of the Invention In the formulation and application of coating and sealing compounds there are any number of physical properties which become relevant depending on the final application. For example, the properties of a paint composition may vary tremendously depending on the nature of the surface of application, the location of this surface, and the amount of contact or use to which this surface is to be subjected. Generally, certain physical properties are more desirable than others including wet adhesion and scrub resistance. In the past, various polymeric systems have been used to bolster any number of sealants, caulks, and paints to increase these characteristics within the end use composition.

For example, Haskins et al, U.S. Patent No. 2,727,01c discloses acrylamides of N-aminoalkyl alkylene urea polymers useful in coating compositions. Hurwitz, U.S. Patent No. 3,369,008 also discloses N(cyclic ureidoalkyl)crotonamideε polymers useful in coating compositions. Dixon et al, U.S. Patent No. 4,111,877 disclose allyl esters of N-alkyl-omega-(alkyleneureido} a ic acids useful for imparting wet adhesion properties re emulsion systems. Sims, U.S. Patent No. 4,104,220 discloses novel alkenyl succinamic ureido compounds useful as functional comonomers for imparting wet adhesion. ^"ong et al, U.S. Patent No. 4,722,965 disclose a chalk-adhesion polymer latex for exterior coatings. Summary of the Invention

The present invention provides a polymerizable monomer for the promotion of wet adhesion having the formula: R' 0

-A-NH-C-Y-CH₂(CH₂)_nN- - H₂),.

Z=C X wherein n = 1 or 2; = 1 or 2; R' = H or CH₃; X = -0-, -CH₂, -NR-; R = H, -C_x,₅ alkyl, -aryl, -CH₂(CH₂)_X-C = N,

-CHOCj.s alkyl, -(CH₂)_x0H, -CH₂CH(OH)CH₃; A = phenylene or

Ci_₅ alkylene; Y = -0-, -NH-, -NHNH-, -0-M-, -NH-M-, or -

NH-NH-M-; and

O R' 0 NH 0 " I

M = -COCH₂-CH-0-, -NH-C-CH₂-, -NH-C-, and -C(CH,)_xO- wherein x = 2 - 5. The monomer may also be synthesized to have vinyl acrylic functionality.

The monomer of the present invention can be used either alone or polymerized in any given polymer system. The polymerizable monomer of the present invention provides far superior wet adhesion when compared to polymers presently commercially available and commonly used in the coatings and paint industries . Detailed Description of the Invention

The present invention discloses monomers useful in polymeric materials, the monomers providing enhanced wet adhesion and scrub resistance. The enhanced wet adhesion monomers of the present invention may be polymerized into polymeric materials or polymers that may be added to other polymers. The instant monomer can be used in polymeric matrices which result in any number of adhesives, caulks, latexes, paints, coatings, and sealants among other matrices. The wet adhesion monomers of the present invention can be used in polymeric compositions that are applied to any number of substrates and subjected to any number of environmental factors. The instant wet adhesion monomer may be applied in any number of ways. Wet adhesion monomers can be copolymerized in latex compositions, paint compositions, coating compositions, and film compositions.

The Monomer The present invention is a monomer for the promotion of wet adhesion having the formula:

R' 0 A-NH-C-Y-CH₂(CH₂)_rN fCH₂)_E

>

Z=C X wherein n = 1 or 2; m = l or 2; R' = H or CHj; X = -0-, -CH₂, -NR-; R = H, -C^ alkyl, -aryl, -CH₂(CH₂)_X-C = N, -CH₂OC,_₅ alkyl, -(CH₂)_x0H, -CH₂CH(OH)CH₃; A = phenylene or d._s alkylene; Y = -0-, -NH-, -NHNH-, -O-M-, -NH-M-, or - NH-NH-M-; and

O R' 0 NH 0 M - -COCH₂-CH-0-, -NH-C-CH₂-, -NH-C-, and -C(CH₂)_xO- wherein x = 2 - 5. The monomer may also be synthesized to have vinyl acrylic functionality.

Synthesis of the monomer of the present invention is initiated by reacting any compound having an active vinyl group and a reactive isocyanate group with a backbone compound having an active hydrogen in the form of a reactive hydroxyl group or a ine group. Generally, isocyanate-type compounds and monomers have been found useful to this end. The preferred isocyanate compound useful in the invention is a compound having a single polymerizable vinyl group and a single monoisocyanare group.

In preparation of the monomer of the present invention a vinyl compound such as alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) is combined with a backbone heterocyclic compounds such as oxazolidinone in the presence of an organic solvent and heat. Generally, any organic solvents found useful in synthesizing the monomer of the present invention include ethyl acetate, hexane, chloroform and the like. Optionally, a reaction catalyst such as dibutyl tin dilaurate may also be used. Backbone compounds which may be allowed to react with m-TMI include any variety of heterocyclic or heteroaliphatic compounds including 1-(2-hydroxyethyl) imidazolidin-2-one, N,N-diethylethylenediamine, 2-(2-aminoethyl)imidazolidin-2-one and the like which when reacted with m-TMI produce polymerizable compounds which are capable of being used in all acrylic systems .

Alternatively, the monomer of the present invention may be synthesized in any manner which permits its use in vinyl acrylic systems. In this instance, instead of using m-TMI, compounds such as 2-vinyl-4,4-dimethyl-2-oxazolin-5-one may be combined with backbone compounds such as N-(2-hydroxyethyl)oxazolidin-2-one, N,N-diethylethylenediamine and 2-(2-aminoethyl) imidazolidin-2-one in a manner that provides the polymerizable compound useful in vinyl acrylic systems. In this instance, the 2-vinyl-4,4-dimethyl-2-oxazolin-5-one has a reactive carbonyl in the five position which results in the five member ring opening when combined with the reactive amine moiety of the backbone compound. The resulting monomer is an imidazoline type compound having an amide linkage which is terminated by a polymerizable olefin group at one end of the monomer. This monomer may then be polymerized with compounds such as vinyl acetate and n-butyl acrylate to provide an emulsion polymer useful again in any type of latex, caulk, adhesive, or other film forming compositions.

In preparation of the polymers of the invention, olymerization occurs through the vinyl group.

Comonomers The polymerizable compound of the present invention may be combined with any number of monomers to form a copolymer. The monomer of the present invention may be polymerized with virtually any other vinyl monomer. Examples of the broad classes of such vinyl monomers include alpha-olefins, vinyl chlorides, vinylidene chlorides, vinyl aromatic monomers, polymerizable alpha, beta-unsaturated carboxylic acids and esters, and other well known monomers.-

The vinyl unsaturated monomer can be an alpha-olefin monomer such as ethylene, propylene, butylene, isobutylene, hexene; styrene, alpha methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, ricinoleic acid, oleic acid, linoleic acid, butadiene, and the like. Alpha-olefins that can also be used in the invention include other C^,. alpha-olefins such as cyclopentene, cyclopentadiene, 1,3-butadiene, 1-hexene, norbornene, etc.

Useful acrylic monomers include methylacrylate, methyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, butyl acrylate, hexyl acrylate, cyclohexylacrylate, (2-hydroxyethyl) methacrylate,

(2-hydroxyethyl) acrylate, (3-hydroxypropyl) methacrylate, (3-hydroxypropyl) acrylate, (pipiridinoethyl) methacrylate, (morpholinoethyl) methacrylate, and the like.

Useful unsaturated dicarboxylic acids include itaconic acid, cinnamic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like; alpha, beta unsaturated dicarboxylic acid esters of the dicarboxylic acid esters described above including aromatic esters, cycloalkyl esters, alkyl esters, hydroxy alkyl esters, alkoxy alkyl esters, and the like.

Vinyl aromatic monomers that can be used with the monomer of this invention include monomers that comprise at least one aromatic group and at least one polymerizable vinyl group. Typical examples of aromatic groups include phenyl, substituted phenyl, naphthyl, phenanthryl, and others. Preferred vinyl aromatic monomers include the styrene family including such monomers as styrene, methyl styrene (vinyl toluene), ethyl styrene, isopropyl styrene, tertiary butyl styrene, etc. 4-hydroxy styrene, 4-chlorostyrene, and styrene with other common ring substituents.

The proportions of each monomer can vary widely. The vinyl monomer may range generally from 1-99 mole-% and the monomer of the present invention may generally range from 0.05-15 mole-%, preferably from about 0.1 mole-% to 9 mole-% and most preferably for reasons of economy and efficacy from about 0.5 mole-% to 3 mole-%. The molar proportions will vary according to the necessary wet adhesion action and scrub properties desired, and the economics of employing a larger amount of the active monomer of the present invention and the requirements of the physical properties.

The monomer of the present invention may be polymerized into either a latex or solution compositions. Polymerization can generally be carried out in a closed vessel under heated conditions. The solution polymeriza¬ tion reaction is generally carried out with the monomers in solution in an inert organic solvent such as tetrahydro- furan, methyl ethyl ketone, acetone, ethyl acetate, or other suitable organic solvents such as organic C-C₂__ alkanols. Organic solvents can also be mixed with compatible amounts of water in emulsions or inverse emulsion systems. Preferred solvents are non-toxic and odorless. Pre-polymer monomeric starting materials used to form polymeric pre-emulsion compositions using the monomer of the present invention are typically dissolved or suspended in the solvent to a desired concentration. Preferably, the polymerization of the invention is typically performed at a concentration of about 10 wt-% to 70 wt-% of the monomers in the solvent material, although somewhat higher or lower concentrations may be employed in some cases .

Polymerization reactions are typically initiated in a conventional manner, preferably by use of a suitable initiator. Examples of suitable initiators include 2,2'-azobis(2-methylpropane nitrile) (AIBN) , dibenzoyl peroxide tertiary butyl peroctoate, cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se or in combination with a reducing agent in the form of an oxidation reduction catalyst system.

During the course of the reaction, the reaction mixture may be agitated and heated preferably in an inert atmosphere (purging with nitrogen, argon, etc.), to about 50-100°C, controlling the reaction temperature to avoid destructive exother s, preferably to about 75-95°C.

Generally, depending upon the final application of the polymeric composition, the polymer may contain anywhere from about 0.05 wt-% to 15.0 wt-% of the monomer of the present invention, preferably from about .10 wt-% to 9.0 wt-% of the present monomer, and most preferably about .5 wt-% to 3.0 wt-% of the monomer of the present invention. However, it should be understood that this concentration may vary given the physical properties to be imparteα to the final system. The molecular weights of the resulting polymers may vary. However, the molecular weight of the resulting solution copoly er is preferably at least approximately 3000. However the molecular weight of these polymers may generally range from 1000 to 1,000,000. Polymerization towards the formulation of latex or dispersion polymers may be completed under substantially similar circumstances except that the medium of polymerization is aqueous instead of organic . The molecular weights of the resulting latex polymers may vary generally from 1000 to 2 million with about 50,000 being a preferred weight. Depending on the comonomers used in the polymers of the present invention, these polymers form a colloidal dispersion suspended in an aqueous carrier which, once applied, forms a readily wetting and scrub resistant film.

Once a monomer of the present invention system is polymerized with comonomers, the emulsion polymer may be formulated into any number of compositions including paints, film coatings, sealants, adhesives, caulks, or the like. The formulation of these systems will vary depending upon the application of the system, i.e., the systems final end use. However, formulation processes include those found within the following examples, as well as those generally known within the art. Generally, again depending upon the physical properties to be imparted to the final system, the monomer will have a concentration with the final system which may range from about 0.001 wt-% to 10.0 wt-%, preferably from about .01 wt-% to 7.0 wt-%, and most preferably from about .10 wt-% to 5.0 wt-%. The following examples illustrate the preparations of monomers, and polymers utilizing the present invention in the preparation of films, caulks, coatings, aqueous latices, and aqueous systems.

ORKING EXAMPLES SET I

The wet adhesion monomer of the present invention was synthesized using various feed stocks including N-(2- hydroxyethyl)oxazolidin-2-one or N,N-diethylethylenediamine in combination with alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) in the presence of an organic solvent.

Monomer Synthesis Working Example 1 The monomer

synthesized from N-(2-hydroxyethyl)oxazolidin-2-one, and m-TMI using the following procedure. Using a 100 ml 3- necked round bottom flash equipped with a N₂ inlet and magnetic spin bar, m-TMI (10.1 grams, 0.05 moles) was added in 25 ml of ethyl acetate. A solution of N-(2- hydroxyethyl)oxazolidin-2-one (6.6 g, 0.05 mol) in 25 ml of ethyl acetate was added to the mix over a 45 minute interval. After approximately 7 hours at 25°C, the reaction mixture was slightly cloudy and after an additional 30 minutes at 25°C, the entire reaction mixture formed a white crystalline mass. The reaction mixture was allowed to stand at 25°C. overnight. The solid was dissolved in about 150 ml hot ethyl acetate. Some insoluble material (about 1 gram) was removed by filtration. The solution was allowed to slowly cool to 25°C. White crystals formed. The produce was placed in a freezer and the crystals were collected by suction filtration. The crystals had a melting point of 129-130^rC. Melting point, Carbon 13 nuclear magnetic resonance spectroscopy, and infrared analysis were completed on the monomer of Example 1 with the following results. Referring to Figure 1, nuclear magnetic resonance spectroscopy (NMR) provided the following data reported by chemical shift (PPM): Carbon No. 1 at 21.8; Carbon No. 2 at 29.4; Carbon No. 3 or 4 at 43.8; Carbon No. 4 or 3 at 44.7; Carbon No. 5 at 55.3; Carbon No. 6 at 61.1; Carbon No. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 8 at 122.0; Carbon No. 10 at 123.9; Carbon No. 11 at 124.0; Carbon No. 12 at 128.3; Carbon No. 13 at 141.3; Carbon No. 14 at 143.5; Carbon No. 15 at 147.1; Carbon No. 16 at 154.5; Carbon No. 17 at 158.6.

The Carbon 13 spectra of the sample exhibits both the proper number of nonequivalent carbons and the correct number of attached protons recorded by the monomer. Upon determination, the melting point of the monomer was 129.0 to 130.0°C.

Infrared scan provided the following results using a KBr pellet: NH amine at 3314 cm^"1 C = 0 (oxazolidinone) at 1737 cm^"1; C = 0 (urethan) at 1715 cm^"1; C = C at 893 cιr.^": ; C = C (aromatic) at 812 cm^"1.

Working Example 2 An analogue of the wet adhesion monomer naving the formula:

was prepared using m-TMI and N,N-diethylethylenediamine in hexane by the following procedure.

Using a 250 ml 3-necked roundbottom flask equipped with a reflux condenser, N, inlet, magnetic spin bar, temperature probe, and a pressure equalizing addition funnel, m-TMI (20.1 g, 0.10 mol) was added in 50 ml hexane. A solution of H,NCH₂CH₂N(CH₂CH₃)2 (11.6 g, 0.10 mol) in 50 ml of hexane was then added over a 45 minute interval. An ice-water bath was used to keep the reaction mixture between 20°C. and 25°C. The slightly cloudy reaction mixture was stirred for 2 hours at 25°C. Ethyl acetate, 15 ml, was added and the clear solution was filtered and placed in the freezer overnight. The white crystals were collected by suction filtration and had a melting point =

63.5-64.5°C.

The monomer of Example 2 was then characterized using

NMR spectroscopy melting point, and infrared scan. Referring to Figure 2, C13 NMR spectroscopy was completed and resulted in the following data (C-13 PPM): Carbcn No.

1 at 11.5; Carbon No. 2 at 21.9; Carbon No. 3 at 30.4;

Carbon No. 4 at 38.2; Carbon No. 5 at 46.6; Carbon Nc. 6 at

52.3; Carbon No. 7 at 54.8; Carbon No. 8 at 112.6; Carbon No. 9 at 122.6; Carbon No. 10 at 124.2; Carbon NO. II at

124.6; Carbon No. 12 at 128.5; Carbon No. 13 at 141.6;

Carbon No. 14 at 143.6; Carbon No. 15 at 147.2; and Carbon

No. 16 at 158.2.

Upon analysis, the melting point of the compound was 63.5 to 64.5°C. Infrared analysis through KBr pellet showed: NH at 3359 and 3322 Cm^"1; C = 0 at 1633 cm^""; Z = C at 882 cm^"!; C = C (aromatic) at 802 cm^"1.

Working Example 3

Synthesis of the monomer having the formula

was then attempted using m-TMI, l-(2-hydroxyethyl) imidazolidin-2-one, and the following process.

Using a 1 liter 3-necked roundbottom flask equipped with a N₂ inlet, magnetic spin bar and a pressure equalizing addition funnel, m-TMI (224.6 g, 1.12 mol), was added with 150 ml CHC13 and 1.0 g of dibutyl tin dilaurate. A solution of the cyclic urea (154.0 g. 1.17 mol) was then added in 250 ml of CHC13 over a one hour interval. The flask was cooled once with cold water to maintain a temperature less than 30°C. After 2 hours at ambient temperature the CHC13 was removed from the reaction mixture with a rotary evaporator to yield an oil. The oil was dissolved in an ethyl acetate/hexane mixture and filtered while hot. White crystals began to form upon cooling.

Evaluation of the monomer resulting from Working Example 3 was then attempted using nuclear magnetic resonance spectroscopy, melting point and infrared analysis. Referring to Figure 3, NMR spectra provided the following data (C-13, PPM): Carbon No. 1 at 21.9; Carbon No. 2 at 29.5; Carbon No. 3 at 38.2; Carbon No. 4 or 5 at 43.1; Carbon No. 5 or 4 at 45.4; Carbon No. 6 at 55.2; Carbon NO. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 9 at 122.1; Carbon No. 10 at 124.0; Carbon No. 11 at 124.1; Carbon No. 12 at 128.3; Carbon No. 13 at 141.4; Carbon No. 14 at 143.6; Carbon No. 15 at 147.3; Carbon No. 16 at 154.9; Carbon No. 17 at 163.1. Upon analysis, the melting point of this monomer was determined to be 94.5 to 95.5°C. An infrared analysis was then completed using a potassium bromide pellet and provided the following data: NH at 3423 and 3264 cm^"'; C = 0 at 1713 cm^"1; NH at 1679 cm^"1; C = C at 896 cm^"1; and C = C (aromatic) at 802 cm^"1.

The NMR spectra of the sample clearly indicated that the desired reaction product was obtained in high purity.

Working Example 4

_.-

A similar monomer synthesized in Example 3 was then synthesized using meta-TMI and 2-(2-aminoethyl) imidazolidin-2-one (AEI) using the following procedure. Using a 500 ml 3-necked roundbottom flask equipped with a pressure equalizing addition funnel, magnetic spin bar, thermometer and a N, inlet was added m-TMI (80.4 g, 0.40 mol.) was added to the flask with 100 ml of chloroform. A solution of AEI (55.6 g, 0.40 mol) in 100 ml of chloroform was added dropwise to the flask over a 1 hour interval while maintaining the reaction temperature between 20-25^cC with an ice/water bath. The reaction mixture was stirred at 24°C overnight and then filtered. The chloroform was removed on a rotary evaporator to yield 140 g of crude product (103%). Recrystallization from ethyl acetate/ethanol afforded a white crystalline solid, having a melting point of 143.5-44.5°C.

Working Example 5

A scale up of Example 4 was then attempted using 1- (2-aminoethyl)imidazolidin-2-one, m-TMI, and the following procedure. Using a 2 liter 3-necked roundbottom flask equipped with a mechanical stirrer, reflux condenser, pressure equalizing addition funnel and a N₂ inlet, a solution of l-(2-aminoethyl)imidazolidin-2-one (173.6 g, 1.34 mol) was added in 500 ml of chloroform to the flask.. A solution of m-TMI (275.5 g, 1.38 mol) in 250 ml of chloroform was added to the flask at a rate such that the temperature of the reaction mixture did not exceed 25°C. The flask was cooled with an ice-water bath. Once completely added, the mixture crystallized. An additional 300 ml CHC13 was added and the mixture was stirred at 25°C. for 2 hours. The mixture was then analyzed by TLC. The slurry of the product in CHC13 was dissolved by warming with a hot water bath. The clear solution was filtered into an Erlenmeyer flask and allowed to cool to 25°C, and subsequently placed in the freezer. A white crystalline solid was isolated by suction filtration and the crude product had a melting point of 138-143°C. The solid was recrystallized and recovered from ethyl acetate/isopropanol (60:40). The recovered crystals had a melting point of 143.0 to 144.5°C. The monomer reaction product of Example 5 was then submitted for structural evaluation by C13 NMR and infrared spectroscopy. Referring to Figure 4, C13 NMR spectroscopy provided the following chemical shift data: Carbon No. 1, 21.5; Carbon No. 2, 30.0; Carbon Nos . 3 or 4, 37.2; Carbon Nos. 4 or 3, 37.4; Carbon Nos. 5 or 6, 43.6; Carbon Nos. 6 or 5, 44.7; Carbon Nos. 7, 54.0; Carbon No. 8, 112.1; Carbon No. 9, 121.7; Carbon No. 10, 122.7; Carbon No. 11, 124.1; Carbon No. 12, 127.7; Carbon No. 13, 139.9; Carbon No. 14, 143.0; Carbon No. 15, 149.0; Carbon No. 16, 156.9; and Carbon No. 17, 162.2. A melting point for the sample was determined to be 143.5-144.5°C. and an infrared scan was run of the sample using a KBr pellet. The infrared scan provided the following data: NH at 3349, 3242 cm^"1; C = 0 at 1689 cm^"1; NH at 1680 cm^"1; NH at 1660 cm^"1; C = C at 890 cm^"1; and C = C aromatic at 804 cm^"1.

The Carbon 13 spectra of the sample exhibit both the proper number of nonequivalent carbons and the correct number of attached protons required by the formula of this monomer.

Working Example 6

A synthesis of a solid monomer having the formula

was then attempted using m-TMI, and l-(2-aminoethyl) imidazoline-2-one (AEI) using the following process. Using a 1 liter 3-necked roundbottom flask equipped with a N₂ inlet, mechanical stirrer, pressure equalizing addition funnel and a thermometer (AEI) (64.5 g, 0.50 mol) was added in 200 ml of ethyl acetate to the flask. A solution of m-TMI (101.5 g, 0.505 mol) in 100 ml of ethyl acetate was added dropwise to the cloudy amine/ethyl acetate mixture. After the addition of about 10 ml of the m-TMI solution, the reaction mixture became clear. The reaction mixture was cooled with a cold water bath to maintain the temperature between 25-3d°C.

A few white crystals began to form on the side of the reaction flask after about 35 ml of the m-TMI solution had been added. Fine crystals were dispersed in the reaction mixture after about 50 ml of the m-TMI solution had been added. A white crystalline slurry was obtained after the addition of 60 to 65 ml of the m-TMI solution. The m-TMI solution was added dropwise over a 1 hour interval. The reaction mixture was stirred with some difficulty upon completion of the addition of the m-TMI solution. An additional 25 ml of ethyl acetate was added to the reaction mixture to facilitate mixing. The mixture was stirred for 3 hours at 25°C. and the white solid was isolated by suction filtration with a Buchner funnel.

The reaction flask was rinsed with 100 ml of ethyl acetate and then it was poured over the crystals in the Buchner funnel. The melting point of the recovered white solid was 138.5-142.0°C. The filter cake was broken up and dried by pulling air through the pulverized solid for 30 minutes with a water aspirator. The weight of the solid was 232.4 g. The solid was air dried overnight, weight = 201.3 g. The filtrate was concentrated and an additional 6.8 g of solid was obtained. The solid was further dried by spreading on a sheet of release paper to obtain 159.8 g of product. Total recovery = 159.8 + 6.8 = 166.6 g (100.9%). The residue collected by concentrating the mother liquor was a mixture of a crystalline compound and an oil. The material was not characterized further.

Emulsion Polymers Emulsion polymeric compositions were then synthesized using the monomers of Working Examples 1, 2, 3 and 6. Generally, emulsion polymers containing the monomer of the present invention were polymerized by charging a reactor with water, a surfactant based defoamer such as Balab 748, commercially available from Witco Chemical Co. , and diammonium phosphate. A catalyst was then charged into the reactor over a delayed period of time as a water carried system of ammonium persulfate and sodium metabisulfite. The pre-emulsion was prepared by first forming a solution of the monomer of the present invention with a surfactant sucr. as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed in Working Examples 7-10 and subsequently adding the solution of monomers and surfactant to a beaker containing water which was being agitated with a paddle-type blade stirrer. The pre-emulsion composition was then added to the reactor and over a delayed period of time, an additional amount of the same catalyst was added to the reactor. Working Example 7 The monomer of Example 6 was used to prepare a pre- emulsion polymer base for use in a paint composition. The pre-emulsion polymer base had the following compound and monomer constituents in the reaction. Pre-Emulsion Constituents Parts B Wei ht

Working Example 8

Using the same process as Example 7 the monomers of Examples 2 and 3 were used to form a pre-emulsion composition. Pre-Emulsion Constituents Parts B t

Using the process of the two preceding Examples the monomers of Example 1 and 6 were used to form a pre- emulsion composition base for Examples 9 and 10.

Workin Exam le 9

Working Example 10

Pre-Emulsion Constituents

H₂0

IGEPAL CA897 (ethoxylated phenol from GAF Corp. ) Example 6 Monomer Diammonium Phosphate n-butyl acrylate Methyl methacrylate Methacrylic Acid

Pigment Grinds

In preparation of paint systems having a polymer containing the wet adhesion monomer of the present invention pigments grinds were formulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first, then adding the extenders in any order after the Ti0₂. Once the pigment had been wet out, the remaining amount of defoamer was added. The pigment composition was then ground at high speed (about 4,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.

Exterior Flat Grind Parts By Weight

Water, DI 91.6

Nopcosperse 44 (dispersant, 7.7

Henkel Corp. ) Nuosept 95 (preservative, 1.5

Nuodox Inc. ) Polyphase AF-1 (mildewcide 4.8

Troy Chemical Corp.) Igepal CO-630 (from GAF Corp.) 3.5 AMP 95 (dispersant, 1.5

Augus Chemical Co. ) Ti0₂ 250.0 Feldspar (available from 190.0

Indusmin, Inc. ) Drew-L464 (Defoamer available 1.98 from Drew Industries)

Exterior Semigloss Grind Parts By Weight

Water, DI 58.3

Tamol 731 (dispersant, 8.6 Rohm & Haas) Igepal CO-630 (surfactant, 3.5 GAF Corp. )

AMP 95 (dispersant, 1.0

Augus Chemical Co. )

Nuosept 95 (preservative, 1.5 Nuodex Inc. )

Polyphase AF-1 (mildewcide, 4.8

Troy Chemical)

Ethylene Glycol 18.6

Ti0₂ 250 . 0 Clay 25 . 0

Drew L464 (defoamer, Drew 1.8

Industries)

373.1

Semi-Gloss and Flat Paints

Paint systems, semigloss as well as flat, were then formulated using the polymeric systems of Working Examples 7-10 and pigment grinds previously formulated by weighing the latex polymer and defoamer into a lined can or stainless steel beaker. The system was then mixed with a three bladed paddle and the pigment grind and water was added to the latex. Cellulosic Natrosol™ thickeners were added along with the propylene glycol and Texanol™. The mixture was slowly and continuously mixed until a vortex formed with agitation increased as needed. The composition was mixed for 10 minutes or until the thickener dissolved. Once formulated, the paint was covered and let stand for 24 hours prior to testing. This process was used to formulate the exterior flat and semi-gloss paint of Examples 11 and 12.

The term "latex" is provided below and both Working Examples 12 and 13 is a generic reference with the polymers within each of the Working Examples 11A through 11J and 12A through 12J being defined as follows: Working Examples Latex

11A 12A Control Latex from Rohm and Haas 11B 12B Control Latex from H. B. Fuller

PD-442 containing Sipo er WAM from Alcolac Example 7A Latex Polymer

Example 7A Latex Polymer (Aged 2 weeks at 50°C) Example 7B Latex Polymer Example 8A Latex Polymer Example 8B Latex Polymer

Example 9A Latex Polymer Example 9B Latex Pol mer

Example 10 Latex

Constituents

Semi-Gloss Pigment Gr

and Haas) Latex

Propylene Glycol Texanol (coalescent,

from Texaco Inc.)

RM-825 (associative thickener, 3.0 3.0 from Rohm & Haas) Nat 250 MHBR thickener, 1.5 1.5 from Aqualon Co. ) Water 239.3 179.1

Drew L464 (defoamer, from 3.1 3.1

Drew Industries)

Working Examples 12A-12J

Constituents Parts B Wei ht

Flat Pigment Grind 1 AC-64 (polymer from Rohm and Haas) Latex

Propylene Glycol Texanol (from Texaco Inc. ) Nat 250MHBR (from Aqualon Co.) Water, DI

Drew L464 (defoamer, from

Drew Industries)

Analysis was then undertaken to determine the relative resistance of each of the examples in Example 12 and 13 towards scrub resistance and wet and dry adhesion measured in gram weight. The results are shown in Tables 1 and 2.

TABLE 1

-31-

TABLE 2

Caulk Compositions

Caulk compositions were then prepared using the wet adhesion monomer synthesized in Example 6. Generally, the caulk of Working Examples 13A and 13B were synthesized by charging a reactor with 400 parts of water, 10 parts of acrylic acid, adjusting with a buffer to a pH of 7 or 8 and then raising the reactor temperature to 80°C under a nitrogen purge. At 50°C, 3.3 parts of Igepal CA-520 (from GAF Corp.) were added to a reactor. At 80°C the pre- emulsion composition was added to the reactor with the immediate addition of a potassium persulfate catalyst. The pre-emulsion composition was added at a rate of 5% over 15 minutes with the remaining 95% being completely added at the end of 3-1/2 hours. During the additions the reactor temperature was maintained at a temperature of between

78-80°C. The temperature of the reaction was held for 30 minutes and then allowed to cool.

-33-

Working Example 13

Weight-%

Pre-Emulsion Composition 13A 13B

Water 120 120 Igepal CA 897 (from GAF Corp.) 5.04 5.20 n-Butyl acrylate 667.0 659 2-Ethyl Hexyl Acrylate 90 90 Methacrylic Acid •^* 20 20 Methacrylonitrile 16 16 Example 6 Monomer 9.6

The caulk compositions containing emulsion polymers having the monomer of the present invention (Example 13B) were shown to improve adhesion to a variety of surfaces when compared to caulk formulations containing polymers without a wet adhesion monomer (Example 13A) .

Working Example 14

A solution polymer for a coating composition was then prepared using the monomer of Example 6 in a 1 liter three-necked roundbottom flask equipped with a mechanical stirrer, addition funnels, reflux condenser and a thermometer. Toluene (150 g ) and the Pre-Solution

Composition (50 gm) was then added to the flask. The reaction mixture was warmed to reflux (approx. H0°C) and the remainder of the Pre-Solution mixture was added over a 4 hour interval and the peroxide initiator was added over a

4-1/2 hour interval.

Pre-Solution Composition Parts by Weight

Butyl acrylate 150

Hydroxyethyl acrylate 125 Butyl methacrylate 100

Methyl methacrylate 60

Styrene 50

Methacrylic acid 15

Example 6 Monomer 6.5 Toluene 150

Lupersol 575M75 (peroxide, from 24.0

Penwalt Chemical Co.

A clear, viscous solution was obtained.

Working Example 15

A coating was then prepared with the resin of Working Example 14 for evaluation as an adhesion promoter. Constituents Parts By Weight Working Example 14 Prepolymer 32.3

Cymel 303 (crosslinking resin 7.5 from American Cyanamid) n-Butanol 4.0

Aromatic 100 (hydrocarbon solvent 4.0 from Worum)

DBE Solvent (coalescent from DuPont) 4.0 Cycat 4040 (acid catalyst from 0.3

American Cyanamid

The coating samples were prepared in a glass jar and applied to a green alkyd base painted wood surface with a bird type applicator. Wet film thickness was 6 ml. The samples were placed in a drying oven at 140°C for 20 minutes. The samples were allowed to equilibrate for two days at ambient temperature and humidity. A Crosshatch wa; scribed into the coating with a razor blade and 1/2 of the board was immersed in water for 30 minutes. The adhesion of the coating to the alkyd was determined with a 3E Company, 610 tape test. No dela ination from the alkyd coated surface was noted from the control or the experimental coating.

WORKING EXAMPLES SET II

An additional set of experiments was undertaken to attempt to develop a vinyl acrylic latex useful in coatings or paint formulations which would exhibit the enhanced wet adhesion found with the previous examples. Initially, the wet adhesion monomer of the present invention was synthesized. This wet adhesion monomer was then further applied within polymer compositions. The polymer compositions were then introduced into semigloss and flat latex paints. The resulting paint formulations were then tested against controls to determine their relative wet adhesion, dry adhesion, and scrub resistance

Monomer Synthesis Generally, the vinyl monomer of this set was synthesized from feed compounds such as 2-vinyl-4,4- dimethyl-2-oxazolin-5-one which were then allowed to react with a feed stock of an imidazolidine compound such as l-(2-amino ethyl)-imidazolidin-2-one (AEI). After a given reaction period in an organic medium, the solid precipitate was generally isolated by filtration. The precipitate was then generally purified by washing and characterized through chemical analysis.

Working Example 1

An attempt to synthesize a wet adhesion monomer having the formula

CH₂=CH

0 using 2-vinyl-4 , 4-dimethyl-2-oxazolin-5-one (VDM) , and AEI and the following process.

Using a 300 ml 3-necked roundbottom flask equipped with an addition funnel, magnetic spin bar, temperature probe and a N₂ inlet, the azlactone (13.1 g., 0.10 mol) was added in 75 ml of CH,C1₂. A solution of AEI (12.9 g., 0.10 mol) in 75 ml of CH₂C1₂ was added to the azlactone over a 60 minute interval. After approximately 10-15 minutes, the clear reaction mixture became slightly cloudy and a white precipitate began to form. The reaction mixture became difficult to stir with the precipitate and an additional 50 ml CH₂C1₂ was added. A slight exotherm occurred during the reaction and the temperature increased from 23°C. to 30^CC. The reaction mixture was stirred at 25°C. for 4 hours and the white solid was isolated by suction filtration. The filter cake was washed once with 100 ml of hexane. The melting point of the solid was 188.5-189.5°C. The compounc was soluble in water.

The monomer of Working Example 1, Set II, was characterized to carbon 13 nuclear magnetic resonance spectra, melting point, and infrared scan. Referring to Figure 5, the NMR spectrum provided the following data (reported in carbon 13 ppm) : Carbon number 1 at 27.2; carbon number 2 at 40.1; carbon number 3 at 40.8; carbon number 4 at 44.9; carbon number 5 at 48.7; carbon number 6 at 59.5; carbon number 7 at 130.5; carbon number 8 at 132.8; carbon number 9 at 167.5; carbon number 10 at 170.3; and carbon number 11 at 179.9.

Upon analysis, the melting point of the monomer was found to be 188.5 to 189.5°C. Infrared scan showed NH amine character at 3386, 3323, and 3359 cm^"1; C = 0 character at 1688 cm^'1; NH amine 1656 cm^"1; and C = C at 1629 cm^"1.

Working Example 2

An attempt to scale up the synthesis of Working Example 1 was then attempted.

Using a 2 liter 3-necked roundbottom flask equipped with a mechanical stirrer, addition funnel, N₂ inlet and a thermometer, vinyl dimethyl azlactone (VDM) (105.0 g, 0.80 mol) was added in 400 ml of ethyl acetate. A dispersion of AEI (103.3 g, 0.80 mol) in 450 ml of ethylacetate was added dropwise over a one hour interval while maintaining the temperature of the reaction mixture between 15-25°C. with an ice-water bath. A white precipitate began to form as soon as the AEI solution was added. The reaction mixture was stirred for an additional 3 hours at 25°C. and the white crystalline solid was isolated by suction filtration and washed with 100 ml of hexane. The crude material had a melting point of 182-185°C. The crude product was recrystallized from a mixture of isopropanol and methanol to afford white crystals having a melting point of 195.0- 196.0°C.

Working Example 3

The pre-emulsion was prepared by first forming a solution of the monomer of the present invention with a surfactant such as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed below and subsequently adding the solution of monomers and surfactant to a beaker containing water which was being agitated with a paddle-type blade stirrer. The reactor was then charged with 4.24 parts of potassium persulfate catalyst and heated to 80°C. with a nitrogen purge. The pre-emulsion composition was then fed into the reactor at a rate of 3% over 15 minutes, another 5 wt-% over the next 30 minutes, and the remaining 92 wt-% over the balance of 3 1/2 hours. The reactor was maintained at about 80^CC. during the feed and the nitrogen purge was shut off.

Pre-Emulsion Constituents Parts By Weight

H₂0 152

Igepal CA897 (ethoxylated phenol surfactant from GAF Corporation) 5.3 TRITON X200 (sodium alkyl aryl polyether sulfonate surfactant from Rohm & Haas) 21.2

Sodium bicarbonate 1.55

Vinyl acetate 625.8 n-butylacrylate 187.5

Example 1 Monomer 9.76

Piqment Grinds

In preparation for the formulation of paint systems having the wet adhesion monomer of the present invention pigment grinds were formulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first adding the extenders in any order after Ti0₂. Once the pigment had been wet out any remaining amount of defoamer was added. The pigment composition was then ground at high speed (about 4,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds. Interior Flat Grind (Parts By Weight)

Water, DI 125.0

Nuosept 95 (preservative, Nuodox Inc.) 2.5

Tamol 731 (dispersant, Rohm & Haas) 9.2

Igepal CO-630 (GAF Corp.) 3.5 AMP 95 (dispersant, Angus Chemical Co.) 2.0 Ti0₂ 190.0

Clay 125.0

Calcium Carbonate 60.0

Attagel 50 (thickener, Engelhard Corp.) 3.0 Drew L464 (defoamer, Drew Industrial Div. ) 1.5

Interior Semigloss Grind (Wt.-%)

Water, DI 66.6

Nuosept 95 (preservative, Nuodox, Inc.) 2.0 Propylene Glycol 17.3

AMP 95 (dispersant, Angus Chemical Co.) 1.5

Tamol SG-1 (dispersant, Rohm & Haas) 7.2

Igepal CO-630 (GAF Corp.) 3.6

Ti0₂ 250.0 Clay 35.0 Drew L464 (defoamer, Drew Industrial Div.) 2.0

Working Example 4 and 5

Flat and se igloss paint systems were then formulated incorporating the polymer system of Example 3 and control polymers by first weighing the latex and defoamer in a lined can or stainless steel beaker. The latexes were mixed with the defoamer using a three bladed paddle stirrer and their respective pigment grinds and water were added to the latex. Thickening constituents were then added to the compositions including a Natrosol (cellulosic thickener) as well as the ethylene glycol constituents and Texanol.

These constituents were slowly added into the vortex cf the mix. Agitation was increased as needed to provide fcr equal mixing of the vortex. The composition was mixed for 10 minutes until the thickener was dissolved. The composition was then covered and let stand for 24 hours. The term "Latex" as provided below is a generic reference with the polymer within each of Working Examples 4A-4C and 5A-5C being defined as follows: Working Example Latex 4A 5A Control PD-124/BHO-20 vinyl acetate butylacrylate copolymer from H. B. Fuller 4B 5B Polymer of Example 4

4C 5C Blend of 75% control polymer and 25% Example 3 polymer

Working Example 4

(Parts By Weight) Constituents 4A - 4B 4C

Flat Pigment Grind Water, DI

PD-124 (BHO-20) (latex, H.B.

Fuller) Latex

Ethylene Glycol Natrosol Plus (thickener,

Aqualon Co. ) Texanol (coalescent, Texaco 10.0 10.0

Co. ) Drew L464 (defoamer, Drew 2.0 2.0 Industrial Div. )

Working Example 5

(Parts B Wei ht Constituents Semigloss Pigment Grind Water, DI

PD-124/BHO-20 (latex, H.B.

Fuller) Latex

Texanol (coalescent, Texaco Co.)

Propylene Glycol Acrysol RM-825

Natrosol 250 MHBR (thickener,

Aqualon Co. ) Drew L464 (defoamer, Drew 2.5 2.5

Industrial Div.)

Working Examples 4A-4C and 5A-5C were then tested to compare the resistance to scrubbing, wet adhesion (measured in grams) and dry adhesion (measured in grams). The results are reported below in Tables 3 and 4.

Table 3

All samples were equivalent in their stability properties. Working Examples 4B and 4C had greater adhesion properties than control Working Example 5A. Working Example 4B containing the monomer of the present invention had superior scrub resistance to the control Working Example 4A.

Regarding the semi-gloss paint formulations, Working Examples 5B and 5C showed greatly improved adhesion compared to Working Example 5A, the control. Overall, the paint compositions having the monomer of the present invention showed superior scrub resistance as well as wet adhesion in both the flat and semi-gloss paint compositions.

The foregoing specification, Examples and data provide a basis for understanding the invention. The invention can be made in a variety of embodiments without departing from the spirit and scope of the invention. Accordingly, the invention resides in the claims hereinafter appended.

Claims

I CLAIM AS MY INVENTION:

1. A monomer comprising:

wherein n = l or 2; m = l or 2; R' = H or CH₃; X = -0-, -CH₂, -NR-; R = H, -d_₅ alkyl, -aryl, -CH₂(CH₂)_y-C = N, -CE₂OC_l.₅ alkyl, -(CH₂)_yOH, -CH,CH(OH)CH₃ wherein y = 1 - 12; A = phenylene or d_₅ alkylene; Y = -0-, -NH-, -NHNH-, -0-M-, -NH-M-, or -NH-NH-M-; and

O R' 0 NH 0

M = -COCH₂-CH-0-, -NH-C-CH₂-, -NH-C-, and -C(CH₂)_xO- wherein x = 2 - 5.

2. The monomer of claim 1 wherein

0 0 CH₃ n rr I

M = -C-0-CH₂CH₂0-, or -C-0-CH₂CH-0-.

3. The monomer of claim 1 wherein

0 0

/ rr

M = -CCH₂CH₂-0- and -CCH,CH₂CH,-0-.

4. A monomer comprising: **

wherein n = l or 2; m = 2; each of R' = independently H or CH₃; Y = -NH- or -0-; Z = -0- or -S-; and R = H or CH₃.

5. The monomer of claim 4 wherein R = H and R' = CH₃; Z = -0-; n = 1; and Y = -NH-. 6. A monomer comprising:

wherein Y = -0- or -NH- and m = 2.

7. The monomer of claim 6 wherein Y = -NH-.

8. A monomer comprising:

0 R'O

// J tr

R'-CH = CH₂CNHC-C-NH₂-CH₂-(CH₂)_nN (CH₂)_E

R' Z=C X wherein n = 1 or 2; m = 1 or 2; X = -0-, -CH₂-, -NR-; R = H, -d.₅ alkyl, -(CH₂)_y0H, -CH₂(CH₂)-C = N, -CH₂0C1-15 alkyl, -(CH₂)_yOH, -CH₂CH(OH)CH₃ wherein y = 1 - 12; R' individually = -H or -CH₃.

9. The monomer of claim 8 wherein X = -NR-; R = H; R' = individually H or -CH₃; = 2; n = 1; and Z = 0.

10. A wet adhesion copolymer comprising a major portion of a first monomer and from about 0.01 mol-% to 15 mol-% of a second monomer of the formula

R' 0 \ "

A A-NH-C-Y-CH₂(CH₂)_rN (CH₂)_tt

Z=C X wherein n = 1 or 2; m = 1 or 2; R' = H or CH₃; X = -0-, -CH₂, -NR-; R = H, -d_₅ alkyl, -aryl, -CH₂(CH₂)_y-C = N, -CHOCi.s alkyl, -(CH₂)_y0H, -CH₂CH(0H)CH₃ wherein y = 1 - 12; A = phenylene or d_₅ alkylene; Y = -0-, -NH-, -NHNH-, -0-M-, -NH-M-, or -NH-NH-M-; and

O R' 0 NH 0

M = -C0CH,-CH-0-, -NH-C-CH₂-, -NH-C-, and -C(CH₂)_x0- wherein x = 2 - 5. -so¬

li. The wet adhesion copolymer of claim 10 wherein the second monomer comprises:

wherein n = 1 or 2; m = 2; each of R' = independently H or CH₃; Y = -NH- or -0-; Z = -O- or -S-; and R = H or CH₃.

12. The wet adhesion copolymer of claim 10 wherein the second monomer comprises:

wherein Y = -0- or -NH- and m = 2.

13. The copolymer of claim 10 wherein the first monomer comprises a vinyl monomer selected from the group consisting of alpha-olefin monomers, acrylic monomers, vinyl aromatic monomers, and alpha-beta unsaturated mono- and di-carboxylic acids and esters thereof.

14. The copolymer of claim 13 wherein the first monomer comprises a vinyl acrylic monomer.

15. A wet adhesion copolymer comprising a major portion of a first monomer and from about 0.01 mol-% to 15 mol-% of a second monomer of the formula

0 R'O

R'-CH = CH₂CNHC-C-NH₂-CH₂-(CH₂)_rN (CH₂)_C

R' Z=C X wherein n = l or 2; m = l or 2; X = -0-, -CH₂-, -NR-; R = H, -d_₅ alkyl, -(CH₂)_yOH, -CH₂(CH₂)-C = N, -CH₂0C1-15 alkyl, -(CH₂)_yOH, -CH₂CH(0H)CH₃ wherein y = 1 - 12; R' individually = -H or -CH₃.

16. The polymer of claim 15 wherein X = -NR-; R = H; R' = individually -H or -CH₃; m = 2; n = 1; and Z = 0.

17. The copolymer of claim 15 wherein the first monomer comprises a vinyl monomer selected from the group consisting of alpha-olefin monomers, acrylic monomers, vinyl aromatic monomers, and alpha-beta unsaturated mono- and di-carboxylic acids and esters thereof.

18. The copolymer of claim 15 wherein the first monomer comprises a vinyl acrylic monomer.

19. An aqueous copolymer latex having enhanced wet adhesion, said latex comprising a major portion of water and dispersed therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:

R' 0 A-NH-C-Y-CH₂(CH₂)_nN (CH₂)_m

Z=C X wherein n = 1 or 2; m = 1 or 2; R' = H or CH₃; X = -0-, -CH₂, -NR-; R = H, -d_₅ alkyl, -aryl, -CH₂(CH₂)_y-C = N, -CH₂OC,_._₅ alkyl, -(CH₂)_yQH, -CH₂CH(OH)CH₃ wherein y = 1 - 12; A = phenylene or d_₅ alkylene; Y = -0-, -NH-, -NHNH-, -0-M-, -NH-M-, or -NH-NH-M-; and

0 R' 0 NH 0

// I rr rr rr

M = -C-0-CH₂-CH-0-, -NH-C-CH₂-, -NH-C-, and -C(CH₂)_x0- wherein x = 2 - 5.

20. The latex of claim 19 wherein the second monomer comprises :

wherein n = 1 or 2; = 2; each of R' •= independently H or CH₃ ; y = -NH- or -0- ; Z = -0- or -S- ; and R = H or CH₃ .

21. The latex of claim 20 wherein the second monomer comprises:

wherein Y = -0- or -NH- and m = 2.

22. An adhesive composition comprising the latex of claim 19.

23. A coating composition comprising the latex of claim 19.

24. A sealant composition comprising the latex of claim 19.

25. A solution copolymer having enhanced wet adhesion, said solution comprising a major portion of organic solvent and solubilized therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:

wherein n = l or 2; m = l or 2; R' = H or CH₃; X = -0-, -CH₂, -NR-; R = H, -d_₅ alkyl, -aryl, -CH₂(CH₂)_y-C = N, -CH₂0d-.₅ alkyl, -(CH₂)_y0H, -CH,CH(0H)CH₃ wherein y = 1 - 12; A = phenylene or d_₅ alkylene; Y = -0-, -NH-, -NHNH-, -0-M-, -NH-M-, or -NH-NH-M-; and

O R' 0 NH 0

M = -C-0-CH₂-CH-0-, -NH-C-CHj-, -NH-C-, and -C(CH₂)_x0- wherein x = 2 - 5.

26. The solution copolymer of claim 25, wherein the second monomer comprises:

wherein n = 1 or 2; m = 2; each of R' = independently H or CH₃; Y = -NH- or -0-; Z = -0- or -S-; and R = H or CH₃.

27. The solution copolymer of claim 25, wherein the second monomer comprises:

wherein Y = -0- or -NH- and m = 2.

28. An adhesive composition comprising the latex of claim 25.

29. A coating composition comprising the latex of claim 25.

30. A sealant composition comprising the latex of claim 25.

31. An aqueous copolymer latex having enhanced wet adhesion, said latex comprising a major portion of water and dispersed therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:

0 R'O rr I //

R'-CH = CH₂CNHC-C-NH,-CH₂-(CH₂)_nN (CH₂)_C

R' Z=C X wherein n = l or 2; m = l or 2; X ■= -0-, -CH₂-, -NR-; R = H, -d_₅ alkyl, -(CH₂)_y0H, -CH₂(CH₂)-C = N, -CH₂0C1-15 alkyl, -(CH₂)_yOH, -CH₂CH(OH)CH₃ wherein y = 1 - 12; R' individually = -H or -CH₃. 32. The latex of claim 31 wherein X = -NR=; R = H; R' = individually -H or -CH₃; m = 2; n = 1; and Z = 0.

33. An adhesive composition comprising the latex of claim 31.

34. A coating composition comprising the latex of claim 31.

35. A sealant composition comprising the latex of claim 31.

36. A solution copolymer having enhanced wet adhesion, said solution comprising a major portion of organic solvent and dissolved therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:

0 R'O

// j //

R'-CH = CH₂CNHC-C-NH₂-CH₂-(CH₂)_nN (CH₂)_C

R' Z=C X wherein n = 1 or 2; m = 1 or 2; X = -0-, -CH₂-, -NR-; R = H, -d_₅ alkyl, -(CH₂)_y0H, -CH₂(CH₂)-C = N, -CH₂0C1-15 alkyl, -(CH₂)_y0H, -CH₂CH(OH)CH₃ wherein y = 1 - 12; R' individually = -H or -CH₃.

37. The solution copolymer of claim 36 wherein X = -NR-; R = H; R' = individually -H or -CH₃; m = 2; n = 1; and Z = 0.

38. An adhesive composition comprising the latex of claim 36.

39. A coating composition comprising the latex of claim 36.

40. A sealant composition comprising the latex of claim 36.