KR20070017395A - Self-initiated water dispersible acrylate ionomer and synthesis - Google Patents

Abstract

The invention detailed herein includes a family of novel multifunctional acrylate ionomer resins that are water dispersible and have built-in photoinitiators. The resins of the present invention are β-keto esters (eg acetoacetate), β-diketones (eg 2,4-pentanedione), β-keto that can participate in Michael addition reactions as "Michael donors". Amides (eg, acetoacetanilide, acetoacetamide), and / or self-photoinitiate through reaction with other β-dicarbonyl compounds. These water dispersible resins are cured under standard ultraviolet (UV) curing conditions to yield a tacky coating without the addition of typical photoinitiators. The present invention further relates to the use of such resins as coatings.

Self-photoinitiation, water dispersible, acrylate, ionomer, coating agent

Description

Self-Photoinitiating Water-Dispersable Acrylate Ionomers And Synthetic Methods

The invention detailed herein includes a family of novel multifunctional acrylate ionomer resins that are water dispersible and have built-in photoinitiators. The resins of the present invention are β-keto esters (eg acetoacetate), β-diketones (eg 2,4-pentanedione) that can participate in the Michael addition reaction as a "Michael donor". ), beta-ketoamide (eg, acetoacetanilide, acetoacetamide), and / or other β-dicarbonyl compounds through self-photoinitiation. These water dispersible resins are cured under standard ultraviolet (UV) curing conditions to yield a tacky coating without the addition of typical photoinitiators. The present invention further relates to the use of such resins as coatings.

The information provided below is not recognized as prior art of the present invention, but is merely provided to assist the reader in understanding.

A disadvantage of using initiators or photoinitiators is that they produce volatile low molecular weight fragments that can be unsafe to the environment.

It is characterized by the presence of acrylate groups as pendant residues and the ability of the resin to cure to provide a tacky coating without the addition of typical photoinitiators under standard UV-curing conditions.

These resins, characterized by the curability of such resins,

Multifunctional acrylates and methacrylates (“acrylates”) are generally used in the manufacture of crosslinked films, adhesives, casting sand binders, composite structures, and other materials. Acrylate monomers and oligomers can be crosslinked by free radical chaining mechanisms, which may require any free radical generating species such as peroxides, hydroperoxides, or azo compounds, which upon heating Or in the presence of an accelerator to decompose at room temperature to form radicals.

Another means of initiation reaction is to decompose the photoinitiator into free radicals using ultraviolet (UV) or electron beam (EB) radiation. For many applications, this method offers the possibility of very fast treatment, since the transformation of the liquid reactive composition into a crosslinked solid upon exposure of UV or EB radiation is essentially instantaneous.

A disadvantage of the use of initiators to achieve free radical reactions is that decomposition of the initiator and photoinitiator produces low molecular weight fragments that can volatilize during and / or after the manufacturing process. Fugitive emissions raise safety concerns for workers, consumers and the environment. For example, such low molecular weight fragments tend to be easily absorbed through the skin and can cause adverse health effects.

Several key approaches have been announced to overcome this limitation. Fugitive release was intended to be solved by forming acrylate monomers / oligomers with “internal” photoinitiators during the manufacturing process or during the leaching of the photoinitiator fragments. It starts with a compound known to function as a photoinitiator (or a suitable derivative), or with appropriate unsaturated groups, ie acrylates or methacrylates, in order to produce novel compounds which function both as monomers / oligomers and photoinitiators. This can be accomplished by "grafting" onto preformed oligomers / polymers to functionalize them or to produce high molecular weight photoinitiators.

Regardless of the effectiveness of these methods, they incur additional manufacturing processes and costs.

Moreover, this approach produces low functional resins. Low functionality is disadvantageous in reactivity and final properties and may require an external catalyst or initiator for crosslinking action.

Photo-polymerizable units of the ionic, UV-curable resins of the invention are produced via Michael addition of β-dicarbonyl compounds to the acrylate receptor. Crosslinked polymer production via Michael addition of acetoacetate donor compounds to multifunctional acrylate acceptor compounds is described in the literature. For example, Mozner and Rheinberger announced the addition of acetoacetate to triacrylates and tetraacrylates (Macromolecular Rapid Communications, 16, 135-138 (1995)). The product formed is a crosslinked gel. As shown in FIG. 1, in one such reaction, Mozner has 1 mol of trimethylol propane triacrylate (TMPTA) having three functional groups and 1 mol of polyethylene glycol (600 molecular weight) diacetoacetate having two functional groups. To (PEG600-DAA). (Each acetoacetate "functional group" reacts twice, so each mol of diacetoacetate has 4 reaction equivalents.) The resulting network is "gelled", or "in the presence of unreacted acrylic functional groups. Hardened ". Further reactions may proceed, but such networks cannot be liquefied with heat or solvents due to effective crosslinking.

More recent effective solutions are described in US Pat. Nos. 5,945,489 and 6,025,410, both of which are assigned to Moy et al and Ashland, Inc., the assignee of the present application. This approach involves the Michael addition reaction of polyfunctional acrylate and acetoacetate in proportions to yield an uncrosslinked, acrylate-functional resin. Such resins crosslink upon exposure to the appropriate UV source in the absence of added photoinitiators.

Ultraviolet (UV) -curable aqueous coatings are attracting attention because they have the advantages of environmental protection, low energy consumption, fast cure rate, rheological control, and adaptation to spraying. Typically curable aqueous dispersions are obtained through separate-emulsification or self-emulsification. Self-emulsification of the acrylate ionomer is accomplished by introducing hydrophilic ionic groups into the backbone of the curable resin. A balance between dispersibility and water resistance can be achieved by incorporating several polyethylene oxide segments into the backbone of the ionic curable resin.

There is a need for water dispersible, UV-curable resins having the advantages of self-photoinitiation common to Michael resins.

Summary of the Invention

The invention detailed herein describes the synthesis of water dispersible, non-gelled, self-photoinitiated acrylate ionomers by combining Michael addition and conventional acrylate ionomer synthesis.

The present invention provides an ionic, UV-curable multifunctional acrylate Michael resin. In the first embodiment illustrated in FIG. 2, the ionic moiety is incorporated into the resin as part of one or more isocyanate-reactive, hydrophilic monomers polymerized into the resin backbone. Isocyanate-reactivity is given by incorporating one or more chemical moieties selected from the group consisting of hydroxyl, primary amines, secondary amines, and thiols. The ionic properties of the monomers are given by one or more chemical moieties selected from the group consisting of carboxylates, sulfonates, ammonium, quaternary ammonium, and sulfonium. Carboxylate and sulfonate residues ultimately make the resin anionic. Ammonium, quaternary ammonium, and sulfonium, on the other hand, ultimately make the resin cationic.

The second cationic embodiment of the invention illustrated in FIG. 3 incorporates a tertiary amine as part of the side chain of the resin backbone.

The present invention provides oligomers used to synthesize the resins of the present invention. The present invention provides a backbone-ionic, isocyanate-terminated, urethane oligomer (FIG. 2A) and at least one isocyanate-terminated urethane oligomer formed from the hydrophilic monomers described above. Each isocyanate-reactive functional group of the hydrophilic monomer is urethane linked with an isocyanate-terminated urethane oligomer.

The present invention provides hydroxy-functional, acrylated Michael oligomers (FIG. 2B). Michael oligomers of the present invention are synthesized from β-dicarbonyl compounds, hydroxy-functional acrylates and polyfunctional acrylate esters.

Each isocyanate terminus of the main chain-ionic, isocyanate-terminated, urethane oligomer (FIG. 2A) is combined with the hydroxy-functional, acrylated Michael oligomer (FIG. 2B) by urethane linkage to the main chain-ionic, polyfunctional of the present invention. Form an acrylate Michael resin (FIG. 2C).

One aspect of the present invention is a β-dicarbonyl monomer having a methylene carbon in the center; Provided are branched-ionic, Michael-added polyfunctional acrylate oligomers comprising first and second multifunctional acrylate monomers that are Michael added to methylene carbon, wherein a portion of the side chain acrylate moieties is reacted with a secondary amine to tertiary An amine group is obtained (FIG. 3).

The anionic Michael resin of the present invention can be dispersed in water with its trialkylammonium salt (FIG. 2D). Cationic resins in both routes 2 and 3 can be dispersed in water as acetate or formate salts (FIG. 3).

The present invention provides ionomer Michael addition resin mixed with a certain amount of water.

The present invention further provides an aqueous dispersion of the ionomer Michael addition resin composition of the present invention suitable for formulating coatings, paints, laminates, sealants, adhesives, casting sand binders, and inks, pigments, gloss modifiers, flow agents and smoothing. And one or more additives selected from the group consisting of other additives.

One aspect of the present invention provides a method of using the resin of the present invention including applying a resin to a substrate, drying the resin, and curing the resin. Curing can be accomplished by exposure to actinic or electron beam radiation, in the presence or absence of an exogenous photo-initiator. Curing can also be accomplished by using typical free radical generators.

One aspect of the present invention provides a polymerization product comprising an ionomer michael addition resin composition cured with a free radical generator. A further aspect of the invention provides a substrate coated with an ionomer michael addition resin composition.

Additional aspects of the invention include providing a resin reactor having a dry atmosphere; Providing a polyol to the reactor; Providing the reactor with a hydrophilic monomer having at least one isocyanate-reactive moiety; Providing a solvent to the reactor; Providing a urethanization catalyst to the reactor; Adding polyfunctional isocyanates; And maintaining the reaction mixture at the reaction-effective temperature, thereby providing a process for the synthesis of main chain-ionic isocyanate end-capping urethane oligomers.

One aspect of the present invention provides that the side chain tertiary amine groups of the resins of the present invention may function as amine enhancers to promote curing of the resin.

One aspect of the present invention provides for curing a water dispersible ionomer composition of the present invention under standard UV-curing conditions to obtain a tacky coating without the addition of typical photoinitiators.

 In one aspect of the invention, a polymerization product is provided. The polymerization product may be a coating, paint, laminate, sealant, adhesive, casting sand binder, ink, or other product or additive that may be included in the final composition, depending on the nature of the ionomers and additives of the present invention. Suitable additives may be selected from the group consisting of pigments, gloss modifiers, flow and leveling agents, and other additives suitable for the desired formulation.

In one aspect, the present invention provides a method of using the resin and ionomer of the present invention including applying the ionomer to a substrate, drying the resin, and curing the resin. Application can be by any method known in the industry including, but not limited to, roll-coating, spray-coating, brush-coating, dip-coating, and electronic coating.

In one aspect of the present invention, there is provided a method of using the ionomer of the present invention. According to one aspect of the invention, the ionomers of the invention are applied to the surface and cured with actinic radiation in the absence of typical photoinitiators. According to one aspect of the invention, the ionomer of the invention is mixed with an external photoinitiator, applied to the surface and cured with actinic radiation. According to one aspect of the invention, the ionomer of the invention is mixed with a peroxide or azo initiator, applied to the surface, and cured using thermal energy in the presence or absence of actinic radiation.

According to one aspect of the present invention, the ionomer of the present invention is mixed with a suitable additive selected from the group consisting of pigments, gloss modifiers, flow agents and levelers, and other additives suitable for the desired formulation, applied to the surface and dried And harden.

1 is a schematic diagram of a representative crosslinked Michael addition resin.

2A is a schematic synthesis of a representative carboxylic acid-functional isocyanate end-capping urethane oligomer.

2B is a schematic synthesis of a representative hydroxy-functional Michael addition polyfunctional acrylate oligomer.

2C is a schematic synthesis of a representative carboxylic acid-functional urethane acrylate michael addition oligomer of the main chain-ionic resin of the present invention.

FIG. 2D is a schematic diagram of the main chain-ionic anionomer showing the trialkylammonium salt of the resin of FIG. 2C. FIG.

3 is a schematic of representative side chain tertiary amine Michael multifunctional acrylate oligomers and cationomers, carboxylic acid salts thereof.

The following paragraphs provide examples detailing the synthesis of new materials as well as their use as coatings. Specific reaction conditions and reaction parameters for any liquid oligomeric resin given by way of example do not limit the invention.

The term monomer is generally defined herein as a molecule or compound containing carbon and having a relatively low molecular weight and simple structure, which is combined with other similar and / or dissimilar molecules or compounds into an oligomer, polymer, synthetic resin, or elastomer. Can be switched.

The term oligomer is defined herein as a polymer molecule consisting of only a few similar and / or dissimilar monomers and / or oligomer units.

The term resin is defined herein as oligomers that can be converted into high molecular weight polymers in combination with other similar and / or dissimilar molecules or compounds.

The term thermoset herein means a high molecular weight polymer product of a resin that solidifies or irreversibly cures upon heating. This property relates to the crosslinking reaction of molecular components induced by heat, radiation, and / or chemical catalysts.

The term "polyol" refers to a polyhydric alcohol having two or more hydroxyl groups. The present invention is understood to include polyols. Terminal diols are any polyols in which the terminal portion of the molecule is hydroxylated.

The term "hydrophilic monomer" refers to any monomer having at least one ionic moiety. Ionic moieties are inherently charged or are chemical groups that can be charged by bonding or dissociating with ions in aqueous solution.

One aspect of the invention provides a water dispersible acrylate ionomer composition. The term “ionomer” as defined herein refers to an ion-containing oligomer composed of ionic and nonionic monomer units. The term “ionomer” further refers to a polymer synthesized from ionic and nonionic oligomers. One aspect of the invention provides a water dispersible acrylate oligomer and a composition containing the oligomer. The oligomers of the invention are synthesized from a combination of ionic and nonionic monomers. In the proper context, the term "ionomer" refers to such oligomers incorporating one or more ionic monomers. A further aspect of the invention provides a polymer coating polymerized from the ionomer oligomers of the invention. In a suitable context, the term "ionomer" refers to a polymer polymerized from one or more ionomer oligomers.

One aspect of the present invention provides both anionic and cationic ionomers, oligomers and polymers. "Anionomers" are oligomers or polymers containing chemical groups that carry a negative charge. "Cationomers" are oligomers or polymers containing chemical groups that bear a positive charge.

One aspect of the invention is a water dispersible, UV-curable, comprising urethane acrylate obtained by reaction of a back-ion functional isocyanate end-capping urethane oligomer with an -OH-containing, self-initiating Michael addition oligomer. , Oligomer, and polyfunctional acrylic Michael resin composition are provided.

Embodiments of the present invention provide an ionomer wherein the backbone is synthesized from hydrophilic monomers comprising carboxylate or sulfonate groups. One embodiment provides a cationomer synthesized from hydrophilic monomers whose main chain comprises ammonium, quaternary amines, or sulfonium groups.

Preferred embodiments of the present invention provide anionomers wherein the isocyanate-reactive, hydrophilic monomers incorporated into the resin backbone are carboxylic acids.

2A shows a schematic diagram of the synthesis of representative carboxylic acid-functional isocyanate end-capped urethane oligomers used in the synthesis of the anionomer resins of the present invention. This figure shows hydroxy-functional carboxylic acids and polyether or polyester polyols which stoichiometrically react with excess polyfunctional isocyanate molecules.

Isocyanate-reactive, hydrophilic monomers of the invention may have one or more isocyanate-reactive moieties or may have more than one isocyanate-reactive moiety. Non-limiting isocyanate-reactive moieties include hydroxyl, primary amines, secondary amines, and thiols. Hydroxyl is preferred. In addition to the isocyanate-reactive moieties, hydrophilic monomers have ionic moieties. Suitable hydrophilic monomers have one or more, preferably two or more, ionic functionalities, but may have more than two ionic functionalities.

Preferred ionic functionalities are acids. Particularly preferred acids are carboxylic acids. Preferred carboxylic acid monomer is dimethylolpropionic acid. Suitable, non-limiting, hydrophilic monomers include bis (hydroxymethyl) butyric acid, N, N-bis (2-hydroxyethyl) glycine, hydroxypivalic acid, malic acid, glycolic acid, and lactic acid.

Isocyanate-terminated urethane oligomers are formed from a central polyol monomer and two or more polyisocyanate monomers. Preferably, the polyol is a terminal diol. If the polyol is more than two hydroxyl groups, it can react with more than two polyisocyanate monomers to form branched structures with multiple isocyanate ends. The first isocyanate end of the oligourethane forms a urethane bond with one isocyanate-reactive moiety on the hydrophilic monomer. If the hydrophilic monomers have one or more isocyanate-reactive moieties, each moiety is urethaneized by a polyisocyanate-terminated urethane oligomer.

The hydroxylated, acrylate-terminated Michael oligomers are urethane-linked with the respective isocyanate-terminated urethane oligomers. Michael oligomers are formed from three monomeric units. The first monomer is a β-dicarbonyl molecule having a central methylene carbon. Hydroxyacrylate monomers and polyfunctional acrylate monomers are Michael added to the methylene carbon.

The polyol residues of the acid-functional isocyanate-terminated urethane oligomers may be polyether polyols, polyester polyols, or mixtures of polyols. Preferably, the polyol has a molecular weight in the range of about 200 to about 5000. More preferably, the polyol has a molecular weight of 1000 to 2000 AMU. The molecular weight of the urethane oligomer is primarily a function of the molecular weight of the polyol spacers incorporated into each oligomer and the number of such spacers.

The polyols may be alkanediols or cycloalkanediols. Non-limiting examples include ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 1,4-cyclohexanedimethanol, 1,2- and 1,4-cyclohexanediol and 2-ethyl-2-butylpropanediol. Also, diol containing ether or ester groups such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and polyethylene having a maximum molecular weight of about 5000, preferably about 2000 and more preferably about 1000 Also suitable are glycols, polypropylene glycols, polybutylene glycols or poly (ethylene glycol adipates). Reaction products of these diols with lactones (eg ε-caprolactone) can also be used as diols. Preferred polyols are poly (neopentyl glycol adipates).

Polyols are tri- or higher functional alcohols such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol or polyethers starting with such alcohols, for example 1 mol of trimethylolpropane and 4 mol May be a reaction product of ethylene oxide.

As a non-limiting example of the invention, the carboxylic acid-functional isocyanate end-capping urethane oligomers are synthesized from polyether or polyester polyols having a number average molecular weight (Mn) in the range of about 200 to about 2000 MW.

As an example of the present invention, carboxylic acid-functional isocyanate end-capping urethane oligomers are synthesized from aliphatic diisocyanates to minimize absorption of ultraviolet (UV) by chromophores other than visceral photoinitiators during curing of the resin. However, aliphatic, cycloaliphatic, or aromatic polyisocyanates can be used. Preferred aliphatic diisocyanates include dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimers ( HDT), and IPDI trimers, without limitation.

2B is a schematic of the synthesis of hydroxyl-containing Michael added oligomers. β-dicarbonyl Michael donors react with polyfunctional acrylate monomers or oligomers in the presence of equimolar amounts of hydroxy-functional acrylate monomers and strong bases. Synthesis of hydroxy-functional acrylate michael addition oligomers is a co-pending application, the entire content of which is incorporated herein by reference for all purposes (yet no serial number is assigned, agent control number 20435/0152). Is disclosed.

In a preferred embodiment, the β-dicarbonyl michael donor is β-ketoester (eg ethyl acetoacetate). Suitably, the present invention also provides β-diketones (eg 2,4-pentanedione), β-ketoanilides (eg acetoacetanilide), β-ketos, depending on the desired resin properties and end use. Amide (eg, acetoacetamide), or a mixture of Michael donors. In a preferred embodiment of the invention, β-dicarbonyl has a functionality where N = 2. Higher functional (ie N = 4, 6 ...) β-dicarbonyl donors are suitable, but the reaction stoichiometry must be adjusted more carefully to avoid unwanted system gelation.

Suitable β-dicarbonyl donor compounds having functional = 2 include ethyl acetoacetate, methyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate, acetoacetanilide, N-alkyl acetoacetide Anilide, acetoacetamide, 2-acetoacetosylethyl acrylate, 2-acetoacetosylethyl methacrylate, allyl acetoacetate, benzyl acetoacetate, 2,4-pentanedione, isobutyl acetoacetate, and 2-methoxy Ethyl acetoacetate, including but not limited to.

Suitable β-dicarbonyl donor compounds having functionality = 4 include 1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanol diacetoacetate, and Ethoxylated bisphenol A diacetoacetates, but are not limited to these.

Suitable β-dicarbonyl donor compounds having functional = 6 include, but are not limited to, trimethylol propane triacetoacetate, glycerin triacetoacetate, and polycaprolactone triacetoacetate.

Preferred β-dicarbonyl donor compounds having functionality = 8 are, but are not limited to, pentaerythritol tetraacetoacetate.

Preferred hydroxy-functional acrylates are 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate, caprolactone acrylate, propylene glycol monoacrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylic Rates, and mixtures thereof, but is not limited to these.

Suitable multifunctional acrylate michael acceptors are selected from diacrylates, triacrylates, tetraacrylates, and pentaacrylates. The range of β-dicarbonyl donors and multifunctional acrylate acceptors offers composition designers the opportunity to exercise a wide range of selectivity regarding the properties of the final product.

Preferred diacrylates are ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate Laterate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl ether Diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Cyclohexane dimethanol diacrylate, ethoxylated neopentyl Recall diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanol diacrylate, epoxy diacrylate, aryl urethane diacrylate, aliphatic urethane diacrylate Acrylates, polyester diacrylates, and mixtures thereof, but are not limited to these.

Preferred triacrylates are trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylic Latex, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryl urethane triacrylate, aliphatic urethane triacrylate, melamine triacrylate, epoxy novolac triacrylate, aliphatic epoxy Triacrylates, polyester triacrylates, and mixtures thereof, but is not limited to these.

Preferred tetraacrylates are di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated Dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylate, aliphatic urethane tetraacrylate, melamine tetraacrylate, epoxy novolac tetraacrylate, and mixtures thereof However, they are not limited thereto.

Preferred pentaacrylates include, but are not limited to, dipentaerythritol pentaacrylate, melamine pentaacrylate, and mixtures thereof.

Michael addition reaction is catalyzed by a strong base. Preferred bases are diazabicycloundecene (DBU) which is sufficiently strong and readily soluble in the monomer mixture. Other cyclic amidines such as diazabicyclo-nonene (DBN) and guanidine are also suitable for catalyzing this polymerization. Group I alkoxide bases, such as potassium tert-butoxide, are usually sufficient to promote the desired reaction if they have sufficient solubility in the reaction medium. Another class of preferred base catalysts, such as quaternary hydroxides and alkoxides such as tetrabutyl ammonium hydroxide or benzyltrimethyl ammonium methoxide, are included to promote the Michael addition reaction. Finally, strong, lipophilic alkoxide bases can be produced from reactions between halide anions (eg, quaternary halides) and epoxide moieties in situ. Such in situ catalysts are described in pending application No. 10 / 255,541, assigned to Atsland Corporation, the assignee of the present application. The entire contents of application 10 / 255,541 are specifically incorporated by reference in their entirety for all purposes.

2C shows the synthesis of carboxylic acid-functional urethane acrylates as a non-limiting example of the invention. Each terminal isocyanate group of the carboxylic acid-functionalized isocyanate end-capping urethane oligomer from FIG. 2A reacts to form a urethane bond with one equivalent of the hydroxyl group-containing Michael addition oligomer of FIG. 2B.

The isocyanate addition reaction can be accelerated by the addition of a suitable catalyst including but not limited to triethylamine, 1,4-diazabicyclo [2.2.2] octane, tin dioctoate or dibutyltin dilaurate. Preferred catalysts include tin dioctoate and dibutyltin dilaurate.

The present invention further provides branched cationic acrylate oligomers comprising ungelled, uncrosslinked Michael addition oligomers having branched acrylic functional groups, wherein some of the groups are derivatized with secondary amines. Secondary amines may be compounds having a number of secondary amine functional groups such as dialkyl amines, dialkyl amines, cycloaliphatic amines, heterocyclic amines, functional secondary amines, and piperazine. Secondary amines may comprise nitrogen covalently bonded to two organic radicals, wherein each radical is a group consisting of linear and branched alkyl, linear and branched alkenyl, and linear and branched alkynyl Is selected from. Two carbon radicals may be cyclized with nitrogen to form a heterocyclic ring.

Another embodiment of the present invention provides oligomers in which one or more ionic groups are linked by side chains of the oligomer backbone. 3 shows the synthesis of representative side chain tertiary amine-containing Michael addition polyfunctional acrylate oligomers. The oligomers include β-dicarbonyl monomers having a central methylene carbon and first and second multifunctional acrylate monomers added Michael to the carbon. Each incorporated multifunctional acrylate monomer residue has one or more side chain acrylate groups.

Suitable and preferred β-dicarbonyl monomers are as described above for the main chain-ionic resin.

Suitable and preferred polyfunctional acrylate monomers are as described above for the main chain-ionic resin.

Michael addition reaction is as described above.

Cationics are formed as shown in FIG. 3. The branched tertiary amine michael addition polyfunctional acrylate oligomers are mixed with acids to form salts thereof. At least about 1 equivalent of water-compatible acid is mixed with the pre-cationic oligomer for neutralization of the amine groups. Non-limiting examples of suitable proton providing organic and inorganic acids include phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, formic acid, and lactic acid. Preferred acids are carboxylic acids. Non-limiting, preferred carboxylic acids include formic acid and acetic acid. Preferred acids are acids which readily volatilize from the emulsion upon drying (eg, but are not limited to formic acid and acetic acid). They yield neutral cured resin coatings with good water resistance.

The present invention includes the bridged resin of FIG. 3 connected via a universal tertiary amine nitrogen atom. The two equivalents of resin in FIG. 3 react with one equivalent of the primary amine. The side chain acrylate moiety of each resin unit is added to the primary amine to form a tertiary amine. The present invention further includes higher oligomers. As the ratio of primary amines to various resins changes, a mixture of bridged lower and higher oligomers can be formed.

In one embodiment, the ionomer is formed from a resin by binding to a counterion in aqueous solution. Water and counterions may be added in any order. Depending on the proper charge of the resin, the counterion comes from a weak basic tertiary amine (pK _b from about 2.5 to about 9.0) or a weak acid (pK _a from about 5.0 to about 3.0), such as formic acid or acetic acid. Preferably, the counterion can be readily dissociated or combined with other ions present at the operating temperatures commonly associated with the expected use of the resin to form neutral, volatile compounds. One skilled in the chemical arts will readily understand that the Kovats index is a term relating to the molecular size and boiling point of a compound, and therefore the index is a measure of the relative volatility of the compound. Those skilled in the art recognize that the determination of the Kobatz index is simply carried out by gas chromatography.

The ionomers of the present invention are dispersed in water at a solid loading of about 10% to about 75% before being applied to the substrate. Preferred loading is about 20% to about 60%. More preferred amounts are from about 30% to about 40%. Amounts are calculated on a weight basis. After application, the ionomer can be dried and cured.

The resin of the present invention is selected from the group consisting of pigments, gloss modifiers, flow agents and leveling agents and other additives suitable for formulating coatings, paints, laminates, sealants, adhesives, casting sand binders, and inks. It can be mixed with the above additives.

The nature of the ionomer system of the present invention can be adjusted to the reactants. Michael donor and multifunctional acrylate monomers may vary with regard to hydroxylated (—OH containing) acrylates such as 2-hydroxyethyl acrylate (HEA) for the synthesis of —OH containing Michael added oligomers. The molecular weight of the polyol, its molecular composition, the stoichiometric ratio of the hydrophilic monomers, and the type of polyfunctional isocyanate used in the reaction also control the properties of the final material. The ability of these materials to form non-stick coatings with good properties in the absence of photo-initiators is also demonstrated.

Ultraviolet photo-polymerization was demonstrated by applying a portion of the composition of the invention to a surface. The composition was plated to the surface to a thickness of about 3 mils or less. The resin was applied to an aluminum or stainless steel substrate by the "draw down" technique. Samples were cured with a Fusion Systems Corp. UV curing unit using a belt-rate of 40 feet / minute and a 600-watt H-bulb delivering a UV dosage of 840 mJ / cm ² .

Coating performance characteristics were determined with various different test suites familiar to those skilled in the art.

Solvent content. Solvent resistance is the ability of a coating to resist solvent attack or film deformation. Rubbing the coating with a cloth saturated with an appropriate solvent is one way to assess when a specific level of solvent resistance is achieved. Rub tests were done using methyl ethyl ketone (MEK) or water (as indicated), using a double rub technique with one move back and forth over the coated surface. In order to standardize the test stroke, 16-oz. Fixed to the rotating end of the ball pin hammer. The double rub technique used the weight of the hammer as the operator held the hammer at the base of the handle. This test was performed until the double rub action cut the film or a significant film abnormality was demonstrated. The method is a variation of the method of ASTM D4752.

Adhesion tests were performed orthogonally on rigid substrates using a modified method of ASTM D3359 by Test Tape Method B, using a 6-blade cutting tool with 3.0 mm spacing. The test tape used was Tesa 4970. ASTM tests show values of OB to 5B, where OB shows complete failure and 5B shows excellent adhesion characteristics.

Example  One: OH -Synthesis of Michael Containing Resin I.

Trimethylolpropane triacrylate (135.54 g, 0.4574 mol), 2-hydroxyethyl acrylate (53.11 g, 0.4574 mol), ethyl acetoacetate (54.11 g, 0.0307 mol), tetra-n-butylammonium bromide (2.41 g , 0.0075 mol), and glycidyl methacrylate (9.71 g, 0.0746 mol) were placed in a 500 ml glass reactor. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, and a temperature monitoring thermocouple. The mixture was allowed to react under stirring. Heat was applied over 50 minutes to raise the temperature to 80 ° C. The reaction mixture was then kept at 80 ° C. for 5 hours until a constant refractive index (1.4796) was obtained. The reaction mixture was cooled to 50 ℃ was added to 2.35 g (0.0112 mol) of ethylene glycol methacrylate phosphate (everolimus methacrylic ^® (Ebecryl) 168, trademark UCB) quenched the catalyst system. The reaction mixture was stirred at 50 ° C. for 15 minutes. The obtained resin had a refractive index of 1.4796, a viscosity of 593 cP at 50 ° C., and an OH number of 109 mg KOH / g.

Example  2: polyurethane Acrylate Ionomer  Synthesis of I.

Polypropylene Glycol (121.79 g, 0.0622 mol; Pluracol ^® P2010, hydroxyl number = 57.3, nominal molecular weight 2000) (Pluracol® BASF Corporation), dimethylolpropionic acid (16.67 g, 0.124 mol ), 133.17 g acetone, and 0.24 g dibutyltin dilaurate were placed in a 1000 ml glass reactor. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-balanced sidearm filled with 55.48 g (0.2488 mol) isophorone diisocyanate (IPDI). The system was kept under a dry nitrogen blanket flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 45 ° C. IPDI was dripped over 1 hour, maintaining temperature at 45 degreeC. After the addition of IPDI, the temperature was raised to 60 ° C. over 3 hours. The reaction mixture was left at 60 ° C. until the end point of 1.72% NCO (22 hours) was reached. Then Example 1 (72.65 g, 0.1244 mol) of OH-containing Michael addition resin I was added gradually over 10 minutes and the mixture was further stirred and heated. Phenothiazine (0.01 g) was added during this step to prevent gelation. The reaction was monitored by FTIR. When the intensity at 2300 cm ⁻¹ (-NCO band) reached a constant minimum (after 18 hours), acetone was removed by vacuum distillation at a pressure of 60 ° C. 40 mmHg. The temperature of the resulting viscous resin was lowered to 45-50 ° C. and 25.10 g (0.248 mol) triethylamine were added. After stirring for 10 minutes and heating to 55 ° C., 400.00 g of deionized water was added and stirred for an additional 10 minutes. The product was a viscous translucent liquid comprising approximately 40% resin aqueous dispersion. An aliquot of the dispersion was further diluted with deionized water to obtain a 30% aqueous dispersion. All dispersions were stable upon storage in the dark of ambient conditions for at least 6 months.

Example  3: polyurethane Acrylate Ionomer II Synthesis.

Step 1. 236.1 g (0.476 equiv) poly (neopentyl glycol adipate) (Fomrez 55-112, hydroxyl number = 113.2) in a 1000 ml glass reactor; Poletez is registered by Witco Chemical. Trademark), 63.8 g (0.951 equiv) dimethylolpropionic acid, 238.1 g ethyl acetate, and 0.5 g dibutyltin dilaurate. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and an additional funnel with a pressure-balanced sidearm filled with 211.5 g (1.91 equiv) isophorone diisocyanate (IPDI). The system was completely filled with dry nitrogen and kept under a dry nitrogen blanket. The reactor contents were stirred and heated to 65 ° C. in 30 minutes. The IPDI was added dropwise over 45 minutes while maintaining the temperature at 65 ° C. The reaction temperature was then raised to 80 ° C. and monitored by FTIR. The reaction proceeded at 80 ° C. until the intensity at ˜3600 cm ⁻¹ (−OH band) was no longer observed and the NCO concentration reached 2.2%.

Step 2. A 500 ml glass reactor was charged with 170.22 g (0.08912 equivalents) of Step 1 product and 46.57 g (0.09804 equivalents) of Example 1's OH-containing Michael addition resin I. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, and a temperature monitoring thermocouple. The contents were stirred and heated to 60 ° C. in 40 minutes and maintained at that temperature until the ˜2300 cm ⁻¹ NCO band reached a minimum constant intensity, as observed by FTIR (18 hours). Triethylamine (13.27 g, 0.1311 equiv) and 419.91 g deionized water were added and ethyl acetate was removed by vacuum distillation at 380-430 mmHg and 60 ° C. A slightly cloudy aqueous dispersion containing about 30% resin was obtained that was stable for no more than 6 months at ambient conditions without light.

Example  4: polyurethane Acrylate Ionomer II Coating properties.

The film of Example 30's 30% aqueous polyurethane acrylate ionomer II was registered with Q-Panel (Q- ^Panel® is a Q-Panel Lab Products company based in Cleveland, Ohio). Trademark), dried at 45 ° C. for 10-15 minutes and fused at 600 mJ / cm ² UV dose of 600 Watt / in. Cured under "H" bulb. The resulting transparent film was hard and not tacky. It passed> 200 water double rub and 40 MEK double rub.

Two formulations of polyurethane acrylate ionomer II in 30% dispersion (69% dispersion / 31% Hubbercarb Q6 calcium carbonate (Herbercarb is J. M. Hubert, Engineered Materials Sector) Registered trademark of JM Huber, Engineered Materials Sector) and 69% dispersion / 31% Zeeospheres W-610 (3M) for coating commercial wooden particle boards). Each was drawn down to two 8-mil thick layers on the particle board and dried at 50 ° C. after each application. The film was cured as described above to obtain a thickness hard film of ˜3.5 mils. They showed excellent adhesion (0% removal) to the substrate in an orthogonal adhesion test.

Example  5: OH -Michael addition resin II Synthesis.

Water soluble triacrylate, SR 9035, (40.5 g, 0.042 mol), 2-hydroxyethyl acrylate (HEA) (4.9 g, 0.042 mol), ethyl acetoacetate (EAA) (5 g, 0.385 mol) And a 100 mL reactor equipped with a thermocell. Add 1.0 g of glycidyl methacrylate (2,3-epoxypropyl methacrylate), 2% w / w, 0.007 mol) and tetrabutyl ammonium bromide (0.252 g, 0.5 w / w) as cocatalyst It was. High temperature induced gelation was inhibited with the addition of some phenothiazines. The reaction mixture was heated to 80 ° C. with a heating mesh and stirred for 4 hours. The reaction yielded a clear, slightly yellow liquid of moderate viscosity. (Viscosity was measured using a Brookfield viscometer.) The liquid was transferred to an amber glass bottle for storage and carbon-13 NMR confirmed that about 97% of the bisubstituted EAA product was obtained. This resin was cured to be tacky at -200 mJ / cm ² . However, the coating was standard 1 lb. Water double rub with hammer used to have very bad water resistance when measured.

Example  6: polyurethane Acrylate Ionomer III Synthesis.

A 100 mL resin pail, equipped with a mechanical stirrer and thermocouple, was purged with nitrogen for about 2 minutes before loading. The purged keg was charged with polyethylene glycol [MW = 200] (7.5 g, 0.0375 mol), dimethanol propionic acid (1.7 g, 0.0125 mol). Three drops of monochlorophenylphosphate were added as a water remover to prevent water catalyzed gelation of the urethane reaction. Synthesis of urethane oligomers was initiated by the slow addition of isophorone diisocyanate (IPDI), (22.2 g, 0.1 mol) and dibutyl tin laurate (2 drops). Exotherm was adjusted to less than 50 ℃. Water soluble triacrylate, SR 9035 (2.4 g) was added to reduce the viscosity of the reaction mixture. Some phenothiazine was added to prevent acrylate gelation at high temperatures. After the addition, the resin was kept under heating until more than 95% of -OH groups were consumed as determined by infrared (FTIR) spectroscopy. After 2 hours, -OH-containing Michael addition resin I (30.65 g, 0.0255 mol), synthesized in Example 1, and HEA (3 g, 0.0255 mol) were added slowly while maintaining the temperature about 40 ° C. The reaction was continued overnight at room temperature. HEA (˜1 g) and some phenothiazine were added and the reaction continued at 40 ° C. for a time until less than 2% of -NCO groups remained in the FTIR. Samples of the resin were applied to an aluminum panel and the properties of the coating were examined. The remaining resin was emulsified by stirring with triethylamine (0.6035 g) and water (70 g) to give a polyurethane acrylate ionomer of 30% dispersion. The white dispersion was stable for several hours until phase separation started.

Example  7: polyurethane Acrylate Ionomer III Coating properties.

An aliquot of the product of Example 6 was applied to an aluminum panel and crosslinked under UV light (600 W / inch "H" bulb lamp with 840 mJ / cm ² dose). After instantaneous evaporation of water in the oven, the resin was cured with a clear, glossy, nonstick coating. The coating had high water resistance (> 200 water-double rub) as well as high solvent resistance (> 200 MEK double rub).

Example  8. Synthesis of Amine-Modified Michael Additive Resin.

1000 ml glass reactor was charged with 501.61 g (1.1720 mol) SR 454 (ethoxylated trimethylolpropane triacrylate, product of Sartomer company), 390.66 g (0.3907 mol) Laromer PE 55 F (poly Ester diacrylate, product of BASF), 78.13 g (0.6004 mol) ethyl acetoacetate, 4.98 g (0.0155 mol) tetrabutylammonium bromide, and 19.92 g (0.1402 mol) glycidyl methacrylate. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, and a temperature monitoring thermocouple. The stirred mixture was heated to 95 ° C. in 1 hour and maintained at that temperature until the refractive index of the mixture reached a constant value (1.4862 at 25 ° C.). Then piperidine (4.69 g, 0.0551 mol) was added and the reaction mixture was allowed to cool to 70 ° C. over 30 minutes with stirring. The final resin had a refractive index of 1.4866 at 25 ° C. and a viscosity of 18,000 cP at 25 ° C.

Example  9. Cationic Acrylate Oligomer emulsion  And coating properties thereof.

Four dram glass vials were weighed with 2.00 g of amine-modified Michael additive resin, 1.00 g deionized water and 0.03 g glacial acetic acid, prepared in Example 10. The mixture was shaken to give a white emulsion that was stable for at least 1 hour.

The film of Ammonion was applied to an aluminum Q panel, dried at 40 ° C. for 30 minutes and fused at 600 mJ / cm ² UVA dose of 600 Watt / in. Cured under "H" bulb. The resulting transparent film was hard and tacky. Passed> 200 water double rub and> 200 MEK double rub.

<Citation of Reference>

All publications, patents, patent application publications, and ASTM test methods cited herein are indicated by each individual publication, patent, patent application publication, and / or ASTM test method to be specifically and individually incorporated by reference. As such, it is incorporated herein by reference for any and all purposes. In particular, co-pending application serial numbers (not yet assigned; Agent Control Numbers 20435/141, 20435/144, 20435/145, 20435/147, 20435/148, and 20435 /) 152) is incorporated herein by reference for any and all purposes. In case of inconsistency, the present disclosure will prevail.

Claims (56)

Michael resin having a backbone structure; And One or more ionic moieties Ionic, UV-curable multifunctional acrylate Michael resin comprising a. The UV-curable resin of claim 1, wherein the ionic moiety is incorporated into the backbone of the resin. The UV-curable resin according to claim 1, wherein the ionic moiety is a side chain of the main chain of the resin. The method of claim 2, wherein the backbone is One or more ionic, isocyanate-terminated, urethane oligomers; And At least one hydroxy-functional Michael resin Main chain-ionic, UV-curable resin comprising a. The method of claim 4, wherein the ionic, isocyanate-terminated, urethane oligomer Isocyanate-reactive, hydrophilic monomers; Polyols; And One or more polyfunctional isocyanates Main chain-ionic, UV-curable resin comprising a. The method of claim 4, wherein the hydroxy-functional Michael resin β-dicarbonyl monomers; Hydroxy-functional acrylate monomers; And Multifunctional Acrylate Main chain-ionic, UV-curable resin comprising a. 6. The main chain-ionic, UV-curable resin of claim 5, wherein said isocyanate-reactive comprises a chemical moiety selected from the group consisting of hydroxyl, primary amine, secondary amine, and thiol. 8. The backbone-ionic, UV-curable resin according to claim 7, wherein the preferred isocyanate-reactive moiety is hydroxyl. 8. The backbone-ionic, UV-curable resin according to claim 7, comprising at least two isocyanate-reactive moieties. 6. The backbone-ionic, UV-curable resin of claim 5, wherein the ionic moiety comprises a chemical moiety selected from the group consisting of carboxylate, sulfonate, ammonium, quaternary amine, and sulfonium. The backbone-ionic, UV-curable resin according to claim 10, wherein the preferred ionic moiety is a carboxylate. 6. The method of claim 5, wherein the isocyanate-reactive, hydrophilic monomer is dimethylolpropionic acid, bis (hydroxymethyl) butyric acid, N, N-bis (2-hydroxyethyl) glycine, hydroxypivalic acid, malic acid, glycolic acid, And main chain-ionic, UV-curable resins selected from the group consisting of lactic acid. 13. The main chain-ionic, UV-curable resin according to claim 12, wherein the preferred isocyanate-reactive, hydrophilic monomer is dimethylolpropionic acid. 6. The main chain-ionic, UV-curable resin according to claim 5, wherein said polyol is selected from the group consisting of polyether polyols and polyester polyols. 15. The main chain-ionic, UV-curable resin according to claim 14, wherein said polyol is selected from the group consisting of poly (neopentyl glycol) adipate, polypropylene glycol, and polyethylene glycol. 15. The main chain-ionic, UV-curable resin of claim 14, wherein the ends for the polyol are the first and second hydroxyls. 6. The main chain-ionic, UV-curable resin according to claim 5, wherein said polyfunctional isocyanate is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic isocyanates. 18. The main chain-ion of claim 17 wherein the preferred polyisocyanate is selected from the group consisting of dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and 2,2,4-trimethylhexamethylene diisocyanate (TMDI). Soluble, UV-curable resins. 7. The main chain-ionic, UV-curable resin according to claim 6, wherein said β-dicarbonyl monomer is selected from the group consisting of β-keto esters, β-diketones, β-ketoamides, and β-ketoanilides. . 20. The main chain-ionic, UV-curable resin of claim 19, wherein the preferred β-dicarbonyl monomer is selected from the group consisting of ethyl acetoacetate, 2,4-pentanedione, and acetoacetanilide. 7. The hydroxy-functional acrylate of claim 6 wherein the hydroxy-functional acrylate is 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate, 2-hydroxybutyl A main chain-ionic, UV-curable resin selected from the group consisting of acrylates, caprolactone acrylates, polyethylene glycol monoacrylates, polypropylene glycol monoacrylates, and mixtures thereof. 22. The main chain-ionic, UV-curable resin according to claim 21, wherein the preferred hydroxy-functional acrylate is 2-hydroxyethyl acrylate (HEA). 7. The backbone-ionic, UV-curable resin according to claim 6, wherein said multifunctional acrylate is selected from the group consisting of diacrylates, triacrylates, tetraacrylates, and pentaacrylates. The method of claim 23 wherein the diacrylate is ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate , Tetraethylene glycol diacrylate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, bisphenol A diglycidyl ether diacrylate, resorci Nol diglycidyl ether diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neo Pentyl glycol diacrylate, cyclohexane dimethanol diacrylate, ethoxyl Neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanol diacrylate, acrylated epoxy diacrylate, aryl urethane diacrylate, A backbone-ionic, UV-curable resin selected from the group consisting of aliphatic urethane diacrylates, polyester diacrylates, and mixtures thereof. The method of claim 23 wherein said triacrylate is trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) Isocyanurate triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryl urethane triacrylate, aliphatic urethane triacrylate, melamine triacrylate, aliphatic epoxy tri A backbone-ionic, UV-curable resin selected from the group consisting of acrylates, epoxy novolac triacrylates, polyester triacrylates and mixtures thereof. The method of claim 23, wherein the tetraacrylate is di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaeryte Lititol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylate, aliphatic urethane tetraacrylate, melamine tetraacrylate, epoxy novolac tetraacrylate, And backbone-ionic, UV-curable resins selected from the group consisting of: and mixtures thereof. 24. The main chain-ionic, UV-curable resin of claim 23, wherein said pentaacrylate is selected from the group consisting of dipentaerythritol pentaacrylate, melamine pentaacrylate, and mixtures thereof. The method of claim 3, wherein Β-dicarbonyl monomers having a central methylene carbon; Two or more polyfunctional acrylates added Michael to the carbon; And At least one secondary amine added to at least one of said acrylates Side chain-ionic, UV-curable resin comprising a. 29. The side-ion, UV-curable resin according to claim 28, wherein said β-dicarbonyl monomer is selected from the group consisting of β-keto esters, β-diketones, β-ketoamides, and β-ketoanilides. . 30. The side-ion, UV-curable resin according to claim 29, wherein the preferred β-dicarbonyl monomer is selected from the group consisting of ethyl acetoacetate, 2,4-pentanedione, and acetoacetanilide. 29. The method of claim 28, wherein the secondary amine comprises nitrogen covalently bonded to two organic radicals, wherein each of said radicals is linear and branched alkyl, linear and branched alkenyl, and linear and branched alky Branched-ionic, UV-curable resins selected from the group consisting of. 32. The side chain-ionic, UV-curable resin of claim 31, wherein two of said radicals cyclize with said nitrogen to form a heterocyclic ring. The side chain-ionic, UV-curable resin according to claim 28, wherein the preferred secondary amine is diethanolamine. Ionic, UV-curable Michael resins according to claim 1; A certain amount of water; And Counterion Ionomer comprising. 34. The work of claim 33 selected from the group consisting of coatings, paints, laminates, sealants, adhesives, casting sand binders, and pigments, gloss modifiers, flow and leveling agents and other additives suitable for formulating ink. Ionomer further comprising the above additives. A substrate coated with the ionic, UV-curable Michael resin according to claim 1. A polymerization product comprising the ionic, UV-curable Michael resin according to claim 1 cured with a free radical generator. The polymerization product of claim 37, wherein the free-radical generator is actinic radiation. 37. The polymerization product of claim 36, wherein the free-radical generator is electron beam radiation. 38. The polymerization product of claim 37, wherein said free-radical generator is a peroxide. 41. The polymerization product of claim 40 wherein said peroxide is selected from the group consisting of methyl ethyl ketone peroxide (MEKP), tert-butyl perbenzoate (TBPB), cumyl peroxide, and t-butyl peroxide. 38. The composition of claim 37 selected from the group consisting of pigments, gloss modifiers, flow agents and leveling agents and other additives suitable for formulating coatings, paints, laminates, sealants, adhesives, casting sand binders, and inks. A polymerization product further comprising at least one additive. Providing a substrate; Applying the ionic Michael resin of claim 1 to the substrate; And Curing the resin Method of using an ionic Michael resin comprising a. The method of claim 43, wherein the applying step comprises a coating method selected from the group consisting of roll-coating, spray-coating, brush-coating, dip-coating, and electronic coating. Providing a resin reactor having a dry atmosphere; Providing a polyol to the reactor; Providing an isocyanate-reactive, hydrophilic monomer to the reactor; Providing a urethanization catalyst to the reactor; Providing a polyisocyanate to the reactor; Maintaining the reaction mixture at the reaction-effective temperature; And Providing a hydroxy-functional, multifunctional acrylated Michael oligomer Method for producing a main chain-ionic, UV-curable ionomer comprising a. 46. The process of claim 45, wherein the preferred isocyanate-reactive, hydrophilic monomer is dimethylolpropionic acid. 46. The main chain-ionic, UV-curable ionomer of claim 45 wherein said urethanization catalyst is selected from the group consisting of dibutyltin dilaurate, tin (II) octoate and diazabicyclo [2.2.2] octane. Method of preparation. 46. The method of claim 45, wherein providing a hydroxy-functional, polyfunctional acrylated Michael oligomer Providing a resin reactor; Providing a polyol polyfunctional acrylate monomer to the reactor; Providing a hydroxyacrylate monomer to the reactor; providing a β-dicarbonyl monomer to the reactor; And Providing a Michael addition catalyst A method for producing a main chain-ionic, UV-curable ionomer comprising a. 49. The method of claim 48, wherein the Michael addition catalyst is a strong base that readily dissolves in the monomer mixture. 49. The process of claim 48, wherein the Michael addition catalyst is diazabicycloundecene, diazabicyclononene, 1,1,3,3-tetramethyl guanidine, Group I alkoxide base, quaternary hydroxides and alkoxides, and in situ A process for preparing a backbone-ionic, UV-curable ionomer selected from the group consisting of lipophilic alkoxide bases resulting from the reaction between a halide anion and an epoxide moiety. The method of claim 45, Addition of a certain amount of water; And optionally Addition of counterions Method of producing a main chain-ionic, UV-curable ionomer further comprising. 52. The work of Claim 51 selected from the group consisting of coatings, paints, laminates, sealants, adhesives, foundry sand binders, and pigments, gloss modifiers, flow and leveling agents and other additives suitable for formulating ink. A method for producing a main chain-ionic, UV-curable ionomer, further comprising adding the above additive. Providing a resin reactor having a dry atmosphere; providing β-dicarbonyl; Providing a multifunctional acrylate; Providing a Michael addition catalyst; And Maintaining the reaction-effective temperature Method for producing a side chain-ionic, UV-curable ionomer comprising a. The method of claim 53, Addition of a certain amount of water; And optionally Addition of counterions Method for producing a side chain-ionic, UV-curable ionomer further comprising. 54. The work of claim 53 selected from the group consisting of coatings, paints, laminates, sealants, adhesives, casting sand binders, and pigments, gloss modifiers, flow agents and leveling agents and other additives suitable for formulating ink. A method for producing a side chain-ionic, UV-curable ionomer, further comprising adding the above additive. At least two equivalents of branched-ionic multifunctional acrylate Michael resin; And Primary amine disubstituted with the resin Oligomerized side chain-ionic, polyfunctional acrylate Michael resin comprising.

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