CN100526343C - Method for promoting michael addition reactions - Google Patents

Abstract

A uniformly dispersed solid reaction accelerator having an average particle size of 0.01-500 microns is disclosed for use in preparing a curable mixture of at least one Michael donor and at least one Michael acceptor. The resulting curable mixtures are useful as coatings, adhesives, sealants and elastomers.

Description

Methods used to facilitate Michael addition reactions

This application claims priority to US Provisional Application No. 60/693850, filed June 24,2005.

This invention was made with government support under Contract No. DE-FG36-04GO14317 awarded by the Department of Energy. The government has certain rights in this invention.

technical field

This invention relates to reaction promoters, including catalysts, which can be used to promote Michael addition reactions. The present invention relates to uniformly dispersed solid reaction accelerators, including but not limited to catalysts, to facilitate the production of multifunctional Michael donors and Response of multifunctional Michael acceptors. The solid reaction accelerator is uniformly dispersed in a curable functional mixture of a multifunctional Michael donor and a multifunctional Michael acceptor. The curable functional mixture is used to make a variety of articles including, but not limited to, bonded laminates, encapsulated and coated substrates.

Background technique

The Michael addition reaction is a known chemical process in which a Michael acceptor reacts with a Michael donor to extend the carbon chain in the Michael addition product. For example, RT Morrison and RN Boyd in "Organic Chemistry", third edition, Allyn and Bacon, 1973, and Clemens and Rector (Journal of Coatings Technology, Vol. 61, No. 770, 1989) introduced Michael plus become. The reaction is believed to take place between a Michael donor and a Michael acceptor in the presence of a reaction accelerator, ie, a base catalyst. However, regardless of the nature of the desired product, homogeneous base catalysis is performed by dissolving the base catalyst in one or all of the reactants or with the aid of a solvent or a phase transfer catalyst.

A curable functional mixture is a mixture of compounds including a Michael donor and a Michael acceptor that reacts over time in the presence of a reaction accelerator to produce a high molecular weight polymer. A problem associated with certain acid-containing curable functional mixtures, including functional mixtures made from acid-containing Michael acceptors and donors, is that the acid can neutralize all or part of the basic reaction accelerator, which would Slowing or inhibiting the Michael addition reaction prevents the desired polymeric product from being produced.

U.S. Patent No. 5,350,875 discloses the use of insoluble basic compounds selected from alkali metal or alkaline earth metal hydroxides, alkoxides, or carbonates as catalysts to carry out monofunctional Michael donors and monofunctional Michael donors at a temperature of 0-150°C. Heterogeneously catalyzed reactions with functionalized Michael acceptors. Filtration of the insoluble base catalyst from the Michael addition product mixture is required to minimize the tendency of the Michael acceptor to polymerize. Additionally, removal of the insoluble catalyst is intended to facilitate the formation of liquid small molecule Michael addition products that can be used as liquid additives such as lubricants and plasticizers. Unfortunately, the removal of insoluble catalysts from curable functional mixtures of multifunctional Michael acceptors and multifunctional Michael donors is undesirable because the functional mixture cures rapidly and is used directly as a binder, sealant or paint. In addition, the use of non-uniform dispersions of insoluble catalyst particles in the curable functional mixture used to make laminated articles results in unacceptable laminates having undesirable properties and appearance. Without constant agitation, non-uniform catalyst particles can also settle, giving adhesives, sealants, elastomers, or coatings an undesirable grainy appearance, which can produce destructive problems in articles made using the composition. Perceived flaws.

Accordingly, there is a need to provide a homogeneously dispersed Michael addition reaction accelerator, including but not limited to catalysts, even in the presence of acid-containing donors, acceptors, and additives or curable functional mixtures that are stable to changes in acid content Under this condition, it is also possible to cure mixtures of multifunctional Michael acceptors and multifunctional Michael donors, the mixture has a long pot life and a short curing time, and the accelerator makes the finished article have a smooth appearance without detectable defects.

The present inventors have discovered a solid reaction accelerator capable of promoting the solidification of a mixture of multifunctional Michael acceptors and multifunctional Michael donors to form a homogeneously dispersed polymer. The accelerator includes but is not limited to a catalyst. Curable functional mixtures are prepared that have a longer pot-life and a higher Short curing time.

Contents of the invention

Accordingly, the present invention provides a method of curing a functional mixture comprising the step of adding a One or more uniformly dispersed solid reaction accelerators with an average particle size of 0.01-500 microns.

The present invention provides a coated article comprising: at least one substrate in contact with a cured functional mixture comprising (a) one or more homogeneously dispersed a solid reaction accelerator; (b) at least one multifunctional Michael donor; (c) at least one multifunctional Michael acceptor.

The present invention also provides a bonded article comprising: at least two substrates in contact with a cured functional mixture comprising (a) one or more homogeneous a dispersed solid reaction accelerator; (b) at least one multifunctional Michael donor; (c) at least one multifunctional Michael acceptor.

The present invention also provides a curable functional mixture comprising: (a) one or more uniformly dispersed solid reaction accelerators having an average particle size of 0.01-500 microns; (b) at least one multifunctional Michael donor (c) at least one multifunctional Michael acceptor.

Detailed ways

In some embodiments, a solid reaction promoter with an average particle size equal to or greater than 0.1 microns is used.

Herein, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid.

As used herein, the term "Michael addition reaction accelerator" means any solid compound capable of promoting the reaction of Michael donors and Michael acceptors to generate Michael addition products (polymers) of the present invention, including but not limited to, for example, catalysts, cocatalysts , one or more of acid scavengers and combinations thereof.

As used herein, a "catalyst" is a compound capable of catalyzing a Michael addition reaction. Without wishing to be bound by theory, it is believed that the catalyst deprives a proton from the Michael donor to form an enolate anion.

As used herein, a "cocatalyst" is a substance capable of activating the catalyst, or shifting the equilibrium between the protonated Michael donor and the enolate anion, thereby increasing the rate of cure of the functional mixture.

As used herein, an "acid scavenger" is a compound capable of reacting with an acid by forming a covalent bond, an ionic bond, or a complex; the reaction between the acid scavenger and the acid eliminates or reduces the acid and the compound other than the acid scavenger Response trends.

As used herein, the term "uniformly dispersed solid reaction accelerator" means any solid reaction accelerator having an average particle size equal to or less than 500 microns, or uniformly dispersed in the curable functional mixture. In some embodiments, the solid reaction accelerator is uniformly dispersed in the curable functional mixture and has an average particle size of 500 microns or less, or an average particle size of 100 microns or less, or an average particle size of 60 microns or less.

Reaction promoters useful in the present invention include any solid organic compound, or any solid inorganic compound, or any polymeric solid, or any combination thereof, capable of proceeding a Michael addition reaction to form a product that is substantially insoluble in the reaction mixture.

In some embodiments, suitable solid reaction accelerators have an average particle size of 0.01-60 microns, including 0.01-20 microns. According to one embodiment, the average particle size of the reaction accelerator can be determined according to the desired adhesive (lamination adhesive with an average particle size of 0.01-10 microns, pressure-sensitive adhesive or structural adhesive with an average particle size of 0.01-20 microns) ), the type of sealant or coating changes.

In some embodiments, a reaction accelerator having an average particle size equal to or less than 500 microns; or equal to or less than 400 microns is used. In some embodiments, a reaction accelerator having an average particle size equal to or less than 200 microns; or equal to or less than 100 microns is used. In some embodiments, a reaction accelerator having an average particle size equal to or greater than 0.01 microns; or equal to or greater than 0.1 microns is used.

Uniformly dispersed solid reaction promoters may be prepared by any suitable technique to obtain a suitable particle size, including but not limited to conventional techniques such as milling, milling or precipitation. The following method may also be used: dissolving the solid reaction accelerator in a suitable solvent, dispersing the resulting solution in all or part of the functional mixture, and then evaporating or extracting the solvent to leave solid particles of suitable size.

Suitable solid reaction accelerators include, but are not limited to, for example, amines, amine functional polymers, amine functional resins, any alkali metal salt, any alkali metal carbonate, any alkaline earth metal carbonate, any alkali metal phosphate, any alkaline earth Metal phosphate, any alkali metal hydrogen phosphate, any alkaline earth metal hydrogen phosphate, any alkali metal phosphate ester, any alkaline earth metal phosphate ester, any alkali metal pyrophosphate Salt, any alkaline earth metal pyrophosphate, any alkali metal salt of a carboxylic acid containing 1 to 22 carbon atoms, any alkaline earth metal salt of a carboxylic acid containing 1 to 22 carbon atoms, any Other suitable transition metal salts of carboxylic acids. According to one embodiment, mixtures of reaction accelerators may also be used in the present invention.

Some additional suitable solid reaction promoters include silicates, including, for example, alkali metal silicates, silicates of metals other than alkali metals, and alkaline earth metal silicates. In some embodiments, aluminum silicate, calcium silicate, sodium silicate, or potassium silicate is used. In some embodiments, sodium silicate or potassium silicate is used.

Other examples of suitable solid reaction accelerators include alkali metal phenates (including, for example, 4-hydroxymethylbenzoic acid sodium salt), alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides (including Such as calcium hydroxide), oxides of metals other than alkali metals, and hydroxides of metals other than alkali metals.

Mixtures of suitable solid reaction accelerators are also suitable.

The uniformly dispersed solid reaction accelerator of the invention promotes the solidification of the mixture of multifunctional Michael acceptors and multifunctional Michael donors to form polymers. The inventors have also found that these mixtures, compared to conventionally catalyzed compositions known in the prior art, still have Longer pot life and shorter curing time.

Without wishing to be bound by any particular theory, it is believed that the reaction promotion occurs either at the surface of uniformly dispersed reaction promoter particles, or by delivery of trace amounts of reaction promoter into the functional mixture. It is also believed that the uniformly dispersed solid reaction accelerator particles can serve as storage sites to replenish any reaction accelerator neutralized by acid residues by exposing new surfaces or further dissolving to maintain a pseudo-equilibrium trace concentration in solution.

It has surprisingly been found that homogeneously dispersed solid reaction accelerators can be significantly more active than heterogeneously dispersed solid catalysts known in the prior art. According to one embodiment, the activity of the uniformly dispersed solid reaction accelerator can be controlled by changing the particle size, the smaller the particle size, the higher the activity.

It has also been found that the addition of small amounts of water increases the activity of functional mixtures catalyzed with uniformly dispersed solid reaction promoters. The addition of small amounts of acid or anhydride will reduce the activity of the functional mixture catalyzed by the homogeneously dispersed solid reaction promoter.

The mixture comprising the uniformly dispersed reaction accelerator is stable against precipitation. A functional mixture cured with a homogeneously dispersed solid reaction accelerator is suitable for bonding two or more substrates, for preparing coated substrates, and for preparing lamination adhesives, product assembly adhesives, household repair adhesives Compounds, pressure sensitive adhesives, sealants, foams and elastomers.

In some embodiments, a mixture containing a uniformly dispersed reaction promoter can be prepared by mixing reaction promoter particles with one or more components of the functional mixture of the present invention. For example, one or more Michael acceptors can be mixed with reaction promoter particles. In some embodiments, mixing is performed using a high speed mixer or homogenizer.

In some embodiments, the mixture containing the uniformly dispersed reaction accelerator is stable and resistant to precipitation in the absence of any thickener, dispersant, thixotropic agent or other compounds that can improve stability. It is contemplated that in some embodiments, when using a reaction promoter having an average particle size of 100 microns or less, the mixture can be prepared without the presence of a stability promoting compound.

In some embodiments, one or more stability promoting compounds may be added, including thixotropic agents such as fumed silica. It is contemplated that in some embodiments, a reaction promoter having an average particle size greater than 100 microns can be used to prepare a mixture comprising a stability promoting compound and a reaction promoter. When a stability-promoting compound is used, in some embodiments, the weight ratio of reaction accelerator to stability-promoting compound is 5 or less; or 4 or less. Independently, in some embodiments where a stability-promoting compound is used, the weight ratio of reaction accelerator to stability-promoting compound is 0.5 or greater; or 1 or greater; or 2 or greater.

Some mixtures containing uniformly dispersed reaction accelerators are stable against sedimentation and have a smooth appearance. Articles with no detectable defects can be prepared using these mixtures.

For example, in some embodiments, the average particle size of the solid reaction promoter is greater than 100 microns, and the mixture includes one or more compounds capable of promoting stability. In some such embodiments, the solid reaction promoter includes one or more silicates.

Independently, for example, in some embodiments, the solid reaction promoter has an average particle size of 100 microns or less and the mixture is free of fumed silica. In some such embodiments, the mixture is free of thixotropic, thickening, or dispersing agents.

Independently, for example, in some embodiments, the solid reaction promoter has an average particle size of 100 microns or less and the mixture comprises one or more non-silicate solid reaction products. In some such embodiments, the reaction mixture comprises one or more carbonate (ie, alkali metal carbonate or alkaline earth metal carbonate) solid reaction promoters.

Independently, for example in some embodiments, the average particle size of the solid reaction accelerator is equal to or less than 100 microns; the mixture is free of thixotropic agents, thickeners or dispersants; the solid reaction accelerator comprises one or more carbonic acid Salt.

As used herein, the term "curable functional mixture" refers to a mixture of compounds capable of reacting over time in the presence of a reaction accelerator to form a high molecular weight polymer solid. Curable functional mixtures include, but are not limited to, adhesives, sealants, elastomers, coatings, and foams, for example.

After mixing, the period of time during which the curable functional mixture remains sufficiently liquid to allow coating, molding or forming operations is referred to as the "pot life". The time required for the mixture to polymerize and cure and exhibit effective end-use properties is referred to as "cure time". Curable mixtures are required to have a long pot life and a short cure time, but those of ordinary skill in the art will understand that pot life and cure time are closely related, so that improved pot life is usually accompanied by poorer cure time, and improved cure time is usually accompanied by Poor shelf life. This relationship is due to a common underlying process driving these two factors: increasing molecular weight of the curable functional mixture.

As used herein, "pot time" is the time at a specified temperature for the viscosity of the curable functional mixture to reach twice the viscosity of a freshly mixed curable functional mixture. The viscosity of the curable functional mixture can be measured using any standard method; one effective method of measuring viscosity is with a Brookfield viscometer, using the viscometer manufacturer's instructions for the type and speed of the spindle selected for the material being tested. A long pot life is considered to be advantageous; when formulated to have a similar curing time, the compositions of the present invention have a longer pot life than conventional compositions known in the art.

A cured functional mixture is prepared by adding one or more homogeneously dispersed solid reaction accelerators to part or all of a curable functional mixture comprising at least one multifunctional Michael donor and at least one multifunctional Michael acceptor .

As used herein, a "Michael donor" is a compound comprising at least one Michael donor functional group, which is a functional group comprising at least one Michael active hydrogen atom, the Michael active hydrogen atom being between C=O and / or a hydrogen atom attached to a carbon atom between two electron-withdrawing groups such as C≡N. Examples of Michael donor functional groups are malonate, acetoacetate, malonamide, acetoacetamide (where the Michael active hydrogen atom is attached to a carbon atom between two carbonyl groups); and cyanoacetate and Cyanoacetamides (in which a Michael active hydrogen atom is attached to the carbon atom between the carbonyl and cyano groups). Compounds containing two or more Michael-active hydrogen atoms are referred to herein as multifunctional Michael donors. As used herein, the "backbone" of a Michael donor refers to the portion of the donor molecule other than one or more functional groups containing Michael active hydrogen atoms.

In some embodiments, at least one Michael donor having two or more independent Michael donor functional groups per molecule is used. In some embodiments, all of the Michael donors comprise two or more independent Michael donor functional groups per molecule.

As used herein, a "Michael acceptor" is a compound comprising at least one functional group having structure (I)

wherein R ¹ , R ² and R ⁴ are independently hydrogen or an organic group such as alkyl (linear, branched or cyclic), aryl, aryl-substituted alkyl (also known as aralkyl radical or alkaryl), and alkyl-substituted aryl (also known as alkaryl or alkylaryl), including derivatives or substituted versions thereof. R ¹ , R ² and R ⁴ may or may not independently contain ether linkages, carboxyl groups, other carbonyl groups, their thio analogs, nitrogen-containing groups, or combinations thereof. R ³ is oxygen, a nitrogen-containing group, or any organic group of the above-mentioned R ¹ , R ² , and R ⁴ . Compounds comprising two or more functional groups comprising structure (I) are referred to herein as multifunctional Michael acceptors. Herein, the "backbone" of a Michael acceptor refers to the part of the acceptor molecule other than structure (I). Any structure (I) can be attached to another (I) group or directly to the backbone.

Suitable Michael donor backbones for use in the present invention include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, and higher alcohols.

Suitable Michael donor and Michael acceptor backbones for the present invention include, but are not limited to, diols such as ethylene glycol, propylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, triethylene glycol, hexylene glycol , dipropylene glycol, cyclohexane dimethanol, tetraethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tripropylene glycol and tricyclodecane dimethanol; triols such as glycerol, propane Oxylated glycerol, trimethylolpropane, and castor oil; polyols, such as pentaerythritol, dipentaerythritol; polyhydroxyl epoxides, and other polyol polymers; sugars, including glucose, fructose, maltose, sucrose, sorbose, and isosorbide; and epoxides, including bisphenol A diglycidyl ether, epoxidized polybutadiene, and epoxidized soybean oil. It is also contemplated that similar alcohols and epoxides, substituted forms and mixtures thereof may be included.

In an embodiment of the present invention, the backbone of the multifunctional Michael acceptor may be the same as or different from the backbone of the multifunctional Michael donor. It is also contemplated that mixtures comprising more than one Michael donor or more than one Michael acceptor may be used.

In embodiments of the present invention, the components may be mixed in any combination and in any order. In some embodiments, the components can be added to the container simultaneously or sequentially and mixed. In some embodiments, two or more components may be combined, stored as a mixture, and later combined with other components to form the curable functional mixture of the present invention.

The curable mixture of the present invention is capable of curing at 23°C in a time equal to or less than 7 days. The mixture is said to have "cured" when a useful strength has developed. For example, the adhesive in the laminate is considered cured if the t-peel test demonstrates significant adhesion, and the elastomer is considered cured if the tensile test demonstrates significant tension. Short cure times are considered to be advantageous; when formulated to have similar pot times, the compositions of the present invention have shorter cure times than conventional compositions of the prior art.

In some embodiments, the cured functional mixture comprises a polymer. In some implementations. The weight average molecular weight (Mw) of the cured functional mixture is 10,000 or greater; or 20,000 or greater; or 50,000 or greater; or 100,000 or greater. Independently, in some embodiments, each molecule of the cured functional mixture comprises more than 30 residues of Michael acceptor molecules; or more than 50 residues of Michael acceptor molecules.

In some embodiments, the cured functional mixture is used without removing the dispersed solid reaction accelerator from the composition. That is, in some embodiments, when the cured functional mixture is used, for example, in coatings, adhesives, sealants, elastomers, or foams, the cured functional mixture contains solids remaining during the curing process. Reaction Accelerator.

The cured functional mixture of the present invention can have any glass transition temperature (Tg) within a wide range. In some embodiments, the Tg of the cured functional compound is equal to or higher than -80°C. Independently, in some embodiments, the Tg of the cured functional mixture is equal to or lower than 120°C. The Tg or Tgs are selected such that the cured functional mixture has the optimum properties required for its intended use.

For example, when the cured functional mixture is to be used as a construction adhesive, the functional mixture is typically selected such that the Tg of the cured functional mixture is equal to or greater than 50°C. As another example, when the cured functional mixture is to be used as a pressure sensitive adhesive, the functional mixture is generally selected so that the Tg of the cured functional mixture is equal to or lower than 15°C; or equal to or lower than 0°C; or equal to or lower than - 25°C; or equal to or lower than -50°C. As another example, when the cured functional mixture is to be used as a lamination adhesive, the functional mixture is typically selected such that the Tg of the cured functional mixture is at or above -30°C; or at or above -15°C; or at or above At -5°C; or equal to or higher than 15°C; or equal to or higher than 30°C.

Some embodiments of the invention include applying a layer of a curable functional mixture to at least one substrate. The layer may be a continuous or discontinuous film. The method of application may be any of a number of methods known to those of ordinary skill in the art, such as brushing, spraying, rolling, rotogravure, offset coating, flow coating, curtain coating, dipping, hot melt Coating, extrusion, coextrusion, similar methods and combinations thereof. In some embodiments, a layer of the curable mixture is applied to the substrate at room temperature. In other embodiments, application may be performed at elevated or reduced temperatures, for example to adjust the viscosity of the curable functional mixture.

A wide variety of substrates can be coated in accordance with the present invention including but not limited to polyolefins such as oriented polypropylene (OPP), SiOx coated OPP, PVDC coated OPP, cast polypropylene, polyethylene, LDPE, PVDC-coated LDPE and polyethylene copolymers; polystyrene; polycarbonate; polyesters such as polyethylene terephthalate (PET), SiOx-coated PET, PVDC-coated PET or poly Ethylene naphthalate (PEN); polyolefin copolymers such as ethylene vinyl acetate, ethylene acrylic acid and ethylene vinyl alcohol (EVOH), polyvinyl alcohol and their copolymers; nylon and hexamethylene isophthalamide ( polyamides such as MXD6); polyimides; polyacrylonitrile; polyvinyl chloride; polyvinylidene chloride and polyacrylates; ionomers; polysaccharides such as regenerated cellulose; and silicones, Examples include rubber or sealant; other natural or synthetic rubber; cellophane; clay-coated paper, cardboard or kraft paper; metallized polymer films and vapor-deposited metal oxides such as _AlOx , SiOx or TiOx coated Polymer films; inks, including polyamide-based inks, polyurethane-based inks, nitrocellulose-based inks, acrylate-based inks, and polyvinyl butyral-based inks.

The substrate is usually in the form of a film or sheet, but this is not required. Depending on the mutual compatibility of the materials, it can be a copolymer, laminate, coextrusion, mixture, coating or combination of any of the above substrates. Alternatively, the substrate may be in the form of a rigid article.

Other suitable substrates include, but are not limited to, for example, glass; flooring materials including concrete; metals including aluminum, iron, steel, and brass; ceramics including porcelain, stoneware; aluminum oxide, silicon oxide, and silicon nitride; asphalt; wood products, such as lumber, plywood, luan, and particle board; and electronic materials, including silicon, germanium, gallium arsenide, indium phosphide, and gallium phosphide.

According to one embodiment, the substrate may also be pretreated prior to coating by corona discharge treatment, plasma treatment, flame treatment, acid treatment and flame treatment, all of which are known in the art.

After the composition has been applied to the first substrate, it can optionally be contacted with another substrate to form a composite. Pressure can optionally be applied to the formed composite, for example by nip or by pressing rollers. In another embodiment of the present invention, the composition can be applied simultaneously or sequentially on both sides of a first substrate, and then the composition can be bonded to two additional substrates simultaneously or sequentially, said The other two substrates can be the same or different. It is also contemplated that the composite structure may be bonded to one or more other substrates using the composition of the present invention or a different composition, either before or after the processes described herein. The first and second substrates bonded in the method of the invention may be the same or different, including for example plastics, metallized plastics, metals and papers, which may have smooth or structured surfaces, which may be Rolls, sheets, films, foils, etc. The functional mixture can be applied, for example, at a level of 0.2-116 g/m2 (0.12-71.2 lb/ream).

According to the present invention, the curable mixture of the present invention undergoes a chemical reaction known as "curing". While the invention is not bound by any particular theory, it is believed that curing begins upon formation of the curable functional mixture and continues at least until the end of the pot life, and may continue thereafter. In some embodiments, a layer of the curable functional mixture is applied to the substrate before the end of the pot life. In some such embodiments, at least one other substrate is contacted with the curable functional mixture layer; the other substrate is typically contacted with the curable functional mixture layer before the end of the shelf life. Thus, in some embodiments, curing is not complete until after the curable mixture is contacted with the substrate. In other embodiments, most or all of the Michael addition reaction is already complete before the curable mixture is contacted with any substrates, or when the curable mixture is contacted with only one substrate. In either case, it is expected that the cured mixture will form an effective bond between the substrates.

According to one embodiment of the invention, curable functional mixtures can be used as adhesives. According to additional embodiments, the curable functional mixtures are useful as coatings, films, polymeric foams, sealants, and elastomers. When used as a coating, the curable mixture is applied to a substrate and then allowed to cure without contacting other substrates with the curable mixture.

The curable functional mixture can be prepared by any conventional technique known in the art. The order of mixing the curable functional mixture components is not critical. According to one embodiment, the curable mixture is formed by mixing the Michael component and the reaction accelerator; any method may be used for mixing. Sufficient agitation is expected to uniformly disperse the solid reaction accelerator, and to dissolve or uniformly disperse the other solid components. In some embodiments, the various components can be mixed on the substrate by alternately applying layers of the various components on the same area of the substrate, or by spraying separate fluids of the various components.

In other embodiments, when the cured mixture is to be used as a sealant, foam, or elastomer, the components are mixed in a mold or other suitable container to form a curable functional mixture, and are maintained at these molds or suitable containers. Alternatively, after mixing the components, the curable functional mixture is placed in molds or other suitable containers and remains in these molds or other suitable containers during the curing reaction.

In some embodiments, little or no volatile compounds are released during curing. For example, in some embodiments, the weight of the curable functional mixture is reduced by 10% or less during curing, based on the initial weight of the curable mixture (ie, the weight of the curable functional mixture as mixed). In some embodiments, the curable functional mixture loses 5% or less, or 2% or less, or 1% or less in weight during curing, based on the initial weight of the curable functional mixture.

In embodiments where the curable functional mixture is to be used to bond the same or different substrates, in some such embodiments, the composite will be heated above 23°C. In some embodiments, the curable mixtures of the present invention are capable of curing at 23°C, but in some such embodiments, it is desirable to speed up or facilitate the curing process by heating the composite to a temperature above 23°C. When such heating is performed, the composite material may be heated to a temperature above 35°C, or above 50°C, or above 100°C. It is also contemplated that in some embodiments, the composite material is maintained at a temperature below 23°C during the curing process.

According to one embodiment, the curable functional mixture can be used as a lamination adhesive. As used herein, a laminating adhesive is an adhesive suitable for bonding two or more planar substrates together. Lamination adhesives are used, for example, to make flexible composites such as food packaging, and rigid laminates, for example to make door panels.

According to another embodiment, the curable functional mixture is an effective sealant. A sealant is a material that is applied at the joint of two articles to fill the gap between the materials to prevent leakage, allowing them to expand and contract differently. Examples of sealants include, but are not limited to, eg, caulking and caulk (for glazing).

According to another embodiment, the curable functional mixture is an effective pressure sensitive adhesive composition. Pressure sensitive adhesives are adhesives that exhibit outstanding tack at room temperature and require only finger or hand pressure to bond securely when in contact with a variety of different surfaces. According to another embodiment, the curable functional mixture cures upon contact with at least one substrate comprising a release coating.

According to another embodiment, the curable functional mixture is an effective product assembly adhesive. Product assembly adhesives are effective in creating articles that permanently join two or more parts with sufficient strength. Examples of product assembly adhesives include, but are not limited to, eg, electronic adhesives such as die attach and package encapsulation adhesives, adhesives used to assemble medical devices, and adhesives used in consumer products.

According to another embodiment, the curable functional mixture is an effective home repair adhesive. A household repair adhesive is a permanent adhesive suitable for repairing damaged articles of metal, plastic, ceramic, wood, or other materials that bonds two or more pieces together to repair Broken products.

A wide variety of laminates can be efficiently fabricated using the polymer compositions and curable mixtures of the present invention. In some embodiments of the invention, the substrates are relatively thin and flat, and the resulting composite is referred to as a laminate. Some examples of substrates for laminates are polyolefins such as polyethylene and polypropylene; polyvinyl chloride; polyesters such as polyethylene terephthalate; polyamides (nylons); ethyl cellulose; fibers Acetate; metallized polypropylene; paper; aluminum foil; other metals; ceramic sheets; and related materials; which may be in rolls, sheets, films, foils and related forms. Other examples of substrates for laminates are woven or nonwoven fabrics which may be produced from one or more of materials such as cotton, wool, rayon, nylon, polyester, polyolefin, glass or ceramic Made of natural fabric or synthetic fibres.

The cured functional mixture can be used for any number of purposes. For example, the cured mixture can be used as an elastomer, bonded to a substrate or as an elastic article. As another example, the cured curable mixture can be formed and cured under conditions capable of producing a foam. As another example, a layer of curable mixture can be applied to a substrate and exposed to air to form a coating; the coating can be continuous or discontinuous; the coating can be protective or decorative , or both; the coating can act, for example, as a paint, another coating or an ink. The cured curable mixture can be used, for example, as one or more of a gasket, sealant, roofing film or membrane.

It should be understood that for the purposes of the specification and claims, the range and ratio limitations recited herein are combinable. For example, if a certain parameter has ranges of 60-120 and 80-110, it should be understood that ranges of 60-110 and 80-120 are also possible. Additionally, independently, for example, if a certain parameter is disclosed as having suitable minimum values of 1, 2, and 3, and if it is disclosed as having suitable maximum values of 9 and 10, then all of the following ranges are possible: 1-9, 1- 10, 2-9, 2-10, 3-9, 3-10.

The scope of the invention is illustrated by the following examples, which are not intended to limit the invention.

Example

These abbreviations and materials are used in the following examples:

Morecure ^™ 2000 = dicarboxylate ester of bisphenol A diglycidyl ether available from Rohm and Haas Company.

SR-306HP ^™ = Tripropylene glycol diacrylate available from Sartomer Corporation.

Miramer ^™ M3160 = trimethylolpropyl triacrylate ethoxylated (6), molecular weight 560, manufactured by Miwon Commerical Co., Ltd. and sold by Rahn USA Co., Ltd.

SS-200 = Sodium silicate powder, 200 mesh size, available from PQ Ltd.

Cab-o-sil ^™ M-5 = fumed silica available from Cabot Limited.

Jeffamine ^™ D-230 = polyether diamine available from Huntsman Ltd.

GTAA = Glyceryl triacetoacetate.

FRP = fiber reinforced plastic

Embodiment 1: the preparation of monomer mixture

Weigh Morcure ^™ 2000 (1650 grams) and SR-306HP ^™ (1350 grams) into a 4-liter stainless steel beaker. The mixture was mechanically stirred and warmed to 50°C, resulting in a clear solution.

Embodiment 2: Preparation of solid catalyst uniformly dispersed in monomer mixture

1 mm zirconium silicate beads (2644 grams) were added to a 1.4 liter horizontal bead mill (Dynomill KDL-Pilot from CB Mills). The monomer mixture (2275 grams) and sodium carbonate (1225 grams) of Example 1 were weighed and added to a 4-liter stainless steel beaker. The mixture was mechanically agitated and circulated through a horizontal bead mill for 145 minutes. The composition of the resulting mixture was 35% sodium carbonate, 36% Morcure ^™ 2000 and 29% tripropylene glycol diacrylate. The volume average particle size of the ground catalyst was 0.84 microns as measured by a Coulter LS-120 laser scattering instrument.

Embodiment 3: Preparation of heterogeneous solid catalyst powder

Sift the sodium carbonate using 35 and 60 mesh sieves. Material that passed through a 35-mesh sieve but not a 60-mesh sieve was used. The resulting powder had an expected particle size of 250-500 microns based on mesh size, with an average size of 380 microns.

Embodiment 4: Preparation of soluble catalyst/monomer solution

Morcure ^™ 2000 (64.4 grams), SR-306HP ^™ (27.6 grams) and potassium acetate (4.5 grams) were heated to 70°C and stirred for 1 hour. The hot mixture was filtered to remove insoluble solids, then allowed to cool to room temperature. A small amount of the sample was titrated with 0.1N hydrochloric acid to determine the amount of dissolved potassium acetate catalyst, the composition of the filtrate was 1.9% potassium acetate, 68.7% Morcure ^™ 2000 and 29.4% tripropylene glycol diacrylate.

Example 5: Preparation of Adhesive Mixture Containing Uniformly Dispersed Solid Catalyst

Morcure ^™ 2000 (11.95 g), SR-306HP ^™ (4.77 g) and the finely ground catalyst/monomer mixture obtained in Example 2 were heated to 50° C. and stirred to prepare Morcure ^™ 2000 with a composition of 66.7%. , a mixture of 28.6% tripropylene glycol diacrylate and 4.7% finely ground sodium carbonate solid catalyst. The mixture was a homogeneous dispersion and no signs of settling were observed after 24 hours at room temperature.

Example 6: Preparation of Adhesive Mixtures Containing Heterogeneous Solid Catalysts

Morcure ^™ 2000 (12.88 grams), SR-306HP (5.52 grams) and the sieved catalyst powder obtained in Example 3 were heated to 50° C. and stirred to obtain a composition of 66.7% Morcure ^™ 2000, 28.6% SR - A mixture of 306HP and 4.7% crude sodium carbonate solid catalyst. The suspension contained observable catalyst particles which settled to the bottom of the vessel after 24 hours at room temperature. The mixture was stirred immediately before use to ensure that the catalyst was suspended in the mixture.

Example 7: Preparation of Adhesive Mixture Containing Dissolved Catalyst

Morcure ^TM 2000 (1.79 g), SR-306HP ^TM (0.77 g) and the soluble catalyst solution prepared in Example 4 were heated to 50° C. and stirred to obtain 68.9% Morcure ^TM 2000, 29.5% SR- A mixture of 306HP ^TM and 1.6% potassium acetate soluble catalyst.

Example 8: Shelf Life of Adhesive Mixture

The binder mixtures of Examples 5, 6, and 7 and a sample of trimethylolpropyl triacetoacetate were equilibrated at 35°C. To each adhesive sample was added 11.61 grams of trimethylol triacetoacetate. The resulting mixture was mixed briefly and then the viscosity was measured using a Brookfield LVDT viscometer using a No. 25 spindle at 100 rpm. Record the initial viscosity. The time when the viscosity reached twice the initial viscosity was recorded as the pot life. The results are listed in Table 1.

Table 1

It can be seen that the adhesive made in Example 5 using the uniformly dispersed solid catalyst has a pot life of greater than 20 minutes, which is a generally accepted minimum in the converting industry. The activity of Example 7 using a soluble catalyst was too high, resulting in an unacceptably short pot life. Example 6 was extremely inactive with no evidence of cure after 24 hours.

Example 9: Preparation of laminated body

Trimethylolpropyl triacetoacetate (11.61 grams) was added to fresh samples of the adhesive mixtures of Examples 5, 6 and 7. These samples were mixed briefly, roll coated onto printed PET film (Dupont 48LBT) using a PolyType laboratory coater, and then 1 mil thick linear low density polyethylene film (PliantGF-10) was coated with adhesive touch. The print on the PET film consisted of Sealtech blue and white inks purchased from Color Converting Industries. Both inks are believed to contain residual acid functionality. The coating weight of the ink measured by weighing was 1.9 g/square meter.

The coating weight of the adhesive under various situations was measured by weighing, and the results are listed in Table 2:

Table 2

The resulting laminate was left to stand at 25° C. and 50% relative humidity for three days before further testing.

Example 10: Appearance of laminated body

The laminate samples prepared in Example 9 were inspected visually and by a 25x stereomicroscope. The laminates produced with the adhesives of Examples 5 and 7 were smooth and uniform. Laminates prepared using the adhesive of Example 6 had observable grains, reducing their appearance.

Example 11: Adhesiveness of laminated body

The t-peel adhesion of the laminate samples of Example 8 was determined according to the following procedure. 1" wide test strips were cut from each laminate and the strips were pulled apart in a tensile tester at a speed of 10 in/min. The maximum force required to separate the two films was recorded as the t-peel bond property. Four test strips are measured for each laminate, and the results are averaged. The results are listed in Table 3:

table 3

It can be seen that despite the high activity observed in Example 8, the laminate prepared using the adhesive of Example 7 was not cured after 3 days. The residual acid from the printing ink is believed to be of sufficient concentration to neutralize a substantial portion of the basic catalyst in the Example 8 binder.

In sharp contrast, the laminate prepared using the adhesive of Example 5 cured within 3 days, resulting in high adhesion, although its pot life was longer than that of Example 7. It is believed that the use of a finely ground solid catalyst provides sufficient basic functionality to neutralize residual acid in the ink, allowing for higher catalyst concentrations while still providing a good cure mechanism.

Laminates prepared using the crude solid binder of Example 6 did not cure, consistent with the low activity observed in Example 8. It can be seen that a finely ground solid catalyst can significantly increase its efficiency.

Example 12: Acrylic base

Prepare an acrylic base by mixing the following ingredients. Disperse SS-200 and Cab-o-sil ^™ M5 in the remaining components using a high speed mixer.

Component Weight %

Mor-cure 2000 38.07

Miramer M 3160 50.24

SS-200 6.76

Jeffamine D-230 2.61

Cab-o-sil ^™ M-5 2.32

Example 13: Adhesive

The acrylic base of Example 12 was mixed with GTAA. The weight ratio of acrylic matrix to GTAA was 80.34 to 19.66.

The pot life of this mixture is about 1 hour. The Brookfield viscosity measured under the conditions of 20°C, 10 rpm, and No. 4 hammer spindle was 2960. The free film of the cured mixture was soft and flexible. The substrate coated with the mixture was cured and immersed in water for 7 days, after which no blistering was observed.

Example 14: Adhesive Evaluation

The adhesive of Example 13 was evaluated by an overlap shear test.

The composition is used to bond a rectangular piece of substrate to another rectangular piece of the same type of substrate to make a composite structure. At one end of the composite structure is a free portion of the rectangular substrate sheet; at the other end is a portion of the rectangular substrate sheet. A "free" portion of a substrate is a portion that is not adjacent to any portion of a different substrate sheet.

The composite structure was placed in a tensile tester with the free portion of one substrate placed in one holder and the free portion of the other substrate placed in the other holder. Use a tensile tester to pull the gripper apart and record the maximum force applied. The test is repeated on four identical samples and the average value of the maximum applied force is recorded. The position of the dropdown is also recorded.

The test was performed on "dry" samples (i.e. samples of composite structures stored under ambient conditions prior to testing), and the test was also performed on separate "wet" samples (i.e. samples of composite structures stored under water prior to testing) conduct. The result is as follows:

Substrate condition Force when pulling apart (kg/cm2 (psi)) Pull out the position Metal Dry 39.5(562) 100% M⁽¹⁾ Metal wet 36.4 (517) 100% M⁽¹⁾ FRP Dry 16.0(227) 100% F⁽²⁾ FRP wet 16.3(232) 100% F⁽²⁾

Note (1): The sample pulls apart when the metal substrate breaks.

Note (2): The sample pulls apart when the FRP substrate breaks.

Claims (10)

1. method that makes the sense mixture solidified, this method may further comprise the steps: adding one or more mean particle sizes in comprising part or all of curable sense mixture that at least a multifunctional Michael gives body and at least a michael acceptor is the homodisperse solid reaction promoter of 0.1-20 micron.

2. the method for claim 1, it is characterized in that described one or more homodisperse solid reaction promoters are selected from: alkali metal phenolate, alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, the oxide compound of the metal beyond the basic metal and the oxyhydroxide of the metal beyond the basic metal, alkalimetal silicate, the silicate of the metal beyond the basic metal, alkaline earth metal silicate, amine, amine functional polymer, the amine functional resins, basic metal salt, alkaline carbonate, alkaline earth metal carbonate, alkali metal phosphate, alkali earth metal phosphate, alkali metal hydrogen phosphate, the alkaline-earth metal hydrophosphate, the alkali metal phosphate ester, the alkali earth metal phosphate ester, alkali metal pyrophosphate, the alkaline-earth metal pyrophosphate salt, the an alkali metal salt that contains the carboxylic acid of 1-22 carbon atom, the alkaline earth salt that contains the carboxylic acid of 1-22 carbon atom, and the metal-salt that contains the carboxylic acid of 1-22 carbon atom.

3. the method for claim 1 is characterized in that, described curable sense mixture also comprises 0-5 weight %: (a) water, or (b) one or more acid, or (c) one or more acid anhydrides, or its combination.

4. the goods of a coating, these goods comprise: with at least one base material that the solidified official can mixture contacts, described mixture comprises one or more homodisperse solid reaction promoters that (a) mean particle size is the 0.1-20 micron; (b) at least a multifunctional Michael gives body; (c) at least a multifunctional michael acceptor.

5. adherent goods, these goods comprise: with at least two base materials that the solidified official can mixture contacts, described mixture comprises one or more homodisperse solid reaction promoters that (a) mean particle size is the 0.1-20 micron; (b) at least a multifunctional Michael gives body; (c) at least a multifunctional michael acceptor.

6. curable sense mixture, this mixture comprises: (a) mean particle size is one or more homodisperse solid reaction promoters of 0.1-20 micron; (b) at least a multifunctional Michael gives body; (c) at least a multifunctional michael acceptor.

7. a laminating adhesive is made by curable sense mixture as claimed in claim 6.

8. a seal gum is made by curable sense mixture as claimed in claim 6.

9. an elastomerics is made by curable sense mixture as claimed in claim 6.

10. foams are made by curable sense mixture as claimed in claim 6.