Toughened Cyanoacrylate Compositions

US007687561B1 (12) Ulllted States Patent (10) Patent No.: US 7,687,561 B1 Misiak (45) Date of Patent: *Mar. 30, 2010 (54) TOUGHENED CYANOACRYLATE 4,556,700 A 12/1985 Harris etal. COMPOSITIONS 4,574,097 A * 3/1986 Honeycutt ............... .. 428/36.1 4,622,414 A 11/1986 McKerVey (75) Inventor: Hanns R. Misiak, Athy (IE) : 3:33;? :t1'a 1 (73) Assignee: Loctite (R&D) Limited, Dublin (113) : 1S{:‘:f:tea‘f*1~ . . . . . 4,855,461 A 8/1989 H ' ( * ) Not1ce: Subject to any d1sc1a1mer, the term ofth1s 4 906 317 A 3/1990 Dims Patent is extended er adjusted under 35 5,234,986 A * 8/1993 McBride ................... .. 524/505 USC 15409) by 393 days 5,312,864 A 5/1994 Wenz et al. . . . . . 6,084,029 A * 7/2000 McGee ...................... .. 525/66 Th1s patent 1s subject to a ter1n1nal d1s- 5,294,529 B1 9/2001 O’Dwyer et 31, claimer. 6,475,331 B1 11/2002 O’C0nn0r et al. 6,677,279 B2 * 1/2004 Patil et al. ............... .. 525/92 R (21) Appl. No.: 11/538,970 OTHER PUBLICATIONS (22) Filed: Oct 5, 2006 H.V. C2070V:2:t;117., ‘I‘CSy12(1r1-0acry1a\t/e ACIl\IheSlVeSC’{l1I{1I-{d1:ld1fl00/CNY0](3Am:Jh(C3l_ sives, , - , . e1st, et., an ostran e1n 0 , e . (51) Int‘ Cl‘ (c1§01\/1'11 1 “C 1 1 Adh ' 3 ' sz 1 [Ad/z ' . . l C , y3.Il03.CI'y 3. C GSIVCS lI1 ruc um eszves: C08K 5/07 (200601) . . . Chemistry and Technology, S.R. Hartshorn, ed., Plenun Press, NY, p. (52) U.S. Cl. ..................... .. 524/357, 524/206, 524/356, 249307 (1986). 524/361; 524/362; 524/3633 524/5023 524/5423 http://inhancepr0ducts.c0m/techn010gy.htm1, Aug. 10, 2006. 524/556; 524/570; 524/581; 524/592; 525/295 * Citedb examiner (58) Field of Classification Search ............... .. 524/356; y 525/295 Primary Examiner—Mark Eashoo See application file for complete search history. Assistant Examiner—Nicole M Buie-Hatcher 74 A A F’ —S C. B (56) References Cited ( ) ttorney, gent, or zrm teVen auman U.S. PATENT DOCUMENTS 4,105,715 A 8/1978 Gleave 4,170,585 A 10/1979 Motegiet al. 4,440,910 A 4/1984 O’C0nn0r 4,450,265 A 5/1984 Harris (57) ABSTRACT The present invention relates to toughened cyanoacrylate compositions. 13 Claims, N0 Drawings US 7,687,561 B1 1 TOUGHENED CYANOACRYLATE COMPOSITIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to toughened cyanoacrylate compo- sitions. 2. Brief Description of Related Technology Cyanoacrylate compositions are well known as one com- ponent reactive adhesives, which are quick bonding and suit- able for applications on variety of substrates. See 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). 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. 4,440,910 (O’Connor) pioneered rubber toughened cyanoacrylate compositions through the use of certain organic polymers as toughening additives that are elastomeric, i.e., rubbery, in nature. The ’910 patent is thus directed to and claims a curable adhesive comprising a sub- stantially solvent-free mixture of: (a) a cyanoacrylate ester, and (b) about 0.5% to about 20% by weight of an elastomeric polymer. The elastomeric polymer is selected from elasto- meric copolymers of a lower alkene monomer and (i) acrylic acid esters, (ii) methacrylic acid esters or (iii) vinyl acetate. More specifically, the ’910 patent notes that as toughening additives for cyanoacrylates, acrylic rubbers; polyester ure- thanes; ethylene-vinyl acetates; fluorinated rubbers; iso- prene-acrylonitrile polymers; chlorosulfonated polyethyl- enes; and homopolymers of polyvinyl acetate were found to be particularly useful. The elastomeric polymers are described in the ’910 patent as either homopolymers of alkyl esters of acrylic acid; copolymers of another polymerizable monomer, such as lower alkenes, with an alkyl or alkoxy ester of acrylic acid; and copolymers of alkyl or alkoxy esters of acrylic acid. Other unsaturated monomers which may be copolymerized with the alkyl and alkoxy esters of acrylic include dienes, reactive halo gen-containing unsaturated compounds and other acrylic monomers such as acrylamides. One group of elastomeric polymers are copolymers of methyl acrylate and ethylene, manufactured by DuPont, under the name of VAMAC, such as VAMAC N123 and VAMAC B-124. VAMAC N123 and VAMAC B-124 are reported by DuPont to be a master batch of ethylene/acrylic elastomer. Henkel Corporation (as the successor to Loctite Corpora- tion) has sold for a number of years since the filing of the ’9 1 0 patent rubber toughened cyanoacrylate adhesive products under the tradename BLACK MAX, which employ as the rubber toughening component the DuPont materials called VAMAC B-124 and N123. In addition, Henkel has sold in the past clear and substantially colorless rubber toughened cyanoacrylate adhesive products, namely, LOCTITE 4203, 4204 and 4205, which employ as the rubber toughening com- ponent the DuPont material, VAMAC G. Notwithstanding the state of the art, it would be desirable to provide alternative toughened cyanoacrylates for a number of reasons, including providing the end user with additional product choices, hedging against raw material supply inter- ruptions or shortages, or regulatory requirements that ham- pers widespread usage of certain raw materials. SUMMARY OF THE INVENTION The present invention is directed to a toughened cyanoacrylate composition which includes, beyond the 10 15 20 25 30 35 40 45 50 55 60 65 2 cyanoacrylate component, a ketone containing material com- ponent, such as one within the following structures: / where ‘R is O O // \\ , /C or C\ and R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substituted by carbonyl functionality and/ or functionalized with a C1 to C3 alkoxy group; R>: where R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substi- tuted by carbonyl functionality and/or functionalized with a C1 to C3 alkoxy group, and R* is H, methyl, or ethyl. In these structures, m, n and p together equal 100 percent. More spe- cifically, m and n are each between 7 and 15 percent and together are between 17.5 and 26 percent. Of course, p rep- resents that percent value substrated from 100 percent. Particularly desirable ketone containing materials accord- ing to these structures include terpolymers of carbon monox- ide, unsaturated ester (e.g., a vinylester or an ester of an unsaturated acid) and ethylene, for instance poly(ethylene- co-vinylacetate-co-carbon monoxide) (“PEVACO”), such as is available commercially from Aldrich or DuPont under the tradename ELVALOY 741, ELVALOY 742 and ELVALOY 4924; and poly(ethylene-co-butylacrylate-co-carbon monox- ide) (also known as a butylacrylate/ethylene/carbon monox- ide co-polymer, “BAECO”), such as is available commer- cially from Aldrich or DuPont under the tradenames ELVALOY HP661, ELVALOY HP662 and ELVALOY HP771; and homopolymers of a vinylketone, such as poly (methylvinylketone) (“PMVK”). In another aspect, the present invention is directed to a method of bonding two or more substrates including the steps of providing at least two substrates; applying, onto at least a portion of a surface of one or both of the at least two sub- strates, a cyanoacrylate composition as noted above; contact- ing the surfaces of the at least two substrates having the cyanoacrylate composition therebetween; and curing the cyanoacrylate composition. In still another aspect, the present invention is directed to a bonded assembly including: a first substrate having a first surface; another substrate having a second surface; and a cured cyanoacrylate composition disposed between the first and second surfaces, the composition having included prior to cure: a cyanoacrylate component and the polymer component as noted above. US 7,687,561 B1 3 In yet another aspect, the present invention is directed to a method of preparing the cyanoacrylate composition as noted above. DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a toughened cyanoacrylate composition, which includes, beyond the cyanoacrylate component, a ketone containing material. The cyanoacrylate component includes at least one 0t-cy- anoacrylate monomer of the formula: H2C=C—COOR1 CN where R1 represents a straight chain or branched chain alkyl group having 1 to 12 carbon atoms (which may be substituted with a substituent such as a halogen atom or an alkoxy group), a straight chain or branched chain alkenyl group having 2 to 12 carbon atoms, a straight chain or branched chain alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group, an aralkyl group or any aryl group. Specific examples of R1 are a methyl group, an ethyl group, an n-propyl group, an isopro- pyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an allyl group, a methallyl group, a crotyl group, a propargyl group, a cyclohexyl group, a benzyl group, a phenyl group, a cresyl group, a 2-chloroethyl group, a 3-chloropropyl group, a 2-chlorobutyl group, a trifluoroethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group and a 2-ethoxyethyl group. Ethyl cyanoacrylate is a particularly desirable choice for use in the inventive compositions. A single ot-cyanoacrylate monomer or a mixture of two or more of these ot-cyanoacrylate monomers can be used. Gen- erally, the above ot-cyanoacrylate monomer used alone as an adhesive, and one or more components such as those set forth below, are used to formulate a commercial composition. The additional components includes, but are not limited to, accel- erators; anionic polymerization inhibitors; radical polymer- ization inhibitors; additives, such as plasticizers, heat stabi- lizers and toughening agents; and/or perfumes, dyes, and pigments. A suitable amount of ot-cyanoacrylate monomer present in the inventive compositions is from about 50 to 99.5% by weight, such as 60 to 95% by weight, desirable 85% by weight, based on the total weight of the composition. The ketone containing material may be within the follow- ing structures: where ‘R is O O 7 or \\c » _O/ \ / \O_ 10 15 20 25 30 35 40 45 50 55 60 65 4 and R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substituted by carbonyl functionality and/ or functionalized with a C1 to C3 alkoxy group; R>: where R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substi- tuted by carbonyl functionality and/or functionalized with a C1 to C3 alkoxy group, and R* is H, methyl, or ethyl. In these structures m and n are each between 7 and 15 percent and together are between 17.5 and 26 percent. Of course, p rep- resents that percent value subtracted from 100 percent. Particularly desirable ketone containing material accord- ing to these structures include those prepared from terpoly- mers of carbon monoxide, unsaturated ester (e.g., a vinylester or an ester of an unsaturated acid) and ethylene, for instance poly(ethylene-co-vinylacetate-co-carbon monoxide) (“PE- VACO”), such as is available commercially under the trade- names ELVALOY 741 , ELVALOY 742 and ELVALOY 4924; and poly(ethylene-co-butylacrylate-co-carbon monoxide) (also known as butylacrylate/ethylene/carbon monoxide co- polymer, “BAECO”), such as is available commercially under the tradenames ELVALOY HP661, ELVALOY HP662 and ELVALOY HP771 ; and homopolymers of a vinylketone, such as poly(methylvinylketone) (“PMVK”). The ketone containing material should be used in the present invention in amounts of about 0.5% to about 30%, for instance about 2.5% to about 20%, such as about 5% to about 15%, by weight based on the total weight of the composition. An anionic polymerization inhibitor is generally added to ot-cyanoacrylate compositions in an amount from about 0.0001 to 10% by weight based on the total weight of the composition, to increase the stability of the composition dur- ing storage. Examples of useful inhibitors include sulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride, organic sultone inhibitors, boron trifluoride and methane sul- fonic acid, aromatic sulfonic acids, aliphatic sulfonic acids, and sulfones. The amount of inhibitor will suitably be any convenient amount in order to slow down cure of the compo- sition. Desirably, inhibitors of anionic polymerization are present at about 0.0001% to about 0.1% by weight based on the total weight of the composition. A radical polymerization inhibitor is generally added to ot-cyanoacrylate compositions as well, in an amount from about 0.001 to 2.0%, particularly 0.03 to 0.5%, based on the total weight of the composition, for the purpose of capturing radicals which are formed by light during storage. Such inhibitors are ordinarily of the phenolic type include, for example, hydroquinone and hydroquinone monomethyl ether. Other inhibitors suitable for use herein include buty- lated hydroxytoluene and butylated hydroxyanisole. A thickener may be added to increase the viscosity of the ot-cyanoacrylate composition. Various polymers can be used as thickeners, and examples include poly(methyl methacry- late) (“PMMA”), poly(ethyl methacrylate) (“PEMA”), meth- acrylate-type copolymers, acrylic rubbers, cellulose deriva- tives, polyvinyl acetate and poly(0t-cyanoacrylate). A suitable amount of thickener is generally about 0.01 to 30% US 7,687,561 B1 5 by weight, preferably 5 .0 to 25% by weight, based on the total weight of the cyanoacrylate composition. Plasticizers may also be added to the cyanoacrylate com- ponent to further aid in durability and impact, heat, and mois- ture resistance. The plasticizer is preferably present in an amount of about 0.05% to about 25%, more preferably about 1% to about 15%, such as about 5% to about 10%, by weight based on the total weight of the composition. Perfumes, dyes, pigments, and the like may be added to the inventive composition depending on use purposes in amounts which do not adversely affect the stability of the 0t-cy- anoacrylate monomer. The use of such additives is within the skill of those practicing in the cyanoacrylate adhesive art and need not be detailed herein. Accelerators that may be useful in the cyanoacrylate com- positions include for example calixarenes, oxacalixarenes, and combinations thereof. Of the calixarenes and oxacalix- arenes, many are known, and are reported in the patent litera- ture. See e.g. U.S. Pat. Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461, the disclosures of each of which are hereby expressly incorporated herein by refer- ence. Another potentially useful accelerator component is a crown ether. A host of crown ethers are known. For instance, examples which may be used herein either individually or in combination, or in combination with the calixarenes and oxacalixarenes described above include 1 5 -crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15 -crown-5, dibenzo -24-crown-8, dibenzo-30-crown-10, tribenzo-18- crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclo- hexyl-12-crown-4, 1,2-decalyl-15 -crown-5, 1,2-naphtho-15 - crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-methyl-benzo-18- crown-6, 1,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vi- nylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6 and 1 ,2-benzo-1,4-benzo-5-oxy- gen-20-crown-7. See U.S. Pat. No. 4,837,260 (Sato), the dis- closure of which is hereby expressly incorporated here by reference. Other suitable accelerators include those described in U.S. Pat. No. 5,312,864 (Wenz), which are hydroxyl group deriva- tives of an (X-, [3- or y-cyclodextrin which is at least partly soluble in the cyanoacrylate; in U.S. Pat. No. 4,906,317 (Liu), which are silacrown compounds to accelerate fixturing and cure on de-activating substrates such as wood, examples of which are within the following structure: R4 I R3—si—oj |— (ocH2cH),. I R5 where R3 and R4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer, R5 is H or CH3 and n is an integer of between 1 and 4. Examples of suitable R3 and R4 groups are R groups, alkoxy groups such as methoxy, and aryloxy groups such as phenoxy. The R3 and R4 groups may contain halogen or other sub stituents, an example being trifluoropropyl. However, groups not suitable as R4 and R5 groups are basic groups such as amino, substituted amino and alkylamino. 10 15 20 25 30 35 40 45 50 55 60 65 6 Specific examples of silacrown compounds useful in the inventive compositions include: H3C\Si/CH3 £O/ \Oj O O dimethylsila-1 1 -crown-4; WW. {I o 0 \Si/ /\ H3C CH3 dimethylsila-14-crown-5; and dimethylsila-17-crown-6. The accelerator component should be included in the com- positions in an amount within the range of from about 0.1% to about 10%, with the range of about 0.5% to about 5% being desirable, and about 0.1% to about 1% by weight based on the total weight of the composition being particularly desirable. See e.g. U.S. Pat. Nos. 4,170,585; 4,450,265; 6,294,629; and 6,475,331, the contents of which are all incorporated herein by reference. It may also be desirable to co-toughen the inventive com- position with a secondary co-toughening component, such as those disclosed inU.S. Pat. No. 4,440,910 (O’Connor), which pioneered rubber toughened cyanoacrylate compositions through the use of certain organic polymers as toughening additives that are elastomeric, i.e., rubbery, in nature. The ’910 patent is thus directed to and claims a curable adhesive comprising a substantially solvent-free mixture of: (a) a cyanoacrylate ester, and (b) about 0.5% to about 20% by weight of an elastomeric polymer. The elastomeric polymer is selected from elastomeric copolymers of a lower alkene monomer and (i) acrylic acid esters, (ii) methacrylic acid esters or (iii) vinyl acetate. More specifically, the ’910 patent notes that as toughening additives for cyanoacrylates, acrylic US 7,687,561 B1 7 rubbers; polyester urethanes; ethylene-vinyl acetates; fluori- nated rubbers; isoprene-acrylonitrile polymers; chlorosul- fonated polyethylenes; and homopolymers of polyvinyl acetate were found to be particularly useful. The elastomeric polymers are described in the ’910 patent as either homopolymers of alkyl esters of acrylic acid; copolymers of another polymerizable monomer, such as lower alkenes, with an alkyl or alkoxy ester of acrylic acid; and copolymers of alkyl or alkoxy esters of acrylic acid. Other unsaturated monomers which may be copolymerized with the alkyl and alkoxy esters of acrylic include dienes, reactive halo gen-containing unsaturated compounds and other acrylic monomers such as acrylamides. One group of elastomeric polymers are copolymers of methyl acrylate and ethylene, manufactured by DuPont, under the name of VAMAC, such as VAMAC N123 and VAMAC B-124. VAMAC N123 and VAMAC B-124 are reported by DuPont to be a master batch of ethylene/acrylic elastomer. Henkel Corporation (as the successor to Loctite Corpora- tion) has sold for a number of years since the filing of the ’9 1 0 patent rubber toughened cyanoacrylate adhesive products under the tradename BLACK MAX, which employ as the rubber toughening component the DuPont materials called VAMAC B-124 and N123. Thus, these DuPont materials may be used to co-toughen the inventive composition. In addition, Henkel has sold in the past clear and substantially colorless rubber toughened cyanoacrylate adhesive products, namely, LOCTITE 4203, 4204 and 4205, which employ as the rubber toughening component the DuPont material, VAMAC G. VAMAC G may be used to co -toughen the inventive compo- sition, as well. VAMAC VCS rubber appears to be the base rubber, from which the remaining members of the VAMAC product line are compounded. VAMAC VCS is a reaction product of the combination of ethylene, methyl acrylate and monomers hav- ing carboxylic acid cure sites, which once formed is then substantially free of processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine. Recently, DuPont has provided to the market under the trade designation VAMAC VMX 1012 andVCD 6200, which are rubbers made from ethylene and methyl acrylate. It is believed that the VAMAC VMX 1012 rubber possesses little to no carboxylic acid in the polymer backbone. Like the VAMAC VCS rubber, the VAMAC VMX 1012 and VCD 6200 rubbers are substantially free of processing aids such as the release agents octadecyl amine, complex organic phos- phate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine, noted above. 10 15 20 25 30 35 40 45 50 8 The inventive composition may be co-toughened with a rubber toughening component having (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), which once the reaction products and/ or dipolymers are formed are then substantially free of processing aids, such as the release agents octadecyl amine (reported by DuPont to be available commercially from Akzo Nobel under the tradename ARMEEN 18D), complex organic phosphate esters (reported by DuPont to be available commercially from R.T. Vanderbilt Co., Inc. under the tradename VANFRE VAM), stearic acid and/ or polyethylene glycol ether wax, and anti-oxidants, such as substituted diphenyl amine (reported by DuPont to be available commercially from Uniroyal Chemical under the tradename NAUGARD 445). Commercial examples of such rubber tougheners include VAMAC VMX 1012 and VCD 6200 rubbers, and these may be used too. Preparation of the compositions and products of the present invention can be achieved by mixing the polyketone material into the cyanoacrylate composition at room tempera- ture. Mixing is performed for a time sufficient to disperse or dissolve the polyketone material into the cyanoacrylate com- position, which can vary depending on the batch size. Gen- erally, only seconds or minutes are required to achieve the desired blending in of the polymer material. The cyanoacrylate compositions of the present invention are useful in bonding two or more substrates. A sufficient portion of the composition may be placed on a surface of one of the two or more substrates. The other substrate is then positioned adjacent to the cyanoacrylate composition and the two substrates are placed in contact to form an assembly, upon curing of the cyanoacrylate. The following non-limiting examples are intended to fur- ther illustrate the present invention. EXAMPLES Referring to Tables 1A-1C below, cyanoacrylate composi- tions labeled Sample Nos. 1-21 were prepared by incorporat- ing into the specified cyanoacrylate the respective amounts indicated of toughening agent and thickener, with mixing for a period of time of about 0.5 to 1 hour at a temperature of about 50-85° C. The samples were also stabilized at the parts per million (“ppm”) level with acid stabilizers and free radical stabilizers. EtCA represents ethyl-2-cyanoacrylate; MeCA represents methyl cyanoacrylate; and MeOEtCA represents methoxyethyl-2-cyanoacrylate. TABLE 1A Components Sample No./Amt. (wt. %) Type Identity 1 2 3 4 5 6 7 8 CA EtCA Bal. — — Bal. Bal. Bal. Bal. Bal. MeCA — Bal. — — — — — MeOEtCA — — Bal. — — — — Toughening PEVACO — — — 10 10 — — — Agent BAECO — — — — 8 10 — ELVALOY 8.5 HP662 Thickener PMMA US 7,687,561 B1 TABLE 1B 10 Components Sample No. /Amt. Wt. % Type Identity 9 10 11 12 13 14* CA E CA MeCA MeOEtCA ELVALOY Bal. Bal. Bal. Tou ghenin g 15 16 17 18 H ’771 ELVALOY H ’742 PVMK ELVALOY H ’662 ELVALOY H ’661 PMMA Agent 7.5 10 10 Thickener *contains 150 ppm o t11e adhesion promoter, itaconic anhydride TABLE 1C Components Sample No./Amt. Wt. % Type Identity 19 20 21* CA MeOEtCA Bal. Bal. Bal. Toughening ELVALOY 8.5 10 — Agent HP771 ELVALOY — — 8 HP4924 Thickener PMMA — 5 6 PEMA 4.0 — — *contains 150 ppm of tlie adhesion promoter, itaconic anhydride Below in Tables 2A-2B are data for fixture time and T peel strength (room temperature and after heat ageing) captured for the samples set forth in Tables 1A-1C. 25 30 35 10 In Tables 2A and 2B, fixture time on EPDM rubber and T peel strength on aluminum and mild steel for cyanoacrylate compositions prepared with several different polyketone tougheners on both aluminum and steel substrates are reported. The results set forth in Tables 2A and 2B indicate that fixture times on EPDM rubber were modestly higher, though within the commercially acceptable working range, for the inventive compositions as compared with compositions with- out the inventive toughener. As regards T peel strength, mea- surements were made at room temperature and after two hours of heat ageing at a temperature of 150° C. The sub- strates used in the T peel strength evaluation were either aluminum or mild steel. Improved results were observed for the inventive composition at room temperature and after heat ageing. TABLE 2A Sample No. Physical Properties 1 2 3 4 5 6 7 8 9 10 11 Fixture Time (Secs) EDPM 15 15 20 45 45 35 40 30 30 30 30 T Peel Strength (N/mm2) Aluminum 0.2 0.2 0.3 2.0 1.2 — — — — — — Steel [mild] 0.4 0.2 0.2 1.6 3.8 1.5 1.6 1.1 1.0 1.0 1.0 T Peel Strength Aluminum 0.0 0.0 1.0 — — — — 1.0 — — 2hrs @ 150° C. (N/mm2) Steel [mild] 0.0 0.0 1.3 — 1.0 1.5 — 1.2 — — TABLE 2B Sample No. Physical Properties 12 13 14 15 16 Fixture Time (Secs) EDPM 22 40 35 30 45 T Peel Strength (N/mm2) Aluminum 1.3 — — 2.3 Steel [mild] 3.0 1.0 3.0 2.1 2.3 T Peel Strength Aluminum — 1.2 — — 2 hrs @ 150° C. (N/mm2) Steel [mild] — 1.0 — — 17 18 19 20 21 30 40 25 35 35 — 2.5 1.8 — — 1.7 2.3 1.4 1.7 4.3 — — — — 1.0 — — — — 1.0 US 7,687,561 B1 11 In Table 3 below, cyanoacrylate compositions labeled Sample Nos. 22-33 were prepared to evaluate the polyketone tougheners used in the inventive composition as contrasted to other tougheners and the polyketone tougheners as used in combination with such other tougheners. Each of these samples was stabilized at the PPM level with added acidic stabilizer. TABLE 3 12 R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substituted by carbonyl functionality and/or functionalized with a C1 to C3 alkoxy group; and the sum of m, n and p is 100 percent. 2. The composition of claim 1, wherein said polyketone material is a member selected from the group consisting of terpolymers of carbon monoxide, unsaturated ester and eth- Sample No. wt. % Physical Properties 22 23 24 25 26 27 CA EtCA MeOEtCA Bal. Bal. Bal. Bal. Bal. Bal. 28 Bal. 29 30 31 32 33 Bal. Bal. Bal. Bal. Bal. Allyl CA BAECO PEVACO VAMAC vcs 5500 ELVALOY 40 6.0 2.0 6.0 8.0 2.0 Tou ghenin g Agent 6.0 4.0 6.0 2.0 6.0 2.0 6.0 2.0 6.0 2.0 6.25 HP662 ELVALOY HP771 PMMA Calixarene Crown Ether Thickener Curing Accelerator 2.5 2.5 0.2 0.5 0.2 Below in Table 4 are data for fixture time and T peel strength captured from the samples set forth in Table 3. TABLE 4 6.0 6.0 1.0 0.12 0.12 0.12 0.12 0.12 ylene; and poly(ethylene-co-butylacrylate-co-carbon mon- oxide). Sample No. Physical properties 22 23 24 25 26 27 28 Fixture Time EPDM 70 80 70 50 75 80 60 (Secs) T Peel Aluminum 2.2 2.1 3.0 2.2 1.7 1.6 1.5 Strength Steel [mild] 2.8 1.8 2.2 1.1 1.3 1.4 1.2 (N/IHIH2) The results in Table 4 indicate among other things that the use of the co-toughenerVAMAC VCS 5500 in the cyanoacry- late composition with PEVACO and without added thickener, demonstrated a T peel strength on aluminum of over 2.0 N/mmz in each measured instance. What is claimed is: 1. A cyanoacrylate composition comprising: at least one ot-cyanoacrylate; and a polyketone material within the following structure: / wherein ‘R is O O 7 at \. » _O/ \ / \O_ 45 50 55 60 65 29 30 31 32 33 50 45 50 60 60 2.0 2.3 2.5 2.5 2.1 1.8 2.3 2.3 1.5 1.0 3. The composition of claim 1, wherein said polyketone material is poly(ethylene-co-vinylacetate-co-carbon monox- ide). 4. The composition of claim 1, wherein said polyketone material is present in an amount sufiicient to toughen said composition once cured. 5. The composition of claim 1, wherein the 0t-cyanoacry- late is represented by compounds of the formula: H2c=C—COOR1 CN wherein R1 represents a straight chain or branched chain substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a straight chain or branched chain substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a straight chain or branched chain substituted or unsubstituted alkynyl group having 2 to 12 carbon atoms, a substituted or US 7,687,561 B1 13 unsubstituted cycloalkyl group, an substituted or unsubsti- tuted aralkyl group or a substituted or unsubstituted aryl group. 6. The composition of claim 5, wherein R1 is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an allyl group, a methallyl group, a crotyl group, a propargyl group, a cyclo- hexyl group, a benzyl group, a phenyl group, a cresyl group, a 2-chloroethyl group, a 3-chloropropyl group, a 2-chlorobu- tyl group, a trifluoroethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group, a 2-ethoxyethyl group and combina- tions thereof. 7. The composition of claim 1, wherein said 0t-cyanoacry- late is an ethyl cyanoacrylate monomer. 8. The composition of claim 1, further comprising a thick- ener. 9. The composition of claim 1, wherein said polyketone material is present in amounts of about 0.5% to about 30% by weight of the composition. 10. The composition of claim 1, wherein said 0t-cyanoacry- late compound comprises an ethyl cyanoacrylate monomer and said polyketone material comprises poly(ethylene-co- Vinylacetate-co-carbon monoxide). 11. The composition of claim 1, further comprising a co- toughener. 12. The composition of claim 11, wherein the co-toughener is a member selected from the group consisting of acrylic 10 15 20 25 14 rubbers; polyester urethanes; ethylene-Vinyl acetates; fluori- nated rubbers; isoprene-acrylonitrile polymers; chlorosul- fonated polyethylenes; homopolymers of polyvinyl acetate; and reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, which once formed are then substantially free of processing aids and anti-oxidants; and combinations thereof. 13. A cyanoacrylate composition comprising: at least one ot-cyanoacrylate; and a ketone containing material within the following struc- ture: R>: wherein R is linear or branched C1 to C7 alkyl, C2 to C7 alkenyl, or C3 to C7 cycloalkyl or cycloalkenyl, interrupted or substituted by carbonyl functionality and/or functionalized with a C1 to C3 alkoxy group; R* is H, methyl, or ethyl; and n is 100 percent.