Cure accelerators for anaerobic curable compositions

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel cure accelerators that can be useful for anaerobic curable compositions, such as adhesives and sealants.

2. Brief Description of Related Technology

Anaerobic adhesive compositions generally are well-known. See e.g. R. D. Rich, “Anaerobic Adhesives” in Handbook of Adhesive Technology, 29, 467-79, A. Pizzi and K. L. Mittal, eds., Marcel Dekker, Inc., New York (1994), and references cited therein. Their uses are legion and new applications continue to be developed.

Conventional anaerobic adhesives ordinarily include a free-radically polymerizable acrylate ester monomer, together with a peroxy initiator and an inhibitor component. Often, such anaerobic adhesive compositions also contain accelerator components to increase the speed with which the composition cures.

Desirable anaerobic cure-inducing compositions to induce and accelerate cure may include one or more of saccharin, toluidines, such as N,N-diethyl-p-toluidine (“DE-p-T”) and N,N-dimethyl-o-toluidine (“DM-o-T”), acetyl phenylhydrazine (“APH”), maleic acid, and quinones, such as napthaquinone and anthraquinone. See e.g., U.S. Pat. No. 3,218,305 (Krieble), U.S. Pat. No. 4,180,640 (Melody), U.S. Pat. No. 4,287,330 (Rich) and U.S. Pat. No. 4,321,349 (Rich).

Saccharin and APH are used as standard cure accelerator components in anaerobic adhesive cure systems. The LOCTITE-brand anaerobic adhesive products currently available from Henkel Corporation use either saccharin alone or both saccharin and APH in most of its anaerobic adhesives. These components however have come under regulatory scrutiny in certain parts of the world, and thus efforts have been undertaken to identify candidates as replacements.

Examples of other curatives for anaerobic adhesives include thiocaprolactam (e.g., U.S. Pat. No. 5,411,988) and thioureas [e.g. U.S. Pat. No. 3,970,505 (Hauser) (tetramethyl thiourea), German Patent Document Nos. DE 1 817 989 (alkyl thioureas and N,N′-dicyclohexyl thiourea) and 2 806 701 (ethylene thiourea), and Japanese Patent Document No. JP 07-308,757 (acyl, alkyl, alkylidene, alkylene and alkyl thioureas)], certain of the latter of which had been used commercially up until about twenty years ago.

Loctite (R&D) Ltd. discovered a new class of materials—trithiadiaza pentalenes—effective as curatives for anaerobic adhesive compositions. The addition of these materials into anaerobic adhesives as a replacement for conventional curatives (such as APH) surprisingly provides at least comparable cure speeds and physical properties for the reaction products formed therefrom. See U.S. Pat. No. 6,583,289 (McArdle).

U.S. Pat. No. 6,835,762 (Klemarczyk) provides an anaerobic curable composition based on a (meth)acrylate component with an anaerobic cure-inducing composition substantially free of acetyl phenylhydrazine and maleic acid and an anaerobic cure accelerator compound having the linkage —C(═O)—NH—NH— and an organic acid group on the same molecule, provided the anaerobic cure accelerator compound excludes 1-(2-carboxyacryloyl)-2-phenylhydrazine. The anaerobic cure accelerator is embraced by:

where R¹-R⁷are each independently selected from hydrogen and C_1-4; Z is a carbon-carbon single bond or carbon-carbon double bond; q is 0 or 1; and p is an integer between 1 and 5, examples of which are 3-carboxyacryloyl phenylhydrazine, methyl-3-carboxyacryloyl phenylhydrazine, 3-carboxypropanoyl phenylhydrazine, and methylene-3-carboxypropanoyl phenylhydrazine.

U.S. Pat. No. 6,897,277 (Klemarczyk) provides an anaerobic curable composition based on a (meth)acrylate component with an anaerobic cure-inducing composition substantially free of saccharin and an anaerobic cure accelerator compound within the following structure

where R is selected from hydrogen, halogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, carboxyl, and sulfonato, and R¹is selected from hydrogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, and aralkyl, an example of which is phenyl glycine and N-methyl phenyl glycine.

U.S. Pat. No. 6,958,368 (Messana) provides an anaerobic curable composition. This composition is based on a (meth)acrylate component with an anaerobic cure-inducing composition substantially free of saccharin and within the following structure

where Y is an aromatic ring, optionally substituted at up to five positions by C_1-6alkyl or alkoxy, or halo groups; A is C═O, S═O or O═S═O; X is NH, O or S and Z is an aromatic ring, optionally substituted at up to five positions by C_1-6alkyl or alkoxy, or halo groups, or Y and Z taken together may join to the same aromatic ring or aromatic ring system, provided that when X is NH, o-benzoic sulfimide is excluded from the structure. Examples of the anaerobic cure accelerator compound embraced by the structure above include 2-sulfobenzoic acid cyclic anhydride, and 3H-1,2-benzodithiol-3-one-1,1-dioxide.

Notwithstanding the state of the art, there is an on-going desire to find alternative technologies for anaerobic cure accelerators to differentiate existing products and provide supply assurances in the event of shortages or cessation of supply of raw materials. Moreover, since certain of the raw materials used in the anaerobic cure inducing composition have to one degree or another come under regulatory scrutiny, alternative components would be desirable. Accordingly, it would be desirable to identify new materials that function as cure components in the cure of anaerobically curable compositions.

SUMMARY OF THE INVENTION

In some non-limiting embodiments, reaction products are provided which are prepared from reactants comprising: a) at least one compound selected from the group of compounds represented by structural Formula (I):

wherein in Formula I: X is arylene or heteroarylene; R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; R³is selected from the group consisting of H, hydroxy, alkoxy, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; and b) at least one compound selected from the group of compounds represented by structural Formula (II):

wherein in Formula II: Z″ is selected from the group consisting of —O—,—S—, and —NH—; q is 1 to 4; R⁶is independently selected from the group consisting of hydroxyalkyl, aminoalkyl, and thioalkyl; and n is at least 1, wherein the reaction product comprises at least two pendant functional groups independently selected from the group consisting of —H, —NH₂and —SH.

In some non-limiting embodiments, reaction products are provided which are prepared from reactants comprising: (a) at least one reaction product prepared from reactants comprising: (i) at least one compound selected from the group of compounds represented by structural Formula (I):

wherein in Formula I: X is arylene or heteroarylene; R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; R³is H, hydroxy, alkoxy, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; and (ii) at least one compound selected from the group of compounds represented by structural Formula (II):

In some non-limiting embodiments, reaction products are provided which are prepared from reactants comprising: (a) a compound selected from the group of compounds represented by structural Formula (III):

In some non-limiting embodiments, reaction products are provided which are prepared from reactants comprising: (a) at least one compound selected from the group of compounds represented by structural Formula (III):

wherein in Formula (III): X is arylene or heteroarylene; R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; each R⁴is independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl, thioalkyl, and —C(O)R⁵; and each R⁵, if present, is independently selected from the group consisting of H, alkyl, hydroxy, and alkoxy, wherein the compound comprises at least two pendant functional groups independently selected from the group consisting of —OH, —NH₂and —SH; (b) at least one isocyanate functional material; and (c) at least one functional material selected from the group consisting of hydroxy functional materials, amino functional materials, thio functional materials, and combinations and mixtures thereof.

Compositions and products prepared from the above reaction products also are provided.

In some non-limiting embodiments, methods of making reaction products are provided which are prepared from reactants comprising reacting: a) at least one compound selected from the group of compounds represented by structural Formula (I):

wherein in Formula I: X is arylene or heteroarylene; R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; R³is H, hydroxy, alkoxy, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; and b) at least one compound selected from the group of compounds represented by structural Formula (II):

wherein in Formula I: Z″ is selected from the group consisting of —O—,—S—, and —NH—; q is 1 to 4; R⁶is independently selected from the group consisting of hydroxyalkyl, aminoalkyl, and thioalkyl; and n is at least 1, wherein the reaction product comprises at least two pendant functional groups independently selected from the group consisting of —OH, —NH₂and —SH.

In some non-limiting embodiments, methods of making reaction products are provided which are prepared from reactants comprising reacting: (a) at least one reaction product prepared from reactants comprising: (i) at least one compound selected from the group of compounds represented by structural Formula (I):

wherein in Formula I: X is arylene or heteroarylene; R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; R³is H, hydroxy, alkoxy, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl; and (ii) at least one compound selected from the group of compounds represented by structural Formula (II):

In some non-limiting embodiments, methods of making reaction products are provided which are prepared from reactants comprising reacting: (a) a compound selected from the group of compounds represented by structural Formula (III):

In some non-limiting embodiments, methods of making reaction products are provided which are prepared from reactants comprising reacting: (a) at least one compound selected from the group of compounds represented by structural Formula (III):

BRIEF DESCRIPTION OF THE FIGURES

The foregoing summary, as well as the following detailed description, will be better understood when read in conjunction with the appended drawings. In the drawings:

FIG. 1 depicts an IR spectra of a DMABA-glycidol reaction product of Example 1 according to the present invention;

FIG. 2 depicts a bar chart of breakloose and prevailing torque on steel threaded fasteners of control adhesive compositions and adhesive compositions including a dimethylamino benzoic acid-glycidol (DMABA-glycidol) based reaction product according to the present invention;

FIG. 3 depicts a bar chart of breakloose and prevailing torque on steel threaded fasteners of control adhesive compositions and adhesive compositions including a toluene diisocyanate-based reaction product according to the present invention; and

FIG. 4 depicts a bar chart of breakloose and prevailing torque on steel threaded fasteners of control adhesive compositions and adhesive compositions including a toluene diisocyanate-based reaction product according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, thermal conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values inclusive of the recited values may be used.

Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

As used herein, the term “composition” is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product which results, directly or indirectly, from combination of the specified ingredients in the specified amounts.

As used herein, “formed from” or “prepared from” denotes open, e.g., “comprising,” claim language. As such, it is intended that a composition “formed from” or “prepared from” a list of recited components be a composition comprising at least these recited components or the reaction product of at least these recited components, and can further comprise other, non-recited components, during the composition's formation or preparation.

As used herein, the phrase “reaction product of” means chemical reaction product(s) of the recited components, and can include partial reaction products as well as fully reacted products.

As used herein, the term “polymer” in meant to encompass oligomers, and includes without limitation both homopolymers and copolymers. The term “prepolymer” means a compound, monomer or oligomer used to prepare a polymer, and includes without limitation both homopolymer and copolymer oligomers. The term “oligomer” means a polymer consisting of only a few monomer units up to about ten monomer units, for example a dimer, trimer or tetramer.

As used herein, the term “cure” as used in connection with a composition, e.g., “composition when cured” or a “cured composition”, means that any curable or crosslinkable components of the composition are at least partially cured or crosslinked. In some non-limiting embodiments of the present invention, the chemical conversion of the crosslinkable components, i.e., the degree of crosslinking, ranges from about 5% to about 100% of complete crosslinking where complete crosslinking means full reaction of all crosslinkable components. In other non-limiting embodiments, the degree of crosslinking ranges from about 15% to about 80% or about 50% to about 60% of full crosslinking. One skilled in the art will understand that the presence and degree of crosslinking, i.e., the crosslink density, can be determined by a variety of methods, such as dynamic mechanical thermal analysis (DMA) using a TA Instruments DMA 2980 DMA analyzer over a temperature range of −65° F. (−18° C.) to 350° F. (177° C.) conducted under nitrogen according to ASTM D 4065-01. This method determines the glass transition temperature and crosslink density of free films of coatings or polymers. These physical properties of a cured material are related to the structure of the crosslinked network.

Curing of a polymerizable composition can be obtained by subjecting the composition to curing conditions, such as but not limited to heating, etc., leading to the reaction of reactive groups of the composition and resulting in polymerization and formation of a solid polymerizate. When a polymerizable composition is subjected to curing conditions, following polymerization and after reaction of most of the reactive groups occurs, the rate of reaction of the remaining unreacted reactive groups becomes progressively slower. In some non-limiting embodiments, the polymerizable composition can be subjected to curing conditions until it is at least partially cured. The term “at least partially cured” means subjecting the polymerizable composition to curing conditions, wherein reaction of at least a portion of the reactive groups of the composition occurs, to form a solid polymerizate. In some non-limiting embodiments, the polymerizable composition can be subjected to curing conditions such that a substantially complete cure is attained and wherein further exposure to curing conditions results in no significant further improvement in polymer properties, such as strength or hardness.

The present inventors have discovered reaction products or resins useful as cure accelerators for anaerobic compositions. The addition of such reaction products as cure accelerators into anaerobic adhesives as a replacement for some or all of the amount of conventional anaerobic cure accelerators (such as toluidine, acetyl phenylhydrazine and/or cumene hydroperoxide) surprisingly provides at least comparable cure speeds and physical properties for the reaction products formed therefrom, as compared with those observed from conventional anaerobic curable compositions. As such, these materials provide many benefits to anaerobic adhesive compositions, including but not limited to: reduced odor and safety concerns, reduced bioavailability, good formulation stability and good solubility in anaerobic curable compositions.

As noted above, in some non-limiting embodiments the present invention provides reaction product(s) prepared from reactants comprising: a) at least one compound selected from the group of compounds represented by structural Formula (I):

wherein in Formula I: X; R¹, R²and R³are as defined above; and b) at least one compound selected from the group of compounds represented by structural Formula (II):

wherein in Formula II: Z″ , n, q, and R⁶are as defined above, wherein the reaction product comprises at least two pendant functional groups independently selected from the group consisting of —H, —NH₂and —SH.

In the compounds of Formula (I) above, X is selected from the group consisting of arylene and heteroarylene.

As used herein, “arylene” means a difunctional group obtained by removal of a hydrogen atom from an aryl group such as is defined below.

“Aryl” means an aromatic monocyclic or multicyclic ring system comprising about 6 to about 14 carbon atoms, preferably about 6 to about 10 carbon atoms. The aryl group can be optionally substituted with one or more “ring system substituents” which may be the same or different, and are as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

“Heteroarylene” means a difunctional group obtained by removal of a hydrogen atom from a heteroaryl group such as is defined below.

“Heteroaryl” means an aromatic monocyclic or multicyclic ring system comprising about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the ring atoms is an element other than carbon, for example nitrogen, oxygen or sulfur, alone or in combination. Non-limiting examples of useful heteroaryls include those containing about 5 to about 6 ring atoms. The “heteroaryl” can be optionally substituted by one or more “ring system substituents” which may be the same or different, and are as defined herein. The prefix aza, oxa or thia before the heteroaryl root name means that at least one of a nitrogen, oxygen or sulfur atom respectively, is present as a ring atom. A nitrogen atom of a heteroaryl can be optionally oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryls include pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-substituted pyridones), isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, phthalazinyl, oxindolyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothienyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindolyl, 1,2,4-triazinyl, benzothiazolyl and the like. The term “heteroaryl” also refers to partially saturated heteroaryl moieties such as, for example, tetrahydroisoquinolyl, tetrahydroquinolyl and the like.

“Ring system substituent” means a substituent attached to an aromatic or non-aromatic ring system which, for example, replaces an available hydrogen on the ring system. Ring system substituents may be the same or different, each being independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, alkylaryl, heteroaralkyl, heteroarylalkenyl, heteroarylalkynyl, alkylheteroaryl, hydroxy, hydroxyalkyl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, halo, nitro, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylthio, arylthio, heteroarylthio, aralkylthio, heteroaralkylthio, cycloalkyl, heterocyclyl, —C(═N—CN)—NH₂, —C(═NH)—NH₂, —C(═NH)—NH(alkyl), Y₁Y₂N—, Y₁Y₂N-alkyl-, Y₁Y₂NC(O)—, Y₁Y₂NSO₂— and —SO₂NY₁Y₂, wherein Y₁and Y₂can be the same or different and are independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, and aralkyl. “Ring system substituent” may also mean a single moiety which simultaneously replaces two available hydrogens on two adjacent carbon atoms (one H on each carbon) on a ring system.

The term “substituted” means that one or more hydrogens on the designated atom is replaced with a selection from the indicated group, provided that the designated atom's normal valency under the existing circumstances is not exceeded, and that the substitution results in a stable compound. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds. By “stable compound” or “stable structure” is meant a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture, and formulation into an efficacious therapeutic agent. The phrase “optionally substituted” means optional substitution with the specified groups, radicals or moieties.

It should be noted that in heteroatom containing ring systems of this invention, there are no hydroxyl groups on carbon atoms adjacent to a N, O or S, as well as there are no N or S groups on carbon adjacent to another heteroatom. Thus, for example, in the ring:

there is no —OH attached directly to carbons marked 2 and 5. It should also be noted that tautomeric forms such as, for example, the moieties:

are considered equivalent in certain embodiments of this invention.

It should also be noted that any carbon as well as heteroatom with unsatisfied valences in the text, schemes, examples and Tables herein is assumed to have the sufficient number of hydrogen atom(s) to satisfy the valences.

When any variable (e.g., arylene, alkyl, R², etc.) occurs more than one time in any constituent or in Formula I, etc., its definition on each occurrence is independent of its definition at every other occurrence.

In the compounds of Formula (I), R¹and R²are each independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl.

“Alkyl” means an aliphatic hydrocarbon group which may be straight or branched and comprising about 1 to about 20 carbon atoms in the chain, about 1 to about 12 carbon atoms in the chain, or about 1 to about 6 carbon atoms in the chain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. “Lower alkyl ” means a group having about 1 to about 6 carbon atoms in the chain which may be straight or branched. The alkyl group may be unsubstituted or optionally substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, —NH(alkyl), —NH(cycloalkyl), —N(alkyl)₂, carboxy and —C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl and t-butyl. In some non-limiting embodiments, R¹and R²are each alkyl, such as methyl.

“Hydroxyalkyl” means a HO-alkyl- group in which alkyl is as previously defined. Preferred hydroxyalkyls contain lower alkyl. Non-limiting examples of suitable hydroxyalkyl groups include hydroxymethyl and hydroxyethyl.

“Alkoxy” means an alkyl-O— group in which the alkyl group is as previously described. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The bond to the parent moiety is through the ether oxygen. “Alkoxyalkyl” means an alkoxy-alkyl- group in which alkoxy and alkyl are as previously defined. Non-limiting examples of suitable alkoxyalkyl groups include methoxyalkyl groups.

“Aminoalkyl” means an amino-alkyl- group in which the alkyl group is a previously described. The bond to the parent moiety is through the alkyl group.

“Thioalkyl” means an thio-alkyl- group in which the alkyl group is as previously described. The bond to the parent moiety is through the alkyl group.

In the compounds of Formula (I) above, R³is selected from the group consisting of H, hydroxy, alkoxy, hydroxyalkyl, alkoxyalkyl, aminoalkyl and thioalkyl. In some non-limiting embodiments, R³is hydroxy or methoxy.

In the compounds of Formula (II) above, Z″ is selected from the group consisting of —O—,—S—, and —NH—; q may be 1 to 4; R⁶may be independently selected from the group consisting of hydroxyalkyl, aminoalkyl, and thioalkyl; and n is at least 1. In another embodiment the reactant represented by Formula (VI) is glycidol:

As discussed above, the reaction product comprises at least two pendant functional groups independently selected from the group consisting of —OH, —NH₂and —SH. In some non-limiting embodiments, the reaction product comprises two or three pendant functional groups. In some non-limiting embodiments, the reaction product comprises two or three pendant hydroxy functional groups.

In one non-limiting embodiment, the compound of Formula (I) is dimethylamino benzoic acid (“DMABA”).

In another non-limiting embodiment, the reaction product is prepared from DMABA (a compound of Formula (I), shown as compound 1 below) and glycidol (a compound of Formula (II), shown as compound 2 below) to form 1,3-dihydroxypropan-2-yl 4-(dimethylamino)benzoate (4-dimethylaminobenzoic-glycidol adduct, shown as compound 3 below) as shown in the reaction scheme below:

In some non-limiting embodiments, the molar ratio of compound(s) of Formula (I) to compound(s) of Formulae (II) can range from about 5:1 to about 1:5, or about 3:1 to about 1:3, or about 1:1.

In some non-limiting embodiments, the reaction is conducted in the presence of a solvent. In some non-limiting embodiments, the compound of Formula (I) is dissolved in solvent prior to reaction with the compound of Formula (II). Non-limiting examples of suitable solvents include, but are not limited to, mineral spirits, alcohols such as methanol, ethanol or butanol, aromatic hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl ether, esters, aliphatics, and mixtures of any of the foregoing. In some embodiments, residual solvent is extracted from the reaction product(s), for example by distillation or chromatography.

In some non-limiting embodiments, the reaction product(s) are purified to remove impurities, such as reaction by-products or impurities that accompany the reactants such as carriers. The reaction product(s) can be purified for example by filtration, stripping or chromatography, such that the purified reaction product(s) are essentially free of impurities, or comprise less than about 1 weight percent of impurities, or are free of impurities.

Methods of making the reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are discussed in detail below.

In some non-limiting embodiments, the present invention provides reaction product(s) (A) prepared from reactants comprising: (1) the above reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) comprising at least two pendant functional groups independently selected from the group consisting of —OH, —NH₂and —SH; and (2) at least one isocyanate functional material.

In some non-limiting embodiments, the reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) can comprise about 5 to about 99 weight percent of the total weight of the reactants used for preparing the reaction product, or about 50 to about 95 weight percent, or about 85 weight percent of the reactants. In some non-limiting embodiments, the isocyanate functional material can comprise about 1 to about 30 weight percent of the total weight of the reactants used for preparing the reaction product, or about 10 to about 30 weight percent, or about 25 weight percent of the reactants.

In some non-limiting embodiments, the reaction product(s) of the hydroxy-, amino- and/or thio functional compound(s) discussed above with isocyanate functional material(s) can have residual isocyanate functionality.

In some non-limiting embodiments, the reaction product of the hydroxy-, amino- and/or thio functional compound(s) with isocyanate functional material(s) can have a number average molecular weight of about 100 to about 20,000 grams/mole, or about 500 to about 5,000 grams/mole, or about 3,000 grams/mole.

As used herein, the term “isocyanate functional material” includes compounds, monomers, oligomers and polymers comprising at least one or at least two —N═C═O functional groups and/or at least one or at least two —N═C═S (isothiocyanate) groups. Monofunctional isocyanates can be used as chain terminators or to provide terminal groups during polymerization. As used herein, “polyisocyanate” means an isocyanate comprising at least two —N═C═O functional groups, such as diisocyanates or triisocyanates, as well as dimers and trimers or biurets of the isocyanates, and mixtures thereof. Suitable isocyanates are capable of forming a covalent bond with a reactive group such as hydroxy functional group. Isocyanates useful in the present invention can be branched or unbranched.

Isocyanates useful in the present invention include “modified”, “unmodified” and mixtures of “modified” and “unmodified” isocyanates. The isocyanates can have “free”, “blocked” or partially blocked isocyanate groups. The term “modified” means that the aforementioned isocyanates are changed in a known manner to introduce biuret, urea, carbodiimide, urethane or isocyanurate groups or blocking groups. In some non-limiting embodiments, the “modified” isocyanate is obtained by cycloaddition processes to yield dimers and trimers of the isocyanate, i.e., polyisocyanates. Free isocyanate groups are extremely reactive. In order to control the reactivity of isocyanate group-containing components, the NCO groups may be blocked with certain selected organic compounds that render the isocyanate group inert to reactive hydrogen compounds at room temperature. When heated to elevated temperatures, e.g., ranging from about 90° C. to about 200° C., the blocked isocyanates release the blocking agent and react in the same way as the original unblocked or free isocyanate.

Generally, compounds used to block isocyanates are organic compounds that have active hydrogen atoms, e.g., volatile alcohols, epsilon-caprolactam or ketoxime compounds. Non-limiting examples of suitable blocking compounds include phenol, cresol, nonylphenol, epsilon-caprolactam and methyl ethyl ketoxime.

As used herein, the NCO in the NCO:OH ratio represents the free isocyanate of free isocyanate-containing materials, and of blocked or partially blocked isocyanate-containing materials after the release of the blocking agent. In some cases, it is not possible to remove all of the blocking agent. In those situations, more of the blocked isocyanate-containing material would be used to attain the desired level of free NCO.

The molecular weight of the isocyanate functional material can vary widely. In alternate non-limiting embodiments, the number average molecular weight (Mn) of each can be at least about 100 grams/mole, or at least about 150 grams/mole, or less than about 15,000 grams/mole, or less than about 5,000 grams/mole. The number average molecular weight can be determined using known methods, such as by gel permeation chromatography (GPC) using polystyrene standards.

Non-limiting examples of suitable isocyanate functional materials include aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, dimers and trimers thereof, and mixtures thereof. When an aromatic polyisocyanate is used, generally care should be taken to select a material that does not cause the polyurethane to color (e.g., yellow).

In some non-limiting embodiments, the aliphatic and cycloaliphatic diisocyanates can comprise about 6 to about 100 carbon atoms linked in a straight chain or cyclized and having two isocyanate reactive end groups.

Non-limiting examples of suitable aliphatic isocyanates include straight chain isocyanates such as ethylene diisocyanate, trimethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate, bis(isocyanatoethyl)-carbonate, and bis(isocyanatoethyl)ether.

Other non-limiting examples of suitable aliphatic isocyanates include branched isocyanates such as trimethylhexane diisocyanate, trimethylhexamethylene diisocyanate (TMDI), 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4,-trimethylhexamethylene diisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, lysinediisocyanate methyl ester and lysinetriisocyanate methyl ester.

Non-limiting examples of suitable cycloaliphatic isocyanates include dinuclear compounds bridged by an isopropylidene group or an alkylene group of 1 to 3 carbon atoms. Non-limiting examples of suitable cycloaliphatic isocyanates include 1,1′-methylene-bis-(4-isocyanatocyclohexane) or 4,4′-methylene-bis-(cyclohexyl isocyanate) (such as DESMODUR W commercially available from Bayer Corp.), 4,4′-isopropylidene-bis-(cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate, 3-isocyanato methyl-3,5,5-trimethylcyclohexyl isocyanate (a branched isocyanate also known as isophorone diisocyanate or IPDI) which is commercially available from Arco Chemical Co. and meta-teframethylxylylene diisocyanate [a branched isocyanate also known as 1,3-bis(1-isocyanato-1-methylethyl)-benzene which is commercially available from Cytec Industries Inc. under the tradename TMXDI (Meta) Aliphatic Isocyanate] and mixtures thereof.

Other useful dinuclear cycloaliphatic diisocyanates include those formed through an alkylene group of from 1 to 3 carbon atoms inclusive, and which can be substituted with nitro, chlorine, alkyl, alkoxy and other groups that are not reactive with hydroxyl groups (or active hydrogens) providing they are not positioned so as to render the isocyanate group unreactive. Also, hydrogenated aromatic diisocyanates such as hydrogenated toluene diisocyanate may be used. Dinuclear diisocyanates in which one of the rings is saturated and the other unsaturated, which are prepared by partially hydrogenating aromatic diisocyanates such as diphenyl methane diisocyanates, diphenyl isopropylidene diisocyanate and diphenylene diisocyanate, may also be used.

Mixtures of cycloaliphatic diisocyanates with aliphatic diisocyanates and/or aromatic diisocyanates may also be used. An example is 4,4′-methylene-bis-(cyclohexyl isocyanate) with commercial isomer mixtures of toluene diisocyanate or meta-phenylene diisocyanate.

Thioisocyanates corresponding to the above diisocyanates can be used, as well as mixed compounds containing both an isocyanate and a thioisocyanate group.

Non-limiting examples of suitable isocyanate functional materials can include but are not limited to DESMODUR W, DESMODUR N 3300 (hexamethylene diisocyanate trimer), DESMODUR N 3400 (60% hexamethylene diisocyanate dimer and 40% hexamethylene diisocyanate trimer), which are commercially available from Bayer Corp.

Other non-limiting examples of suitable polyisocyanates include ethylenically unsaturated polyisocyanates; alicyclic polyisocyanates; aromatic polyisocyanates; aliphatic polyisocyanates; halogenated, alkylated, alkoxylated, nitrated, carbodiimide modified, urea modified and biuret modified derivatives of isocyanates; and dimerized and trimerized products of isocyanates.

Non-limiting examples of suitable ethylenically unsaturated polyisocyanates include butene diisocyanate and 1,3-butadiene-1,4-diisocyanate. Non-limiting examples of suitable alicyclic polyisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)-2,2-propane, bis(isocyanatocyclohexyl)-1,2-ethane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane and 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane.

Non-limiting examples of suitable aromatic polyisocyanates include α,α′-xylene diisocyanate, bis(isocyanatoethyl)benzene, α, α,α′,α′-tetramethylxylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, mesitylene triisocyanate and 2,5-di(isocyanatomethyl)furan, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene diisocyanate, benzene triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, tolylidine diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene, 3,3′-dimethoxy-biphenyl-4,4′-diisocyanate, triphenylmethane triisocyanate, polymeric 4,4′-diphenylmethane diisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 4-methyldiphenylmethane-3,5,2′,4′,6′-pentaisocyanate, diphenylether diisocyanate, bis(isocyanatophenylether)ethyleneglycol, bis(isocyanatophenylether)-1,3-propyleneglycol, benzophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate and dichlorocarbazole diisocyanate.

In some non-limiting embodiments, the isocyanate functional material comprises at least one triisocyanate or at least one polyisocyanate trimer. Non-limiting examples of such isocyanates include aromatic triisocyanates such as tris(4-iso-cyanatophenyl)methane (DESMODUR R), 1,3,5-tris(3-isocyanato-4-methylphenyl)-2,3,6-trioxohexahydro-1,3,5 triazine (DESMODUR IL); adducts of aromatic diisocyanates such as the adduct of 2,4-tolylene diisocyanate (TDI, 2,4-diisocyanatotoluene) and trimethylolpropane (DESMODUR L); and from aliphatic triisocyanates such as N-isocyanatohexylaminocarbonyl-N,N′-bis(isocyanatohexyl)urea (DESMODUR N), 2,4,6-trioxo-1,3,5-tris(6-isocyanatohexyl)hexahydro-1,3,5-triazine (DESMODUR N3390), 2,4,6-trioxo-1,3,5-tris(5-isocyanato-1,3,3-trimethylcyclo-hexylmethyl)hexahydro-1,3,5-triazine (DESMODUR Z4370), and 4-(isocyanatomethyl)-8-octane diisocyanate. The above DESMODUR products are commercially available from Bayer Corp. Also useful are the biuret of hexanediisocyanate, polymeric methane diisocyanate, and polymeric isophorone diisocyanate. Trimers of hexamethylene diisocyanate, isophorone diisocyanate and tetramethylxylylene diisocyanate

In some non-limiting embodiments, the isocyanate functional material is a cycloaliphatic compound, such as a dinuclear compound bridged by an isopropylidene group or an alkylene group of 1 to 3 carbon atoms.

In some non-limiting embodiments, the isocyanate functional material is a diisocyanate, such as methylene bis(phenyl isocyanate) (also known as MDI); 2,4-toluene diisocyanate (2,4-TDI); a 80:20 mixture of 2,4- and 2,6-toluene diisocyanate (also known as TDI); 3-isocyanatomethyl-3,5,5-trimethyl cyclohexylisocyanate (IPDI); m-tetramethyl xylene diisocyanate (TMXD); hexamethylene diisocyanate (HDI); and 4,4′-methylene-bis-(cyclohexyl isocyanate) (commercially available as Desmodur W).

In some non-limiting embodiments, the isocyanate functional materials can comprise isocyanate functional (meth)acrylates.

In some non-limiting embodiments, hydroxy functional reaction product(s) of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with isocyanate functional materials to form urethane linkages. In some non-limiting embodiments, the hydroxy functional reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with polyisocyanate compound(s) to form an isocyanate functional urethane prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, amino functional reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with isocyanate functional materials to form urea linkages. In some non-limiting embodiments, the amino functional reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with polyisocyanate compound(s) to form an isocyanate functional urea prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, thiol functional reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with isocyanate functional materials to form carbamothioate linkages. In some non-limiting embodiments, the thiol functional reaction product of compound(s) of Formula (I) and compound(s) of Formula (II) are reacted with polyisocyanate compound(s) to form an isocyanate functional carbamothioate prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, the reaction product can have residual isocyanate functionality which can be further reacted with hydroxy, amino and/or thio functional acrylates, combinations thereof (such as acrylates having hydroxy and amino functionality), and mixtures thereof (such as hydroxy functional acrylate(s) and thio functional acrylate(s)), as discussed in detail below.

and b) at least one compound selected from the group of compounds represented by structural Formula (II):

The reaction of compound(s) of Formula (I) and compound(s) of Formula (II) can be carried out in the presence of a solvent as discussed above. In some non-limiting embodiments, the compound(s) of Formulae (I) and/or (II) can be solubilized in the solvent. The compound(s) of Formula (II) can be added to the mixture, allowed to exotherm and, if needed, heated at a temperature of about 0° C. to about 60° C., or about 60° C., for about 2 hours to about 7 days. The solvent can be removed by vacuum, if desired, for example at a temperature of about 60° C. and 100 torr and cooled, if desired.

wherein in Formula (III): X, R¹, R², R⁴and R⁵are as described above and the reaction product comprises at least two pendant functional groups independently selected from the group consisting of —OH, —NH₂and —SH; and (b) at least one isocyanate functional material such as are described above. Suitable moieties X, R¹, R²for compounds of Formula (III) are described in detail above with respect to compounds of Formula (I). Each R⁴is independently selected from the group consisting of H, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl, thioalkyl, and —C(O)R⁵. In some non-limiting embodiments, R⁴is —C(O)R⁵or —CH₃. Each R⁵, if present, is independently selected from the group consisting of H, alkyl, hydroxy, and alkoxy. In some non-limiting embodiments, R⁴is hydroxy. In some non-limiting embodiments, suitable compounds of Formula (III) can include tolyliminodiethanol, such as 2,2′-(p-Tolyliminodiethanol):

In some non-limiting embodiments, suitable compounds of Formula (III) can include phenyldiethanolamine, such as N-phenyldiethanolamine:

In some non-limiting embodiments, the compound(s) of Formula (III) can comprise about 5 to about 75 weight percent of the total weight of the reactants used for preparing the reaction product. In some non-limiting embodiments, the isocyanate functional material can comprise about 5 to about 75 weight percent of the total weight of the reactants used for preparing the reaction product, or about 15 to about 30 weight percent, or about 25 weight percent.

In some non-limiting embodiments, hydroxy functional reaction product(s) of compound(s) of Formula (III) are reacted with isocyanate functional materials to form urethane linkages. In some non-limiting embodiments, the hydroxy functional reaction product of compound(s) of Formula (III) are reacted with polyisocyanate compound(s) to form an isocyanate functional urethane prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, amino functional reaction product of compound(s) of Formula (III) are reacted with isocyanate functional materials to form urea linkages. In some non-limiting embodiments, the amino functional reaction product of compound(s) of Formula (III) are reacted with polyisocyanate compound(s) to form an isocyanate functional urea prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, thiol functional reaction product of compound(s) of Formula (III) are reacted with isocyanate functional materials to form carbamothioate linkages. In some non-limiting embodiments, the thiol functional reaction product of compound(s) of Formula (III) are reacted with polyisocyanate compound(s) to form an isocyanate functional carbamothioate prepolymer and subsequently reacted with a reactive (meth)acrylate monomer, such as a hydroxy functional (meth)acrylate, to produce a di(meth)acrylate based polymer or resin which includes a functional accelerator moiety.

In some non-limiting embodiments, the reaction product can have residual isocyanate functionality which can be further reacted with hydroxy, thio and/or amino functional materials, such as hydroxy, thio and/or amino functional acrylates, as discussed in detail below.

In some non-limiting embodiments, the reaction product(s) are purified to remove impurities, such as reaction by-products or impurities that accompany the reactants such as carriers, as discussed above. Methods of making the reaction products of compound(s) of Formula (III); and (b) isocyanate functional material(s) are discussed in detail below.

In some non-limiting embodiments, the reactants can further comprise at least one compound selected from the group of compounds represented by structural Formula (IV):

wherein in Formula IV: R¹is selected from the group consisting of aryl and heteroaryl; X is selected from the group consisting of a direct bond, —O—, —S—, —NH—, alkylene, cycloalkylene, heterocyclylene, arylene, alkarylene, and heteroarylene; Y is a substituted alkylene group comprising an alkylene backbone having at least two contiguous carbon atoms and which optionally can be interrupted by one or more —O—, —S—, or —NH— moieties, provided that each —O—, —S—, or —NH— moiety of Y, if present, is not adjacent to an —O—, —S—, or —NH— of X, wherein the alkylene group of Y has substituents which are independently selected from the group consisting of —OH, —NH₂, —SH, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two hydrogen atoms on the same carbon atom of Y are replaced by carbonyl, and wherein at least two substituents of Y are each independently selected from the group consisting of —OH, —NH₂, and —SH, and provided that each of the —OH, —NH₂, -or —SH groups is not attached to the same carbon atom of Y or an —O—, —S—, or —NH— backbone moiety of Y.

As used herein, “alkylene” means a difunctional group obtained by removal of a hydrogen atom from an alkyl group such as is defined below. Non-limiting examples of alkylene groups include methylene, ethylene and propylene.

“Heterocyclene” means a difunctional group obtained by removal of a hydrogen atom from a heterocyclyl group such as is defined below. “Heterocyclyl” means a non-aromatic saturated monocyclic or multicyclic ring system comprising about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the atoms in the ring system is an element other than carbon, for example nitrogen, oxygen or sulfur, alone or in combination. There are no adjacent oxygen and/or sulfur atoms present in the ring system. Preferred heterocyclyls contain about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heterocyclyl root name means that at least a nitrogen, oxygen or sulfur atom respectively is present as a ring atom. Any —NH in a heterocyclyl ring may exist protected such as, for example, as an —N(Boc), —N(CBz), —N(Tos) group and the like; such protections are also considered part of this invention. The heterocyclyl can be optionally substituted by one or more “ring system substituents” which may be the same or different, and are as defined above. The nitrogen or sulfur atom of the heterocyclyl can be optionally oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, lactam, lactone, and the like.

“Alkarylene” means a difunctional group obtained by removal of a hydrogen atom from an alkaryl group such as is defined below. “Alkaryl” or “alkylaryl” means an alkyl-aryl- group in which the alkyl and aryl are as previously described. Preferred alkylaryls comprise a lower alkyl group. C non-limiting example of a suitable alkylaryl group is tolyl. The bond to the parent moiety is through the aryl.

In the compounds of Formula (IV), Y is a substituted alkylene group comprising an alkylene backbone having at least two contiguous carbon atoms. The alkylene group Y optionally can be interrupted by one or more —O—, —S—, or —NH— moieties, provided that each —O—, —S—, or —NH— moiety of Y, if present, is not adjacent to an —O—, —S—, or —NH— of X. The alkylene group of Y has substituents which are independently selected from the group consisting of —OH, —NH₂, —SH, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two hydrogen atoms on the same carbon atom of Y are replaced by carbonyl. As used herein, “cycloalkyl” means a non-aromatic mono- or multicyclic ring system comprising about 3 to about 10 carbon atoms, about 5 to about 10 carbon atoms, or about 5 to about 7 ring atoms. The cycloalkyl can be optionally substituted with one or more “ring system substituents” which may be the same or different, and are as defined above. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Non-limiting examples of suitable multicyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl and the like.

At least two substituents of Y are each independently selected from the group consisting of —OH, —NH₂, and —SH, provided that each of the —OH, —NH₂, -or —SH groups is not attached to the same carbon atom of Y or an —O—, —S—, or —NH— backbone moiety of Y. In some non-limiting embodiments, Y comprises two or three —OH substituents.

In some non-limiting embodiments, compound(s) according to Formula (IV) are represented by structural Formula IV(a) below:

wherein R¹and Y are as described above.

In some non-limiting embodiments, compounds according to Formula (IV) are represented by structural Formula IV(b) and structural Formula IV(c) as illustrated below:

wherein X and R¹are as described above.

In one embodiment, a compound according to Formula (IV) is represented by structural Formula (A1):

In another embodiment, a compound according to Formula (IV) is represented by structural Formula (B1):

In another embodiment, a compound according to Formula (IV) is represented by structural Formula (C1):

In another embodiment, a compound of the present invention according to Formula (IV) is represented by structural Formula (D1):

In some non-limiting embodiments, the compound(s) of Formula (IV) can comprise about 1 to about 50 weight percent of the total weight of the reactants used for preparing the reaction product.

In some non-limiting embodiments, the reaction products can further comprise at least one reaction product(s) B prepared from reactants comprising: (a) at least one compound selected from the group of compounds represented by structural Formula (V):

wherein in Formula V: R¹is selected from the group consisting of aryl and heteroaryl; and (b) at least one compound selected from the group of compounds represented by structural Formula (VI) and structural Formula (VII):

wherein in Formula VI: X is selected from the group consisting of a direct bond, —O—, —S—, —NH—, alkylene, cycloalkylene, heterocyclylene, arylene, alkarylene, and heteroarylene; Y is a substituted alkylene group comprising an alkylene backbone having at least two contiguous carbon atoms and which optionally can be interrupted by one or more —O—, —S—, or —NH— moieties, provided that each —O—, —S—, or —NH— moiety of Y, if present, is not adjacent to an —O—, —S—, or —NH— of X, wherein the alkylene group of Y has substituents which are independently selected from the group consisting of —OH, —NH₂, —SH, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two hydrogen atoms on the same carbon atom of Y are replaced by carbonyl, and wherein at least two substituents of Y are each independently selected from the group consisting of —OH, —NH₂, and —SH, and provided that each of the —OH, —NH₂, -or —SH groups is not attached to the same carbon atom of Y or an —O—, —S—, or —NH— backbone moiety of Y; and R²is selected from the group consisting of —OR, —NHR, alkyl, and arylalkyl, wherein R is H, alkyl or arylalkyl; and

wherein in Formula VII: Z and Z′ are each independently selected from the group consisting of —O—, —S—, and —N(R³)—, wherein R³is H or alkyl; m is at least 1; each R⁴is independently selected from the group consisting of hydroxyalkyl, aminoalkyl, thioalkyl, hydroxyl substituted cycloalkyl, arylalkyl having at least one —OH, —NH₂, or —SH group, and heteroarylalkyl having at least one —OH, —NH₂, or —SH group, provided that there is no more than one R⁴substituent attached to a substitutable ring carbon atom; and p is 1 or 2.

In Formula V above, R¹is selected from the group consisting of aryl and heteroaryl. In some non-limiting embodiments, R¹is phenyl. A non-limiting example of a suitable compound of Formula (II) is phenylhydrazine, represented by structural Formula V(a):

In Formula VI above, X is selected from the group consisting of a direct bond, —O—, —S—, —NH—, alkylene, cycloalkylene, heterocyclylene, arylene, alkarylene, and heteroarylene. In some non-limiting embodiments, X is —O—.

In Formula VI, Y is a substituted alkylene group comprising an alkylene backbone having at least two contiguous carbon atoms and which optionally can be interrupted by one or more —O—, —S—, or —NH— moieties, provided that each —O—, —S—, or —NH— moiety of Y, if present, is not adjacent to an —O—, —S—, or —NH— of X. The alkylene group of Y has substituents which are independently selected from the group consisting of —OH, —NH₂, —SH, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two hydrogen atoms on the same carbon atom of Y are replaced by carbonyl. At least two substituents of Y are each independently selected from the group consisting of —OH, —NH₂, and —SH, provided that each of the —OH, —NH₂, -or —SH groups is not attached to the same carbon atom of Y or an —O—, —S—, or —NH— backbone moiety of Y. R²is selected from the group consisting of —OH, —OR, NHR, alkyl, and arylalkyl, wherein R is an alkyl or an arylalkyl group. In some non-limiting embodiments, Y comprises two or three —OH substituents.

In some non-limiting embodiments, compound(s) of Formula (VI) can be represented by Formulae (VI(a)), (VI(b)) or (VI(c)):

In Formula VII above, Z and Z′ are each independently selected from the group consisting of —O—, —S—, and —N(R³)—, wherein R³is H or alkyl. The variable m is at least 1. In some non-limiting embodiments, m is 1 or 2. Each R⁴is independently selected from the group consisting of hydroxyalkyl, aminoalkyl, thioalkyl, hydroxyl substituted cycloalkyl, arylalkyl having at least one —OH, —NH₂, or —SH group pendant from the alkyl group or the aryl group of the arylalkyl, and heteroarylalkyl having at least one —OH, —NH₂, or —SH group pendant from the alkyl group or the aryl group of the heteroarylalkyl. In some non-limiting embodiments, R⁴is hydroxyalkyl. The variable p can be 1 or 2.

In some non-limiting embodiments, compound(s) of Formula (VII) can be represented by structural Formulae (VII(a)) or (VII(b)):

In some non-limiting embodiments, the molar ratio of compound(s) of Formula (V) to compound(s) of Formulae (VI) and/or (VII) can range from about 5:1 to about 1:5, or about 3:1 to about 1:3, or about 1:1.

In some non-limiting embodiments, the reaction product(s) B can comprise about 1 to about 50 weight percent of the total weight of the reactants used for preparing the reaction product.

In some non-limiting embodiments, the reaction products can further comprise at least one reaction product(s) C prepared from reactants comprising: (a) at least one compound selected from the group of compounds represented by structural Formula (VIII):

wherein in Formula VIII: R⁵is selected from the group consisting of hydroxyalkyl and carboxyalkyl; and (b) at least one compound selected from the group of compounds represented by structural Formula (II):

wherein in Formula II: Z″, q, n, and R⁶are as defined above.

In one embodiment of the present invention, the reactant represented by Formula (VIII) is:

(“SPH”), which is the reaction product of succinic anhydride and phenyl hydrazine and can be prepared according to U.S. Pat. No. 6,835,782, incorporated by reference herein. In some embodiments, reaction products of SPH and glycidol can be represented by structural Formula (D1) and/or (D2):

In some non-limiting embodiments, the molar ratio of compound(s) of Formula (VIII) to compound(s) of Formulae (II) can range from about 5:1 to about 1:5, or about 3:1 to about 1:3, or about 1:1.

In some non-limiting embodiments, the reaction is conducted in the presence of a solvent. In some non-limiting embodiments, some of the compounds are dissolved in solvent prior to reaction with other reactants. Non-limiting examples of suitable solvents include, but are not limited to, mineral spirits, alcohols such as methanol, ethanol or butanol, aromatic hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl ether, esters, aliphatics, and mixtures of any of the foregoing. In some embodiments, residual solvent is extracted from the reaction product(s), for example by distillation or chromatography.

In some non-limiting embodiments, the reactants for preparing the reaction products of (1) the isocyanate functional material(s) and (2) the reaction product of compound(s) of Formulae (I) and (II) or the compound of Formula (III) can further comprise at least one functional material selected from the group consisting of hydroxy, amino and/or thio functional materials, combinations thereof (such as acrylates having hydroxy and amino functionality), and mixtures thereof (such as hydroxy functional acrylate(s) and thio functional acrylate(s)), as discussed in detail below

These functional materials can be reacted with the hydroxy-, amino- and/or thio functional compound(s) and the isocyanate functional material(s) concurrently or post-reacted with the reaction product of the hydroxy-, amino- and/or thio functional compound(s) and the isocyanate functional material(s), as desired.

In some non-limiting embodiments, the compound of Formula (III) is phenyldiethanolamine, the isocyanate functional material is toluene diisocyanate, the hydroxy functional material is hydroxyethyl acrylate and the reactants further comprise a polyol such as bisphenol A. In some non-limiting embodiments, phenyldiethanolamine, toluene diisocyanate, hydroxyethyl acrylate and bisphenol A can be reacted according to the generalized reaction scheme below:

The above reaction is described in greater detail in the Examples below.

Non-limiting examples of suitable hydroxy functional materials include hydroxy functional (meth)acrylates and hydroxy functional vinyl ethers.

The phrase “hydroxyl-functional (meth)acrylate” means any hydroxyl-substituted acrylate or methacrylate compound that would be suitable for making and using a capped urethane material. Non-limiting examples of suitable hydroxy functional (meth)acrylates include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and mixtures thereof. Other non-limiting examples of suitable hydroxy functional (meth)acrylates include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate (PETA), and 4-hydroxybutyl acrylate.

The phrase “hydroxy functional vinyl ether” means any hydroxy-substituted vinyl ether that would be suitable for making and using a capped urethane oligomer. Non-limiting examples of suitable hydroxy functional vinyl ethers can be selected from the group consisting of hydroxyethyl vinyl ethers, hydroxypropyl vinyl ethers, hydroxybutyl vinyl ethers and mixtures thereof, such as ethylene glycol monovinyl ether, and cyclohexane dimethanol monovinyl ether.

In some non-limiting embodiments, the hydroxy-functional material having at least one acrylate group can have a number average molecular weight of about 80 to about 1,000 grams/mole, or about 100 to about 800 grams/mole, or about 110 to about 600 grams/mole.

In some non-limiting embodiments, the hydroxy-functional material having at least one acrylate group can comprise about 1 to about 30 weight percent of the reactants used for preparing the urethane, or about 2 to about 15 weight percent of the reactants, or about 3 to about 12 weight percent of the reactants.

The reaction products of the present invention can have a number average molecular weight ranging from about 500 to about 10,000 grams/mole, or about 1000 to about 7000 grams/mole.

Anaerobic curable compositions generally are based on a (meth)acrylate component, together with an anaerobic cure-inducing composition. In some non-limiting embodiments, the anaerobic curable composition of the present invention is based on the (meth)acrylate component, together with an anaerobic cure-inducing composition, which preferably has at least reduced levels of APH (such as about 50% or less by weight of that which is used in conventional anaerobic curable compositions), is substantially free of APH (less than about 10 weight percent, less than about 5 weight percent or less than about 1 weight percent) or is free of APH. In place of some or all of APH is the inventive cure accelerator, such as compounds of Formula I or the above reaction products.

(Meth)acrylate monomers suitable for use as the (meth)acrylate component in the present invention may be selected from a wide variety of materials, such as those represented by H₂C═CGCO₂R⁸, where G may be hydrogen, halogen or alkyl groups having from 1 to about 4 carbon atoms, and R⁸may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups having from 1 to about 16 carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone and the like.

Additional (meth)acrylate monomers suitable for use herein include polyfunctional (meth)acrylate monomers, for example di-or tri-functional (meth)acrylates such as polyethylene glycol di(meth)acrylates, tetrahydrofuran(meth)acrylates and di(meth)acrylates, hydroxypropyl(meth)acrylate (“EPMA”), hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylates (“TMPTMA”), diethylene glycol dimethacrylate, triethylene glycol dimethacrylates (“TRIEGMA”), tetraethylene glycol di(meth)acrylates, dipropylene glycol di(meth)acrylates, di-(pentamethylene glycol) di(meth)acrylates, tetraethylene diglycol di(meth)acrylates, diglycerol tetra(meth)acrylates, tetramethylene di(meth)acrylates, ethylene di(meth)acrylates, neopentyl glycol di(meth)acrylates, and bisphenol-A mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate (“EBIPMA”), and bisphenol-F mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate.

Still other (meth)acrylate monomers that may be used herein include silicone (meth)acrylate moieties (“SiMA”), such as those taught by and claimed in U.S. Pat. No. 5,605,999 (Chu), incorporated herein by reference.

Other suitable monomers include polyacrylate esters represented by the formula

wherein R⁴is a radical selected from the group consisting of hydrogen, halogen and alkyl of from 1 to about 4 carbon atoms; q is an integer equal to at least 1, and preferably equal to from 1 to about 4; and X is an organic radical containing at least two carbon atoms and having a total bonding capacity of q plus 1. With regard to the upper limit for the number of carbon atoms in X, workable monomers exist at essentially any value. As a practical matter, however, a general upper limit is about 50 carbon atoms, preferably 30, and most preferably about 20.

For example, X can be an organic radical of the formula:

wherein each of Y¹and Y²is an organic radical, preferably a hydrocarbon group, containing at least 2 carbon atoms, and preferably from 2 to about 10 carbon atoms, and Z is an organic radical, preferably a hydrocarbon group, containing at least 1 carbon atom, and preferably from 2 to about 10 carbon atoms.

Other classes of useful monomers are the reaction products of di- or tri-alkylolamines (e.g., ethanolamines or propanolamines) with acrylic acids, such as are disclosed in French Pat. No. 1,581,361.

Non-limiting examples of useful acrylic ester oligomers include those having the following general formula:

wherein R⁵represents a radical selected from the group consisting of hydrogen, lower alkyl of from 1 to about 4 carbon atoms, hydroxy alkyl of from 1 to about 4 carbon atoms, and

wherein R⁴is a radical selected from the group consisting of hydrogen, halogen, and lower alkyl of from 1 to about 4 carbon atoms; R⁶is a radical selected from the group consisting of hydrogen, hydroxyl, and

m is an integer equal to at least 1, e.g., from 1 to about 15 or higher, and preferably from 1 to about 8; n is an integer equal to at least 1, e.g., 1 to about 40 or more, and preferably between about 2 and about 10; and p is 0 or 1.

Typical examples of acrylic ester oligomers corresponding to the above general formula include di-, tri- and tetraethyleneglycol dimethacrylate; di(pentamethyleneglycol)dimethacrylate; tetraethyleneglycol diacrylate; tetraethyleneglycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; butyleneglycol dimethacrylate; neopentylglycol diacrylate; and trimethylolpropane triacrylate.

While di- and other polyacrylate esters, and particularly the polyacrylate esters described in the preceding paragraphs, can be desirable, monofunctional acrylate esters (esters containing one acrylate group) also may be used. When dealing with monofunctional acrylate esters, it is highly preferable to use an ester which has a relatively polar alcoholic moiety. Such materials are less volatile than low molecular weight alkyl esters and, more important, the polar group tends to provide intermolecular attraction during and after cure, thus producing more desirable cure properties, as well as a more durable sealant or adhesive. Most preferably, the polar group is selected from the group consisting of labile hydrogen, heterocyclic ring, hydroxy, amino, cyano, and halo polar groups. Typical examples of compounds within this category are cyclohexylmethacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethylacrylate, and chloroethyl methacrylate.

Another useful class of monomers is prepared by the reaction of a monofunctionally substituted alkyl or aryl acrylate ester containing an active hydrogen atom on the functional substituent. This monofunctional, acrylate-terminated material is reacted with an organic polyisocyanate in suitable proportions so as to convert all of the isocyanate groups to urethane or ureido groups. The monofunctional alkyl and aryl acrylate esters are preferably the acrylates and methacrylates containing hydroxy or amino functional groups on the nonacrylate portion thereof. Acrylate esters suitable for use have the formula

wherein X is selected from the group consisting of —O— and

and R⁹is selected from the group consisting of hydrogen and lower alkyl of 1 through 7 carbon atoms; R⁷is selected from the class consisting of hydrogen, chlorine and methyl and ethyl radicals; and R⁸is a divalent organic radical selected from the group consisting of lower alkylene of 1 through 8 carbon atoms, phenylene and naphthylene. These groups upon proper reaction with a polyisocyanate, yield a monomer of the following general formula:

wherein n is an integer from 2 to about 6; B is a polyvalent organic radical selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl and heterocyclic radicals both substituted and unsubstituted; and R⁷, R⁸and X have the meanings given above.

The hydroxy- and amine-containing materials suitable for use in the preparation of the above monomeric products are exemplified by, but not limited to, such materials as hydroxyethyl acrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, 3-hydroxypropyl methacrylate, aminopropyl methacrylate, hydroxyhexyl acrylate, t-butylaminoethyl methacrylate, hydroxyoctyl methacrylate, and the like.

The proportions in which the reactants may be combined can be varied somewhat; however, it is generally preferred to employ the reactants in chemically equivalent amounts up to a slight excess, e.g., 1 equivalent excess of the polyisocyanate. As used herein the expression “chemically equivalent amount” refers to the amount needed to furnish one isocyanate group per hydroxy or amino group.

The reaction may be accomplished in the presence or absence of diluents. Preferably diluents which include the hydrocarbons, such as aliphatic, cycloaliphatic and aromatic hydrocarbons, for example, benzene, toluene, cyclohexane, hexane, heptane and the like, are employed but other diluents, such as methyl isobutyl ketone, diamyl ketone, isobutyl methacrylate, triethyleneglycol dimethacrylate, and cyclohexyl methacrylate can also be beneficially utilized, if desired, especially where complete compatibility with the sealant system is desired.

The temperature employed in the reaction may also vary over a wide range. Where the components are combined in approximately chemical equivalent amounts or with slight excess of the isocyanate reactant, useful temperatures may vary from room temperature or below, e.g., 10° C. to 15° C., up to and including temperatures of 100° C. to 175° C. Where reacting the simpler isocyanates, the components are preferably combined at or near room temperature, such as temperatures ranging from 20° C. to 30° C. In the preparation of the high molecular weight isocyanate adducts using an excess of the isocyanate, the reactants may be combined at room temperature or preferably heated at temperatures ranging from about 40° C. to about 150° C. Reactions conducted at about 90° C. to 120° C. have been found to proceed quite smoothly.

Of course, combinations of these (meth)acrylate monomers may also be used.

The (meth)acrylate component can comprise from about 10 to about 90 percent by weight of the composition, such as about 60 to about 90 percent by weight, based on the total weight of the composition.

In some non-limiting embodiments, the reactants can further comprise at least one polyol. As used herein, the term “polyol” includes compounds, monomers, oligomers and polymers comprising at least two hydroxyl groups (such as diols) or at least three hydroxyl groups (such as triols), higher functional polyols and mixtures thereof. Suitable polyols are capable of forming a covalent bond with a reactive group such as an isocyanate functional group.

Non-limiting examples of suitable polyols include hydrocarbon polyols, polyether polyols, polyester polyols and mixtures thereof. As used herein, hydrocarbon polyol means saturated aliphatic polyols, unsaturated aliphatic polyols such as olefins, alicyclic polyols and aromatic polyols.

Non-limiting examples of suitable diols include straight chain alkane diols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-ethanediol, propane diols such as 1,2-propanediol and 1,3-propanediol, butane diols such as 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, pentane diols such as 1,5-pentanediol, 1,3-pentanediol and 2,4-pentanediol, hexane diols such as 1,6-hexanediol and 2,5-hexanediol, heptane diols such as 2,4-heptanediol, octane diols such as 1,8-octanediol, nonane diols such as 1,9-nonanediol, decane diols such as 1,10-decanediol, dodecane diols such as 1,12-dodecanediol, octadecanediols such as 1,18-octadecanediol, sorbitol, mannitol, and mixtures thereof. In some non-limiting embodiments, the diol is a propane diol such as 1,2-propanediol and 1,3-propanediol, or butane diol such as 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. In some non-limiting embodiments, one or more carbon atoms in the polyol can be replaced with one or more heteroatoms, such as N, S, or O, for example sulfonated polyols, such as dithio-octane bis diol, thiodiethanol such as 2,2-thiodiethanol, or 3,6-dithia-1,2-octanediol.

Other non-limiting examples of suitable diols include those represented by the following formula:

wherein R represents C₀to C₁₈divalent linear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkylene radical or mixtures thereof; C₂to C₁₈divalent organic radical containing at least one element selected from the group consisting of sulfur, oxygen and silicon in addition to carbon and hydrogen atoms; C₅to C₁₈divalent saturated cycloalkylene radical; or C₅to C₁₈divalent saturated heterocycloalkylene radical; and R′ and R″ can be present or absent and, if present, each independently represent C₁to C₁₈divalent linear or branched aliphatic, cycloaliphatic, aromatic or aryl, heterocyclic, polymeric, or oligomeric saturated alkylene radical or mixtures thereof.

Other non-limiting examples of suitable diols include branched chain alkane diols, such as propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 2-methyl-butanediol. 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, dibutyl 1,3-propanediol, polyalkylene glycols such as polyethylene glycols, and mixtures thereof.

In some non-limiting embodiments, the diol can be a cycloalkane diol, such as cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanols (CHDM), such as 1,4-cyclohexanedimethanol, cyclododecanediol, 4,4′-isopropylidene-biscyclohexanol, hydroxypropylcyclohexanol, cyclohexanediethanol, 1,2-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 4,4′-isopropylidene-biscyclohexanol, bis(4-hydroxycyclohexanol)methane, and 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^2,6]decane and mixtures thereof.

In some non-limiting embodiments, the diol can be an aromatic diol, such as dihydroxybenzene, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol and dihydroxytoluene; bisphenols, such as, 4,4′-isopropylidenediphenol (Bisphenol A), 4,4′-oxybisphenol, 4,4′-dihydroxybenzophenone, 4,4′-thiobisphenol, phenolphthalein, bis(4-hydroxyphenyl)methane, 4,4′-(1,2-ethenediyl)bisphenol and 4,4′-sulfonylbisphenol; hydrogenated bisphenols, halogenated bisphenols, such as 4,4′-isopropylidenebis(2,6-dibromophenol), 4,4′-isopropylidenebis(2,6-dichlorophenol) and 4,4′-isopropylidenebis(2,3,5,6-tetrachlorophenol); alkoxylated bisphenols, which can have, for example, ethoxy, propoxy, α-butoxy and β-butoxy groups; and biscyclohexanols, which can be prepared by hydrogenating the corresponding bisphenols, such as 4,4′-isopropylidene-biscyclohexanol, 4,4′-oxybiscyclohexanol, 4,4′-thiobiscyclohexanol and bis(4-hydroxycyclohexanol)methane, the alkoxylation product of 1 mole of 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol-A) and 2 moles of propylene oxide, hydroxyalkyl terephthalates such as meta or para bis(2-hydroxyethyl)terephthalate, bis(hydroxyethyl)hydroquinone and mixtures thereof.

In some non-limiting embodiments, the diol can be an heterocyclic diol, for example a dihydroxy piperidine such as 1,4-bis(hydroxyethyl)piperazine; a diol of an amide or alkane amide [such as ethanediamide(oxamide)], for example N,N′,bis(2-hydroxyethyl)oxamide; a diol of a propionate, such as 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate; a diol of a hydantoin, such as bishydroxypropyl hydantoin; a diol of a phthalate, such as meta or para bis(2-hydroxyethyl)terephthalate; a diol of a hydroquinone, such as a dihydroxyethylhydroquinone; and/or a diol of an isocyanurate, such as dihydroxyethyl isocyanurate.

Non-limiting examples of trifunctional, tetrafunctional or higher polyols suitable for use include branched chain alkane polyols such as glycerol or glycerin, tetramethylolmethane, trimethylolethane (for example 1,1,1-trimethylolethane), trimethylolpropane (TMP) (for example 1,1,1-trimethylolpropane), erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, alkoxylated derivatives thereof (discussed below) and mixtures thereof.

In some non-limiting embodiments, the polyol can be a cycloalkane polyol, such as trimethylene bis(1,3,5-cyclohexanetriol); or an aromatic polyol, such as trimethylene bis(1,3,5-benzenetriol).

Further non-limiting examples of suitable polyols include the aforementioned polyols which can be alkoxylated derivatives, such as ethoxylated, propoxylated and butoxylated. In alternate non-limiting embodiments, the following polyols can be alkoxylated with from 1 to 10 alkoxy groups: glycerol, trimethylolethane, trimethylolpropane, benzenetriol, cyclohexanetriol, erythritol, pentaerythritol, sorbitol, mannitol, sorbitan, dipentaerythritol and tripentaerythritol. Non-limiting examples of suitable alkoxylated polyols include ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated trimethylolethane, and mixtures thereof.

In some non-limiting embodiments, the polyol can be an unsaturated aliphatic polyol such as NISSO GI-1000 hydroxy terminated, hydrogenated 1,2-polybutadiene (HPBD resin) having a calculated number average molecular weight of about 1500 and a hydroxyl value of about 60-120 KOH mg/g commercially available from Nippon Soda Co Ltd.

In some non-limiting embodiments, the polyol for use in the present invention can be an SH-containing material, such as a dithiol or polythiol. Non-limiting examples of suitable polythiols can include, but are not limited to, aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, heterocyclic polythiols, polymeric polythiols, oligomeric polythiols and mixtures thereof. As used herein, the terms “thiol,” “thiol group,” “mercapto” or “mercapto group” refer to an —SH group which is capable of forming a thiourethane linkage, (i.e., —NH—C(O)—S—) with an isocyanate group or a dithiourethane linkage (i.e., —NH—C(S)—S—) with an isothiocyanate group.

In some non-limiting embodiments, the polyol can be one or more polyether polyol(s). Non-limiting examples of polyether polyols include poly(oxyalkylene)polyols or polyalkoxylated polyols. Poly(oxyalkylene)polyols can be prepared in accordance with known methods. In a non-limiting embodiment, a poly(oxyalkylene)polyol can be prepared by condensing an alkylene oxide, or a mixture of alkylene oxides, using an acid- or base-catalyzed addition with a polyhydric initiator or a mixture of polyhydric initiators, such as ethylene glycol, propylene glycol, glycerol, and sorbitol. Compatible mixtures of polyether polyols can also be used. As used herein, “compatible” means that two or more materials are mutually soluble in each other so as to essentially form a single phase. Non-limiting examples of alkylene oxides can include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides, such as styrene oxide, mixtures of ethylene oxide and propylene oxide. In some non-limiting embodiments, polyoxyalkylene polyols can be prepared with mixtures of alkylene oxide using random or step-wise oxyalkylation. Non-limiting examples of such poly(oxyalkylene)polyols include polyoxyethylene polyols, such as polyethylene glycol, and polyoxypropylene polyols, such as polypropylene glycol.

Other polyether polyols include block polymers such as those having blocks of ethylene oxide-propylene oxide and/or ethylene oxide-butylene oxide. In some non-limiting embodiments, the polyether polyol comprises a block copolymer of the following formula:

HO—(CHR₁CHR₂—O)_a—(CHR₃CHR₄—O)_b—(CHR₅CHR₆—O)_c—H

where R₁through R₆can each independently represent hydrogen or methyl; and a, b, and c can each be independently selected from an integer from 0 to 300, wherein a, b, and c are selected such that the number average molecular weight of the polyol is less than about 32,000 grams/mole, or less than about 10,000 grams/mole, as determined by GPC.

In some non-limiting embodiments, polyalkoxylated polyols can be represented by the following general formula:

wherein m and n can each be a positive integer, the sum of m and n being from 5 to 70; R₁and R₂are each hydrogen, methyl or ethyl; and A is a divalent linking group such as a straight or branched chain alkylene which can contain from 1 to 8 carbon atoms, phenylene, and C₁to C₉alkyl-substituted phenylene. The values of m and n can, in combination with the selected divalent linking group, determine the molecular weight of the polyol. Polyalkoxylated polyols can be prepared by methods that are known in the art. In a non-limiting embodiment, a polyol such as 4,4′-isopropylidenediphenol can be reacted with an oxirane-containing material such as ethylene oxide, propylene oxide or butylene oxide, to form what is commonly referred to as an ethoxylated, propoxylated or butoxylated polyol having hydroxyl functionality.

In some non-limiting embodiments, the polyether polyol can be PLURONIC ethylene oxide/propylene oxide block copolymers, such as PLURONIC R and PLURONIC L62D, and/or TETRONIC tetra-functional block copolymers based on ethylene oxide and propylene oxide, such as TETRONIC R, which are commercially available from BASF Corp.

As used herein, the phrase “polyether polyols” also can include poly(oxytetramethylene)diols prepared by the polymerization of tetrahydrofuran in the presence of Lewis acid catalysts such as, but not limited to boron trifluoride, tin (IV) chloride and sulfonyl chloride.

In some non-limiting embodiments, non-limiting examples of suitable polyether polyols include poly(propylene oxide)diols, copoly(ethylene oxide-propylene oxide)diols, and poly(tetramethylene oxide)diols.

In some non-limiting embodiments, the polyether polyol can be POLYMEG® 2000 polytetramethylene ether glycol (linear diol having a backbone of repeating tetramethylene units connected by ether linkages and capped with primary hydroxyls having a molecular weight of about 1900-2100 and a hydroxyl number of about 53.0 to about 59.0), commercially available from Lyondell.

In other embodiments, the polyether polyol can be TERATHANE® 1000 polytetramethylene ether glycol is a blend of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups: HO(CH₂CH₂CH₂CH₂—O—)_nH in which n averages 14 and having a hydroxyl number of 107-118, commercially available from INVISTA, or POLYMEG® 1000.

In some non-limiting embodiments, the polyol can be one or more polyester polyol(s). In some non-limiting embodiments, the polyester polyol is selected from the group consisting of polyester glycols, polycaprolactone polyols, polycarbonate polyols and mixtures thereof. Non-limiting examples of suitable polyester polyols include any well-known di-, tri-, or tetrahydroxy-terminated polyesters such as polylactone polyesters and polyester polyols produced by the polycondensation reactions of dicarboxylic acids or their anhydrides with di-, tri-, or tetra-alcohols.

Non-limiting examples of such polyester polyols include polyester glycols, polycaprolactone polyols, polycarbonate polyols and mixtures thereof. Polyester glycols can include the esterification products of one or more dicarboxylic acids having from four to ten carbon atoms, such as, but not limited to adipic, succinic or sebacic acids, with one or more low molecular weight glycols having from two to ten carbon atoms, such as, but not limited to ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and 1,10-decanediol. Esterification procedures for producing polyester polyols are described, for example, in the article D. M. Young et al., “Polyesters from Lactone,” Union Carbide F-40, p. 147.

Non-limiting examples of polycaprolactone polyols include those prepared by condensing caprolactone in the presence of difunctional active hydrogen material such as water or low molecular weight glycols, for example ethylene glycol and propylene glycol. Non-limiting examples of suitable polycaprolactone polyols can include CAPA polycaprolactone polyols commercially available from Solvay Chemical of Houston, Tex., such as CAPA 2085 linear polyester diol derived from caprolactone monomer, terminated by primary hydroxyl groups, and having a mean molecular weight of 830 and a typical OH value of 135 mg KOH/g, and the TONE series from Dow Chemical of Midland, Mich., such as TONE 0201, 0210, 0230 and 0241. In some non-limiting embodiments, the polycaprolactone polyol has a molecular weight ranging from about 500 to about 2000 grams per mole, or about 500 to about 1000 grams per mole.

Non-limiting examples of polycarbonate polyols include aliphatic polycarbonate diols, for example those based upon alkylene glycols, ether glycols, alicyclic glycols or mixtures thereof. In some non-limiting embodiments, the alkylene groups for preparing the polycarbonate polyol can comprise from 5 to 10 carbon atoms and can be straight chain, cycloalkylene or combinations thereof. Non-limiting examples of such alkylene groups include hexylene, octylene, decylene, cyclohexylene and cyclohexyldimethylene. Suitable polycarbonate polyols can be prepared, in non-limiting examples, by reacting a hydroxy terminated alkylene glycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or diaryl carbonate, such as diphenyl or dinaphthyl carbonate, or by reacting of a hydroxy-terminated alkylene diol with phosgene or bischoloroformate, in a manner well-known to those skilled in the art. Non-limiting examples of suitable polycarbonate polyols include POLY-CD 210 hydroxyl-terminated 1000 MW poly(1,6-hexanediol)carbonate polyol commercially available from Arch Chemical.

Mixtures of any of the above polyols can be used.

In some non-limiting embodiments, the polyol can have a number average molecular weight of about 100 to about 10,000 grams/mole, or about 500 to about 5,000 grams/mole, or about 600 to about 3500 grams/mole.

In some non-limiting embodiments, the polyol can comprise about 10 to about 90 weight percent of the reactants used for preparing the urethane, or about 30 to about 70 weight percent of the reactants, or about 35 to about 65 weight percent of the reactants.

Recently, additional components have been included in traditional anaerobic adhesives to alter the physical properties of either the formulation or the reaction products thereof. For instance, one or more of maleimide components, thermal resistance-conferring co reactants, diluent components reactive at elevated temperature conditions, mono- or poly-hydroxyalkanes, polymeric plasticizers, and chelators (see U.S. Pat. No. 6,391,993, incorporated herein by reference) may be included to modify the physical property and/or cure profile of the formulation and/or the strength or temperature resistance of the cured adhesive.

When used, the maleimide, co reactant, reactive diluent, plasticizer, and/or mono- or poly-hydroxyalkanes, may be present in an amount within the range of about 1 percent to about 30 percent by weight, based on the total weight of the composition.

The inventive compositions may also include other conventional components, such as free radical initiators, free radical co-accelerators, and inhibitors of free radical generation, as well as metal catalysts.

A number of well-known initiators of free radical polymerization are typically incorporated into the inventive compositions including, without limitation, hydroperoxides, such as cumene hydroperoxide (“CHP”), para-methane hydroperoxide, t-butyl hydroperoxide (“TBH”) and t-butyl perbenzoate. Other peroxides include benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, t-butyl cumyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2-di-t-butylperoxypentane and combinations thereof.

Such peroxide compounds are typically employed in the present invention in the range of from about 0.1 to about 10 percent by weight, based on the total weight of the composition, with about 1 to about 5 percent by weight being desirable.

As noted, conventional accelerators of free radical polymerization may also be used in conjunction with the inventive anaerobic cure accelerators, though in amounts less than that used in the past. Such accelerators are typically of the hydrazine variety (e.g., APH), as disclosed in U.S. Pat. No. 4,287,350 (Rich) and U.S. Pat. No. 4,321,349 (Rich). Maleic acid is usually added to APH-containing anaerobic cure systems. One benefit of the present invention is that the inventive anaerobic cure accelerators render the use of such acids unnecessary in preparing anaerobic adhesive compositions.

Co-accelerators of free radical polymerization may also be used in the compositions of the present invention including, without limitation, organic amides and imides, such as benzoic sulfimide (also known as saccharin) (See U.S. Pat. No. 4,324,349).

Stabilizers and inhibitors (such as phenols including hydroquinone and quinones) may also be employed to control and prevent premature peroxide decomposition and polymerization of the composition of the present invention, as well as chelating agents [such as the tetrasodium salt of ethylenediamine tetraacetic acid (“EDTA”)] to trap trace amounts of metal contaminants therefrom. When used, chelating agents may ordinarily be present in the compositions in an amount from about 0.001 percent by weight to about 0.1 percent by weight, based on the total weight of the composition.

The inventive anaerobic cure accelerators may be used in amounts of about 0.1 to about 5 percent by weight, such as about 1 to about 2 percent by weight, based on the total weight of the composition. When used in combination with conventional accelerators (though at lower levels than such conventional accelerators), the inventive accelerators should be used in amounts of 0.01 to 5 percent by weight, such as 0.02 to 2 percent by weight, based on the total weight of the composition.

Metal catalyst solutions or pre-mixes thereof are used in amounts of about 0.03 to about 0.1 percent by weight.

Other additives such as thickeners, non-reactive plasticizers, fillers, toughening agents (such as elastomers and rubbers) and other well-known additives may be incorporated therein where the art-skilled believes it would be desirable to do so.

The present invention also provides methods of preparing and using the inventive anaerobic adhesive compositions, as well as reaction products of the compositions.

The compositions of the present invention may be prepared using conventional methods which are well known to those persons of skill in the art. For instance, the components of the inventive compositions may be mixed together in any convenient order consistent with the roles and functions the components are to perform in the compositions. Conventional mixing techniques using known apparatus may be employed.

The compositions of this invention may be applied to a variety of substrates to perform with the desired benefits and advantages described herein. For instance, appropriate substrates may be constructed from steel, brass, copper, aluminum, zinc, and other metals and alloys, ceramics and thermosets. The compositions of this invention demonstrate particularly good bond strength on steel, brass, copper and zinc. An appropriate primer for anaerobic curable compositions may be applied to a surface of the chosen substrate to enhance cure rate. Or, the inventive anaerobic cure accelerators may be applied to the surface of a substrate as a primer. See, e.g., U.S. Pat. No. 5,811,473 (Ramos).

In addition, the invention provides a method of preparing an anaerobic curable composition, a step of which includes mixing together a (meth)acrylate component, an anaerobic cure inducing composition comprising an anaerobic cure accelerator compound of Formula (I) or a reaction product as discussed above.

The invention also provides a process for preparing a reaction product from the anaerobic curable composition of the present invention, the steps of which include applying the composition to a desired substrate surface and exposing the composition to an anaerobic environment for a time sufficient to cure the composition.

This invention also provides a method of using as a cure accelerator for anaerobic curable composition, compound of Formula (I) or a reaction product as discussed above.

And the present invention provides a method of using an anaerobic cure accelerator compound, including (I) mixing the anaerobic cure accelerator compound in an anaerobic curable composition or (II) applying onto a surface of a substrate the anaerobic cure accelerator compound and applying thereover an anaerobic curable composition. Of course, the present invention also provides a bond formed between mated substrates with the inventive composition.

In view of the above description of the present invention, it is clear that a wide range of practical opportunities are provided. The following examples are illustrative purposes only, and are not to be construed so as to limit in any way the teaching herein.

EXAMPLES
Example 1
Synthesis of DMABA-Glycidol Reaction Product

An investigation was performed to evaluate reaction product(s) of 4-(dimethylamino)benzoic acid and glycidol as replacements for APH cure accelerator, for example, in anaerobic curable compositions, such as adhesives.

The inventive anaerobic cure accelerators were prepared in accordance with the synthetic scheme depicted below:

4-(Dimethylamino)benzoic acid and glycidol were reacted in the presence of acetonitrile in amounts and the manner described below to form DMABA-glycidol reaction products (adducts) as shown in Table 1:

TABLE 1

Reagents and Materials:

Reagent
1
2
Acetonitrile
3

MW
165.19
74.08
41.05
239.27

% Active
98
96
99
x

Density (g/ml)
x
1.117 @ 25 C.
0.786
x

Theoretical

Yield:

Amount (g)
25.00
10.07
100 ml
28.39

mmols
118.65
130.52
x
118.65

To a 3 necked, 500 ml round-bottomed flask equipped with magnetic stirring, a reflux condenser, pressure equilibrated addition funnel, nitrogen purge and thermo-probe was added DMABA (1) and acetonitrile. The DMABA was poorly soluble in acetonitrile at 80° C. Glycidol was added over ˜20 minutes and the mixture was stirred overnight at 80° C. In the morning it was apparent that a considerable amount of the DMABA solubilized (violet color and less solid evident). The reaction was continued over the weekend (˜92 hours). In the morning the lavender mixture was completely dissolved. The mixture was cooled at about 25° C. and the resulting solid was filtered, and minimally washed with acetonitrile. The filtrate contained some solid as it continued to cool. The solid and the filtrate were screened by FTIR to determine the qualitative extent of the reaction. The filtrate was concentrated in vacuo to a solid. Both solids were dried in vacuo at 50° C. and <200 mTorr until constant weight was reached. The melting point of the product as determined by DSC was 106° C.

56.5% of

Theoretical

Weight
Yield

DMABA-Glycidol Adduct
Pale Lavender Solid
16.04 g

DMABA-Glycidol Adduct
Paste-like Solid
18.34 g

from Filtrate

The DMABA-glycidol adduct was analyzed by FT-IR (shown in FIG. 1) and ¹H NMR. ¹H NMR (DMSO-d6, 300 MHz)δ 7.75, 6.60, 4.20, 4.10, 3.75, 3.45, 2.90, and 2.0. Proton Nuclear Magnetic Resonance analysis was performed using a Varian 300 MHz Gemini Spectrophotometer. Melting points were obtained on a TA Instrument 2920 Differential Scanning Calorimeter.

Preparation of Anaerobic Curable Compositions

Selected components were premixed prior to mixing with the remaining components of the anaerobic base composition, as follows:

Premix A:

Component
% by weight

Polyethylene glycol
95

dimethacrylate

Phenolic Stabilizer
5

The components of Premix A were mixed by conventional stirring at about 25° C.

Premix B:

Component
% by weight

Propylene glycol
73.5

Water (deionized)
23

Chelating agent
3.5

The components of Premix B were mixed by conventional stirring at about 25° C.

Premixes A and B were used to prepare the Formulations according to Table 2 as follows:

TABLE 2

Formulation

A
B
C

Material
Parts
Parts
Parts

Polyethylene glycol (PEG) dimethacrylate
62.67
62.67
62.67

Premix A
0.80
0.80
0.80

Premix B
1.50
1.50
1.50

Saccharin
3.78
3.78
3.78

Aerosil R972 Fumed Silica
1.80
1.80
1.80

Polyethylene Glycol Monooleate
26.85
27.65
26.48

N,N-Diethyl-p-toluidine (DEPT)
0.80
0.00
0.00

DMABA-Glycidol Adduct
0.00
0.00
1.17

Cumene hydroperoxide (CHP)
1.80
1.80
1.80

Total
100.00
100.00
100.00

The first five components were mixed in the order listed in Table 2. The components were mixed using a stainless steel propeller-type mixer such that the components were dissolved. As the components were mixed, the thickener components slowly ‘dissolved into’ the formulation and thickened to form a mixture. Some components required additional mixing time (minimally overnight) to completely dissolve. The remaining components were added to the mixture and mixed as above. DEPT was included in Formulation A as an additional accelerator. The DMABA-glycidol adduct from above was included in Formulation C as an additional accelerator. No additional accelerator was used in Formulation B (Control).

Physical Property Evaluation

A DMABA-glycidol adduct cure system (Formulation C) of the present invention was compared with the formulations containing conventional cure component DEPT (Formulation A) and the Control Formulation B (no additional accelerator) by 82° C. accelerated stability and adhesion tests on steel nut/bolt specimens.

Shelf Life Stability

The 82° C. stability of the formulations was determined according to an evaluation in which the formulation is judged to have acceptable shelf stability if the adhesive formulation remains liquid for 3 hours or longer at 82° C. Three specimens of each of the above Formulations A-C were evaluated at 82° C. As shown in Table 3, the samples of Formulation C of the present invention generally provided comparable stability at 82° C. to samples of Formulation A containing DEPT.

TABLE 3

82° C. Stability

Formula
1
2
3

A
<60
<90
<60

B
<60
<60
<60

C
<60
<90
<60

Fixture Times

Breakloose/prevail adhesion testing was performed according to ASTM D5649. Breakloose torque is the initial torque required to decrease or eliminate the axial load in a seated assembly. Prevailing torque, after initial breakage of the bond, is measured at any point during 360° rotation of the nut. Prevailing torque is normally determined at 180° rotation of the nut. Steel ⅜×16 nuts and bolts were degreased with 1,1,1-trichloroethylene, adhesive was applied to the bolt, and the nut was screwed onto the bolt with a steel collar as a spacer.

Twenty nut and bolt specimens were assembled for each adhesive formulation tested. For the break/prevail adhesion tests, the specimens were maintained at ambient temperature for 15 minutes, 30 minutes, 1 hour and 24 hours after assembly (five specimens each). The break and prevail torque strengths (in-lb_f) were then recorded for five specimens of each adhesive formulation after 15 minutes, 30 minutes, one hour and after 24 hours at ambient temperature (25° C.) and 45-50% relative, humidity, respectively. The torque strengths were measured using a calibrated automatic torque analyzer. The data for these evaluations is set forth below in Table 4 and FIG. 2.

This data indicates that Formulation B in accordance with this invention exhibited generally similar breakloose and prevail properties at room temperature compared to traditional anaerobic (meth)acrylate-based adhesives when applied and cured on the substrates.

TABLE 4

15 minutes
30 minutes
1 hour
24 hour

15
30
60
1440

180

180

180

180

Sample

Breakloose
Prevail
Breakloose
Prevail
Breakloose
Prevail
Breakloose
Prevail

A
+/−
62
6
85
6
122
4
191
9

7
0
7
0
10
2
12
7

B
+/−
62
6
61
6
88
6
131
6

7
0
6
0
15
0
11
1

C
+/−
63
6
74
6
76
7
159
5

5
0
8
0
9
0
23
3

Hypothetical Synthesis of a DMABA-Glycidol Resin Reaction Product

The following abbreviations have the following meanings as used herein:

- Bi(Oct)₃means bismuth 2-ethylhexanoate, 70% in 2-ethylhexanoic acid from King Industries.
- BHT means butylated hydroxytoluene.
- DBTDL means dibutyltin dilaurate.
- IPDI means isophorone diisocyanate.
- MeHQ means paramethoxyphenol or monomethyl ether hydroquinone.
- MW means number average molecular weight.
- TRIEGMA means triethylene glycol di-methacrylate.

The DMABA-glycidol reaction product of Example A can be used to prepare a resin of the present invention. The following components in Table 5 can be reacted as discussed below to form an accelerating resin according to the present invention:

TABLE 5

Weight

Reagent
(g)
Moles
Equiv. Ratio
Weight %

IPDI
72.58
0.327
2.000
25.28%

CAPA 2085
131.75

1.000
45.88%

polycaprolactone

polyol

2-Hydroxyethyl
23.54
0.163
0.500
8.20%

Methacrylate

DMABA-Glycidol
18.30
0.082
0.500
6.37%

Adduct

IRGANOX 1010
0.14

phenolic antioxidant¹

MeHQ
0.14

DBTDL
0.11

0.04%

Bi(Oct)3
0.37

0.13%

TRIEGMA
40.21

14.00%

Theoretical Yield (g):
287.15

¹IRGANOX 1010 phenolic antioxidant commercially available from Ciba Specialty Chemicals.

Premix 35, CAPA 2085 polycaprolactone polyol, IPDI, TRIEGMA, IRGANOX 1010 phenolic antioxidant, MeHQ, and DBTDL is added to a reaction flask and stirred at 75° C. for 1 hour under dry air. HEMA is added and the mixture stirred for 1 hour at 75° C. The reaction product can be titrated for “B” stage NCO. The DMABA-glycidol adduct and Bi(Oct)₃are added and the mixture stirred for 10 hours at 75° C. Theoretical IR shows 0.04 wt % NCO remaining. Theoretical Yield: 268.4 g of a light yellow, very viscous resin having a theoretical molecular weight of 3023.8 g/mole and 45.9 weight percent theoretical soft segment.

Example 2
Resin Preparation A
Synthesis of toluene diisocyanate-based reaction product (resin):

One skilled in the art would understand that other suitable acrylates, isocyanates, etc., such as are discussed above, can be used in the generalized reaction scheme.

Procedure

Into a 1-liter jacketed glass reactor equipped with mechanical stirrer and a dried air blanket was added Isobomyl methacrylate (309.0 grams), a stabilizer solution (6.76 grams of a solution of 1.96 grams BHT and 1.96 grams MEHQ dissolved in 93.86 grams Isobornyl methacrylate), 66.9 grams hydrogenated bisphenol A, 67.0 grams N-Phenyldiethanolamine and 0.59 grams dibutyltindilaurate.

The mixture was heated to 70° C. and the jacket temperature was maintained at that temperature. Toluene diisocyanate (200 g of an 80/20 mixture of the 2,4, and 2,6 isomers) was added rapidly. The reaction temperature was allowed to rise to 125° C. over a period of 5 minutes and mixed until the reaction mixture cooled to 70° C. over a period of 1.5 hours.

Hydroxypropyl methacrylate was then added (215.9 grams) and the reaction temperature increased to 83° C. in 10 minutes. The reaction mixture was allowed to cool down to 70° C. and was stirred for an additional 2 hours. The reaction product was a clear water white high viscosity liquid.

Resin Preparations B and C
Synthesis of 2,2′-tolyliminodiethanol-based reaction products (resins)

Resin Preparation B:

The following components in Table 6 were reacted as discussed below to form an accelerating resin according to the present invention:

TABLE 6

Equiv.

Reagent
Weight (g)
Moles
Ratio
Weight %

IPDI
106.54
0.479
2.000
24.27%

CAPA 2085
194.27

1.000
44.25%

polycaprolactone polyol

2-Hydroxyethyl Methacrylate
34.55
0.240
0.500
7.87%

IRGANOX 1010 phenolic
0.22

antioxidant

MeHQ
0.22

2,2′-Tolyliminodiethanol
18.65
0.120
0.500
4.25%

DBTDL
0.21

0.05%

Bi(Oct)3
0.53

0.12%

Isobornyl Methacrylate
83.84

19.10%

Theoretical Yield (g):
439.04

CAPA 2085 polycaprolactone polyol, IRGANOX 1010 phenolic antioxidant, MeHQ, IPDI, IBOMA (isobornyl methacrylate) and DBTDL were added to a reaction flask and stirred at 75° C. for 1.5 hours under dry air. HEMA was added and the mixture stirred for 1 hour at 75° C. The 2,2′-Tolyliminodiethanol and Bi(Oct)₃were added and the mixture was stirred for 8 hours at 75° C. Yield: 424.4 g of a viscous resin having a theoretical molecular weight of 3004.5 g/mole and 44.2 weight percent theoretical soft segment.

Resin Preparation C:

The following components in Table 7 were reacted as discussed below to form an accelerating resin according to the present invention:

TABLE 7

Equiv.

Reagent
Weight (g)
Moles
Ratio
Weight %

TMXDI
138.05
0.565
2.000
27.77%

2,2′-Tolyliminodiethanol
55.0
0.283
1.000
11.06%

CD 570¹
203.96
0.529
1.000
41.02%

IRGANOX 1010 phenolic
0.21

antioxidant

MeHQ
0.21

DBTDL (I)
0.47

0.09%

DBTDL (II)
0.03

0.01%

Hexanediol Dimethacrylate (I)
74.25

14.93%

Hexanediol Dimethacrylate (II)
25.00

5.03%

Theoretical Yield (g):
497.18

99.92%

¹Sartomer CD570 two mole ethoxylated hydroxy ethyl methacrylate

having the structure:

IRGANOX 1010 phenolic antioxidant, MeHQ, TMXDI (m-tetramethylxylylene diisocyanate), HDDM I (portion I of hexanediol dimethacrylate) and DBTDL I were added to a reaction flask and 2,2′-Tolyliminodiethanol was added portionwise into a reaction flask and allowed to exotherm to 80° C. The reaction product was stirred at 75□ C for 1 hour under dry air. CD 570, HDDM II and DBTDL II were added and the mixture was stirred for 2 hours at 75° C. Yield: 487.94 g of a light amber, flowable resin having a theoretical molecular weight of 1453.8 g/mole.

Preparation of Anaerobic Curable Compositions

Selected components were premixed prior to mixing with the remaining components of the anaerobic base composition, as follows:

Premix A:

Component
% by weight

Polyethylene glycol
95

dimethacrylate

Phenolic Stabilizer
5

The components of Premix A were mixed by conventional stirring at about 25° C.

Premix B:

Component
% by weight

Propylene glycol
73.5

Water (deionized)
23

Chelating agent
3.5

The components of Premix B were mixed by conventional stirring at about 25° C.

Premixes A and B were used to prepare the Anaerobic Curable Compositions B according to Tables 8-12 as follows:

TABLE 8

Formulation

1
2
3
4

Material
Order
Weight %
Weight %
Weight %
Weight %

Polyethylene glycol (PEG) dimethacrylate
5
12.67
12.67
12.67
12.67

Polyethylene glycol (PEG) mono oleate
5
10.00
10.00
10.00
10.00

Premix A
5
0.80
0.80
0.80
0.80

Premix B
5
1.50
1.50
1.50
1.50

Polyethylene glycol (PEG) dimethacrylate
1
50.00
68.65
50.00
69.45

PEG 200 Monooleate-Supplemental
2
18.65
0.00
19.45
0.00

Saccharin (BS) (o-Benzoic sulfamide)
4
3.78
3.78
3.78
3.78

N,N-Diethyl-p-toluidine (DEPT)
6
0.80
0.80
0.00
0.00

Toluene Diisocyanate Adduct Resin of
6
0.00
0.00
0.00
0.00

Example A (7.5% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00

Example B (4.25% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00

Example C (11.06% Accelerator)

Cumene hydroperoxide (CHP)
3
1.80
1.80
1.80
1.80

t-Butyl Hydroperoxide
3
0.00
0.00
0.00
0.00

100.00
100.00
100.00
100.00

TABLE 9

Formulation

5
6
7
8
9
10

Material
Order
Weight %
Weight %
Weight %
Weight %
Weight %
Weight %

Polyethylene glycol (PEG) dimethacrylate
5
12.67
12.67
12.67
12.67
12.67
12.67

Polyethylene glycol (PEG) mono oleate
5
10.00
10.00
10.00
10.00
10.00
10.00

Premix A
5
0.80
0.80
0.80
0.80
0.80
0.80

Premix B
5
1.50
1.50
1.50
1.50
1.50
1.50

Polyethylene glycol (PEG) dimethacrylate
1
20.00
39.45
20.00
39.45
20.00
39.45

PEG 200 Monooleate-Supplemental
2
19.45
0.00
19.45
0.00
19.45
0.00

Saccharin (BS) (o-Benzoic sulfamide)
4
3.78
3.78
3.78
3.78
3.78
3.78

N,N-Diethyl-p-toluidine (DEPT)
6
0.00
0.00
0.00
0.00
0.00
0.00

Toluene Diisocyanate Adduct Resin of
6
30.00
30.00
0.00
0.00
0.00
0.00

Example A (7.5% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
30.00
30.00
0.00
0.00

Example B (4.25% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00
30.00
0.00

Example C (11.06% Accelerator)

Cumene hydroperoxide (CHP)
3
1.80
1.80
1.80
1.80
1.80
1.80

t-Butyl Hydroperoxide
3
0.00
0.00
0.00
0.00
0.00
0.00

100.00
100.00
100.00
100.00
100.00
100.00

TABLE 10

Formulation

11
12
13
14
15
16

Material
Order
Weight %
Weight %
Weight %
Weight %
Weight %
Weight %

Polyethylene glycol (PEG) dimethacrylate
5
12.67
12.67
12.67
12.67
12.67
12.67

Polyethylene glycol (PEG) mono oleate
5
10.00
10.00
10.00
10.00
10.00
10.00

Premix A
5
0.80
0.80
0.80
0.80
0.80
0.80

Premix B
5
1.50
1.50
1.50
1.50
1.50
1.50

Polyethylene glycol (PEG) dimethacrylate
1
0.00
19.45
0.00
19.45
0.00
19.45

PEG 200 Monooleate-Supplemental
2
19.45
0.00
19.45
0.00
19.45
0.00

Saccharin (BS) (o-Benzoic sulfamide)
4
3.78
3.78
3.78
3.78
3.78
3.78

N,N-Diethyl-p-toluidine (DEPT)
6
0.00
0.00
0.00
0.00
0.00
0.00

Toluene Diisocyanate Adduct Resin of
6
50.00
50.00
0.00
0.00
0.00
0.00

Example A (7.5% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
50.00
50.00
0.00
0.00

Example B (4.25% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00
50.00
50.00

Example C (11.06% Accelerator)

Cumene hydroperoxide (CHP)
3
1.80
1.80
1.80
1.80
1.80
1.80

t-Butyl Hydroperoxide
3
0.00
0.00
0.00
0.00
0.00
0.00

100.00
100.00
100.00
100.00
100.00
100.00

TABLE 11

Formulation

17
18
19
20
21
22

Material
Order
Weight %

Polyethylene glycol (PEG) dimethacrylate
5
12.67
12.67
12.67
12.67
12.67
12.67

Polyethylene glycol (PEG) mono oleate
5
10.00
10.00
10.00
10.00
10.00
10.00

Premix A
5
0.80
0.80
0.80
0.80
0.80
0.80

Premix B
5
1.50
1.50
1.50
1.50
1.50
1.50

Polyethylene glycol (PEG) dimethacrylate
1
20.00
40.05
20.00
40.05
20.00
40.05

PEG 200 Monooleate-Supplemental
2
20.05
0.00
20.05
0.00
20.05
0.00

Saccharin (BS) (o-Benzoic sulfamide)
4
3.78
3.78
3.78
3.78
3.78
3.78

N,N-Diethyl-p-toluidine (DEPT)
6
0.00
0.00
0.00
0.00
0.00
0.00

Toluene Diisocyanate Adduct Resin of
6
30.00
30.00
0.00
0.00
0.00
0.00

Example A (7.5% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
30.00
30.00
0.00
0.00

Example B (4.25% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00
30.00
30.00

Example C (11.06% Accelerator)

Cumene hydroperoxide (CHP)
3
0.00
0.00
0.00
0.00
0.00
0.00

t-Butyl Hydroperoxide
3
1.20
1.20
1.20
1.20
1.20
1.20

100.00
100.00
100.00
100.00
100.00
100.00

TABLE 12

Formulation

23
24
25
26
27
28

Material
Order
Weight %

Polyethylene glycol (PEG) dimethacrylate
5
12.67
12.67
12.67
12.67
12.67
12.67

Polyethylene glycol (PEG) mono oleate
5
10.00
10.00
10.00
10.00
10.00
10.00

Premix A
5
0.80
0.80
0.80
0.80
0.80
0.80

Premix B
5
1.50
1.50
1.50
1.50
1.50
1.50

Polyethylene glycol (PEG) dimethacrylate
1
0.00
20.05
0.00
20.05
0.00
20.05

PEG 200 Monooleate-Supplemental
2
20.05
0.00
20.05
0.00
20.05
0.00

Saccharin (BS) (o-Benzoic sulfamide)
4
3.78
3.78
3.78
3.78
3.78
3.78

N,N-Diethyl-p-toluidine (DEPT)
6
0.00
0.00
0.00
0.00
0.00
0.00

Toluene Diisocyanate Adduct Resin of
6
50.00
50.00
0.00
0.00
0.00
0.00

Example A (7.5% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
50.00
50.00
0.00
0.00

Example B (4.25% Accelerator)

Tolyliminodiethanol Adduct Resin of
6
0.00
0.00
0.00
0.00
50.00
50.00

Example C (11.06% Accelerator)

Cumene hydroperoxide (CHP)
3
0.00
0.00
0.00
0.00
0.00
0.00

t-Butyl Hydroperoxide
3
1.20
1.20
1.20
1.20
1.20
1.20

100.00
100.00
100.00
100.00
100.00
100.00

The components were mixed in the order listed in Tables 8-12 using a stainless steel propeller-type mixer such that the components were dissolved. As the components were mixed, the thickener components slowly ‘dissolved into’ the formulation and thickened to form a mixture. Some components required additional mixing time (minimally overnight) to completely dissolve. Toluene diisocyanate adduct resin or Tolyliminodiethanol adduct resin were included as an accelerator in Formulations 5-28 in different amounts as shown in Tables 9-12.

Physical Property Evaluation

Toluene diisocyanate adduct resins (Formulations 5, 6, 11, 12, 17, 18, 23 and 24) or Tolyliminodiethanol adduct resins (Formulations 7-10, 13-16, 19-22 and 25-28) of the present invention were compared with formulations containing conventional cure component saccharin and DEPT (Formulations 1-4) by 82° C. accelerated stability and adhesion tests on steel nut/bolt specimens.

Shelf Life Stability

The 82° C. stability of the formulations was determined in a manner as discussed in Example 1 above in which the formulation is judged to have acceptable shelf stability if the adhesive formulation remains liquid for 3 hours or longer at 82° C. Three specimens of each of the above Formulations 1-28 were evaluated at 82° C. As shown in Table 13, the samples of Formulations 5-28 of the present invention can provide generally acceptable stability at 82° C.

TABLE 13

Controls
with CHP
with tBuOOH

82 C. Stability

82 C. Stability

82 C. Stability

Sample 1
Sample 2
Sample 3

Sample 1
Sample 2
Sample 3

Sample 1
Sample 2
Sample 3

Formula
minutes
minutes
minutes
Formula
minutes
minutes
minutes
Formula
minutes
minutes
minutes

1
>180
>180
>180
5
>180
>180
>180
17
>180
>180
>180

2
>180
>180
>180
6
>180
>180
>180
18
>180
>180
>180

3
>180
>180
>180
7
<30
<30
<30
19
<60
<60
<60

4
>180
>180
>180
8
<60
<30
<60
20
<30
<30
<60

5
>180
>180
>180
9
>180
>180
>180
21
<90
<120
<120

6
>180
>180
>180
10
>180
>180
>180
22
<60
<60
<60

11
>180
>180
>180
23
>180
>180
>180

12
>180
>180
>180
24
>180
>180
>180

13
<30
<30
<30
25
<30
<30
<30

14
<30
<30
<30
26
<30
<30
<30

15
>180
>180
>180
27
<30
<30
<30

16
<30
<30
<30
28
<30
<30
<30

Fixture Times

Breakloose/prevail adhesion testing was performed according to ASTM D5649 in a manner as discussed above. The break and prevail torque strengths (in-lb_f) were recorded for five specimens of each adhesive formulation after 15 minutes, 30 minutes, one hour and after 24 hours at ambient temperature (25° C.) and 45-50% relative humidity, respectively. The data for these evaluations is set forth below in Tables 14-17 and FIGS. 3 and 4.

In FIG. 3, breakloose and prevail data depicted as 1-6, 11 and 12 correspond to Formulations 1-6, 11 and 12 above, respectively. Formulations 5, 6, 11 and 12 include the Toluene Diisocyanate Adduct Resin of Example A as an accelerator.

In FIG. 4, breakloose and prevail data depicted as 1-4, 17, 18, 23 and 24 correspond to Formulations 1-4, 17, 18, 23 and 24 above, respectively. Formulations 17, 18, 23 and 24 include the Toluene Diisocyanate Adduct Resin of Example A as an accelerator.

This data indicates that Formulations 5-28 in accordance with this invention exhibited similar breakloose and prevail properties at room temperature compared to traditional anaerobic (meth)acrylate-based adhesives when applied and cured on the substrates.

TABLE 14

Breakloose/180 Prevail (in lbs)

15 minutes
30 minutes
1 Hour
24 Hour

15
30
60
1440

Formula

Break
180 Prevail
Break
180 Prevail
Break
180 Prevail
Break
180 Prevail

1
+/−
62
5
72
4
101
12
132
19

6
1
17
5
12
7
10
14

2
+/−
82
9
94
61
118
67
139
127

2
7
17
35
11
53
7
71

3
+/−
54
7
53
6
72
6
168
26

8
0
11
0
13
0
8
4

4
+/−
53
6
58
6
80
5
128
106

11
1
12
0
7
1
67
35

5
+/−
53
6
66
6
77
5
214
44

8
0
7
0
12
1
18
18

6
+/−
51
6
60
6
100
9
240
245

11
1
7
0
19
11
45
35

7
+/−
50
6
51
6
65
4
127
26

7
0
5
1
12
3
8
6

8
+/−
59
6
61
5
93
27
163
124

12
0
13
3
22
27
13
32

9
+/−
60
6
80
4
113
11
205
28

9
0
14
2
10
6
24
3

TABLE 15

Breakloose/180 Prevail (in lbs)

15 minutes
30 minutes
1 Hour
24 Hour

15
30
60
1440

Formula

Break
180 Prevail
Break
180 Prevail
Break
180 Prevail
Break
180 Prevail

10
+/−
68
5
94
16
117
96
180
205

15
2
7
15
26
52
5
50

11
+/−
48
6
77
6
74
4
188
95

6
0
19
0
16
2
17
29

12
+/−
53
6
72
6
76
4
311
270

6
1
11
0
15
2
35
22

13
+/−
48
7
58
7
76
5
88
20

8
0
11
1
8
1
7
8

14
+/−
46
6
73
6
85
5
153
115

6
1
10
1
11
2
18
38

15
+/−
61
6
82
4
108
6
203
34

8
0
13
2
9
2
13
10

16
+/−
74
5
112
41
130
112
216
175

15
2
10
23
4
18
10
27

17
+/−
48
6
79
6
85
5
175
56

23
0
16
0
13
1
8
22

18
+/−
58
6
88
6
72
11
200
273

8
0
11
0
11
8
32
25

TABLE 16

Breakloose/180 Prevail (in lbs)

15 minutes
30 minutes
1 Hour
24 Hour

15
30
60
1440

Formula

Break
180 Prevail
Break
180 Prevail
Break
180 Prevail
Break
180 Prevail

19
+/−
57
6
74
6
65
4
129
29

10
0
13
0
4
2
10
7

20
+/−
72
6
99
5
71
30
175
137

10
1
16
1
36
22
15
40

21
+/−
73
6
95
4
102
8
220
40

4
0
11
1
5
2
29
11

22
+/−
74
6
104
35
98
25
151
103

5
0
19
21
9
4
15
49

23
+/−
63
6
65
6
75
5
228
135

14
0
9
0
7
2
26
43

24
+/−
71
6
65
6
96
6
286
298

20
1
7
1
15
1
22
39

25
+/−
57
6
59
6
70
6
90
13

8
1
8
1
15
0
12
3

26
+/−
66
7
73
6
68
6
166
136

9
0
12
0
7
0
15
61

TABLE 17

Breakloose/180 Prevail (in lbs)

15 minutes
30 minutes
1 Hour
24 Hour

15
30
60
1440

Formula

Break
180 Prevail
Break
180 Prevail
Break
180 Prevail
Break
180 Prevail

27
+/−
49
7
78
5
86
3
246
32

4
1
6
2
8
2
15
15

28
+/−
72
6
91
28

176
138

12
2
29
17

24
56

Cure accelerators for anaerobic curable compositions

Information

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Date Filed

Date Published

Inventors

Original Assignees

CPC

US Classifications

International Classifications

Abstract

Description

Claims