KR101840906B1 - Cyanoacrylate compositions - Google Patents

Abstract

In addition to the cyanoacrylate component, there is also provided a cyanoacrylate-containing composition comprising an anhydride and a maleimide-containing compound, an itaconimide-containing compound or an nadimide-containing compound. The cured products of the cyanoacrylate compositions of the present invention exhibit improved moisture resistance and / or heat resistance.

Description

[0001] CYANOACRYLATE COMPOSITIONS [0002]

The present invention relates to a cyanoacrylate-containing composition comprising an anhydride and a maleimide-containing compound, an itaconimide-containing compound or an nadimide-containing compound in addition to the cyanoacrylate component. The cured products of the cyanoacrylate compositions of the present invention exhibit improved moisture resistance and / or heat resistance.

Cyanoacrylate adhesive compositions are well known and widely used as fast-curing instant adhesives having a wide variety of applications. H.V. Coover, D.W. Dreifus and J.T. O'Connor, "Cyanoacrylate Adhesives" in Handbook of Adhesives, 27, 463-77, I. Skeist, ed., Van Nostrand Reinhold, New York, 3rd ed. (1990). ≪ / RTI > See also G.H. Millet, "Cyanoacrylate Adhesives" in Structural Adhesives: Chemistry and Technology, S.R. Hartshorn, ed., Plenun Press, New York, p. 249-307 (1986).

U.S. Pat. No. 5,288,794 (Attarwala) relates to an improved cyanoacrylate monomer adhesive formulation wherein at least three substituents on the aromatic ring are characterized and two or more of the substituents are electron-withdrawing An effective amount for enhancing the heat resistance of the polymerized adhesive of a mono, poly or heteroaromatic compound is provided. Examples of aromatic compounds include 2,4-dinitrofluorobenzene; 2,4-dinitrochlorobenzene; 2,4-difluoronitrobenzene; 3,5-dinitromaleimide-containing compounds, itaconimide-containing compounds or nadimide-containing compounds; 2-chloro-3,5-dinitro maleimide-containing compounds, itaconimide-containing compounds or nadimide-containing compounds; 4,4'-difluoro-3,3'-dinitrophenylsulfone; Pentafluoronitrobenzene; Pentafluoromaleimide-containing compounds, itaconimide-containing compounds or nadimide-containing compounds; alpha, alpha, alpha-2-tetrafluoro-p-tolunitrile and tetrachloroterephthalonitrile.

Prior to its discovery in the aforementioned 5,288,794 patent, there have been many attempts to improve the thermal stability of cyanoacrylate adhesive bonding.

For example, U.S. Pat. No. 3,832,334 relates to the addition of maleic anhydride, which is reported to produce cyanoacrylate adhesives with increased heat resistance while maintaining a fast cure rate (upon curing).

U.S. Pat. No. 4,196,271 relates to tri-, tetra- and higher carboxylic acids or anhydrides thereof, which are reported to be useful for improving the heat resistance of cured cyanoacrylate adhesives.

U.S. Patent No. 4,450,265 relates to the use of phthalic anhydride to improve the heat resistance of cyanoacrylate adhesives. More specifically, the 4,450,265 patent relates to an adhesive composition comprising a polymeric component comprising an ester of at least one 2-cyanoacrylic acid, and claims for it, wherein the composition is water Characterized in that it further comprises a specific proportion of phthalic anhydride effective to favorably affect the strength and / or durability of the adhesive bond formed from the composition under exposure. Effective amounts have been reported ranging from 0.1% to 5.0% by weight of the composition, e.g. 0.3% to 0.7% by weight. The 4,450,265 patent reported superiority of phthalic anhydride (less pronounced in the case of stainless steel wrap shear than in aluminum) compared to compositions where maleic anhydride was used without additives.

U.S. Pat. No. 4,532,293 relates to the use of benzophenone tetracarboxylic acids or anhydrides thereof and is described as providing cyanoacrylate adhesives with excellent heat resistance.

U.S. Patent No. 4,490,515 relates to cyanoacrylate compositions containing certain maleimide or nadimide compounds to improve high temperature strength properties.

Despite the current efforts to improve the heat resistance of the cyanoacrylate compositions and the state of the art, there is a need to improve the thermal stability of the cyanoacrylate compositions, There is a need to provide improved cure reaction products of the above cyanoacrylate compositions without damage and improved moisture resistance and / or heat resistance.

Thus, in addition to the cyanoacrylate component, there is provided a cyanoacrylate composition comprising an anhydride and a maleimide-containing compound, an itaconimide-containing compound or an nadimide-containing compound.

Containing compound, an anhydride and a maleimide-containing compound, an itaconimide-containing compound, or an nadimide-containing compound, as shown in the Examples, one is present but the other is absent, (1) 2) Compared to similar cyanoacrylate compositions in which the anhydride itself is present but the maleimide-containing compound, itaconimide-containing compound or nadimide-containing compound is not present, Such as moisture resistance and / or heat resistance.

The present invention also relates to a method of joining two substrates together, comprising applying the composition to at least one substrate and then joining the substrates together.

The present invention also relates to the reaction product of the composition of the present invention.

The present invention also relates to a process for the preparation of the composition of the invention and to a process for imparting improved moisture resistance and / or heat resistance to a cured product of a cyanoacrylate composition without impairing at least one of fixing time, stability or hue will be.

The present invention will be more fully understood by reading the following section entitled " DETAILED DESCRIPTION OF THE INVENTION ".

Brief Description of the Drawings Fig. 1 shows the results of a wet-aged wet sheeting for 100 hours and 1,000 hours on a grit blasted mild steel substrate for a cyanoacrylate composition having two different anhydrides and maleimide- And a bar graph comparing strength with LOCTITE 460, the control.
Figure 2 shows the results of thermal aging for 168 hours and 1000 hours on cyanoacrylate compositions having two different levels of anhydride and maleimide-containing compounds on a grit blasted mild steel substrate and then comparing the retained lap shear strength with the comparative Loctite 460 ≪ / RTI >

As described above, the present invention relates to a cyanoacrylate composition comprising an anhydride and maleimide-containing compound, an itaconimide-containing compound or an nadimide-containing compound in addition to the cyanoacrylate component.

The cyanoacrylate component includes cyanoacrylate monomers which may be selected with many substituents such as H ₂ C═C (CN) -COOR where R is C _{1 -15} alkyl, alkoxyalkyl, cycloalkyl, alkenyl, Aralkyl, aryl, allyl, and haloalkyl groups. Preferably, the cyanoacrylate monomer is selected from the group consisting of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate (such as n-butyl- Octyl cyanoacrylate, allyl cyano acrylate,? -Methoxyethyl cyano acrylate, and combinations thereof. Particularly preferred is? -Methoxyethyl cyanoacrylate.

The cyanoacrylate component is included in the composition in an amount ranging from about 50% to about 99.98% by weight of the total composition, preferably in a range from about 90% to about 99% by weight, particularly preferably in an amount of about 95% .

The anhydride typically should be an aromatic anhydride, such as phthalic anhydride, or a hydrogenated version thereof, such as 3,4,5,6-tetrahydrophthalic anhydride. Partially hydrogenated variants of the isomeric variants and phthalic anhydrides thereof can also be used. In addition, aliphatic anhydrides such as dimethyl maleic anhydride may also be used.

The maleimide-, nadimide- or itaconimide-containing compounds should be selected from the following structures IX to XI and combinations of two or more thereof:

Where m may range from 1 to 15, p may range from 0 to 15, each R ² is independently selected from hydrogen or lower alkyl, and J comprises an organic or organosiloxane radical Is a monovalent or multivalent moiety.

More specific examples of maleimide, nadimide and itaconimide include those in which m ranges from 1 to 6, p is 0, R ² is independently selected from hydrogen or lower alkyl,

Substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl containing at least one linker selected from hydrogen, alkyl or substituted alkyl, wherein each R is independently hydrogen, alkyl or substituted alkyl. Containing hydrocarbylene, a polysiloxane, a polysiloxane-polyurethane block copolymer, and combinations of two or more of the foregoing. Those corresponding to structure IX, X or XI, which are monovalent or multivalent radicals selected from water, and combinations of any two or more thereof.

As will be readily appreciated by those skilled in the art, one or more of the above-described monovalent or polyvalent groups may contain one or more of the above-described linkers to form the "J" appendage of the maleimide, nadimide or itaconimide group It is possible to use a wide variety of linkers such as, for example, alkyl, alkenyl, alkynyl, Heterocyclyl, oxyheterocyclic, thiocycloalkyl, thiocycloalkyl, thiocycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclyl, oxyheterocyclyl, thioalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycycloalkenyl, Heterocyclyl, heterocyclyl, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thio Wherein the heteroaryl is selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, Aminoalkenyl aryl, aminoalkenyl aryl, carboxyalkenyl aryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl, carboxyaryl, carboxyarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, Aminoalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, thioalkynyl, , Carboxyalkenylene, oxyalkynylene, thioalkynylene, aminoalkynylene, carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxyalkylene, Cycloalkylene, cycloalkylene, heterocycloalkylene, heterocycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene, carboxycycloalkenylene, oxyarylene, thioarylene, aminoarylene, carboxyarylene, oxyalkylarylene, thioalkylarylene , Aminoalkylarylene, carboxyalkylarylene, oxyarylalkylene, thioarylalkylene, aminoarylalkylene, carboxyarylalkylene, oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene , Oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxyarylalkynylene, oxyalkynylarylene , Thioalkynylarylene, aminoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxy Heteroaromatic, heteroaromatic, heteroaryl, heteroaryl, heteroatom-containing divalent or polycyclic moiety, oxyheteroatom-containing divalent or polycyclic moiety, thioheteroatom-containing divalent or polycyclic moiety, aminoheteroatom-containing Divalent or polycyclic moieties, carboxyheteroatom-containing divalent or polyvalent cyclic moieties, disulfides, sulfonamides, and the like can be produced.

In addition, in the maleimide, the nadimide and the itaconimide, m may range from 1 to 6 and p may range from 0 to 6, and J is selected from:

Saturated straight chain or branched chain alkyl containing up to 20 substituents on the alkyl chain or an aryl moiety optionally substituted as part of the backbone of the alkyl chain and having up to about 20 carbon atoms;

Siloxanes of the structure

Wherein each R ³ is independently hydrogen, alkyl or substituted alkyl, each R ⁴ is independently hydrogen, lower alkyl or aryl, d is in the range of 1 to 10, e is in the range of 1 to 10 , f is in the range of 1 to 50);

The polyalkylene oxide of Structure XII below

Wherein each R is independently hydrogen, alkyl or substituted alkyl, r is from 1 to 10, s is from 1 to 10, and f is from 1 to 50;

The aromatic group of Structure XIII

Wherein each Ar is a monosubstituted or disubstituted or trisubstituted aromatic or heteroaromatic ring having from 3 to 10 carbon atoms and Z is optionally saturated as a substituent on the alkylene chain or as part of the backbone of the alkylene chain A saturated straight chain alkylene or branched chain alkylene containing cyclic moieties;

The polyalkylene oxides of Structure XIV

Wherein each R is independently hydrogen, alkyl or substituted alkyl, r is 1 to 10, s is 1 to 10, and q ranges from 1 to 50;

Disubstituted or trisubstituted aromatic moieties of structure XV

Wherein each R is independently hydrogen, alkyl or substituted alkyl, t is in the range of from 2 to 10, u is in the range of from 2 to 10, and Ar is monosubstituted or disubstituted with from 3 to 10 carbon atoms Disubstituted or trisubstituted aromatic or heteroaromatic ring);

The aromatic groups < RTI ID = 0.0 >

Wherein each R is independently hydrogen, alkyl or substituted alkyl, t is 2 to 10, k is 1,2 or 3, g is in the range of 1 to about 50, each Ar is independently selected from the group consisting of It is as, E is -O- or -NR ⁵ - (wherein, R ⁵ is hydrogen or lower alkyl), W is a linear or branched alkyl, alkylene, oxyalkylene, being an ester or polyester);

Siloxanes of the structure

Wherein each R ³ is independently hydrogen, alkyl or substituted alkyl, each R ⁴ is independently hydrogen, lower alkyl or substituted aryl, each of d and e is 1 to 10, f is an integer from 1 to 50, being);

A polyalkylene oxide of the following structure XXII containing a substituent selected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl,

Wherein each R is independently hydrogen, alkyl or substituted alkyl, r and s are each in the range of 1 to 10, and f is 1 to 50;

The urethane group of Structure XXIII

(Wherein each of R ⁶ are independently hydrogen or lower alkyl, and each R ⁷ is independently from 1 to 18 carbon atoms to which an alkyl, aryl or arylalkyl group, each of R ⁸ is optionally substituted with Ar , from about 100 alkyl or alkyloxy chain having the following atoms in the chain, U is -O-, -S-, -N (R) - or -P (L) _1,2 - (where, R is the Each L is independently = O, = S, -OR, or -R, and v is 0 to 50;

Polycyclic alkenyl; or

And mixtures of any two or more thereof.

Particularly preferred maleimide-containing compounds include those having two maleimide groups with an aromatic group therebetween, such as phenyl, biphenyl, biphenyl or naphthyl linkages.

The anhydride should be used in an amount in the range of about 1.0 wt% or less, such as about 0.01 wt% to about 0.5 wt%, preferably about 0.05 wt% to about 0.2 wt%.

The maleimide-containing compound, itaconimide-containing compound, or nadimide-containing compound may contain up to about 5 weight percent, such as from about 0.01 weight percent to about 3 weight percent, such as from about 0.1 weight percent to about 2 weight percent, Particularly preferably in an amount of about 1% by weight.

Preferably, the anhydride should be used in an amount of from about 0.01% to about 0.5% by weight, and the maleimide-containing compound, itaconimide-containing compound, or nadimide- It should be used in an amount of% by weight.

The cyanoacrylate compositions of the present invention may also contain accelerators such as, for example, calixarenes and oxacaric selenes, sila crown, crown ethers, cyclodextrins, poly (ethylene glycol) di (meth) acrylates, ethoxylated hydrogenated compounds, May be included.

Calicylenes and oxalicarines are known and reported in the patent literature. See, for example, U.S. Patent Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461, each of which is expressly incorporated herein by reference in its entirety.

For example, with regard to calixarenes, the following structures are useful in the present invention:

In this regard, R < ¹ > is alkyl, alkoxy, substituted alkyl or substituted alkoxy; R ² is H or alkyl; n is 4, 6 or 8;

One of the particularly preferred calixarenes is tetrabutyltetra [2-ethoxy-2-oxoethoxy] calix-4-allene.

Crown ether hosts are known. Crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10 Crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown- Crown-5, 1,2,4-naphthyl-16-crown-5, 1,2-naphtho-15-crown- 18-crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6,1,2- Vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6,1,2-t- butyl- cyclohexyl- 18- crown- 6, asymmetrically dibenzo-22- 6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7. See U.S. Patent No. 4,837,260 (Sato), the disclosures of which are expressly incorporated herein by reference. A large number of sila crown have also been known and reported in the literature.

Specific examples of silacrown compounds useful in the compositions of the present invention include:

Dimethylsilyl-11-crown-4;

Dimethylsilyl-14-crown-5;

And dimethylsilyl-17-crown-6.

See, for example, U.S. Patent No. 4,906,317 (Liu), the disclosures of which are expressly incorporated herein by reference.

Many cyclodextrins may be used in connection with the present invention. For example, U.S. Patent No. 5,312,864 (Wenz), the disclosure of which is incorporated herein by reference in its entirety, as a hydroxyl group derivative of an alpha, beta or gamma -cyclodextrin that is at least partially soluble in cyanoacrylate Quot ;, which are expressly incorporated herein by reference, are appropriately selected for use in the present invention as the first promoter component.

For example, poly (ethylene glycol) di (meth) acrylates suitable for use in the present invention include those of the following structure:

Wherein n is in the range of more than 3, such as 3 to 12, particularly preferably n is 9. More specific examples include PEG 200 DMA (where n is about 4), PEG 400 DMA (where n is about 9), PEG 600 DMA (when n is about 14), and PEG 800 DMA ), Where the number (e.g., 400) represents the average molecular weight (i.e., 400 g / mol) of the glycol moiety excluding the two methacrylate groups in the molecule, expressed in g / mol. A particularly preferred PEG DMA is PEG 400 DMA.

Also suitable among the ethoxylated hydrogenated compounds (or ethoxylated fatty alcohols that may be used) may be selected from those having the following structure:

In the formula, C _m is a linear or branched alkyl or alkenyl may be straight Al, m is 1 to 30, for example an integer from 5 to 20, n is from 2 to 30, such as an integer from 5 to 15, R is H or it may be an alkyl, such as C _{1 -6} alkyl.

When used, the promoter encapsulated by the structure is present in the range of from about 0.01% to about 10% by weight of the total composition, preferably in the range of from about 0.1% to about 0.5% by weight, particularly preferably about 0.4% Should be included in the composition in such amounts.

Stabilizer packages are also commonly found in cyanoacrylate compositions. The stabilizer package may comprise one or more free radical stabilizers and anionic stabilizers, and the identity and amount of each is well known to those skilled in the art. See, for example, U.S. Patent Nos. 5,530,037 and 6,607,632 (the disclosures of each of which are hereby incorporated herein by reference).

The cyanoacrylate compositions of the present invention may contain other additives such as certain acidic substances (e.g., citric acid), thixotropic agents or gelling agents, thickening agents (e.g., polymethylmethacrylate), dyes, and combinations thereof .

In another aspect of the invention, a method of joining two substrates together is provided, comprising applying the composition described above to at least one substrate and then aligning the substrates together for a time sufficient to secure the adhesive.

In another aspect of the present invention, there is provided a reaction product of the composition described above.

In another aspect of the present invention, a method of making the composition described above is provided. The process comprises providing a cyanoacrylate component and blending it with an anhydride and a maleimide-containing compound, an itaconimide-containing compound or an nadimide-containing compound.

The invention will be further illustrated by the following examples.

Example

All samples were prepared by mixing together the above-mentioned components for a time period of about 30 minutes.

Referring to Table 1 above, seven samples were prepared using the beta -methoxyethyl cyanoacrylate base. Sample No. 1 was used as a control without the addition of anhydride and maleimide; Samples Nos. 2 and 3 were used as controls in which maleimide was added at different levels and Samples Nos. 4 and 5 were used as controls in which the anhydrides were added at different levels. Sample Nos. 6 and 7 included a combination of anhydride and maleimide with constant anhydride levels.

Table 2 below shows the results of humidity and thermal aging of these seven samples. More specifically, each of the seven samples was applied to a grit blasted mild steel lap shear substrate offset by a further grit blasted mild steel lap shear substrate so that a bonded line superimposed on the lap shear assembly could be formed . Five specimen copies were prepared for each sample. A set of assemblies were placed under humidity conditions for the indicated times, and then the opposite ends of the assembly were forced to separate them laterally to determine the lap shear strength. Other sets of assemblies were placed under thermal aging conditions for the indicated times and the lap shear strength was determined in the same manner.

As can be seen from Table 2, the strength retained between the initial measurement for samples Nos. 6 and 7 and the measurement after 168 hours of humidity aging, and the strength observed after 168 hours of thermal aging for samples Nos. 6 and 7, ≪ / RTI > compared to Sample Nos. 1-3 and 5, respectively.

Referring to the following Table 3, eight samples were prepared using the? -Methoxyethyl cyanoacrylate base as shown in Table 1 above. Sample Nos. 8 and 9 were used as controls without the addition of anhydride maleimide; Sample No. 11 was used as the maleimide added control and Sample No. 10 was used as the control with the anhydrous addition. Sample Nos. 12-15 contained different anhydrides and maleimide levels comprised a combination of maleic anhydride and certain anhydrides.

Table 4 below shows the results of humidity and thermal aging of these seven samples. More specifically, as in the samples recorded in Table 2, each of the 10 samples (8 of Table 3 and commercially available Loctite 460 and 408) was placed on the lap shear assembly so that the overlap lines in the lap shear assembly could be formed Another grit blasted mild steel lap shear substrate was applied to a grit blasted mild steel lap shear substrate which was offset thereon. Five specimen copies were prepared for each sample. A set of assemblies was placed under humidity conditions for the indicated times, then the opposing ends of the assemblies were forced to separate them laterally to determine the lap shear strength. Other sets of assemblies were placed under thermal aging conditions for the indicated times and the lap shear strength was determined in the same manner.

As can be seen from Table 4, the strength retained between the initial measurement and the measurement after 100 hours and 1000 hours of humidity aging for Sample Nos. 12-15 and 168 hours and 1000 hours for Sample Nos. 12 and 14-15 All of the later observed intensities exhibited a surprising increase compared to any of Sample Nos. 8-11 and 16-17. See also FIGS. 1 and 2, respectively, for the bar graphs of selected humidity and thermal aging data of these samples.

Typical ethyl cyanoacrylate compositions have an upper operating temperature of about 80 ° C. That is, when the temperature is exceeded, the cured cyanoacrylate composition often exhibits a sacrifice of bond strength at the onset of decomposition. Additive chemicals (such as phthalic anhydride) could increase this limit, but cyanoacrylate compositions with such additives have the drawback of an increase in fixation time, an undesirable phenomenon.

The use of a maleimide-containing compound or an itaconimide-containing compound or an nadimide-containing compound together with an anhydride allows the formulation of cyanoacrylate compositions to exhibit improved humidity and / or thermal aging resistance upon curing.

Claims (19)

(a) a cyanoacrylate component,
(b) anhydrides of dimethyl maleic anhydride in an amount in the range of 0.01 wt% to 1 wt%, and
(c) a maleimide-containing compound in an amount ranging from 0.01% by weight to 3% by weight, an itaconimide-containing compound or a nordium-containing compound
≪ / RTI > The composition of claim 1, wherein the anhydride is phthalic anhydride. The composition of claim 1, further comprising a stabilizing amount of an acidic stabilizer and a free radical inhibitor. The composition of claim 1, wherein the cyanoacrylate component is selected from materials of the structure H ₂ C═C (CN) -COOR, wherein R is C _1-15 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, Aryl, allyl, and haloalkyl groups. 2. The composition of claim 1, wherein the cyanoacrylate component comprises beta-methoxyethyl-2-cyanoacrylate. 3. The composition of claim 1, further comprising a promoter component selected from the group consisting of calixarenes, oxalicylenes, sila crowns, cyclodextrins, crown ethers, poly (ethylene glycol) di (meth) acrylates, ethoxylated hydrogenated compounds, ≪ / RTI > 7. The composition of claim 6, wherein the calixarene is tetrabutyltetra [2-ethoxy-2-oxoethoxy] calix-4-arene. 7. The composition of claim 6 wherein the crown ether is selected from the group consisting of 15-crown-5, 18-crown-6, dibenzo-18- crown-6, benzo-15- crown- Crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24 -Crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl- -Crown-5, 1,2-methyl-benzo-18-crown-6,1,2-methylbenzo-5,6-methylbenzo-18- Vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6,1,2-t-butyl- cyclohexyl-18- crown- 6, asymmetric dibenzo Crown-6, 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7, and combinations thereof. 7. The composition of claim 6, wherein the poly (ethylene glycol) di (meth) acrylate is of the structure:

Wherein n is greater than three. The composition of claim 1, further comprising an additive selected from the group consisting of impact modifiers, thixotropic agents, thickeners, dyes, and combinations thereof. A reaction product of the composition according to claim 1. Applying the cyanoacrylate adhesive composition according to claim 1 to at least one substrate, and
Joining the substrates together for a time sufficient to secure the adhesive
≪ / RTI > wherein the two substrates are bonded together. Providing a cyanoacrylate component, and
Maleic anhydride, an anhydride of dimethyl maleic anhydride in an amount within the range of 0.01 wt% to 1 wt%, and a maleimide-containing compound in an amount within a range of 0.01 wt% to 3 wt%, an itaconimide-containing compound Or the nadimide-containing compound
Lt; RTI ID = 0.0 > 1, < / RTI > Providing a cyanoacrylate composition; And
A maleic anhydride-containing compound in an amount within a range of 0.01 wt% to 1 wt%, an anhydride of dimethyl maleic anhydride, and an amount of an maleimide-containing compound in an amount within a range of 0.01 wt% to 3 wt% Or the nadimide-containing compound
/ RTI > and / or < RTI ID = 0.0 > heat < / RTI > resistance to the cured product of the cyanoacrylate composition. An improvement is an anhydride of dimethyl maleic anhydride in an amount ranging from 0.01% to 1% by weight based on the cyanoacrylate component, and a maleimide-containing compound in an amount ranging from 0.01% to 3% by weight, Containing compound or an nadimide-containing compound to improve the moisture resistance and / or heat resistance of the cured reaction product of the cyanoacrylate composition. The composition of claim 1, wherein the anhydride is present in an amount ranging from 0.05% to 0.2% by weight. The composition of claim 1 wherein the maleimide-containing compound, itaconimide-containing compound, or nadimide-containing compound is present in an amount ranging from 0.1% to 2% by weight. The composition of claim 1, wherein the anhydride is present in an amount of from 0.01% to 0.5% by weight and the maleimide-containing compound, itaconimide-containing compound or nadimide- ≪ / RTI > The composition of claim 1, wherein the anhydride is present in an amount of 0.1 wt% and the maleimide-containing compound, itaconimide-containing compound, or nadimide-containing compound is present in an amount of 2 wt%.

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