# Patent

## Title
Biomass based Michael addition compositions

## Abstract

Functional mixtures and polymer compositions are provided, each comprising at least one multi-functional Michael acceptor, at least one multi-functional Michael donor, in which at least 20% of either the donor or acceptor or a combination of the donor and acceptor is derived from bio-based materials and at least one catalyst.

## Background
This is a non-provisional patent application of co-pending U.S. provisional patent application Ser. No. 60/612,739 filed Sep. 24, 2004.


The present invention is directed to providing chemical components from biologically based (bio-based) feedstocks that are used in carbon based Michael addition reactions to prepare coatings, adhesives, sealants, elastomers, foams and films.
Many compositions that are used to prepare coatings, adhesives and sealants are prepared from chemical components derived from petroleum based feedstocks. For example, U.S. Patent Application No. 20030083436 discloses a composition, useful as an adhesive, comprising a product of a reaction between an α,β-unsaturated multi-carboxylic acid ester and a particular polyester or polyamide compound with methylene groups adjacent to carbonyl groups, in the presence of a non-amine strong base catalyst such as an alkali alkoxide.
One limitation of compositions derived from petroleum based feedstocks is that large quantities of energy are consumed during their production. In addition, the compositions suffer significant price fluctuations as a result of fluctuating prices for petroleum based feedstocks. Therefore, it is desirable therefore to utilize carbon based Michael addition reactions wherein one or more reactants are bio-based or “sustainable” to lessen dependence on petroleum feedstocks. Bio-based feedstocks include but are not limited to saccharides, polysaccharides, starch and corn products (e.g. isosorbide), cellulose, cellulose derivatives, modified celluloses, crop oils (e.g. soya and castor oils), fats (e.g. glycerol and fatty acids), or proteins. It is also desirable to provide compositions that are curable with the Michael addition reaction; that cure at room temperature; that use one or more catalysts that are less likely to be undesirably toxic and/or undesirably reactive. Use of such bio-based chemical components provides more stable long term pricing, lowered adverse impact on the environment by avoiding use of non-renewable resources, and allows for the development of compostable or biodegradable products.
Accordingly, the present invention provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one weakly basic catalyst;

wherein the at least one Michael acceptor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock, wherein the catalyst is selected from the group consisting of sodium salts of carboxylic acids, magnesium salts of carboxylic acids, aluminum salts of carboxylic acids, chromium salts of alkyl carboxylic acids having 6 or fewer carbon atoms, chromium salts of aromatic carboxylic acids, potassium salts of alkyl mono-carboxylic acids having 6 or fewer carbon atoms, potassium salts of multi-carboxylic acids, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, and alkali metal pyrophosphates and mixtures thereof;

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one basic catalyst;

wherein the at least one Michael acceptor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock, wherein the basic catalyst is selected from the group consisting of tertiary amine catalysts, tetramethyl guanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), hydroxides, ethoxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, and alkali metal pyrophosphates and mixtures thereof; bicarbonates, potassium bicarbonate, phosphates, hydrogenphosphates, or the anion of a Michael donor.

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one catalyst;

wherein the at least one Michael acceptor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock.

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one weakly basic catalyst;

wherein the at least one Michael donor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock, and wherein the catalyst is selected from the group consisting of sodium salts of carboxylic acids, magnesium salts of carboxylic acids, aluminum salts of carboxylic acids, chromium salts of alkyl carboxylic acids having 6 or fewer carbon atoms, chromium salts of aromatic carboxylic acids, potassium salts of alkyl mono-carboxylic acids having 6 or fewer carbon atoms, potassium salts of multi-carboxylic acids, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, alkali metal pyrophosphates and mixtures thereof;

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one basic catalyst;

wherein the at least one Michael donor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock, and wherein the basic catalyst is selected from the group consisting of tertiary amine catalysts, tetramethyl guanidine (TMG), 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU), hydroxides, ethoxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, alkali metal pyrophosphates, the anion of a Michael donor and mixtures thereof.

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one catalyst;

wherein the at least one Michael donor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture, and whose chemical backbone is derived from bio-based feedstock.

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one weakly basic catalyst;

wherein at least one Michael donor is present whose chemical backbone is derived from bio-based feedstock, wherein at least one Michael acceptor is present whose chemical backbone is derived from bio-based feedstock, wherein the sum of the weights of the donor and acceptor whose chemical backbone is derived from bio-based feedstock are greater than 20% by weight, based on the total weight of the functional mixture, and wherein the catalyst is selected from the group consisting of sodium salts of carboxylic acids, magnesium salts of carboxylic acids, aluminum salts of carboxylic acids, chromium salts of alkyl carboxylic acids having 6 or fewer carbon atoms, chromium salts of aromatic carboxylic acids, potassium salts of alkyl mono-carboxylic acids having 6 or fewer carbon atoms, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, alkali metal pyrophosphates, and mixtures thereof.

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one basic catalyst;

wherein at least one Michael donor is present whose chemical backbone is derived from bio-based feedstock, wherein at least one Michael acceptor is present whose chemical backbone is derived from bio-based feedstock, wherein the sum of the weights of the donor and acceptor whose chemical backbone is derived from bio-based feedstock are greater than 20% by weight, based on the total weight of the functional mixture, and wherein the basic catalyst is selected from the group consisting of tertiary amine catalysts, tetramethyl guanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), hydroxides, ethoxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal phosphate esters, alkali metal pyrophosphates, the anion of a Michael donor and mixtures thereof;

    
    


The present invention also provides a functional mixture comprising:

    
    
        (i) at least one multi-functional Michael acceptor;
        (ii) at least one multi-functional Michael donor; and
        (iii) at least one catalyst;

wherein at least one Michael donor is present whose chemical backbone is derived from bio-based feedstock, wherein at least one Michael acceptor is present whose chemical backbone is derived from bio-based feedstock, wherein the sum of the weights of the donor and acceptor whose chemical backbone is derived from bio-based feedstock are greater than 20% by weight, based on the total weight of the functional mixture.

    
    


The present invention also provides a polymer composition comprising structural units R1 and R2, optionally in combination with structural units R3 and or R4:




wherein m and n are integer values greater than or equal to 1 and the molar ratio of (m*R1+R3):(n*R2+R4) is less than or equal to 2:1; wherein R5, R6, R7 and R8 are organic radicals; wherein R9 is an organic radical selected from H and CH3; wherein R10 is an organic radical selected from H, R1 and R3; and wherein at least 20% by weight of the total of R5, R6, R7 and R8, based on the total weight of the polymer composition, is derived from bio-based feedstock.

The polymer compositions of the invention are characterized by the corresponding ratios of Michael donors and Michael acceptors. According to one embodiment, the polymer compositions have a ratio of acrylate group to AcAc group of 1:1.
According to a separate embodiment, the polymer composition comprises a structural formula (I):




wherein R3 is selected from H, C1-C22, OC1-OC22, another acceptor adduct and other organic radicals including at least one element other than carbon; wherein R2, R3 and R4 are organic radicals described below, and wherein the at least 20% by weight of R1 chemical backbone is derived from bio-based feedstock, or the at least 20% by weight of R2 chemical backbone is derived from bio-based feedstock, or the at least 20% by weight of R3 chemical backbone is derived from bio-based feedstock, or the at least 20% by weight of R4 chemical backbone is derived from bio-based feedstock, or at least 20% by weight of combinations of R1-R4 chemical backbones are derived from bio-based feedstock or all R1-R4 chemical backbones are derived from bio-based feedstock. The polymer composition of structural formula (I) comprises at least one multi-functional Michael acceptor and at least one multi-functional Michael donor, wherein the acceptor or the donor or the combination of acceptor and donor is derived from bio-based feedstock.

The invention also provides a photocurable polymer composition requiring little (less than 1 wt. %) to no added photoinitiator.
The invention also provides a photocurable composition using a functional mixture in combination with a photolatent base.
The invention also provides methods for preparing functional mixtures of the invention described above comprising the step of: adding one or more catalysts selected from the group consisting of weakly basic catalysts, basic catalysts and other catalysts to a portion of, up to and including all, the functional mixture.
The invention also provides methods for curing functional mixtures containing photolatent base comprising the step of treating the functional mixtures with one or more of following selected from the group consisting of actinic radiation, ultraviolet radiation, or electron beam (EB) radiation. As used herein, “(meth)acrylate” means acrylate or methacrylate; “(meth)acrylic” means acrylic or methacrylic; and “(meth)acrylamide” means acrylamide or methacrylamide.
The present invention includes the use of compounds with functional groups capable of undergoing a Michael addition reaction. Michael addition is taught, for example, by RT Morrison and RN Boyd in Organic Chemistry, third edition, Allyn and Bacon, 1973. The reaction is believed to take place between a Michael donor and a Michael acceptor, in the presence of a catalyst.
A “Michael donor,” as used herein, is a compound with at least one Michael donor functional group, which is a functional group containing at least one Michael active hydrogen atom, which is a hydrogen atom attached to a carbon atom that is located between two electron-withdrawing groups such as C═O and/or C≡N. Examples of Michael donor functional groups are malonate esters, acetoacetate esters, malonamides, and acetoacetamides (in which the Michael active hydrogens are attached to the carbon atom between two carbonyl groups); and cyanoacetate esters and cyanoacetamides (in which the Michael active hydrogens are attached to the carbon atom between a carbonyl group and a cyano group). A compound with two or more Michael active hydrogen atoms is known herein as a multi-functional Michael donor. A Michael donor may have one, two, three, or more separate functional groups that each contain one or more Michael active hydrogen atoms. The total number of Michael active hydrogen atoms on the molecule is the functionality of the Michael donor. As used herein, the “backbone” or “skeleton” of the Michael donor is the portion of the donor molecule other than the functional group containing the Michael active hydrogen atom(s).
One or more bio-based Michael components are usefully employed in accordance with the invention, including but not limited to a bio-based Michael donor, a bio-based Michael acceptor and the combination of a bio-based Michael donor and a bio-based Michael acceptor. The functional mixtures are curable and polymer compositions resulting from them may be capable of further reaction. A curable functional mixture or polymer composition based on carbon Michael donors and acceptors may contain more than one donor and/or more than one acceptor. In embodiments where several Michael donors and/or acceptors are present, combinations of donors and acceptors whose chemical skeletons are based on both or either petroleum based and bio-based feedstock are used, as long as the weight percent of reactant derived from bio-based feedstock is greater than 25 percent by weight, based on the total weight of the functional mixture or polymer composition.
A “bio-based Michael donor” as used herein, is a compound with at least one Michael donor functional group, in which the Michael donor functional groups, as defined previously, are placed on a “backbone” molecule derived from either sugars, starch, cellulose, crop oils, animal fats, or animal proteins. Examples of such bio-based Michael donors are the acetoacetates of mono- and di-saccharides such as glucose, maltose, fructose or sucrose. Additional examples are the acetoacetates of glycerol, sorbitol, mannitol, isosorbide, castor oil, 1,3 propanediol, polysaccharides such as dextrins, starches, modified starches, polylactides, and polyalkanoates. For example, one process of producing saccharide acetoacetates is described in U.S. Pat. No. 4,551,523, as illustrated below.




A “Michael acceptor,” as used herein, is a compound with at least one functional group with the structure (II)




where R11, R12, and R14 are, independently, hydrogen or organic radicals such as for example, alkyl (linear, branched, or cyclic), aryl, aryl-substituted alkyl (also called aralkyl or arylkyl), and alkyl-substituted aryl (also called alkaryl or alkylaryl), including derivatives and substituted versions thereof R11, R12, and R14 may or may not, independently, contain ether linkages, carboxyl groups, further carbonyl groups, thio analogs thereof, nitrogen-containing groups, or combinations thereof. R13 is oxygen, a nitrogen-containing group, or any of the organic radicals described above for R11, R12, and R14. A compound with two or more functional groups, each containing structure (II), is known herein as a multi-functional Michael acceptor. The number of functional groups containing structure (II) on the molecule is the functionality of the Michael acceptor. As used herein, the “backbone” or “skeleton” of the Michael acceptor is the portion of the donor molecule other than structure (II). Any structure (II) may be attached to another (II) group or to the skeleton directly.

A “bio-based Michael acceptor” as used herein, is a compound with at least one Michael acceptor functional group, in which the functional groups, as defined previously, are placed on a “backbone” (R3 structure (II) above) molecule derived from either sugars, starch, cellulose, crop oils, fats, or proteins. Examples of such bio-based Michael acceptor include but are not limited to the di-acrylate of epoxidized soya oil, as illustrated, the di-acrylate of 1,3 propanediol, acrylates of sorbitol, mannitol, castor oil, glucose, sucrose, maltose or propoxylated glyceryl triacrylate.




The present invention includes the use of at least one catalyst. A “catalyst,” as used herein, is a compound that will catalyze a Michael addition reaction. While the invention is not limited to any specific theory, it is believed that the catalyst abstracts a hydrogen ion from the Michael donor. According to one embodiment, the catalyst is basic. According to a separate embodiment, the catalyst is weakly basic. According to a separate embodiment, the Michael acceptor and donor have a low acid content relative to the concentration of the catalyst. According to another embodiment, the Michael donor and acceptor are independent of the type of catalyst employed.
In some embodiments, one or more optional adjuvants may be used. Adjuvants are materials that are not Michael donors, Michael acceptors, or catalysts; adjuvants are also called herein “non-functional ingredients.” Adjuvants are chosen to improve the properties of either the functional mixture or cured polymer composition. Suitable adjuvants include, but are not limited to for example, such materials as solvents, tackifiers, emulsifiers, polymers, plasticizers, blowing agents, expandable microspheres, pigments, dyes, fillers, stabilizers and thickeners. Adjuvants are preferably chosen and used in a way that does not interfere with the practice of the invention (for example, adjuvants will preferably be chosen that do not interfere with the admixing of the ingredients, the cure of functional mixture, the application to substrate, or the final properties of the cured functional mixture). In addition to adjuvants, the addition of one or more adhesion promoters are usefully employed in functional mixtures and polymer compositions of the invention.
In the practice of the present invention, the skeleton of the multi-functional Michael acceptor may be the same or different from the skeleton of the multi-functional Michael donor. In some embodiments, one or more polyhydric alcohols are used as at least one skeleton. Polyhydric alcohols suitable as skeletons for either the multi-functional Michael acceptor or the multi-functional Michael donor include, but are not limited to for example, alkane diols, alkylene glycols, alkane diol dimers, alkane diol trimers, glycerols, pentaerythritols, polyhydric polyalkylene oxides, other polyhydric polymers, and mixtures thereof. Additional polyhydric alcohols suitable as skeletons include, for example, cyclohexane dimethanol, hexane diol, trimethylol propane, glycerol, ethylene glycol, propylene glycol, pentaerythritol, neopentyl glycol, diethylene glycol, dipropylene glycol, butanediol, 2-methyl-1,3-propanediol, trimethylolethane, similar polyhydric alcohols, substituted versions thereof, and mixtures thereof.
Further examples of polyhydric alcohols suitable as skeletons in the present invention include, for example, polyhydric alcohols with molecular weight of 150 or greater (in addition to those named herein above). Also, mixtures of suitable polyhydric alcohols are suitable.
In some embodiments, the skeleton of the multi-functional Michael donor or the multi-functional Michael acceptor or both is an oligomer or a polymer. A polymer, as used herein and as defined by F W Billmeyer, JR. in Textbook of Polymer Science, second edition, 1971 (“Billmeyer”) is a relatively large molecule made up of the reaction products of smaller chemical repeat units. Normally, polymers have 11 or more repeat units. Polymers may have structures that are linear, branched, star shaped, looped, hyper-branched, or cross-linked; polymers may have a single type of repeat unit (“homopolymers”) or they may have more than one type of repeat unit (“copolymers”). Copolymers may have the various types of repeat units arranged randomly, in sequence, in blocks, in other arrangements, or in any mixture or combination thereof.
Polymers have relatively high molecular weights. Polymer molecular weights can be measured by standard methods such as, for example, size exclusion chromatography or intrinsic viscosity. Generally, polymers have number-average molecular weight (Mn) of 1,000 or more. Polymers may have extremely high Mn; some polymers have Mn above 1,000,000; typical polymers have Mn of 1,000,000 or less.
“Oligomers,” as used herein, are structures similar to polymers except that oligomers have fewer repeat units and lower molecular weight. Normally, oligomers have 2 to 10 repeat units. Generally, oligomers have Mn of 400 to 1,000.
In some embodiments, the functional mixture will be made and used as a “batch.” That is, a certain amount of functional mixture will be formed in a container and then used as desired. Also contemplated are embodiments in which the functional mixture is made and used continuously, such as, for example, by adding all the ingredients or packs to a continuous-stream device such as, for example, an extruder.
In the practice of the present invention, the ingredients may be assembled in any combination, in any order. In some embodiments, the ingredients will be added simultaneously or in sequence to a container and admixed. In some embodiments, two or more ingredients will be mixed together and stored as a mixture (herein called a “pack”), to be combined with further ingredients at a later time to form the functional mixture of the present invention. When some ingredients are mixed together to form a pack, the remaining ingredients, even if stored in pure form, will also be called “packs” herein. Embodiments in which the ingredients are stored in two or more packs are herein called “multi-pack” embodiments.
In some embodiments, the functional mixture of the present invention is a two-pack composition. The term “two-pack” is used herein to mean that all the ingredients necessary for Michael addition to occur are contained in the admixture obtained by admixing the first pack and the second pack. It is contemplated that some embodiments of the present invention will involve using the functional mixture obtained by admixing the first pack and the second pack without adding any adjuvants to the admixture obtained by admixing the first pack and the second pack. Also contemplated are embodiments in which the first pack, the second pack, and one or more adjuvants are admixed to form the functional mixture of the present invention.
In the practice of two-pack embodiments of the present invention, the first pack contains at least one multi-functional Michael acceptor, and the second pack contains at least one multi-functional Michael donor. In the practice of two-pack embodiments of the present invention, one or both of the first pack and the second pack contains at least one catalyst. In some two-pack embodiments, the first pack, or the second pack, or both packs, contains further optional adjuvants. In some two-pack embodiments, the ingredients for each pack are chosen so that no one pack will contain all three of a Michael acceptor, a Michael donor, and a catalyst.
Also contemplated are embodiments that involve the use of at least one compound that is both a Michael acceptor and a Michael donor; such a compound has both at least one Michael donor functional group and at least one functional group with structure (II). It is contemplated that such a compound would not be used in the same pack as a compound that is effective as a catalyst for Michael addition.
In some embodiments of the present invention, one or more of the ingredients of the functional mixture are dissolved in a solvent or otherwise carried in a fluid medium (for example, as an emulsion or dispersion). If a solvent or other fluid medium is used with one or more ingredients, the solvents or other fluid media of the plural ingredients may be chosen independently of each other. In some embodiments, the functional mixture is substantially free of solvent. As defined herein, a material is “substantially free of solvent” if that material contains at least 75% solids by weight based on the total weight of that material. By “solids” is meant herein the weight all Michael donors, all Michael acceptors, all polymers, all materials that are solid when pure at 25° C., and all materials with boiling point above 200° C. In some embodiments, the functional mixture is at least 80% solids, or at least 90% solids, or at least 95% solids, or at least 98% solids, by weight based on the weight of the functional mixture.
Also contemplated are “low solids” embodiments, which are embodiments in which the functional mixture contains less than 75% solids by weight based on the weight of the functional mixture. In some low solids embodiments, the solids may be dissolved in a fluid medium or dispersed in a fluid medium or a combination thereof. In low solids embodiments, the non-solid ingredients may include one or more non-aqueous compounds, or water, or a combination thereof. In some low solids embodiments, the functional mixture contains 20% solids or higher, by weight based on the weight of the functional mixture. In some low solids embodiments, one or more Multi-functional Michael donor, one or more multi-functional Michael acceptor, or one or more of each, is a polymer.
According to one embodiment, donors and acceptors with skeletons with Mn less than 1000 are used. Such donors and acceptors are either monomeric or oligomeric. Examples of such skeletons are neopentyl glycol, trimethylolpropane, glycerol, glucose, sorbitol, mannitol, 1,3 propanediol, tripropylene glycol, polyethylene glycols of 200 to 600 Mn, pentaerytritol, ethylene glycol, propylene glycol, hexanediol, tricyclodecanedimethylol, 2,2,4-trimethyl-1,3-pentandiol, 1,3 propanediol, bis-phenol A di glycidyl epoxy, 1,4 butanediol, cyclohexanedimethanol, alkoxylated and propoxylated versions of glycerol, neopentyl glycol, hexanediol, cyclohexanedimethanol, bisphenol A di glycidyl epoxy, tri-ethylene glycol, tetra-ethylene glycol. Functional mixtures in which both donor and acceptor are based on skeletons of Mn less than 1000 are especially useful for solventless adhesives and related applications which require use of no solvent. Such mixtures have low initial viscosity without the use of solvent which can be applied by a variety of processes at temperatures below 50° C. and more preferably below 45° C. and most preferably below 40° C. Such mixtures have an unusual combination of ease of processing, good pot-life, and fast cure rate. According to one embodiment, donors and acceptors with skeletons with Mn greater than 1000 are used. Such donors and acceptors are oligomeric or polymeric. Examples of such skeletons are castor oil, polysaccharides such as dextrins, starches, modified starches, polyalkanoates, polylactides, polyvinyl alcohols, polyvinyl acetate copolymers, polyacrylates, polyesters, polyethers. Functional mixtures in which one or both donor and/or acceptor are based on skeletons of Mn greater than 1000 are especially useful for solvent based adhesives and related solvent based applications as well as for films, foams and elastomers. Such higher molecular weight compositions have a desirable combination of performance characteristics including fast green strength development, high elongation and elastomeric character, and unusual toughness.
Upon addition of one or more photo initiators, some polymers of the present invention are photocurable. According to one embodiment, the polymers require little (less than 1 percent by weight based on the total weight of the functional mixture) to no added photoinitiator. These polymers have built in photo initiation capability enabling them to cure using conventional actinic radiation, including LV radiation under conventional photocure conditions. The photocurable polymers have weight average molecular weights greater than 1,000, including those greater than 5,000, including those greater than 10,000 and including those greater than 20,000. The polymers may be usefully employed to prepare, for example, photocurable hot melts. (The polymers can also be post-cured by exposing them to actinic radiation. The photo curability of polymers of the invention provides a significant advantage over oligomeric compositions, as described in U.S. Pat. Nos. 5,945,489 and 6,025,410 in that the oligomeric compositions, due to low molecular weight, require a high dose of actinic radiation or high levels of photoinitiator. Alternatively, the polymeric compositions of this invention exhibit high molecular weight initially thereby requiring only low levels of radiation or photoinitiator to have utility as articles including adhesives, sealants, foams, and elastomers.
According to separate embodiments, photo generated amine base catalysts (photo latent bases), are added to the functional mixture for curing. “Photo latent base” herein means a compound that effectively generates amine base upon exposure to visible, UV, or other actinic radiation thereby catalyzing a carbon Michael reaction.
“Externally added” herein means a compound that is not a Michael donor, a Michael acceptor, a catalyst (as defined herein above for the practice of the present invention), or a product of the cure process in a composition of the present invention.
Independently, in some embodiments of the present invention, the functional mixture contains no compounds with epoxide groups. Independently, in some embodiments of the present invention, the functional mixture contains no compounds with isocyanate groups. Independently, in some embodiments of the present invention, the functional mixture contains no compounds with reactive groups capable of chemical reactions effective for curing other than compounds with reactive groups that participate in the Michael addition reaction.
By manipulating reaction equivalents ratios of donors and acceptors, reactant functionalities, catalysts and amounts thereof, and adjuvants levels or levels of other additives, those having skill in the art can prepare polymers of the invention that have linear, branched and cross-linked structures.
In the functional mixtures of the present invention, the relative proportion of multi-functional Michael acceptors to multi-functional Michael donors can be characterized by the reactive equivalent ratio, which is the ratio of the number of all the functional groups (II) in the functional mixture to the number of Michael active hydrogen atoms in the functional mixture. In some embodiments, the reactive equivalent ratio is 0.1:1 or higher; or 0.2:1 or higher; or 0.3:1 or higher; or 0.4:1 or higher; or 0.45:1 or higher. In some embodiments, the reactive equivalent ratio is 3:1 or lower; or 2:1 or lower; or 1.2:1 or lower; or 0.75:1 or lower; or 0.6:1 or lower.
In some embodiments, it is contemplated that the cured functional mixture will have few or no unreacted functional groups (II).
Some embodiments are contemplated in which the cured functional mixture has few or no unreacted multifunctional Michael acceptor molecules but does have a useful amount of unreacted functional groups (II). In some embodiments, the presence of unreacted functional groups (II) in the cured functional mixture, either with or without unreacted multifunctional Michael acceptor molecules, will be desirable (for example, if it is intended to conduct further chemical reactions. In other embodiments, it will be desirable for the cured functional mixture to have few or no unreacted multifunctional Michael acceptor molecules, or it will be desirable for the cured functional mixture to have few or no unreacted functional groups (II); in such embodiments, it is contemplated that the practitioner will readily be able to choose a reactive equivalent ratio that will be low enough to make it likely that the cured functional mixture will have few or no unreacted multifunctional Michael acceptor molecules or to have few or no unreacted functional groups (II), as desired. Analogously, the cured functional mixture can have a useful amount of unreacted donor groups.
In some embodiments of the present invention, multi-functional Michael donors, multi-functional Michael acceptors, catalysts, and any other ingredients are chosen so that the functional mixture thereof is homogeneous (i.e., the mixture will not phase separate upon standing or curing). Also envisioned are embodiments in which the functional mixture contains one or more ingredients dispersed as a suspension in liquid; it is useful in some of such embodiments that the suspension be stable (i.e., that the solids do not settle or coagulate upon standing or curing).
The practice of the present invention involves the use of at least one multi-functional Michael acceptor. In some embodiments, the skeleton of the multi-functional Michael acceptor is the residue of a polyhydric alcohol, such as, for example, those listed herein above. In some embodiments, the skeleton of the multi-functional Michael acceptor may be a polymer. In some embodiments, the skeleton of the multi-functional Michael acceptor may be an oligomer.
Some suitable multi-functional Michael acceptors in the present invention include, for example, molecules in which some or all of the structures (II) are residues of (meth)acrylic acid, (meth)acrylamide, fumaric acid, or maleic acid, substituted versions thereof, or combinations thereof, attached to the multi-functional Michael acceptor molecule through an ester linkage or an amide linkage. A compound with structures (II) that include two or more residues of (meth)acrylic acid attached to the compound with an ester linkage is called herein a “multi-functional (meth)acrylate.” Multi-functional (meth)acrylates with at least two double bonds capable of acting as the acceptor in Michael addition are suitable multi-functional Michael acceptors in the present invention. Some suitable multi-functional (meth)acrylates are, for example, multi-functional acrylates (compounds with two or more residues of acrylic acid, each attached via an ester linkage to the skeleton; also called MFAs).
It is to be understood herein that an acceptor that is described as “an acrylate of” (or as “diacrylate of” or as “triacrylate of”, etc.) a compound or that is described as an “acrylated” compound has a structure that could be formed by reacting that compound with acrylic acid. In many cases, the acceptor so described is actually made by performing such a reaction, though the acceptor so described could in fact be made by other methods. It is contemplated that some suitable acceptors will be described as “acrylated” or as “acrylate of” (or “diacrylate of” or “triacrylate of”, etc.) compounds with hydroxyl groups, amine groups, epoxide groups, other groups that are thought to react with carboxyl groups, or combinations thereof. For example, the acceptor




is described as acrylated butane diol and is also described as the diacrylate of butane diol; it is contemplated this acceptor could be made by reacting butane diol with acrylic acid, though the same structure could be made by any method. For another example, if a known diglycidyl ether compound had the structure (III):





then the MFA described as the “diacrylate of III” would have the following structure:





Examples of suitable multi-functional Michael acceptors that are MFAs include, but are not limited to for example, diacrylates of one or more of the following: alkyl diols, glycols, ether-containing diols (such as, for example, dimers of glycols, trimers of glycols, and polyalkylene diols), alkoxylated alkyl diols, polyester oligomer diols, bisphenol A, ethoxylated bisphenol A, and polymers with at least two hydroxyl groups. Also suitable are triacrylates of similar triols, including, for example, alkyl triols and alkoxylated alkyl triols. Additionally suitable are tetra-, penta-, and higher acrylates of similar polyhydric compounds. Bio-based Michael acceptors include but are not limited to acceptors derived from epoxidized soya, saccharides, castor oil, glycerol, 1,3-propanediol, propoxylated glycerol, Lesquerella oil, is isosorbide, sorbitol, and mannitol.
Further examples of suitable MFAs include di-, tri-, tetra-, and higher acrylates of compounds that have two or more functional groups, other than hydroxyl groups, that are capable of forming ester linkages with acrylic acid. Such MFAs include, for example, diacrylates of compounds with two epoxide groups, such as, for example, epoxy resins, diglycidyl ether, bisphenol A diglycidyl ether, ethoxylated bisphenol A diglycidyl ether, and mixtures thereof.
Also among suitable multi-functional Michael acceptors are compounds with two or more functional groups each containing structure (II) in which one or more of the functional groups containing structure (II) is the residue of (meth)acrylamide. In other suitable multi-functional Michael acceptors, at least one functional group containing structure (II) is a residue of (meth)acrylamide, and at least one functional group containing structure (II) is a functional group other than a residue of (meth)acrylamide.
The practice of the present invention involves the use of at least one multi-functional Michael donor. In some embodiments of the present invention, the skeleton of the multifunctional Michael donor is the residue of a polyhydric alcohol, such as, for example, those listed herein above. In some embodiments, the skeleton of the multi-functional Michael donor may be a polymer, such as for example, a poly alkylene oxide, a polyurethane, a polyethylene vinyl acetate, a polyvinyl alcohol, a polydiene, a hydrogenated polydiene, an alkyd, an alkyd polyester, a polyolefin, a halogenated polyolefin, a polyester, a halogenated polyester, a (meth)acrylate polymer, a copolymer thereof, or a mixture thereof. Bio-based Michael donors include but are not limited to donors derived from epoxidized soya, saccharides, castor oil, glycerol, 1,3-propanediol, propoxylated glycerol, Lesquerella oil, isosorbide, sorbitol and mannitol.
In embodiments in which the skeleton of a multi-functional Michael donor is a polymer, the Michael donor functional group may be pendant from the polymer chain, or it may be incorporated into the polymer chain, or a combination thereof.
In suitable multi-functional Michael donors, the functional groups with Michael active hydrogens may be attached to the skeletons in any of a wide variety of arrangements. In some embodiments, the multi-functional Michael donor has the structure




where n is 2 or more, R15 is





R17 is





R16, R18, R19, R20, and R21 are, independently, H, alkyl (linear, cyclic, or branched), aryl, arylkyl, alkaryl, or substituted versions thereof; and R is a residue of any of the polyhydric alcohols or polymers discussed herein above as suitable as the skeleton of a multi-functional Michael donor. In some embodiments, R16 will be the residue of a Michael acceptor. In some embodiments, one or more of R16, R18, R19, R20, and R21 will be attached to further functional groups with Michael active hydrogens.

In some embodiments, n is 3 or more. In some embodiments, the composition contains more than one multi-functional Michael donor. In such embodiments, the mixture of multi-functional Michael donors can be characterized by the number-average value of n. In some embodiments, the mixture of multi-functional Michael donors in the composition has a number average value of n of 4 or less, or 3 or less.
Some suitable multi-functional Michael donors include, for example, acetoacetoxy substituted alkyl (meth)acrylates; amides of malonic acid, amides of acetoacetic acid, alkyl esters of malonic acid, and alkyl esters of acetoacetic acid, where the alkyl groups may be linear, branched, cyclic, or a combination thereof.
Some suitable multi-functional Michael donors are, for example, alkyl compounds with two or more acetoacetate groups. Such multi-functional Michael donors include, for example, alkyl diol diacetoacetates (also known as alkyl diol bisacetoacetates) such as, for example, butane diol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentylglycol diacetoacetate, the diacetoacetate of 4,8-Bis (hydroxymethyl)tricyclo[5.2.1.02,6]decane, 2-methyl-1,3-propanediol diacetoacetate, ethylene glycol diacetoacetate, propylene glycol diacetoacetate; cyclohexanedimethanol diacetoacetate; other diol diacetoacetates; alkyl triol triacetoacetates (also known as alkyl triol trisacetoacetates), such as, for example, trimethylol propane triacetoacetate, pentaerythritol triacetoacetate, glycerol trisacetoacetate, or trimethylolethane triacetoacetate; and the like. Some further examples of suitable multi-functional Michael donors include tetra-, penta-, and higher acetoacetates of polyhydric alcohols (i.e., polyhydric alcohols on which four, five, or more hydroxyl groups are linked to acetoacetate groups through ester linkages), including, for example, pentaerythritol tetraacetoacetate, dipentaerythritol pentaacetoacetate, and dipentaerythritol hexaacetoacetate.
Some additional examples of suitable multi-functional Michael donors are glycol ether diacetoacetates (also known as glycol ether bisacetoacetates), such as, for example, diethylene glycol diacetoacetate, dipropylene glycol diacetoacetate, polyethylene glycol diacetoacetate, and polypropylene glycol diacetoacetate.
Some other suitable multi-functional Michael donors are those with a single Michael donor functional group per molecule, where that Michael donor functional group has two Michael active hydrogen atoms. Such multi-functional Michael donors include, for example, alkyl mono-acetoacetates (i.e., a compound whose structure is an alkyl group with a single attached acetoacetate group).
Additional examples of suitable multi-functional Michael donors include compounds with one or more of the following functional groups: acetoacetate, acetoacetamide, cyanoacetate, and cyanoacetamide; in which the functional groups may be attached to one or more of the following skeletons: polyesters, polyethers, (meth)acrylic polymers, and polydienes.
Alternatively, Michael donors are the reaction product of acceptors and excess donors. For example the reaction product of a multifunctional acceptor and excess acetoacetonate.
Some suitable multi-functional Michael donors include, for example, oligomers and polymers that are made from monomers that include acetoacetoxyethyl methacrylate (AAEM) and one or more of the following: (meth)acrylic acid, esters of (meth)acrylic acid, amides of (meth)acrylic acid, substituted versions thereof, and mixtures thereof. It is contemplated that, in some embodiments, at least one such oligomer or polymer will be used that is made from monomers that include 10% by weight or more of AAEM, based on the weight of all monomers used to make that oligomer or polymer.
Some suitable multi-functional Michael donors are multifunctional acetoacetate functional polyester polymers and acetoacetate functional polyesteramides.
Mixtures of suitable multi-functional Michael donors are also suitable.
One category of multi-functional Michael donors arc known as malonates. Malonates have




(where R15, is R17, and R18 are defined herein above). Malonates may or may not be used; that is, in such embodiments, non-malonate multi-functional Michael donors are used.

According to one embodiment, at least one soluble weakly basic catalyst is used. A catalyst is “soluble” as defined herein if it meets the following solubility criterion. A suitable test mixture is selected; the test mixture may be a single multi-functional Michael acceptor, a mixture of two or more multi-functional Michael acceptors, a single multi-functional Michael donor, or a mixture of two or more multi-functional Michael donors. The test mixture is part or all of the functional mixture in which the weakly basic catalyst will be used. The ratio of the weight of that catalyst to be used in the functional mixture to the sum of the weights of all multi-functional Michael acceptors and all multi-functional Michael donors in the functional mixture is herein called X1. The ratio of the sum of the weights of the ingredients of the test mixture to the sum of the weights of all the multi-functional Michael acceptors and all the multi-functional Michael donors in the functional mixture is herein called X2. Then, to perform the solubility test, at least enough catalyst is added to the test mixture so that the ratio of the weight of catalyst to the weight of test mixture is Y or more, where Y=X1/X2. The mixture of catalyst and test mixture is subjected to the dissolution procedure defined herein below, and the amount of catalyst actually dissolved in the test mixture is determined thereby. If the ratio of the weight of actually-dissolved catalyst to the weight of test mixture is Y or greater, the catalyst is considered to be soluble.
One useful way of practicing the above solubility test is to choose a test mixture that contains one or more Michael donors but does not contain any Michael acceptors. Another useful way of practicing the above solubility test is to choose a test mixture that contains one or more Michael acceptors but does not contain any Michael donors.
The dissolution procedure used for determining solubility is defined herein as follows. The mixture of catalyst and test mixture is heated to 75° C. for 2 hours; if the resulting mixture is clear (i.e., it shows no haze or sediment visible to the unaided eye), then the catalyst is considered to be soluble. If the resulting mixture is clear after heating to temperature below 75° C., or if the resulting mixture is clear when mixed at any temperature below 75° C., or if the resulting mixture is clear at a time less than 2 hours after the catalyst was added to the test mixture, the catalyst is considered to be soluble. If, after 2 hours at 75° C., the resulting mixture is not clear, it is filtered through 45-60 μm fritted glass; and the filtrate is titrated with dilute HCl to determine the amount of catalyst that is actually dissolved in the test mixture.
When a filtrate is titrated with dilute HCl, one acceptable procedure is as follows. An amount of filtrate estimated to contain between 0.1 and 0.2 milliequivalents (meq) of catalyst is dissolved in 30 ml of denatured alcohol. This solution of filtrate is then titrated with aqueous 0.1 molar HCl to a sharp endpoint. Titrating may be done by using any of a wide variety of methods and/or apparatus known in the art. For example, an RTS822 recording titration system manufactured by Radiometer Analytical SAS may be used. The progress and the endpoint of the titration may be measured by any of a wide variety of methods and/or apparatus known in the art, for example using electrodes such as, for example a glass electrode and a reference electrode, such as, for example, pHG201 and REF201 electrodes from Radiometer Analytical SAS. After the endpoint is detected, the following amounts are calculated by standard methods: the moles of catalyst present in solution of filtrate, and the amount (wt. %) of catalyst actually dissolved in the test mixture.
In general, in the practice of the present invention, a catalyst is soluble if enough catalyst dissolves in the test mixture to provide sufficient catalyst in the functional mixture so that, when the functional mixture is formed, cure will take place. In some embodiments, catalyst dissolves in the test mixture in the amount of 0.1 gram or more of catalyst per 100 grams of test mixture; or 0.2 grams or more of catalyst per 100 grams of test mixture; or 0.5 grams or more of catalyst per 100 grams of test mixture; or 1 gram or more of catalyst per 100 grams of test mixture. If the mixture of catalyst and test mixture is mixed at temperature lower than 75° C., or for less time than two hours, or both, and a sufficient weight of catalyst is actually dissolved in the test mixture, then the catalyst is considered to be soluble.
In some embodiments of the present invention, at least one soluble weakly basic catalyst is used in the form of pure material. By “pure material” is meant herein material that has a level of purity that is readily obtainable from commercial manufacturers or has a higher level of purity.
In other embodiments of the present invention, the functional mixture is formed by adding a solution of soluble weakly basic catalyst to other ingredients. By “solution of soluble weakly basic catalyst” is meant herein a homogeneous mixture of a solvent (which is a non-functional ingredient, as defined herein above) and a soluble (as defined herein above) weakly basic catalyst. The solvent in such embodiments may be water or an organic solvent, such as, for example, hydrocarbons, alcohols, and ketones. Water is known to be suitable. For example, in some embodiments, a solution of a soluble weakly basic catalyst is added to one or more multi-functional Michael acceptors. Some suitable solutions of soluble weakly basic catalyst have concentration of soluble weakly basic catalyst of 50% or higher, or 65% or higher, by weight based on the weight of the solution. In some embodiments involving addition of a solution of soluble weakly basic catalyst, the pack containing the soluble weakly basic catalyst, or the functional mixture, is subjected to elevated temperature or reduced pressure or both to remove some or all of the solvent. In some embodiments in which the functional mixture is subjected to elevated temperature to remove solvent, it is contemplated that such removal of solvent will be performed in a manner that does not interfere with applying the functional mixture to substrate and/or with cure of the functional mixture; for example, solvent removal may be performed after the functional mixture is applied to substrate, in which case it is contemplated that solvent removal and curing might take place fully or partially at the same time as each other. In other embodiments involving addition of a solution of soluble weakly basic catalyst, the solvent is left in place; that is, no steps are taken to remove the solvent. According to one embodiment, all solvent is removed before coating the composition.
In the practice of some embodiments of the present invention in which a solution of soluble weakly basic catalyst is added to a pack or to the functional mixture, the pack to which the solution of soluble weakly basic catalyst is added, or the functional mixture, will appear homogeneous.
In some embodiments of the present invention in which a solution of soluble weakly basic catalyst is added to a pack or to the functional mixture, the resulting admixture will appear cloudy. In such embodiments, it is contemplated, without limiting the invention to any model or theory, that the cloudiness occurs because the solvent used in the solution of soluble weakly basic catalyst is incompatible or insoluble with other ingredients; that the solvent remains as a separate phase; and that the solvent exists as droplets dispersed throughout the volume of the pack. It is further contemplated that, when such a dispersion of solvent droplets occurs, the soluble weakly basic catalyst may remain in the solvent droplets, or the soluble weakly basic catalyst may migrate out of the solvent and become dissolved in the other ingredients, or the soluble weakly basic catalyst may partition in some proportion between the solvent droplets and the other ingredients. In these embodiments, regardless of the location of the soluble weakly basic catalyst, as long as the soluble weakly basic catalyst is capable of meeting the solubility criterion defined herein above, packs or functional mixtures that include such dispersions of solvent droplets are considered suitable in the practice of the present invention.
As an example, in some embodiments, a soluble weakly basic catalyst is dissolved in water to form an aqueous solution, and that aqueous solution is then mixed with one or more multi-functional Michael acceptors.
The soluble weakly basic catalyst of the present invention is selected from the following: sodium salts of carboxylic acids, magnesium salts of carboxylic acids, aluminum salts of carboxylic acids, chromium salts of alkyl carboxylic acids 1 to 22 carbon atoms, including 6 or fewer carbon atoms, chromium salts of aromatic carboxylic acids, potassium salts of alkyl mono-carboxylic acids having 1 to 22 carbon atoms, including 6 or fewer carbon atoms, potassium salts of multi-carboxylic acids, and mixtures thereof. By “mono-carboxylic acid” is meant herein a carboxylic acid with one carboxyl group per molecule. By “multi-carboxylic acid” is meant herein a carboxylic acid with more than one carboxyl group per molecule. Among sodium, magnesium, and aluminum salts of carboxylic acids are, for example, sodium, magnesium, and aluminum salts of the following types of carboxylic acids: aromatic carboxylic acids, alkyl carboxylic acids with 7 to 22 carbon atoms, alkyl carboxylic acids with 6 or fewer carboxylic acids, and mixtures thereof.
In some embodiments, the soluble weakly basic catalyst of the present invention is selected from the following: sodium salts of alkyl mono-carboxylic acids with 7 to 22 carbon atoms, sodium salts of alkyl mono-carboxylic acids with 6 or fewer carbon atoms, potassium salts of alkyl mono-carboxylic acids with 6 or fewer carbon atoms, and mixtures thereof.
A catalyst is “weakly basic,” as defined herein, if it is a basic compound with the characteristic that the pKa of its conjugate acid is greater than or equal to 3 and also is less than or equal to 11. In some embodiments, the pKa of the conjugate acid of the soluble weakly basic catalyst is 3.5 or greater; or 4 or greater. In some embodiments, the pKa of the conjugate acid of the soluble weakly basic catalyst is 7.5 or less; or 5.5 or less; or 4.9 or less. The pKa of the conjugate acid of a base is a well known characteristic, and values of pKa's for the conjugate acids of many bases have been published, for example in the Handbook of Chemistry and Physics, 82nd edition, CRC press, 2001. While pKa's are sometimes measured in dilute aqueous solution, the pKa itself is a characteristic of a compound, whether or not the compound is actually used in an aqueous solution.
If the conjugate acid of the soluble catalyst is a multi-carboxyl carboxylic acid, the soluble catalyst is considered weakly basic if the first pKa (i.e., the pKa representing the dissociation constant of the first hydrogen ion) is greater than or equal to 3 and is less than or equal to 11. Subsequent dissociation constants may have any value. Some suitable soluble weakly basic catalysts are, for example, potassium acetate, sodium octoate, potassium caprylate and chromium acetate. Mixtures of suitable soluble weakly basic catalysts are also suitable.
Some weakly basic catalysts include, for example, sodium carbonate, potassium carbonate, and sodium hydrogenphosphate.
In some cases, multifunctional Michael acceptor compounds, as supplied by a manufacturer, contain some amount (usually a relatively small amount) of a salt of a carboxylic acid. It is contemplated that the present invention can be practiced with multifunctional Michael acceptors that do contain such salts, with multifunctional Michael acceptors that do not contain such salts, or with a mixture thereof. Frequently, the acceptors may contain an acid. According to one embodiment, the acid is neutralized with a base prior or during use for the purpose of not inhibiting the reaction. According to a separate embodiment, the catalyst is generated in-situ.
In some embodiments, a suitable multifunctional Michael acceptor, as supplied by a manufacturer, contains at least one salt that is suitable as a weakly basic catalyst. Such multifunctional Michael acceptors are contemplated to be used in the practice of the present invention. In some cases, the amount of salt that is present in the multifunctional Michael acceptor, as supplied by the manufacturer, is low enough that it would be desirable, in the practice of the present invention, to use an additional amount of weakly basic catalyst, which may be the same or different from the one already present in the multifunctional Michael acceptor.
In some embodiments, the practice of the present invention involves the use of one or more basic catalysts (i.e., a compound that is effective as a catalyst for the Michael addition reaction and is not a weakly basic catalyst). Such other catalysts are known to include, for example, strong bases such as, for example, basic compounds the conjugate acids of which have pKa greater than 11. Strong bases include, for example, alkoxides, tri-basic alkali metal phosphates, acetoacetonates, amidines, guanidines, diaza compounds, alkyl amines, tetraalkyl ammonium salts that are strong bases, derivatives thereof, and mixtures thereof. Further compounds known to function as other catalysts are blocked catalysts, which are amine or ammonium compounds that are used in combination with carboxylic acids that either evaporate or decarboxylate under curing conditions. Blocked catalysts are described, for example in U.S. Pat. No. 5,219,958. Some blocked catalysts use amidine compounds, quaternary ammonium compounds, or mixtures thereof in combination with carboxylic acid that either evaporates or decarboxylates under curing conditions.
In some embodiments of the present invention, the functional mixture contains no blocked catalyst. Independently, in some embodiments, the functional mixture of the present invention contains no strong base. Independently, in some embodiments, the functional mixture of the present invention contains no catalyst that is not a weakly basic catalyst.
In some embodiments of the present invention, the functional mixture, prior to the onset of the cure process, does not include any anions (herein called “donor-derived anions”) that can be created by removing a Michael active hydrogen atom from a Michael donor compound. An example of donor-derived anion is an acetoacetonate anion, which can be created by removing a Michael active hydrogen atom from an acetoacetate group. Similar donor-derived anions can be created by removing a Michael active hydrogen atom from any one of the Michael donor functional groups described herein above. Without limiting the invention to any particular theory, it is contemplated that, in some embodiments, after the functional mixture is formed, once the cure process has begun, some compound that contains one or more donor-derived anions may be formed as an intermediate during the Michael addition reaction.
In some embodiments of the present invention, the functional mixture does not contain any mono-functional Michael acceptors or donors, which are known to cause chain stopping. In other embodiments, the functional mixture contains at least one mono-functional Michael acceptor. As used herein, a “mono-functional Michael acceptor” is a Michael acceptor (as defined herein above) that has exactly one structure (II) in each molecule. Some mono-functional Michael acceptors include, for example, (meth)acrylic acid and esters thereof that have one structure (II) per molecule, including, for example, alkyl (meth)acrylates.
In some embodiments of the present invention, the functional mixture does not contain any mono-functional Michael donors. In other embodiments, the functional mixture contains at least one mono-functional Michael donor, in addition to at least one multi-functional Michael donor. As used herein, a “mono-functional Michael donor” is a Michael donor (as defined herein above) that has exactly one Michael active hydrogen in each molecule.
It is contemplated that the ingredients of the functional mixture of the present invention will be chosen so that Michael addition will take place under the conditions of practicing the invention. For example, a particular multi-functional Michael acceptor may undergo the Michael addition reaction with some multi-functional Michael donors less readily than with other multi-functional Michael donors. For example, methacrylate groups usually react more readily with cyanoacetate groups than with acetoacetate groups. Further, some soluble weakly basic catalysts promote the Michael addition reaction more strongly than others. However, even if the reaction between a specific multi-functional Michael donor and a specific multi-functional Michael acceptor is slow or ineffective, in some cases it will be possible to speed the reaction or make it effective by employing a more basic catalyst, using larger amounts of basic catalyst, heating the mixture or combinations thereof. The practitioner of the invention will readily be able to choose an effective combination of ingredients to achieve the desired speed of curing in the practice of the present invention.
In the practice of the present invention, the functional mixture is formed by admixing the ingredients; the admixing may be performed by any means. In some embodiments, the ingredients are all liquids, and they may be admixed simply by placing the ingredients in a container and stirring. If any ingredient is a solid, it is contemplated that sufficient agitation will be provided to dissolve or suspend the solid in the functional mixture. In some embodiments, the various ingredients may be admixed on a substrate, for example by applying alternate layers of various ingredients or by spraying separate streams of various ingredients onto the same area of the substrate.
The functional mixture of the present invention, when it is freshly mixed, should have a useful viscosity at 23° C. One useful means of measuring viscosity is with a Brookfield viscometer, with the spindle type and rotation speed chosen according to the instructions of the viscometer manufacturer as appropriate for the material to be measured. Generally, conditions for using Brookfield viscometer properly involve, for example, choosing spindle and rotation speed that give a reading on the instrument scale of 10% to 90% of full scale. For some embodiments, #4 spindle is appropriate. In some embodiments, the freshly-mixed functional mixture will be a liquid with viscosity of 0.01 Pa*s (10 cps) or higher. The freshly-mixed functional mixture will be a liquid with viscosity of 10,000 Pa*s (10,000,000 cps) or less. The desired viscosity will be determined by the means used to mix the ingredients and the means used to mold the functional mixture or apply it to a substrate. In some embodiments involving application of the functional mixture to substrate, viscosity of the functional mixture is 0.1 Pa*s (100 cps) or greater; or 0.2 Pa*s (200 cps) or greater; or 0.4 Pa*s (400 cps) or greater. Independently, in some embodiments involving application of the functional mixture to substrate, viscosity is 2,000 Pa*s (2,000,000 cps) or less; or 1,000 Pa*s (1,000,000 cps) or less; or 500 Pa*s (500,000 cps) or less. In embodiments involving use of the cured functional mixture as elastomer and/or as polymeric foam, the preferred viscosity is usually higher than the preferred viscosity for functional mixtures that are applied to substrate.
The functional mixture of the present invention is capable of curing at 23° C. in 7 days or less. The fact that curing takes place can be verified by measuring the pot life of the functional mixture (i.e., the time from the formation of the functional mixture until the viscosity of the mixture rises until it is so high that the functional mixture can no longer be molded or applied to a substrate) at 23° C. The viscosity of the freshly-mixed functional mixture may be measured by any standard method at 23° C.; one useful viscosity measurement method is the use of a Brookfield viscometer, as discussed herein above.
One useful measure of the pot life is the time (herein called the “viscosity quintupling time”) required for the viscosity of the functional mixture to reach a value that is 5 times the viscosity of the freshly mixed functional mixture. A useful alternative measure of the pot life is the time (herein called the “viscosity doubling time”) required for the viscosity of the functional mixture to reach a value that is 2 times the viscosity of the freshly mixed functional mixture. It is contemplated that, when two mixtures are compared, the mixture with the longer viscosity quintupling time will also have the longer viscosity doubling time. Another useful alternative meaure of the pot life is the time required for the viscosity of the functional mixture to reach a value that is 10 times the viscosity of the freshly mixed functional mixture. Still another useful alternative meaures of the pot life is the time required for the viscosity of the functional mixture to reach a value that is 100 times the viscosity of the freshly mixed functional mixture.
Yet another useful measurement is the half life of the cure reaction. In general, it is contemplated that, when two mixtures are compared, the mixture with the longer half life will also have a longer viscosity quintupling time. The half life of the cure reaction is determined as follows. The functional mixture is studied using any known analytical method to measure the concentration of functional groups containing structure (II) (such functional groups are herein called “structure II-groups”) present before the curing reaction begins and to measure, as a function of time (measured from the moment when the functional mixture is formed), the concentration of structure II-groups that have reacted in the curing reaction. The ratio of the concentration of structure II-groups that have reacted in the curing reaction to the concentration of structure II-groups that were present before the curing reaction began is herein called “conversion.” The half life of the curing reaction is the time required for conversion to reach 0.50. The half life may be assessed by any of a wide variety of methods.
One method of assessing the half life of the curing reaction is the line-fit method, which is performed as follows. At each time, conversion is measured and is used to calculate the “reaction progress ratio,” herein defined as (conversion)/(1−conversion). The values of reaction progress ratio as a function of time are fit to a straight line using a standard linear least-squares method. The half life of the cure reaction is then the reciprocal of the slope of the straight line thus determined. The line-fit method of assessing the half life is suitable when a person of ordinary skill in the art would consider the dependence of reaction progress ratio vs. time to be linear; if a person of ordinary skill in the art would consider the dependence of reaction progress ratio versus time to be nonlinear, then some other method of assessing the half life of the reaction would be used.
In some embodiments, pot life of the functional mixture is 5 minutes or more; or 10 minutes or more; or 25 minutes or more. Independently, in some embodiments, pot life is 7 days or less; or 1 day or less; or 8 hours or less; or 2 hours or less; or 30 minutes or less.
In other embodiments, a shorter pot life of the functional mixture is desirable. In some shorter pot life embodiments, pot life of the functional mixture is 30 seconds or more; or 1 minute or more; or 2 minutes or more. Independently, in some shorter pot life embodiments, pot life is 20 minutes or less; or 10 minutes or less; or 5 minutes or less. For example, some embodiments in which the cured functional mixture will be used as a foam or elastomer will desirably be shorter pot life embodiments.
In some embodiments of the present invention, the functional mixture contains at least one acid scavenger. An acid scavenger, as defined herein, is a compound that is not a soluble weakly basic catalyst of the present invention and that is capable of reacting with an acid, either a carboxylic acid or another acid. By “reacting with an acid” is meant herein that the acid scavenger is capable of interacting with the acid (for example, by forming a covalent bond, an ionic bond, or a complex) to form a temporary or permanent product; the interaction between the acid scavenger and the acid eliminates or reduces the tendency of the acid to participate in interactions with compounds other than the acid scavenger. Some examples of acid scavengers are tertiary amines (such as, for example, triethanol amine), aziridines (such as, for example, ethyleneimine), carbodiimides, organic titanium compounds, organic zirconates, weak base ion exchange resins, nitrogen containing resins (such as, for example, poly-2-ethyl-2-oxazoline and polyvinylpyrolidone), alkali metal carbonates and bicarbonates (such as, for example, potassium carbonate), and mixtures thereof. Some organic titanium compounds known to be effective as acid scavengers are, for example, tetra butyl titanate, tetra isopropyl titanate, and titanium acetylacetate, sold by DuPont Co. as, respectively, TyzorTM TnBT, TyzorTM TPT, and TyzorTM AA.
In some embodiments in which one or more acid scavengers are used, the acid scavenger includes one or more carbodiimide (CDI). Carbodiimides have the chemical structure

    
    
        R31—N═C═N—R22 

where R31 and R22 are, independent of each other, hydrocarbon structures or structures that contain, in addition to carbon and hydrogen, and at least one heteroatom (i.e., an atom other than hydrogen or carbon) such as, for example, oxygen, nitrogen, sulfur, or phosphorus. For example, R31 and R22 may be chosen from alkyl, aryl, alkyl-substituted aryl, aryl-substituted alkyl, and mixtures thereof. In some embodiments, at least one R31 and R22 contains at least one ether link, thioether link, ester link, urethane link, or amide link. Also contemplated are carbodiimides in which one or both of R31 and R22 is a polymer.

    
    


In some embodiments, the acid scavenger of the present invention includes one or more carbodiimide that has the structure known as a polycarbodiimide (pCDI):




where n is 2 or greater, and where R23, R24, and R25 are each independently chosen from the groups described herein above as suitable for R31 and R22. The R24 groups may be all the same or may be any number (up to n) of different groups. In some embodiments, at least one of R23 and R25 contains at least one ether link, thioether link, ester link, urethane link, or amide link. In some embodiments, at least one of R23 and R25 has molecular weight of 200 or greater. In some embodiments, R24 groups are chosen from alkyl, aryl, alkyl-substituted aryl, and combinations thereof. A pCDI in which all of the R14 groups are chosen from aryl, alkyl-substituted aryl, and mixtures thereof are known herein as “aromatic pCDIs.” In some embodiments, at least one pCDI is used. In some embodiments, at least one pCDI is used in which the R24 groups are all the same.

Some embodiments of the present invention involve applying a layer of the functional mixture to a substrate. The layer may be a continuous or discontinuous film. The method of application may be by any of a number of ways known to those having ordinary skill in the art, such as, for example, brushing, spraying, roller coating, rotogravure coating, flexographic coating, flow coating, curtain coating, dipping, hot melt coating, extrusion, co-extrusion, similar methods, and combinations thereof. In some embodiments, application of a layer of functional mixture to substrate is performed at ambient temperature. In other embodiments, the application may be performed at elevated temperature, for example to adjust the viscosity of the functional mixture.
In other embodiments, particularly those in which the cured functional mixture will be used as a foam or as an elastomer, the functional mixture may be formed by mixing the ingredients in a mold or other suitable container and kept therein during the cure reaction. Alternatively, after the ingredients are mixed, the functional mixture may be placed into a mold or other suitable container and kept therein during the cure reaction.
In some embodiments, the functional mixture may be dried. That is, after the first pack and second pack are mixed together but before the functional mixture is put to use, a period of time may elapse, to allow any volatile compounds, such as, for example, solvents, if any volatile compounds are present, to evaporate. During this period of time, in some embodiments, the functional mixture may be exposed to reduced pressure or to a moving atmosphere. Drying may be performed before, during, or after the cure reaction takes place. Independently, in embodiments involving applying the functional mixture to a substrate or placing it into a mold, drying may be performed before, during, or after the functional mixture is applied to substrate or placed into a mold.
In some embodiments, few or no volatile compounds are released during the cure process. For example, in some embodiments, the weight of the functional mixture reduces by 10% or less, based on the initial weight of the functional mixture (i.e., the weight of the freshly-mixed functional mixture), during the cure process. In some embodiments, the weight of the functional mixture reduces by 5% or less, or 2% or less, or 1% or less, based on the initial weight of the functional mixture, during the cure process.
In some embodiments that involve applying a layer of the functional mixture to a substrate, one or more substrates may be treated prior to contact with the functional mixture, using one or more of treatments such as, for example, corona discharge or coating with chemical primer. In other embodiments, the substrate is contacted with the functional mixture of the present invention without prior treatment. The functional mixture may be applied, for example, at a level of 0.2 to 116 g/m2 (0.12 to 71.2 lb/ream).
In embodiments in which the functional mixture will be used to bond substrates to each other, after a layer of the functional mixture has been applied to a first substrate, the layer may then be contacted with another substrate to form a composite. The composite so formed is optionally subjected to applied pressure, such as passing it between rollers to effect increased contact of the substrates with the composition; such pressure is often applied before the cure reaction is substantially complete. In another embodiment of the invention, layers of the functional mixture may be simultaneously or sequentially applied to both surfaces of a first substrate, which layers are then simultaneously or sequentially contacted with two further substrates, which may be the same, or different. It is further contemplated that the composite construction may sequentially be bonded to other substrate(s) using the functional mixture of the invention, or a different composition before or after the process described herein. The first and second substrates to be bonded in the method of this invention may be the same or different and include, for example plastics, metallized plastics, metal, and paper, which may have smooth or structured surfaces.
Among embodiments in which the functional mixture will be used to bond substrates to each other, in some of these embodiments, the composite will be heated above 23° C. The functional mixture of the present invention is capable of cure at 23° C., but in some embodiments it is desirable to hasten or otherwise improve the cure process by heating the composite to temperature above 23° C. When such heating is performed, the composite may be heated to temperatures above 35° C., or above 50° C., or above 100° C. Also contemplated are embodiments in which the composite is maintained at temperature below 35° C. during the cure process.
Among embodiments in which the functional mixture will be used to bond substrates to each other, in some of these embodiments, most or all of the Michael addition reaction is completed before the functional mixture is in contact with any substrate or while the functional mixture is in contact with only one substrate.
In other embodiments in which the functional mixture will be used to bond substrates to each other, a substantial part the Michael addition reaction takes place when the functional mixture is in contact with at least two substrates. In some of such embodiments, at least 25 mole % of the Michael addition reactions that take place occur when the functional mixture is in contact with at least two substrates; in other such embodiments, at least 50 mole %, or at least 75 mole %, or at least 90 mole % of the Michael addition reactions that take place occur when the functional mixture is in contact with at least two substrates.
According to another embodiment, the functional mixture is a useful pressure sensitive adhesive composition. According to another embodiment, the functional mixture is cured in contact with at least one substrate which contains a release coating. According to another embodiment, the cured functional mixture has a Tg less than 50° C., including less than 30° C. and less than 25° C., and is applied to a polymer film with or without using a solvent. A wide range of laminates are usefully prepared using polymer compositions and functional mixtures of the invention. In some embodiments of the present invention, the substrates are relatively thin and flat, and the resulting composites are called laminates. Some examples of substrates for laminates are polyalkylenes, such as polyethylenes and polypropylenes, polyvinyl chloride, polyesters such as polyethylene terephthalate, polyamides (nylon), ethyl cellulose, cellulose acetate, metallized polypropylene, paper, aluminum foil, other metals, ceramic sheet materials, etc., which may be provided in the form of rolls, sheets, films, foils etc. Further examples of substrates for laminates are woven or non-woven fabrics, which may be constructed of fibers using one or more natural or synthetic fibers made of materials such as, for example, cotton, wool, rayon, nylon, polyester, polyalkylene, glass, or ceramics.
An adhesive suitable for bonding substrates together to form a laminate is known herein as a “laminating adhesive.”
In the practice of the present invention, substrates that may be bonded to each other by the functional mixture of the present invention to form laminates may be the same as each other or different from each other.
The cured functional mixture may be used for any of a wide variety of purposes. For example, the cured functional mixture may be used as an elastomer, either bonded to a substrate or as an elastomeric article. When used as an elastomer it is preferable that at least one donor or acceptor or both have a molecular weight greater than 1000, more preferably greater than 2000, and most preferably greater than 5000. For another example, the cured functional mixture may be formed and cured under conditions that produce a foam. For a further example, a layer of the functional mixture may be applied to a substrate and then left exposed to air to form a coating; such a coating may be continuous or discontinuous; it may be protective or decorative or both; it may function, for example, as a paint, as another type of coating, or as an ink. The use for cured functional mixture may be, for example, as one or more of a gasket, a sealant, a roofing membrane, or a film.
The cured functional mixture may be characterized by measuring its glass transition temperature (Tg). The glass transition temperature may be measured by Dynamic Mechanical Analysis (DMA) in flexural mode at 1 hertz (1 cycle/sec). The Tg is identified as the peak in the curve of tan delta versus temperature. The DMA test may be performed on the cured functional mixture by itself, or the DMA test may be performed while the cured functional mixture is in contact with other materials. For example, if the cured functional mixture is in a layer between substrates in a composite, the entire composite may be tested in the DMA test; persons skilled in the art will readily know how to ignore any peaks in the curve of tan delta versus temperature that are due to substrates or to materials other than the cured functional mixture. In some embodiments (herein called “multi-Tg” embodiments), the cured functional mixture will have more than one peak in the curve of tan delta versus temperature.
The statement that a cured functional mixture “has a Tg of” a certain value is to be understood herein to mean that the cured functional mixture either has a sole Tg of that certain value or that the cured functional mixture has multiple peaks in the curve of tan delta versus temperature, one of which has a peak of that certain value.
The cured functional mixture of the present invention may have any of a wide range of Tg's. In some embodiments, the cured functional mixture will have a Tg of −80° C. or higher. Independently, in some embodiments, the cured functional mixture will have a Tg of 120° C. or lower. The Tg or multiple Tg's will be chosen to give the best properties that are desired for the intended use of the cured functional mixture.
For example, when the cured functional mixture is intended for use as a structural adhesive, the functional mixture will usually be chosen so that the cured functional mixture will have a Tg of 50° C. or higher. As another example, when the cured functional mixture is intended for use as a pressure-sensitive adhesive, the functional mixture will usually be chosen so that the cured functional mixture will have a Tg of 15° C. or lower; or 0° C. or lower; or −25° C. or lower; or −50° C. or lower. As yet another example, when the cured functional mixture is intended for use as a laminating adhesive, the functional mixture will usually be chosen so that the cured functional mixture will have a Tg of −30° C. or higher; or −15° C. or higher; or −5° C. or higher; or 15° C. or higher; or 30° C. or higher.
It is to be understood that for purposes of the present specification and claims that the range and ratio limits recited herein can be combined. For example, if ranges of 60 to 120 and 80 to 110 are recited for a particular parameter, it is understood that the ranges of 60 to 110 and 80 to 120 are also contemplated. Additionally, if minimum range values of 1 and 2 are recited, and if maximum range values of 3, 4, and 5 are recited, then the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5.


EXAMPLES
Materials and Abbreviations


    SR-259=polyethylene glycol (200) diacrylate, from Sartomer Co.
    MorcureTM 2000=diacrylate of diglycidyl ether bisphenol-A, from Rohm and Haas Co.
    SR-610=polyethylene glycol (600) diacrylate, from Sartomer Co.
    EB-860=epoxidized soya acrylate, from UCB Surface Specialties, Inc.
    RX-03749=low acid epoxidized soya acrylate, from UCB Surface Specialties, Inc.
    RX-04852=low acid epoxidized soya acrylate, from UCB Surface Specialties, Inc.
    EB-8402=urethane acrylate oligomer, from UCB Surface Specialties, Inc.
    NPG bis AcAc=neopentylglycol bisacetoacetate
    TMP tris AcAc=trimethylol propane trisacetoacetate
    PNE tetra AcAc=pentaerythritol tetraacetoacetate
    V-O2-L2=solution of aliphatic polycarbodiimide, equivalent weight 385 g/mol,
    
        40% concentration in water, manufactured by Nisshinbo
    
    
    XL-1422=aromatic polycarbodiimide; supplied as solution of 50% concentration
    
        in solvent; solvent removed before use herein,
        manufactured by Rohm and Haas Company
    
    
    GF-10=linear low density polyethylene film, thickness 0.025 mm (1 mil)
    GF-19=high slip linear low density polyethylene film, thickness 0.025 mm (1 mil)
    48 g PET=corona treated polyethylene terephthalate, thickness 0.012 mm (0.48 mil)
    OPP=corona treated oriented polypropylene, thickness 0.044 mm (1.75 mil)
    75 LBW=oriented polypropylene, thickness 0.019 mm (0.75 mil)
    70 SPW=oriented polypropylene, thickness 0.018 mm (0.70 mil)
    EmblemTM 1500=nylon from Honeywell, thickness 0.015 mm (0.60 mil)
    48LBT=polyester film, thickness 0.012 mm (48 gauge)
    92LBT=polyester film, thickness 0.023 mm (92 gauge)

T-Peel Test Procedure:



In the T-peel test, a layer of functional mixture is applied to a first film. Any solvents or other volatile compounds present in the functional mixture are substantially removed before, during, or after application of the layer. Then, a second film (of the same material as the first film or a different material from the first film) is contacted with the layer of functional mixture, and the laminate so formed is pressed between nip rollers. The functional mixture is cured or allowed to cure.
The laminate is stored under ambient conditions (20-25° C.) for various durations prior to testing.
A strip of laminate of width 25 mm (1 inch) is cut, and the strip is peeled apart in a tensile tester at speed of 4.2 mm/sec (10 in/min). The T-peel result is recorded as the maximum load (in grams of load) required to pull the strip apart. Also recorded is location of the failure during the peel test: “A” if the adhesive failed at the bond between the adhesive and at least one substrate, “S1” if the first film failed, and “S2” if the second film failed. For each duration of storage prior to testing, a T-peel result and a failure mode are reported.
Example 1
Preparation of MFA1 and MFA 2
Each of the following mixtures (MFA1 and MFA2) was prepared by mixing solid potassium acetate with the remaining ingredients:

    
    
        MFA1=5.6 g MorcureTM 2000, 2.4 g SR-259, 0.1 g potassium acetate
        MFA2=7.38 g MorcureTM 2000, 3.16 g SR-610, 0.1 g potassium acetate
    
    


Example 2
Functional Mixtures FM1 and FM2
The following functional mixtures were formed by stirring together the ingredients listed:

    
    
        FM1=8.1 g MFA1, 5 g TMP Tris AcAc
        FM2=10.64 g MFA2, 5 g TMP Tris AcAc
    
    


Example 3
Test Results on FM1 and FM2
The T-peel test, as defined above, was performed, with the substrates, coat weight (CW), and results were as follows:




















7-day T-



Substrate
Substrate
CW
7-day
Peel


FM #
#1
#2
g/m2 (lb/ream)
Failure
grams







1
OPP
OPP
1.5 (0.9)
A
170


1
OPP
GF19
1.1 (0.7)
S2
600


1
GF19
Emblem
1.3 (0.8)
S1
435




1500


1
48 g PET
GF19
1.1 (0.7)
S2
482


2
GF19
75 LBW
1.26 (0.77)
S1
656


2
70 SPW
75 LBW
2.10 (1.29)
S1
624









Example 4
Pot Life Measurements
First, an acrylate mixture (AM1) was made by mixing SR-259 and MorcureTM 2000 in the ratio of SR-259 to MorcureTM 2000 of 15:85 by weight.
Then, mixtures were formed by adding an amount (“X” grams) of an aqueous solution of potassium acetate (KOAc) to AM1. The concentration of the aqueous solution of potassium acetate was 70% potassium acetate, based on the weight of the aqueous solution. Each mixture was hazy when formed at room temperature. Each mixture contained 14.78 g of AM1.
Then, each mixture was mixed with 9.00 g of neopentylglycol bis(acetoacetate). The initial viscosity and the viscosity as a function of time of each mixture was measured at 25° C. with Brookfield viscometer, #4 spindle, 60 rpm. A plot of the natural log of viscosity versus time was made, and the slope of that line was determined with a linear least-squares fit. The time required for viscosity to double (“doubling time”) is the natural log of 2 divided by the slope of that line. The results for pot life test mixtures (PLTM) were as follows:

















KOAc
initial
doubling




solution
viscosity
time



PLTM #
grams1
Pa * s (cps)
minutes









1
0.37
1.04 (1040)
32.7



2
0.65
1.10 (1100)
14.0







note



1the amount “X” defined above.






It is expected that, if the experiment were carried out until the viscosity reached a value that was at least 5 times the initial viscosity, then the data would be fit by the same linear least-squares fit. In such a case, the viscosity quintupling time would be found by multiplying the viscosity doubling time by the ratio of the natural log of 5 to the natural log of 2. Thus the viscosity quintupling time of PLTM1 is expected to be approximately 76 minutes, and the viscosity quintupling time of PLTM2 is expected to be approximately 33 minutes. It is expected that, if these measurements were made at 23° C., the viscosity quintupling times of PLTM1 and PLTM2 would be less than 8 hours.

Example 5
Preparation of Sodium Octoate
The sodium octoate was prepared by stirring 3.60 g of octanoic acid in 3 g of water and neutralizing with 2.00 g of aqueous sodium hydroxide (50%). 5 g of water was used for dilution and rinse. A waxy solid formed which was dissolved by adding about 10 ml of ethanol. pH paper indicated a pH of about 8. The total solution was evaporated on a watch glass on a steam bath under a flow of nitrogen to give 4.04 g white solid. The solid was titrated in ethanol with aqueous HCl: the titer was 5.88 mmol/g. Estimated purity was 97.6%
Example 6
Solution of Potassium Acetate in MFA
The MFA was a mixture of 70 wt % MorcureTM 2000 and 30 wt % Sartomer SR-610. The MFA mixture (956 g) and 24.5 g of anhydrous potassium acetate were combined in a 2 liter, 4-necked round-bottom flask fitted with a mechanical stirrer, dry-air sparge and thermocouple and heated on a heating mantle. The heat to the mantle was controlled through a controller connected to the thermocouple. While maintaining a slow flow of dry air, the mixture was stirred and heated gradually to 75° C. and held for 1 hr at 75° C. Most of the salt appeared to be dissolved. The mixture was cooled to about 60° C. and a vacuum was applied to the flask to help remove entrapped air bubbles. The mixture was vacuum filtered hot on Whatman GF/A glass microfibre filter to give a clear, viscous resin: viscosity (Brookfield, spindle #4, 3 rpm, 25° C.) 137 Pa*s (137,000 cP). Titration showed potassium acetate concentration was 2.41 wt % based on the total weight of the MFA plus potassium acetate (theory charged=2.50 wt %).
Example 7-8
Other Solutions of Carboxylate Salts in MFA
The multifunctional acrylate mixture of Example 6 and various carboxylate salts were combined in a 100 ml, 3-necked round-bottom flask fitted with a mechanical stirrer and thermocouple and heated on a heating mantle. The heat to the mantle was controlled through a controller connected to the thermocouple. The mixture was stirred and gradually heated to 75° C. and held at 75° C. for the time shown below as “T75.” If all of the salt did not appear to be dissolved, the mixture was vacuum filtered hot on a sintered glass funnel to give a clear, viscous resin. The mixture was then titrated to determine the amount of carboxylate salt actually dissolved, shown below as “% diss,” the weight percent of salt based on the total weight of the MFA plus carboxylate salt. The results are shown below:




















Salt
T75


Viscosity


No.
MFA (g)
Salt type
(g)
(hour)
Filtered?
% diss
Pa * s (cP)






















7
96.0
potassium
5.0
2
Yes
3.57
384(2) (384,000)




acetate


8
99.0
potassium
1.25
1
No
1.25
38(3) (38,000)




acetate





note


(2)Brookfield, #4 spindle, 0.6 rpm, 25° C.


note


(3)Brookfield, #4 spindle, 12 rpm, 25° C.






Example 9
Preparation of trimethylolpropane tris(acetoacetate)
A 1 liter, 4-neck round-bottom flask fitted with mechanical stirrer, pressure equalizing addition funnel (nitrogen inlet), thermocouple connected to a controller and mantle for heating, a 5-plate Oldershaw column and vacuum type distilling head with finger type condenser and stopcock to control the reflux ratio was charged with 201 g (1.50 mol) trimethylolpropane, 100 g (0.63 mol) tert.-butyl acetoacetate and 282 g of toluene. An additional 626.5 g (3.96 mol) of tert.-butyl acetoacetate was charged to the addition funnel. A slow nitrogen flow was maintained through the addition funnel and reactor and the mixture was heated to about 111° C. Reflux began when the flask contents reached about 111° C. and the reflux ratio/take-off was adjusted to keep the head temperature between 82-84° C. The additional tert.-butyl acetoacetate was gradually added over about 4 hr as 442 ml of distillate was collected. The pot temperature increased gradually to 117° C. during the addition. Distillation continued: the pot temperature gradually increased to 132° C. and the head temperature increased to 109° C. over an additional 2.3 hr. Total distillate collected was 472 g determined to be 70.59% tert.-butanol or 100.1% of theory.
The product was isolated by passing it through a wiped-film evaporator: one pass at 100° C., 100 mm pressure and a second pass at 120° C. and >5 mm pressure (mechanical vacuum pump, full vacuum). Isolated yield was 98%.
Example 10
Michael Reaction Half Lives
The experiments were carried-out in a 1 oz capped vial equilibrated in a 25° C. thermostated water bath. For each reaction, 4.2 g of the catalyst/multifunctional acrylate mixture (from Examples 8-11) were weighed and equilibrated for at least 1 hr. in the water bath. Separately, the trimethylolpropane tris(acetoacetate) was equilibrated at 25° C. At time ‘0’, 2.00 g of trimethylolpropane tris(acetoacetate) was weighed into the reaction vial and well mixed with a metal spatula, capped and replaced into the water bath. The vial was stirred briefly and samples were withdrawn at about 30, 60 and 120 min (20, 40 and 60 min for the higher catalyst concentration) and evaluated by nmr analysis. 1H nmr spectra were recorded on a Bruker AvanceTM 500 instrument and analyzed and integrated using WIN-NMR software.
The NMR samples of the reaction mixtures were made-up in CDCl3 solvent which contained acetic acid (20 ml acetic acid/20 ml CDCl3) to quench the Michael reaction. There was generally some precipitate formed when the samples were prepared, which was assumed to be the catalyst salt, but this did not appear to interfere with obtaining the spectrum. The multifunctional acrylate containing MorcureTM 2000 shows two absorbencies centered at □ 7.12 and 6.81 ppm assigned to aromatic protons of the MorcureTM structure; these do not change during the Michael reaction and are used as internal standard; the sum of the integrals of these two absorbencies is added together, and the sum is Integral B. The three protons on the acrylate bond appeared as three groupings in the region □ 6.5-5.8 ppm and are integrated together, and the sum is Integral A.
The normalized concentration of acrylate (herein called “[Acrylate]N”) is thus:

[Acrylate]N=(Integral A)/(Integral B)

As reaction occurs, acrylate is used-up in proportion to the moles of reaction, and conversion can be calculated relative to the normalized acrylate integration at time 0, which is the same as [Acrylate]N for the multifunctional acrylate mixture itself. The conversion of acrylate as a function of sampling time (“t”) is thus simply calculated:

AN0=[Acrylate]N at time=0

ANT=[Acrylate]N at time=t

Conversion=(AN0−ANT)/AN0

The half life was determined as described above, and the results were as follows:













Example


Half Life


No.
MFA source
Catalyst
(min)


















10a
Example 6
potassium
110




acetate


10b
Example 7
potassium
45




acetate


10c
Example 8
potassium
313




acetate









The table shows the dose relationship of reaction rate with catalyst concentration.

Example 11-12
Solutions of Further Salts in MFA Mixture
Using the methods of Example 8, the following salts were dissolved in MFA mixture:



















Salt
T75




No.
MFA (g)
Salt type
(g)
(hour)
Filtered?
% diss





















11
64.9
sodium acetate
0.805
2
Yes
0.22


12
69.8
sodium octoate
1.74
2
Yes
0.53









Example 13-15
Further Michael Reaction Half Lives
Using the methods of Example 10, various MFA/salt mixtures were combined with trimethylolpropane tris(acetoacetate), and the half lives were measured, with the results as follows:













Example


Half Life


No.
MFA source
Catalyst
(min)


















13
Example 6
potassium acetate
423


14
Example 11
sodium acetate
3393


15
Example 12
sodium octoate
1698









The table shows smaller, but not zero, reactivity of the sodium acetate and sodium octoate catalysts.
Example 16
Laminating Adhesive
The following mixtures were made:
Pack F=7.55 g MorcureTM 2000, 1.33 g SR-259, and 0.25 g potassium acetate
Pack G=2.5 g NPG Bis AcAc and 2.5 g PNE Tetra AcAc
Pack F and Pack G were combined to form a functional mixture, which was subjected to a T-peel test as defined herein above, using a first film of 92LBT and second film of aluminum foil of thickness 0.025 mm (1 mil), with a coat weight of 1.8 g/m2 (1.1 lb/ream). After one day, T-peel load was 182 g with failure mode of A; after 7 days, T-peel load was 120 g with failure mode of A.
Examples 17-20
Laminating Adhesives with Acid Scavenger
The following mixtures were made:
M28=7.37 g MorcureTM 2000 and 3.16 g SR-610
Pack H1=10.53 g M28, 0.11 g potassium acetate, and 0.8 g V-O2-L2
Pack H2=10.53 g M28, 0.103 g potassium acetate, and 0.34 g XL-1422
Pack J=5 g TMP Tris AcAc
FM17=11.44 g Pack H1 plus 5 g Pack J
FM19=10.98 g Pack H2 plus 5 g Pack J
FM17 and FM19 were subjected to T-peel tests as follows:
























Coat Weight
18-hour T-
18-hour T-
24-hour T-
24-hour T-
48-hour T-
48-hour T-


Example No.
Adhesive
First Film
Second Film
g/m2
Peel
Peel
Peel
Peel
peel
peel







17
FM17
GF10
92LBT
2.4 (1.5)
494
A
NT(7)
NT(7)
494
S1


18
FM17
48LBT
GF19
2.0 (1.2)
435
S2
NT(7)
NT(7)
647
S2


19
FM19
GF10
92LBT
2.2 (1.36)
NT(7)
NT(7)
447
A
565
A


20
FM19
48LBT
GF19
2.1 (1.27)
NT(7)
NT(7)
235
S2
376
S2





note


(7)not tested






Example 21
A first pack was made as follows: 6.74 grams MorcureTM 2000 were mixed with 2.89 grams SR-259 at 60° C. and then allowed to cool to ambient temperature. To the mixture was added 0.36 grams potassium acetate solution (70% concentration by weight in water, based on the weight of the potassium acetate solution), with stirring; the pack appeared clear. Then 0.85 grams V-02-L2 (40% concentration by weight in water, based on the weight of the V-02-L2 solution) was added to the pack and stirred thoroughly; the pack appeared cloudy.
A second pack contained 6 grams TMP tris AcAc.
The pot life of a mixture of the two packs was measured as follows: 10.84 grams of the first pack was pre-weighed into a 30 ml vial and conditioned at 35° C. for an hour in a water bath. In a separate vial, TMP tris AcAc was conditioned at 35° C. for 1 hour. Six grams of the TMP tris AcAc was then added to the pre-weighed first pack and mixed thoroughly. Viscosity measurements were taken while the mixture was in the water bath (35 C) with a Brookfield Viscometer using a LV 25 spindle. The initial viscosity was 436 mPa*s (436 cps), and the viscosity doubled in 34 minutes. Thus, pot life at 35° C. was 34 minutes.
It is contemplated that, if the pot life had been measured at 25° C., the pot life would have been less than 8 hours.
A mixture of the two packs was tested by the T-Peel test. The mixture was coated onto the first substrate at 35° C. Results were as follows:
















24 Hour T-


Substrates
Coat Weight
24 Hour t-
peel Failure


#1/#2
g/m2 (lb/ream)
peel (Grams)
Mode







GF19/92LBT
3.1 (1.9)
529
S1









Examples 22-27
Additional Functional Mixtures
The following functional mixtures were prepared by mixing the listed ingredients. “PAW” is a solution of potassium acetate in water, concentration of 70% potassium acetate by weight, based on the weight of the solution. Each functional mixture had a ratio of moles of acetoacetate groups to moles of acrylate groups of 1:1. The “batch size” is the sum of the weights of all acrylate compounds and acetoacetate compounds, excluding the weight of the PAW. The amount of each acetoacetate compound is characterized in the table below according to the molar percentage of acetoacetate groups contributed by that compound. Similarly, amount of each acrylate compound is characterized in the table below according to the molar percentage of acrylate groups contributed by that compound. For example, in FM4, half of the acetoacetate groups are on NPE Bis AcAc and half are on TMP Tris AcAc; and three-quarters of the acrylate groups are on MorecureTM 2000, while one quarter of the acrylate groups are on EB-860.



















NPG Bis AcAc
TMP Tris AcAc
Morecure TM 2000
EB-860
Rx03749
EB-8402













% of moles of
C % of moles of acrylate




FM #
acetoacetate groups
groups
PAW (g)
Batch size (g)


















22
50
50
100



0.25
14.20


23
50
50
75
25


0.4
15.09


24
50
50
75

25

0.4
16.87


25
50
50
60


40
0.4
16.59


26
50
50
60

40

0.5
19.36









Example 27
Results of Testing the Functional Mixtures of Examples 22-26
The peel test, as defined above, was performed using LBT and Al foil (thickness 0.254 mm (1 mil)) as the substrates. Coat weights and peel results were as follows:

















CW
7-day
7-day Peel



FM #
g/m2 (lb/ream)
Failure
grams









22
2.0 (1.2)
A
294



23
2.6 (1.6)
A
335



24
4.4 (2.7)
A
358



25
2.3 (1.4)
A
405



26
4.7 (2.9)
A
360










Example 28
Pot Life Measurement at 23° C.
Mixture MFA28 was made by mixing 70 parts by weight MorcureTM 2000 with 30 parts by weight SR-259. Then FM28 was made by mixing 6 grams TMA tris AcAc, 9.63 grams MFA33, and 0.34 grams of PAW (as defined herein above). As a function of time, the viscosity of FM28 was measured with Brookfield viscometer with LV25 spindle at 23° C. The rotation rate (rpm) was chosen for each reading as appropriate (as discussed herein above). The results were as follows.














T(8)
Visc(9)



















0
1814



1
1718



2
1680



3
1584



4
1555



5
1622



6
1699



7
1843



8
2035



9
2352



10
2745



11
3283



12
4032



13
5040



14
6345



15
8016



16
10390



17
13390



18
17320



19
21880



20
27970



21
35670



22
44690



23
54470



24
64320



25
75450



26
103800



27
103400



28
116700



29
138880



30
116100



31
172000



32
183800







note



(8)time (minutes)



note



(9)viscosity in milliPascal * seconds (mPa * s), same values as cps.






The viscosity doubling time was between 11 and 12 minutes. The viscosity quintupling time was between 15 and 16 minutes. The viscosity reached 10 times the original value between 18 and 19 minutes, and it reached 100 times the original value between 31 and 32 minutes.
Example 29
Impact of Acid Levels of Reactants on Cure Rate
Mixture 1 was made by mixing 5 parts by weight neopentyl glycol NP bis AcAc, 14.8 parts by weight of EB-860TM a high acid epoxidized soya acrylate and 0.33 parts by weight of potassium carbonate. Curing time was greater than 19 hours. By comparison, using the same amounts of NPG bis AcAc and potassium carbonate with 14.8 parts by weight of RX-04852TM a low acid epoxidized soya acrylate (acid #<0.5), a curing time of 11.5 minutes was observed.
Example 30
Glycerin tris acetoacetate was prepared by reacting glycerine with t-butyl acetoacetate in a manner similar to that of example 9. Glycerin tris acetoacetate is a clear liquid with viscosity of 187 cps at 22 C.
















Glycerol tris acetoacetate
33.0%



SR-259
12.3%



Morcure 2000
49.4%



Potassium acetate (70% aqueous soln)
1.76%



V-O2L2
3.54%



Viscosity @ 35 C.
1030 cps



Pot-life
19 minutes



T-peel adhesion (92 LBT//GF-19)



Coat weight
3.5 lb/ream



(cured 5 days at 23 C.)
film tear (>976 g/in)



(cured 45 minutes at 45 C.)
film tear










Example 31
1,3 propane diol acetoacetate was prepared by reacting 1,3 propanediol with t-butyl acetoacetate in a manner similar to that of example 9. 1,3 propane diol acetoacetate is a clear liquid with viscosity of 28 cps at 22 C.
















1,3 propanediol bis acetoacetate
20.6%



SR-259
 6.9%



Morcure 2000
24.2%



RX-04852
37.9%



Potassium acetate (70% aqueous soln)
 8.2%



V-O2L2
 2.2%



Viscosity @ 35 C.
1257 cps



Pot-life
15.5 minutes



Appearance of cured polymer
tough, rubbery solid










Example 32
















Neopentyl glycol bis acetoacetate
20.7%



Morcure 2000
27.8%



RX-04852
41.6%



Potassium acetate (70% aqueous soln)
 7.7%



V-O2L2
 2.2%



Viscosity @ 35 C.
2390 cps



Pot-life
19 minutes



Appearance of cured polymer
tough, rubbery solid

## Claims

1. A functional mixture comprising:
(i) at least one multi-functional Michael acceptor;
(ii) at least one multi-functional Michael donor; and
(iii) at least one weakly basic catalyst, wherein the pKa of the conjugate acid of said weakly basic catalyst is 5.5 or less;

wherein the at least one Michael acceptor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture and whose chemical backbone is derived from bio-based feedstock.

2. An article formed by a process comprising the step of curing the functional mixture of claim 1, wherein said article is an adhesive, sealant, elastomer, a foam, a film, a coating or a combination thereof.

3. A biodegradable or compostable polymer composition formed by a process comprising curing the functional mixture of claim 1.

4. The functional mixture of claim 1, wherein said functional mixture has at least 75% solids by weight based on the total weight of said functional mixture.

5. The functional mixture of claim 1, wherein said functional mixture is capable of curing at 23° C. in 7 days or less.

6. A functional mixture comprising:
(i) at least one multi-functional Michael acceptor;
(ii) at least one multi-functional Michael donor; and
(iii) at least one basic catalyst;

wherein the at least one Michael acceptor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture and whose chemical backbone is derived from bio-based feedstock, wherein said feedstock comprises epoxidized crop oils.

7. The functional mixture of claim 6, wherein said Michael acceptor comprises di-acrylate of epoxidized soya oil.

8. An article formed by a process comprising the step of curing the functional mixture of claim 6 wherein said article is an adhesive, sealant, elastomer, a foam, a film, a coating or a combination thereof.

9. A biodegradable or compostable polymer formed by a process comprising the step of curing the functional mixture of claim 6.

10. The functional mixture of claim 6, wherein said functional mixture has at least 75% solids by weight based on the total weight of said functional mixture.

11. The functional mixture of claim 6, wherein said functional mixture is capable of curing at 23° C. in 7 days or less.

12. A functional mixture comprising:
(i) at least one multi-functional Michael acceptor;
(ii) at least one multi-functional Michael donor; and
(iii) at least one basic catalyst, wherein the pKa of the conjugate acid of said weakly basic catalyst is 5.5 or less;

wherein the at least one Michael donor is present in an amount greater than 20% by weight, based on the total weight of the functional mixture and whose chemical backbone is derived from bio-based feedstock.

13. An article formed by a process comprising the step of curing the functional mixture of claim 12 wherein said article is an adhesive, sealant, elastomer, a foam, a film, a coating or a combination thereof.

14. A biodegradable or compostable polymer composition formed by a process comprising the step of curing the functional mixture of claim 12.

15. The functional mixture of claim 12, wherein said functional mixture has at least 75% solids by weight based on the total weight of said functional mixture.

16. The functional mixture of claim 12, wherein said functional mixture is capable of curing at 23° C. in 7 days or less.

17. A functional mixture comprising:
(i) at least one multi-functional Michael acceptor,
(ii) at least one multi-functional Michael donor; and
(iii) at least one weakly basic catalyst, wherein the pKa of the conjugate acid of said weakly basic catalyst is 5.5 or less;

wherein the sum of the weights of the donor and acceptor whose chemical backbone is derived from bio-based feedstock are greater than 20% by weight, based on the total weight of the functional mixture, and wherein the catalyst is selected from the group consisting of sodium salts of carboxylic acids, magnesium salts of carboxylic acids, aluminum salts of carboxylic acids, chromium salts of alkyl carboxylic acids having 6 or fewer carbon atoms, chromium salts of aromatic carboxylic acids, potassium salts of alkyl mono-carboxylic acids having 6 or fewer carbon atoms, potassium salts of multi-carboxylic acids, potassium salts of phosphoric acid esters, and mixtures thereof.

18. An article formed by a process comprising the step of curing the functional mixture of claim 17 wherein said article is an adhesive, sealant, elastomer, a foam, a film, a coating or a combination thereof.

19. A biodegradable or compostable polymer composition formed by a process comprising the step of curing the functional mixture of claim 17.