Adhesive and sealant compositions
United States Patent Skoultchi 1 Apr. 29, 1975 ADHESIVE AND SEALANT COMPOSITIONS [75] Inventor: Martin M. Skoultchi, Somerset, NJ. [56] References cued [73] Assignee: National Starch and Chemical UNITED STATES PATENTS Corporation, Bridgewater N 3.775.385 11/1973 Ozono et a1. 260/895 A 22 Filed: Oct. 29, 1973 OTHER PUBLICATIONS pp No 410 912 Oster, Chem, Abs., 57, pp. 4816, d, (Aug. 20, 1962).  
  Primary Examiner-Harry Wong, Jr. [52] US. Cl 260/895 R; 117/124; 117/l28.4;  
 117/139; 117/161; 260/318 R; 260/4217; [57] ABSTRACT 6 6 Anaerobic curing compositions useful as anaerobic 260 l 5 E 6 88 adhesives and sealants are described, said composil 4 5 4 7 tions comprising mixtures of polymerizable acrylic and I t cl a C0/8f 5/ substituted acrylic monomers and diazonium salts at [58] Field 0 &#34;85811113667555 R 89.5 A 77.5 AP latent pmymerizatio&#34; catalysts therefor ADHESIVE AND SEALANT COMPOSITIONS This invention relates to anaerobic curing compositions utilizing polymerizable acrylic and substituted acrylic monomers and diazonium salts as latent polymerization catalysts therefor. The compositions are stable for periods of time extending to a half-year or more in the presence of air or oxygen, but cure rapidly (setup, polymerize) in the absence of air or oxygen and in the presence of certain metals thereby finding use as anaerobic adhesives and sealants.  
  Anaerobic curing compositions are known and well described in the prior art. U.S. Pat. No. 2,628,178 issued Feb. 10, 1953 (General&#39; Electric) describes the preparation of anaerobic curing compositions which relied on the oxygenation of certain monomers until at least 0.1% of active oxygen was introduced into the monomer. The oxygenated monomer remained stable until polymerization was initiated by the absence of air. A more recent patent, U.S Pat. No. 2,895,950 issued July 21, 1959 (Krieble), describes compositions containing defined polymerizable polyacrylate ester monomers together with hydroperoxide catalysts. Typical catalysts described therein include cumene hydroperoxide, methyl ethyl ketone hydroperoxide, as well as certain oxygenated compounds, for example, oxygenated Z-methyl butene-l and oxygenated cyclohexane. Later patents dealing with anaerobic curing sealants all rely on use of catalysts which are of the peroxide, hydroperoxide or perester class of compounds.  
  1 have now found that anaerobic curing compositions characterized in possessing an extended shelf life of a half-year or more in the presence of air or oxygen together with the ability to polymerize or set-up rapidly when excluded from air or oxygen and in contact or 3 presence of certain metals can be formed comprising the mixture of a polymerizable acrylic or substituted acrylic monomer and diazonium salts. These properties render the compositions particularly useful in the anaerobic bonding of adjacent or closely facing surfaces at least one of which is metal, for example, the mating threads of a nut and bolt.  
  My composition utilize polymerizable compounds (unoxygenated) corresponding to the general formula:  
 wherein R is selected from the group consisting of hydrogen, methyl, ethyl,  
  RI R is selected from the group consisting of hydrogen,  
 chlorine, methyl and ethyl;  
 R&#34; is selected from the group consisting of hydrogen,  
 hydroxy, and  
  011, and  
 m is an integer equal to at least 1, e.g., from 1 to 8 or higher and preferably from 1 to 4 inclusive;  
 n is an integer equal to at least 1, e.g., from 1 to 20 or more; and  
 p is one of the following: 0 to l.  
  Monomers useful in this invention and which come within the above general formula include, for example, ethylene glycol dimethyacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, dimethacrylic ester of tetraethylene glycol, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, and other polyether diacrylates and dimethacrylates.  
  The above class of monomers is in essence described in U.S. Pat. No. 3,043,820 issued July 10, 1962 (to R. H. Krieble).  
  A second class of polymerizable monomers useful in my compositions correspond to the general formula:  
 R represents hydrogen, chlorine, methyl or ethyl, R represents alkylene with 2-6 carbon atoms. R represents (Cl-1 in which m is an integer of fromOto 8, A  
  P, C C  
  /C C C 1 or H H CH v/CH C and 2 represents H an integer of from 1 to 4.  
  Typical monomers of this class include, for example, dimethacrylate of bis(ethylene glycol) adipate, dimethacrylate of bis(ethylene glycol) maleate, dimethacrylate of bis(diethylene glycol) phthalate, dimethacrylate of bis(tetraethylene glycol) phthalate, dimethacrylate of bis(tetraethylene glycol) malonate, dimethacrylate of bis(tetraethylene glycol) sebacate, dimethacrylate of bis(ethylene glycol) phthalate, dimethacrylate of bis(- tetraethylene glycol) maleate, and the diacrylates and a -chloroacrylates corresponding to said dimethacrylates, and the like.  
  The above class of monomers is in essence described in U.S. Pat. No. 3,457,212 issued July 22, 1969 (Sumitomo Chemical Company, Ltd.).  
  Also useful herein are monomers which are isocyanatehydroxyacrylate or isocyanateaminoacrylate reaction products which may be characterized as acrylate terminated polyurethanes and polyureides or polyureas. These monomers correspond to the general formula:  
  1 II A X C NH B l wherein X is selected from the group consisting of O and and R is a member selected from the group consisting of hydrogen and lower alkyl of l to 7 carbon atoms: A represents the organic residue of an active hydrogen containing acrylic ester and the methyl, ethyl and halogen homologs thereof; i.e., an acrylate ester containing hydroxy or amino functional groups on the alkyl portion thereof wherein the active hydrogen has been removed; n is an integer from 1 to 6 inclusive; and B is a monoor polyvalent organic radical selected from the group consisting of alkyl, alkylene, alkenyl, cycloalkyl, cycloalkylene, aryl, aralkyl, alkaryl, poly(oxyalkylene), poly(carboalkoxyalkylene), and heterocyclic radicals both substituted and unsubstituted.  
  Typical monomers of this class include the reaction product of monoor polyisocyanate, for example, toluene diisocyanate, with an acrylate ester containing a hydroxy or amino group in the non-acrylate portion thereof, for example, hydroxyethyl methacrylate.  
  The above class of monomers is in essence described in U.S. Pat. No. 3,425,988 issued Feb. 4, 1969 (Loctite Corporation).  
  In addition to the monomers already described, other useful monomers are monofunctional acrylate esters and their derivatives, i.e., esters containing one acrylate group or derivatives thereof. Such monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butyl acrylate, n-octyl acrylate, 2- ethylhexyl acrylate, decylmethacrylate, dodecyl methacrylate, cyclohexyl methacrylate, tert.-butyl methacrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N-tert.-butyl acrylamide, N-tert.-octyl acrylamide, N-butoxyacrylamide, gamma-methacryloxypropyl trimethoxysilane, 2-cyanoethyl acrylate, 3- cyanopropyl acrylate, tetrahydrofurfuryl chloroacrylate, and the like.  
  The monomers useful herein are seen to be polymerizable monomers having one or more acrylic or substituted acrylic groups as a common, unifying characteristic, and for convenience may be generically termed acrylic and substituted acrylic monomers.  
  By the term unoxygenated as used in connection with monomers, it is intended to designate monomers which have not been oxygenated within the meaning described in U.S. Pat. No. 2,628,178.  
  It is understood that the various monomers useful herein are not required to be in a highly purified state. The monomers may be comprised of commercial grades in which inhibitors, stabilizers, or other additives or impurities may be present, as well as those pre pared in the laboratory or in pilot plant scale.  
  My compositions utilize catalysts which are stable or stabilized diazonium salts and correspond to the general formula:  
  In the above formula, a is an integer of l, 2 or 3 taken so as to equalize the valence charge of the salt and Ar is any aryl or substituted aryl radical and includes diazonium substituted aryl radicals. X is an anion such as is ordinarily found in known diazonium salts and is taken so as to act as a counter-ion to the aryl diazonium cation moiety of the salt. X includes, for example, F, Cl&#34;, Br, S0 H ArSOf, Ar(SO and Q QJ; Ar is an aryl or substituted aryl radical. Y represents a stabilizing agent for the diazonium salt such as are well known in the art and may or may not be present. Y includes, for example, ZnCl BF l-lgCl PtCl PtCh, and AuCl ln usual practice, the stabilizing agent complexes with the diazonium salt and therefore is present in approximately stoichiometric amounts. Many diazonium salts in which the anion is selected from the group S0 H80 ArSOf, and  
 Ar(SO may not require a stabilizing agent.  
  For illustrative purposes, typical diazonium salts useful in the compositions of this invention include, for example, bis( 2-methyl-4-chlorobenzenediazonium) naphthalenedisulfonate, bis(2-methoxy-4- nitrobenzenediazonium) naphthalenedisulfonate, bis[- 4-( N,N-diethylamino )-2-methoxybenzenediazonium1 tetrafluoroborate, bis( 3-nitro-4- chlorobenzenediazonium) tetrachlorozincate, bis(4- nitrobenzenediazonium) sulfate, 1,4-tetramethylene bis(4,4-diazo) benzoate zinc chloride complex and bis[4-(N-phenylamino) benzenediazonium] sulfate.  
  The amount of catalyst used in my compositions should be an amount effective to initiate polymerization of the monomer when the composition is in contact with or closely adjacent to a selected metal, later described, and in the absence of air or oxygen. Such effective amounts of catalyst will vary mainly depending on the monomer component of the composition and also depending on the metal with which it is to be used. For most applications, however, the amount of catalyst, i.e. the diazonium salt, will range from about 0.01 or less to 10% or more, based on the weight of the monomer. The preferred amount of catalyst will range from about 0.2 to 2%, based on the weight of the monomer. It can be understood that mixtures of diazonium salts may also be employed as catalysts herein.  
  If the dissolving of the catalyst in the monomer presents a problem or if a relatively larger amount of a particular catalyst is necessary in connection with a monomer in which solubility is difficult, then solvents which dissolve the diazonium salt and themselves are soluble in the monomer may be employed. Common solvents for diazonium salts are described in the literature and include, for example, alkanols such as methanol, ethanol, butanol; substituted and unsubstituted formamides such as formamide and N,N-dimethyl formamide; and water. Methanol and ethanol are the preferred solvents. In most instances, only that minimum amount of solvent is used so as to dissolve the diazonium salt.  
  In preparing my compositions, it is within the scope of my invention that the required acrylic monomer may be a mixture of acrylic monomers rather than a single acrylic monomer, and there may also be utilized, in combination therewith, other non-acrylic, ethylenically unsaturated copolymerizable comonomers such as unsaturated hydrocarbons, unsaturated esters and ethers, vinyl esters, and the like. Typical optional comonomers include: vinyl acetate, methyl vinyl ether, methyl vinyl ketone, poly(ethylene maleate), allyl alcohol, allyl acetate, l-octene, styrene, etc.  
  In certain applications, and largely dependent on the particular acrylic monomer being utilized, such nonacrylic, polymerizable comonomer(s) may be added to constitute up to about 60%, by weight, of the monomer composition. Preferably, however, the optional, nonacrylic comonomer will constitute no more than 50%, by weight, of the monomer composition, and most preferably, it will constitute no more than 30%, by weight, of the monomer composition.  
  Optionally, the compositions may also contain a minor amount, up to 50%, by weight, of a polymeric thickener, for example, a low or high molecular weight polymer or prepolymer. Illustrative of such polymeric thickeners is a commercially available methacrylate polymer sold by E. I. DuPont de Nemours and Company, under the trademark ELVACET 2042.  
  In order to further modify the properties of my compositions, they may optionally contain plasticizers such, for example, as dibutyl phthalate or triethylene glycol. Other optional ingredients include, inorganic thickeners, organic and inorganic fillers, cut glass fibers, as well as visible or ultraviolet fluorescent dyes.  
  My compositions can be formulated with or without a stabilizer compound added to the monomeric composition to prevent or retard the premature decomposition of the diazonium salt catalyst. Useful stabilizer compounds are materials classified in the chemical literature as Lewis acids and their salts. They include the stabilizing agents previously described in connection with the stabilizing of the diazonium salts as well as, for example, sulfosalicylic acid, sulfuric acid, toluene sulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, and the lithium, sodium and potassium salts of these acids, aluminum chloride, etc. When such optional stabilizer compounds are used, they are used in concentrations of from about 0.00] to 1%, by weight, of the total composition. The desirability or necessity of utilizing these stabilizer compounds can easily be recognized by the practitioner in the art.  
  In order to prepare my anaerobic-curing composition, it is merely necessary to mix the desired amount of diazonium salt (at times dissolved in a small amount of solvent) with the selected acrylic monomer or monomers which may optionally contain non-acrylic copolymerizable monomer. Optional ingredients can be premixed into the monomer or alternatively admixed into the prepared composition.  
  The curing or polymerization of my compositions is initiated by the absence of air or oxygen and the contact of the adhesive with selected metal surfaces. The metals effective with the compositions described herein include iron, copper, tin, aluminum and silver and their alloys. Cadmium, chromium, nickel and zinc chromate platings have also been found to be useful in connection with my compositions. The surfaces provided by the metals, alloys, and metallic platings which are useful in initiating the cure of these compositions will, for convenience, be grouped into the term active metal surfaces and be understood to include but not be limited to all of the metallic entities mentioned above. As used herein, the term active metal will designate any metal, alloy or metallic plating capable of initiating the polymerization of my compositions on 5 contact therewith in the absence of air or oxygen.  
  In order to maintain or increase the bond strength of the resultant cured polymer, one may utilize an acrylic monomer having an alcoholic or other relatively polar group substituted thereon. Examples of such polar groups in addition to the hydroxy group include, amino, amido, cyano, mercapto, and halogen polar groups. I-Iydroxy group containing monomers are preferred. Esters having a labile hydrogen atom or atoms are also desirable. Examples of acrylic monomers within this category include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, diacetone acrylamide, 2- cyanoethyl acrylate, 3-cyanopropyl acrylate, 2- chloroethyl acrylate, glycerol monomethacrylate, 2-hydroxy-3-chloropropyl methacrylate, etc.  
  Where the effect of a polar substituted monomer is desired without its actual use, in some instances a small amount (usually no more than 8%, by weight of the total composition) of an alkanol may be admixed to the composition. Such useful alkanols include, for example, methanol, ethanol, isopropanol, butanol, etc. While analogous mercapto compounds may be used in place of the alkanols with a comparable beneficial effect, their use is not favored mainly because of their unpleasant, strong odor.  
  The compositions of this invention cure (polymerize or set) at ambient temperatures but heat may be used to accelerate the rate of curing. Compositions containing significant amounts of hydroxy substituted acrylic monomer are further crosslinked by the application of heat resulting in increased bond strength.  
  The following examples will further describe and illustrate the practice of this invention but they are not intended to limit its scope. In these examples the compositions were prepared by mixing the indicated ingredients in amounts given as&#39;parts by weight (pbw) unless otherwise specified. The ingredients are identified in the following tables, I and IA.  
 Table I Designation in the Examples Ingredient Table IA Designation in the Examples Ingredient Monomer AA ethylcneglycol dimethacrylatc Monomer BB hydroxyethyl methacrylatc Monomer CF hydroxypropyl acrylate Monomer DD hydroxypropyl methaerylatc Monomer EE hydroxyethyl acrylate Monomer FF pentaerythritol triacrylate Monomer GG trimethylolpropane triacrylate Monomer HH triethyleneglycol diacrylatc Monomer ll triethyleneglycol dimethacrylate neopentylglycol diacrylate ethylcneglycol diacrylatc Methyl acrylate ethyl methacrylate butyl acrylate octyl acrylatc poly(butylene maleate) dimethacrylate (M.W. 2000) poly(propylene glycol) dimethaerylate (M.W. l025) reaction product of 2 moles hydroxyethyl acrylate and l mole toluene diisocyanate reaction product of 2 moles toluene diisocyanate, 1 mole poly(butylene adipate-phthalate) and 2 moles hydroxyethyl methacrylate Monomer .U Monomer KK Monomer LL Monomer MM Monomer NN Monomer O Monomer PP Monomer QQ Monomer RR Monomer SS Monomer TT reaction product of 2 moles toluene diisocyanate,  
  l mole poly(propylene glycol) and 2 moles hydroxyethyl acrylate Monomer UU methyl methacrylate Monomer VV polypropylene glycol (M.W. 200) monomcthacrylate Monomer WW polyethylene glycol (M.W. 200) monomethacrylate Monomer XX acrylamide Monomer YY isobutyl methacrylate Monomer ZZ N-(isobutoxymethyl)acrylamide EXAMPLES 1 11 These examples illustrate representative compositions of this invention prepared with a variety of diazonium salts.  
 Ingredients (parts by weight) Example Monomer Catalyst l 100 AA 0.5 A 2 I00 AA 0.5 B* 3 100 AA 0.5 C 4 100 AA 0.5 D* 5 100 AA 0.5 E* 6 l00 AA 0.5 F 7 I00 AA 0.5 G 8 I00 AA 0.5 H* 9 100 AA 0.5 I  
 I0 100 AA 0.5 J l l 100 AA 0.5 K  
 EXAMPLES 12 21 These examples illustrate the use of various concentrations of catalyst in the compositions of this invention.  
 Ingredients (parts by weight) Example Monomer Catalyst 12 100 BB 0125 A 13 100 BB 025 A I4 I00 BB 0.50 A 15 I00 BB L00 A 16 100 BB 1.50 A I7 I00 BB 0.| B 18 100 BB 0.25 B 19 I00 BB 0.50 B 20 I00 BB l.00 B 21 100 BB l.50 B  
  The compositions of these examples were each evaluated in the finger-tight lock test. The bond strength of the bond between the nut and bolt formed with the composition after curing at room temperature for 2 hours was measured by means of a torque wrench. The torque required to move the nut on the threads initially,  
 5 one-half turn and a full turn is noted in Table ll, to-  
 gether with results obtained with the finger-tight lock test.  
 EXAMPLES 22 44 The following examples illustrate the use of various monomers in the compositions of this invention. .Re-  
 sults obtained with the respective compositions in the finger-tight lock test are given in the last column.  
 required methanol to dissolve the diazonium salt The compositions of the above examples were each evaluated in a finger-tight lock test known in the art. About 2 or 3 drops of each composition were placed on the exposed threads of separate %-24 iron bolts (degreased) and immediately thereafter a nut (degreased) lngredients (parts by weight) Lock Test with mating threads was run onto the bolt so that the Example Monomer Catalyst Time (mmutcs) nut was directly in the thread area of the applied composition. Measurements were made of the time-periods 22 I00 CC 0.5 A :8 necessary with each composition at room temperature &#39;88 i-2E 7 to achieve a finger-tight lock such that the nut could 55 25 100 DD 05 E 50 not be moved on the threads with fingers. if; :88 g-g g The results obtained with the various compositions 28 100 BB A 15 re iven in the followin table. 29 100 BB 0.5 E 15 a g g 30 100 FF 0.5 A 3] lOO G6 0.5 A 92 32 100 HH 0.5 E E -L0Ck Test 60 33 100 n 0.5 E I20 xample Tlme (minutes) 34 00 JJ 0 5 E 40 8 35 too KK 0.5 A 15 2 13 36 100 LL 0.5 A* ovemlght 37 100 MM 0.5 A* overnight 3 38 100 NN 0.5 A* overnight 4 39 I00 00 0.5 A* overnight 2 40 PP 1.0 E 60 7 7 41 I00 00 1.0 E 30 8 42 100 RR 1.0 E 35 9 g 43 100 $5 1.0 E 30 44 I00 TT 2.0 E 25 10 5 ll 30 required methanol to dissolve the diazonium salt EXAMPLE 45 75 These examples illustrate compositions prepared utilizing various comonomer combinations. The compositions were evaluated in the finger-tight lock test and for bond strength after curing at room temperature for two hours by means of the torque wrench.  
 EXAMPLES 76 93 Ingredients (pbw) H Example Monomer Catalyst Time (minutes) lnltlal Lock Test 90 BB l0 AA 70 BB 30 AA 90 BB l0 AA 70 BB 30 AA 90 BB AA 70 BB 30 AA 90 BB 10 NN 80 BB NN 90 BB l0 NN 80 BB 20 NN 90 BB 10 OO 80 BB 20 OO 90 BB 10 OO 80 BB 20 OO 90 BB 10 UU 80 BB 20 UU 90 BB 10 UU 80 BB 20 UU 80 BB 20 VV 80 BB 20 VV 80 BB 20 VV 80 BB ZOWW 80 BB 20WW 80 BB 20 XX 80 BB 20 XX 80 BB 20 XX 80 BB 20 YY 80 BB 20 YY 80 BB 20 YY 80 BB Z0 Z2 80 BB 20 ZZ Torque (inch-pounds) 15 turn Full Turn 9 l5 l5 l5 l9 3O 2l5 I80 2O 2O l5 15 Ingredients (pbw) Monomer Torque (inch-pounds) and Lock Test Full Example Plasticizer Catalyst Time (minutes) Initial /zTurn Turn 76 90 BB 0.5 A ll 180 I0 GLY* 77 70 BB 0.5 A ll 60 120 50 3O GLY 78 90 BB 0.5 B 29 60 I80 l0 GLY 79 70 BB 0.5 B 39 lo 40 60 30 GLY 80 90 BB 0.5 E 4 5O 65 65 Continued Ingredients (pbw) Monomer Torque inch-pounds) and Lock Test Full Example Plasticizcr Catalyst Time (minutes) Initial Turn Turn 8l 70 BB 0.5 E 4 10 40 60 30 GLY 82 90 BB 0.5 A 9 I 2X6 250 I0 TEG* 83 70 BB 0.5 A [4 30 45 50 30 TEG 84 90 BB 0.5 B 23 I30 240 240 10 TEG 85 70 BB 0.5 B 24 60 90 95 3O TEG 86 90 BB 0.5 A I3 50 45 85 1O DBP* 87 90 BB 0.5 E 8 55 40 40 I0 DBP 89 70 BB 0.5 E 26 30 20 30 DBP 90 90 BB 0.5 A I2 70 80 I25 DOP* 91 70 BB 0.5 A 25 35 15 3O DOP 92 90 BB 0.5 E I9 75 50 30 10 DOP 93 70 BB 0.5 E 28 30 20 DOP Legend: GLY glycerol TEG triclhylenc glycol DBP dihutyl phlhulutc DOP dioctyl phthalutc EXAMPLE 94 checked daily for their performance in the finger-tight While my compositions are generally sufficiently stable for commercial purposes without the use of added stabilizers, it has been found that their stability (shelf life) may be significantly extended, where it is desired to do so, by the addition to the composition of small amounts of stabilizer compounds previously described, namely, Lewis acids and their salts. The instability of my compositions is exhibited and made most apparent by their delayed or partial or complete loss of cure (polymerization) under conditions that would lead to the cure of stable (unaged) compositions. Ordinarily, when stabilizer compounds ar used, the amount employed will range from about 0.001 to 1%, by weight, of the total composition.  
  The effect of employing various stabilizer compounds is illustrated in this example where representative compositions without and with added stabilizer are evaluated in the finger-tight lock test after undergoing accelerated aging carried out at 50C. In this accelerated aging procedure, a polyethylene bottle about half filled with the test composition is aged in an oven having a temperature of about 50C. The test samples are locking test. As an approximate correlation between oven aging and aging at room temperature, one day of aging in the oven is about equivalent to one month of shelf life or aging at room temperature.  
  Thus, a composition consisting of 100 parts of hydroxyethyl methacrylate and 0.5 parts of bis[4-(N,N- diethylamino) benzenediazonium] tetrachlorozincate with no added stabilizer showed the following characteristics on aging at 50C. as evaluated in the fingertight lock test.  
 No. of Days Lock Test at 50C. Time (minutes) 0 l5 3 l4 7 l6 9 31 10 did not cure No. of Days Lock Test Stabilizer Concentration at 50C. Time (minutes) p-toluenesulfonic acid 0.0571 0 I9 50 I8 0.10% 0 18 50 30 0.20 0 20 50 3O p-toluenesulfonic acid 0.05% 0 23 sodium salt 50 30 0.10% 0 23 50 33 sulfuric acid 0.l07z 0 20 50 29 0.20% 0 26 50 28 boron trifluoridc ethcratc 0.05% 0 34 50 0.5071 0 34 40 31 50 did not cure zinc chloride 0.50% 0 30 10 50 did not cure Lock Test Time (minutes) No. of Days at 50C.  
  I6 35 did not cure On the addition of p-toluenesulfonic acid to the composition at the indicated amounts and their subsequent aging at 50C., result in the finger-tight lock test were obtained as follows.  
  Lock Test Time (minutes) Concentration Nov of Days Stabilizer at 50C.  
 P-toluenesulfonic acid did not cure EXAMPLES 95 100 These examples show the utility of several compositions representative of this invention employed in connection with various metal surfaces. Each of the compositions was evaluated in the finger-tight lock test employing degreased /s-24 bolts and nuts of cadmium plated steel, zinc chromate plated steel, nickel plated steel, iron and copper.  
  ited to instances where one of the bonded substrates is a metal. This unusual composition is comprised of hydroxyethyl acrylate in combination with bis(2-methyl- 4-chlorobenzenediazonium) naphthalenedisulfonate. Operable compositions can be prepared employing concentration ranges with respect to the required monomer and diazonium salt and any optional ingredients which are generally comparable to those previously given for the main compositions of this invention.  
  A composition was prepared by adding 0.5 parts of bis(2-methyl-4-chlorobenzenediazonium) naphthalenedisulfonate to 100 parts of hydrox yethyl acrylate with thorough mixing. About two drops of the composition was placed between the major surfaces of two glass microscope slides and the slides were arranged to be at right angles to each other to form a square overlap. The thus formed laminate was allowed to cure for twelve hours at room temperature after which period it was impossible for one slide to be moved on or removed from the other. When the slides were broken apart it was observed that the composition had fully polymerized forming a solid film. When the procedure was repeated using a composition which omitted the diazonium salt catalyst, no evidence of polymerization was observed even after 48 hours.  
  The stability of this composition is comparable to that achieved generally with compositions of this invention.  
  As will be recognized by those skilled in the art, my invention provides anaerobic curing compositions useful as adhesives and sealants which can be prepared in various formulations to provide a range of bond strength, polymerization rates, viscosities and shelf stability. Variations may be made in ingredients, proportions and procedures as long as such variations are within the scope of the following claims.  
 I claim:  
  1. An anaerobic curing composition stable when exposed to air comprising a non-aqueous mixture of a polymerizable acrylic or substituted acrylic monomer selected from the group consisting of Ingredients (pbw) Example Monomer Catalyst Metal Lock Test Time (minutes) 100 BB 100 EE cadmium plated steel zinc chromate plated ste nickel plated steel iron iron (heat treated) copper 100 BB 100 BB 100 EE I00 EE EXAMPLE 101 As already described and illustrated in the above examples, in order that my compositions polymerize or cure, the compositions require both the absence of air or oxygen and the contact of an active metal. Unexpectedly, l have found that a composition comprised of 15 16 wherein droxy or amino substituted on the alkyl portion R is selected from the group consisting of hydrogen, thereof, and the methyl, ethyl and chlorine homomethyl, ethyl, logs thereof, n is an integer from 1 to 6, and B is a O monoor polyvalent organic radical selected from II 5 the group consisting of alkyl, alkylene, alkenyl, cy- 2 and Z&#39; 2 cloalkyl, cycloalkylene, aryl, aralkyl, alkaryl, poly- (oxyalkylene), poly(carboalkoxyalkylene), and R is selected from the group consisting of hydrogen, tf sg f radicals both substituted and unsubsti- Rffh q l methyl and ethyl; d. monofunctional acrylate and methacrylate esters 18 se ected from the group consisting of hydrogen, and the hydroxy amide cyano, chloro, and Silane substituted derivatives thereof; and from about 0.01 to 10% by weight of the monomer of diazo- O 5 C CH nium salt sufficient to initiate polymerization of 2 said acrylic monomer at room temperature in the absence of air or oxygen and on contact with an active metal surface. m an Integer l to 83 and an Integer from 1 m 2. The composition of claim 1 wherein the diazonium 20; and p is O or 1; salt corresponds to the formula il 11: X u) or 1) I (b) H C C I wherein C-O- (-R&#39; O-) -C-R&#34;C- Ar is an aryl or substituted aryl radical, I! H H X is an anion selected from the group consisting of O 0 O F&#39;, Cl: Br, 50,&#34;, H80 ArSO Ar&#39;(SO and Ar(SO Ar is an aryl or substituted aryl CH radical;  
 2 a is integer of l, 2 or 3 taken so as to equalize the valence charge of the diazonium salt, and Y is a stabilizing agent for the diazonium salt selected from wherein the group consisting of ZnCl BF HgCl PtCl and AUC13. R represents hydrogen, chlorine, methyl or ethyl I 3. The composition of claim 2 further containing sta- R represents alkylene with 2-6 carbon atoms,  
  5 bihzer compound selected from the group consisting of R represents (CH in Which m is an integer of 3 L d l h f from O to 8, ewis act 5 an ts t ereo 4. The composition of claim 1 wherein the diazonium salt is bis[4-(N,N-diethylamino)benzenediazonium] 0 m, B i C tetrachlorozincate. H 40 5. The composition of claim 1 wherein the diazonium salt is bis[4-(N,N-diethylamino)-2- methoxybenzenediazonium] tetrafluoroborate. 6. The composition of claim 1 wherein the diazonium C C r salt is bis[4-(N,N-dimethylamino)benzenediazonium] H C tetrachlorozincate.  
 H 3 7. The composition of claim 1 wherein the diazonium salt is bis[4(-N-ethyl-N-hydroxyethylamino)ben- 3 zenediazonium] tetrachlorozincate.  
 , and 8. The composition of claim 1 wherein the diazonium salt is bis(2-methyl-4-chlorobenzenediazonium)naphthalenedisulfonate.  
  9. The composition of claim 1 wherein the diazonium salt is bis(2-chlorobenzenediazonium) tetrachlorozin- O cate. 10. The composition of claim 1 wherein the diazo- (c) A X C NH B nium salt is bis(2,5-dichlorobenzenediazonium) tetrachlorozincate. n 11. The composition of claim 1 wherein the diazonium salt is 2-methoxy-4-(3&#39;-methoxy-4&#39;- wherem X 15 Selected from the group conslstmg of diazobenzenediazonium tetrachlorozincate. and 12. The composition of claim 1 wherein the diazonium salt is bis(3-nitro-4-chlorobenzenediazonium) -N- tetrachlorozincate. 13. The composition of claim 1 wherein the diazoand R a member Selected from the group conslstmg nium salt is bis(2-methoxy-4-nitrobenzenediazonium) of hydrogen and lower alkyl of l to 7 carbon atoms, h h l lf A represents the organic residue of an active y 14. The composition of claim 1 wherein the diazodrogen Containing acrylic ester wherein the active nium salt is bis(2-methoxy-4-nitrobenzenediazonium) hydrogen has been removed, said ester being hytetrachlorozincate.  
 n represents an integer of from 1 to 4;  
  15. The composition of claim 1 wherein the diazonium salt is bis(4-nitrobenzenediazonium) tetrafluoroborate.  
  16. The composition of claim 1 wherein the diazonium salt is bis[4-(N-phenylamino)benzenediazonium] sulfate.  
  17. An anaerobic curing composition according to claim 1 comprising polymerizable hydroxyethyl acrylate monomer and from about 0.01 to by weight of monomer of bis(2-methyl-4- chlorobenzenediazonium) naphthalene disulfonate sufficient to initiate polymerization of said monomer at room temperature in the absence of oxygen.  
  18. An anaerobic curing composition according to claim 1 comprising polymerizable hydroxyethyl methacrylate and bis[4-(N,N,-diethylamino)benzenediazonium] tetrachlorozincate.  
  19. An anaerobic curing composition according to claim 1 comprising polymerizable hydroxypropyl methacrylate and bis [4-(N,N-diethylamino)benzenediazonium] tetrachlorozincate.  
  20. An anaerobic curing composition according to claim 1 comprising polymerizable reaction product of 2 moles of toluene diisocyanate, 1 mole of poly(propylene glycol) and 2 moles of hydroxyethyl acrylate and as catalyst therefor bis[4-N,N-diethylamino)benzenediazonium] tetrachlorozincate.  
  21. A method of adhering closely facing surfaces, at least one being an active metal surface, which comprises interposing between said surfaces the-composition of claim 1 and permitting said composition to cure in the absence of air or oxygen until said composition is set.  
  22. A method of adhering closely facing surfaces, at least one being an active metal surface. which comprises interposing between said surfaces the composition of claim 2 and permitting said composition to cure in the absence of air or oxygen until said composition is set.