SE411358B - ANAEROBIC ADHESIVE OR SEALING CONTAINING AN ORGANIC FERROCEN ASSOCIATION AS ACTIVATOR - Google Patents

Description

15 20 25 30 35 H0 7404281-3 the assessment of anaerobic materials is the material's cure rate and its ability to cure when placed in slots. In the case of fast-running production lines, where glued or sealed objects cannot be stored for a long time, and when repairing equipment that must be quickly put back into operation, the greatest possible curing rate of the material is desirable, provided, of course, that it high cure rate does not cause adverse effects, e.g. too strong embrittlement of the cured material or loss of others. desirable properties. Another and particularly important factor, when it comes to anaerobic materials, is their curing properties in gaps. As the gap (i.e. the gap between two objects to be sealed or joined) becomes larger, the risk of access of atmospheric oxygen increases, and the surface of the binder which comes into contact with oxygen also becomes larger. Consequently, the inability to achieve complete curing within wide gaps has been a common problem associated with many anaerobic materials.

Typical anaerobic materials contain accelerators, i.e. ingredients, which do not impair the storage stability of the product, but are capable of increasing the curing rate as soon as curing has begun under the prevailing conditions of use. Thus, although these ingredients increase the cure rate of the products, they have been of little or no importance in creating the ability to cure in gaps. Technically, an increased cure rate can also be obtained by using pretreatment agents in the form of chemical compounds, which are applied to a surface before the application of the anaerobic material and thereby cause a sharp increase in the cure rate. Such agents cannot be added directly to the anaerobic material due to their extremely high activity and tendency to reduce the storage life of the product. Typical examples of such pretreatment agents or activators are given in U.S. Pat. No. 3,591 H38. Various organometallic compounds are commonly used as such activators.

An anaerobic material or a combination of an anaerobic material and a surface activator thereof, which gives a higher cure rate, preferably also in combination with the ability to harden in a gap of, for example, between about 0.13 and 0.75 mm width, would mean a particularly useful and desirable improvement in the field of anaerobic materials and a major advance in sealing and gluing techniques.

The present invention relates to anaerobic materials, containing a polymerizable acrylic acid ester monomer, an activator which contains a ferrocene component and which preferably consists of ferrocene, a ferrocene-containing polymer, an acyl, alkyl, hydroxyalkyl, alkenyl e-eraryl derivatives of ferrocene or a mixture thereof, and a peroxy polymerization initiator for the monomer in the form of a hydroperoxide or perester compound. The invention also includes a fast curing material which contains the material just mentioned and in addition a strong acid.

The invention comprises a two-part anaerobic agent, of which the acrylic acid ester monomer and the peroxy initiator together with optionally the acid or activator form a first part and the acid or activator or both are used as a second part. In this two-part system, the second part is usually used as a pretreatment agent or activator before the application of the first part, but the second part can also be mixed with the first immediately before use.

The materials described above entail outstanding use properties, compared with known preparations for similar purposes.

For example, a curing speed which is equal to or greater than that which can be achieved with most known systems can be achieved, and this without adverse effect on the strength, flexibility, toughness e-d of the formed joint. Such negative results are often associated with the application of known fast curing systems. In addition, the materials according to the invention have been found to give an improved through-curing in gaps of considerable width, e.g. up to 0.5 mm and in some cases even larger, e.g. up to about 0.75 mm.

This is a highly surprising and unexpected result, especially when using a surface activator. It has been found that the most rapidly curing systems often give the worst crevice curing properties, which is probably due to an extremely strong surface polymerization, whereby the effective polymerization accelerators are enclosed in a highly viscous layer near the surface and prevented from migrating inwards to the middle of the crevice. It was therefore highly surprising and unexpected to find the combination of properties which has now been achieved by the anaerobic materials described herein.

As indicated above, the anaerobic material has as necessary elements a polymerizable monomer and a peroxy initiator, which with respect to the polymerization is latent in the presence of oxygen, but is capable of polymerizing the monomer at room temperature within a reasonable time. syrerß's inherent effect has ceased. The most suitable monomers for use in anaerobic materials are polymerizable acrylic acid esters, preferably those having a molecular weight of at least about 130. When used in the products of the invention, they preferably form at least a portion of the acrylic acid monomer. of a di- or other polyacrylic acid ester. Such multifunctional monomers provide crosslinked polymers, which act as more effective and durable sealants and binders.

The polyacrylic acid esters can be represented by the formula (1) wherein R 2 represents a hydrogen or halogen atom or an alkyl group having at most 4 carbon atoms, q is an integer at least equal to 1 and preferably in the range 1 - H, and X represents an organic radical having at least 2 carbon atoms and with a total bonding capacity of q + 1. No definite upper limit for the number of carbon atoms in X can be stated, because usable monomers exist at practically every value. In practice, however, an upper limit may generally be set at about 50 carbon atoms, preferably about 30 and most preferably about 20 carbon atoms.

For example, X may represent an organic radical of the formula -Y 1 -olèzä-oyz- wherein Y 1 and Y 2 each represent an organic radical, preferably a hydrocarbon group, containing at least 2 carbon atoms, preferably between 2 and 10 carbon atoms, and Z represents an organic radical, preferably a hydrocarbon group, preferably containing between 2 and about 10 carbon atoms. Other useful polyacrylic acid ester monomers are the isocyanate monoacrylate reaction products disclosed in U.S. Patent Nos. 3,425,988 and the reaction products of di- or trialkylolamines (eg, ethanolamines or propanolamines) with acrylic acids; disclosed in French Patent 1,581,361.

The most preferred acrylic acid esters that can be used in the indicated materials are polyacrylic acid esters of the formula H = 714011281 '-3 - 5 "v" a * a *: f HC = CCO- -C- - C 1 -C-- --- CC = CH (2) 2 12 11 13 | 1 | 2 2 RRRRXR m / p An wherein R 1 represents a hydrogen atom, an alkyl group having at most H carbon atoms, an E hydroxyalkyl group having at most 4 carbon atoms or R 2 represents a hydrogen atom, halogen atom or alkyl group having not more than 4 carbon atoms, R 3 represents a hydrogen atom or hydroxyl group or -O-C - $ == CH 2 R 2 m is a positive integer, for example up to 15 or higher, preferably at most 8, n is a positive integer, for example up to H0 - or higher, preferably in the range 2 - 10, and p is 0 or 1.

Examples of polyacrylic acid esters of formula 2 are di- and tetraethylene glycol dimethacrylate, di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di (chloroacrylate), diglycerol diacrylate, diglycerol tetramethacrylacrylate, trimethylacrylate acrylate.

Although di- and other polyacrylic acid esters, in particular the polyacrylic acid esters mentioned in the preceding paragraph, are particularly suitable, monofunctional acrylic acid esters (esters containing a single acrylate group) can also be used. When using monofunctional acrylic acid esters, it is most convenient to choose an ester which has a relatively polar alcohol group. Such materials are less volatile than lower molecular weight alkyl esters, and in particular the polar group tends to create intermolecular attraction during and after curing, resulting in more favorable curing properties and at the same time a more durable sealant or binder. The polar group is most preferably a labile hydrogen atom, a heterocyclic ring or a hydroxy, amino, cyano or halogen group. Typical compounds of this category are cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethyl acrylate and chloroethyl methacrylate.

As stated above, the anaerobic materials referred to herein are prepared by mixing a peroxy initiator with one or more acrylic acid esters. The peroxy initiators used in the materials of the invention are hydroperoxides, preferably organic hydroperoxides, and organic peresters. The hydroperoxides are superior and are preferably used.

The nature of the hydroperoxides is not critical to the invention in its broader sense. The most common hydroperoxides can be represented by the formula Ru (OH) z, where R 4 represents a hydrocarbon group containing up to 18 carbon atoms and z is 1, 2 or 3.

Preferably z = 1 and Ru represents an alkyl, aryl or aralkyl hydrocarbon group having 3 to 12 carbon atoms. Of course, the group Ru can hold any substituent or bridge (hydrocarbon group or other group) which does not adversely affect the hydroperoxide for the purpose intended. Examples of such hydroperoxides are cumene hydroperoxide, tertiary butyl hydroperoxide, methyl ethyl ketone hydroperoxide and hydroperoxides formed by oxidation of various hydrocarbons, e.g. methylbutene, cetane and cyclohexene, as well as various ketones and ethers, e.g. certain compounds of formula 2 above.

The peresters used in materials according to the invention are organic compounds which contain the group -CO-OOCE. The most commercially common products contain either two such groups or preferably a single such group. These compounds can be represented by the formula A-CO-OOB, where A and B each represent a hydrocarbon group having up to 10 carbon atoms, preferably an alkyl, aryl or aralkyl group. When the perester contains more than one perester bridge, A may mean Rs-co-ooß and / or ß beuyaa ks-oo-cos-aß, where Rs 1: 6 denotes hydrocarbon groups having up to 10 carbon atoms, wherein Rs is preferably is an alylene, arylene or alkarylene group, RB is preferably an alkyl, aryl or aralkyl group and B has the meaning given above. Of course, A, B, R and R may additionally contain any substituent or bridge (neither hydrocarbon group nor other group) which has no detrimental effect on the perester for its intended use.

Examples of suitable peresters such as polymerization initiators include t-butyl peracetate, t-butyl peroxyisobutyrate, di-t-butyl diperphthalate, t-butyl perbenzoate, 2,6-dimethyl-2,5-bis (benzoyl peroxy) hexane and t-butyl peroximalaleic acid . -u-s. 10 15 20 25 30 35 40 ""? ¿O4é3 {ëz> The peroxy initiators can be used in widely varying amounts, e.g. up to about 20% of the total weight of the material. Usually, however, they do not exceed 10% of the weight of the material, because higher contents can have an adverse effect on the strength and durability of the cured material. In some cases, levels lower than 0.1% may be used, but about 0.1% of the total weight of the material is generally a lower limit.

Preferably, the amount of peroxy initiator is between about 0.1 and the weight of the material.

The materials of the present invention also require an effective amount of an activator in the form of an organic compound containing a ferrocenyl group capable of accelerating the curing of the polymerizable materials set forth herein. The activator may be ferrocene, a ferrocene-containing polymer, or an acyl, aryl, alkyl, hydroxyalkyl or alkenyl derivative of ferrocene or a mixture thereof. By the term "effective amount" is meant herein an amount or concentration which depends on the activity of the particular activator used, which is sufficient to increase the cure rate and / or improve the joint hardening ability of the polymerizable material, as compared with the inactivated material. By the term "ferrocene-containing polymer" is meant both polymers containing ferrocene in the backbone and polymers in which the ferrocenyl groups form the juxtaposed group Ferrocene is a crystalline substance of the formula (C5H5) 2Fe. Ferrocene, its derivatives and its polymers are to a large extent about 5% stable organometallic compounds, which fulfill special functions in the anaerobic material. Particularly surprising was the discovery that ferrocene and its derivatives and polymers can be incorporated in significant amounts into the mixture of polymerizable acrylic acid ester and peroxy polymerization initiator. It has been considered that the incorporation of transition metal compounds, in particular ferrous compounds, generally impairs the stability of the anaerobic material. However, it has been found that ferrocene and its derivatives and polymers can be incorporated in amounts of up to about 1% or more of the weight of the anaerobic material without compromising the shelf life of the product (provided that the acidic substance listed below is not included). .

However, no particular benefit is obtained by using larger amounts, so this is not recommended. When the activator is added to the mixture of polymerizable acrylic acid ester monomer and peroxy polymerization initiator, it is preferably used in an amount of between about 0.005 and about 1%, preferably between 0.05 and 0.3%, by weight of the anaerobic material. As indicated above, the activator can be added directly to the anaerobic material, or it can be used separately or in combination with the acid as a second part of a two-part adhesive. In addition to ferrocene, many derivatives thereof are suitable for use in materials of the invention. Useful aryl derivatives include the phenyl derivative and alkyl-, hydroxyl- and carboxyl-substituted phenyl compounds. Useful acyl derivatives include acetyl, benzoyl, benzenesulfonyl, carbonyl, acid ester and aldehyde compounds. The alkyl, cycloalkyl, hydroxyalkyl and alkenyl derivatives are (apart from economic considerations) not limited in the number of carbon atoms. Preferably, however, these groups contain at most 20 carbon atoms, most preferably at most 10 carbon atoms. The substituents may be present on one or both of the cyclopentadienyl rings. Multiple and / or mixed substituents may be present on one or both of the cyclopentadienyl rings. Any substituents can be used which do not completely spoil the ability of the ferrocenyl group to activate the cure. Suitable polymers may contain ferrocene units such as side groups to the chain of the molecule or may be polymers of the ferrocene itself or of its derivatives, e.g. an alkyl adduct containing not more than 6 carbon atoms. One or both of the cyclopentadienyl groups in a ferrocene moiety contained in the polymer may be substituted.

There is no particular limit to the molecular weight of such polymers, but for practical reasons relatively low viscosity values are preferred, which presupposes the use of lower molecular weights, e.g. up to about 20 dicyclopentadienyl iron units.

An disadvantageous property of ferrocene is its relatively high volatility, which is important when the anaerobic material is applied to a mechanical part to be glued or sealed, some time before the composition of the part. The volatility limits the open sizing time of the material. However, volatility can be regulated, e.g. by using the polymers or derivatives proposed according to the invention containing strongly polar groups, e.g. the acid esters. An example of such an acid ester is the reaction product of hydroxyethylferrocene and maleic anhydride.

Activator reactivity, i.e. its effect on the cure rate of the anaerobic material depends on the type of activator compound selected. Thus, the cure rate can be controlled by the appropriate choice of ferrocene derivatives or derivative mixture, whereby the cure mechanism can be adapted to the conditions of use from case to case. The cure rate appears to increase relative to that obtained with ferrocene using 30 ss, 40 '7læÛ4281-3 substituent groups which tend to give off electrons to the iron nucleus (eg alkyl or cycloalkyl group), and appear under the influence of groups which have a tendency to take up electrons (eg acyl or alkenyl groups) The electron donating groups are preferred because they tend to maintain the cure rate obtained with unsubstituted ferrocene. Although most electron-accepting groups have joint-curing or bonding properties that are better than those previously known, they tend to give a lower cure or bond rate than unsubstituted ferrocene.

The ingredients described above are used in combination with a strong acid, preferably an acid, whose pKa is below about 3.0, preferably below 2.0 and most preferably not more than 1.5. The acid should be sufficiently soluble in the rest of the anaerobic material in order to be able to be distributed homogeneously throughout the polymerizable mass. Although not absolutely necessary, it is preferred that the acid be an organic acid. Although acids with extremely low pKa value work exceptionally well, it is not necessary to use extremely strong acids, and it is often desirable to avoid their use in view of the attendant risks and corrosion problems. Mixtures of several acids can also be used. Examples of acids which correspond to the above definition are sulfonic acids, e.g. toluenesulfonic acid, nitrotoluenesulfonic acid and propanesulfonic acid, dichloro- and trichloroacetic acid and phosphonic acids, e.g. benzenephosphonic acid. Other useful acids are maleic acid, malonic acid and acetylenic acids, e.g. acetylenecarboxylic acid and acetylenedicarboxylic acid, and saccharin, with maleic acid and / or saccharin being preferred.

When the acid is added to the mixture of polymerizable acrylic acid ester monomer and peroxy polymerization initiator (in the absence of the activator, which is then used as a second component),% of the anaerobic acid should be present in an amount of between about 0.01 and about 5 weight of material. Larger amounts can be used, but this is unnecessary and usually does not bring any benefits in the form of increased curing speed and through-curing ability. A suitable amount range is between about 0.1 and about U%, preferably between about 0.2 and about 3% by weight of the anaerobic material.

When the activator and the acid are mixed and used together as a second component, the ratio of these two can vary widely. It is important, however, that a sufficient amount of each be used in HU 7401081-3. Since the second component (part) is preferably applied as a surface treatment agent, the ingredients are preferably dissolved in a volatile solvent. A suitable activator content in the solvent is between 0.05 and 10%, preferably between 0.1 and 5%, by weight of the solvent. Comparable levels of the strong acid are between 0.1 and 5%, preferably between 0.5 and 3%.

The solvent used is one that evaporates easily, e.g. one which evaporates from a thin film in less than about 5 minutes, preferably in less than 2 minutes, at room temperature.

When used in aerosol containers, it is also possible to use solvents which are liquid at the pressure prevailing in the pressure vessel, but are gaseous under normal atmospheric pressure and temperature conditions. Examples of solvents which can generally be used, individually or in different combinations, are benzene and toluene, chlorinated and / or fluorinated hydrocarbons, e.g. trichloromonofluoroethane, methylene chloride, methyl chloroform, trichloroethylene and trichloroethane, paint solvents, e.g. acetone, ethyl acetate and methyl ethyl ketone, as well as alcohols, e.g. ethanol, propanol and isopropanol. The solution of the active ingredients can be applied directly to the intended joint surfaces, after which the binder evaporates and leaves a layer of the activator on the joint surfaces. Since the pretreatment agent can be applied in several layers or in a layer of any thickness, the amounts of active ingredients dissolved in the solvent are not a critical factor, and the general areas of use have been set forth above.

As is well known, there are many additives which can be incorporated into anaerobic materials. Several of these additives can be used in materials of the present invention. The most common Ä additives are latent polymerization accelerators, i.e. substances which do not themselves initiate the curing, but accelerate the curing after it has been triggered by the polymerization initiator. Many different polymerization accelerators are known, and the present invention involves the use of any polymerization accelerator which can be incorporated into the anaerobic material without adversely affecting its essential intended properties. However, due to the exceptional curing properties of materials according to the invention, no particular polymerization accelerators are generally needed.

Useful accelerators which may optionally be added are primary, secondary or tertiary organic amines, containing up to 20, preferably 15, carbon atoms, organic sulphimides, 10 15 20 25 30 35 40 74011281 -3 11 _ _ _ .H_lm ___, _ containing up to 15 carbon atoms, and amides containing up to about 10 carbon atoms. These accelerators are generally used in amounts of between 0.2 and about 5% of the weight of the material.

Other common additives are polymerization inhibitors, which provide protection against accidental polymerization of the acrylic acid ester monomer, before the material is used, e.g. during storage. The quinones have been found to be particularly effective polymerization inhibitors and can be used in the present context. Examples are β-naphthoquinone, 2-methoxy-1,4-naphthoquinone and β-benzoquinone. Other inhibitors are hydroquinone and stable, nitroxide-free radicals. These inhibitors are usually used at levels of between 0.005 and 0.05% by weight of the anaerobic material.

Other typical ingredients that can be used to give the material desirable properties are thickeners, dyes, binders and thixotropic agents. These materials can be used in desired combinations and proportions, provided that they do not adversely affect the anaerobic nature of the material or other essential properties thereof.

The described anaerobic materials can be used in many different processes for gluing objects. For example, the ingredients indicated may be mixed and the whole mixture as such applied to the articles. In this case, it is most convenient to mix all the ingredients, except the strong acid or activator, in advance. In view of the rapid curing of the ready-mixed system, the last ingredient is added immediately before gluing. Even in such a procedure, however, great care must be taken in view of the extremely high cure rate. It should often be difficult to both apply the material and then assemble the objects in the correct position, before a considerable hardening has taken place.

It is generally most convenient to carry out the gluing using surface activating agents, wherein either the acid or the activator combination is applied to one or both joint surfaces in a first step. The rest of the material (the monomer initiator mixture f on the material and any additives to be used) is applied to one or both joint surfaces in a separate step. In this way, the gluing can be carried out much faster, since the various active ingredients have been brought into contact with each other, and there is therefore little risk that excessive curing will have time to take place before the gluing is completed.

Unlike many prior art surfactants, the strong acid and activators of the present invention do not readily undergo any chemical degradation under the action of oxygen, so they can be applied to the joint surfaces well in advance of the application of the rest of the binder or sealant. This can be extremely advantageous when working in production lines.

After application of the material to the joint surfaces, the objects are maintained in the given mutual position, in which they are to be joined, until the curing has progressed sufficiently far. Although slightly longer curing times are required for larger joints or gaps, it has generally been found that the curing progresses within a few minutes to the extent that no further retention of the objects is required. In very narrow joints, e.g. of the order of 0.075 mm or less, "fixation" usually occurs within a few seconds.

As indicated above, the curing also proceeds when applying the surface activator technique through rather wide joints, e.g. of width 0.5 mm or even larger, within a reasonably short time. This was a very surprising and unexpected phenomenon, as explained above. The following exemplary embodiments illustrate methods, materials and adhesive dressings within the scope of the invention. Unless otherwise stated, quantity ratios and concentrations are by weight.

Example 1 An anaerobic comparative material was prepared by adding 4% cumene hydroperoxide to polyethylene glycol dimethacrylate (number average molecular weight 330). The mixture was treated with 0.05% tributylamine to remove any acid residues that might remain in the monomer. Three samples were taken from this comparative material, and the first of these samples remained unchanged. The second sample was charged with 0.01% ferrocene, and the third sample was charged with 0.01% pentanedione iron. The storage stability of the three samples was then determined by means of a standardized stability test, in which a test tube with the sample was placed in a bath with a constant temperature of 8200. The time elapsed until the first gelled material appeared in the test tube was taken as a measure on the storage stability of the product. g Approximately 30 minutes is considered to be the minimum acceptable time for material of this type, and a preferred time is 60 minutes. The stability of the first test was found to be 295 minutes, the second test 200 minutes and the third test less than 1 minute. This example reveals the surprisingly good stability of anaerobic materials which have been added with ferrocene. Example 2 Another sample was taken from the anaerobic comparative material of Example 1, and this sample was added with 0.05% ferrocene.

This sample was then used in combination with a surfactant, consisting of 2% by weight of trichloroacetic acid in methyl chloroform.

The curing properties of the combination were measured by determining the "fixture time" on glass sheets of 25 X 75 mm. In this test, the activating agent of about 25 mm was applied to one end portion of each of two dyes. equal glass sheets, after which the solvent was allowed to evaporate. A drop of the anaerobic material was then applied to the thus pretreated surface of one glass sheet, and the pretreated surface of the other glass sheet was immediately contacted with and across the treatment layer of the first glass sheet. The time was noted until one disc could not be moved relative to the other by applying weak pressure with one finger. In this test, the fixture time was found to be less than 5 seconds.

The same test was repeated with the joint width between the two glass sheets set at approx. 0.5 mm using metal wire with a diameter of 0.5 mm as a spacer between the sheets. The fixture time in this sample was found to be less than 5 minutes. The anaerobic comparison material was not fixed at this joint width within ZH hours. Example 3 Another sample was taken from the anaerobic comparative material of Example 1, and this sample was charged with 1% by weight of toluenesulfonic acid. The test given in Example 2 was repeated, but the surface activator in the present example was 0.5%. solution of the ferrous in methyl chloroform. The bonding time on glass sheets in this test was about 2 seconds, and the bonding time on glass sheets with a joint width of 0.5 mm was less than 5 minutes.

Example 4 Two surface activators were prepared for use in this example, namely a surface activator A containing 2% by weight of nitrotoluenesulfonic acid and 1% of ferrocene and a surface activator B containing 2% by weight of nitrotoluenesulfonic acid and 0.5% by weight of ferrocene.

A comparative activator containing only 0.5% ferrocene (and no strong acid) was also used. In all cases the solvent was methyl chloroform. Each surfactant was then used in combination with several different mixtures of monomers and peroxy initiators, as shown in Table I. In all cases, the polymerizable monomer consisted of the polyethylene glycol dimethyl acrylate of Example 1. the following combinations were tested with respect to fixture time on glass sheets, and in all cases this time was at most 10 seconds. The materials were also tested on glass sheets with 0.5 mm joint spacing. The peak times are summarized in Table I.

Table I Peroxy- Fixing time (min) on glass sheets, 0.5 mm initiator joint Activator A Activator B Control test Cumin hydroperoxide 7 10> 60 (4% by weight) t-butyl perbenzoate 5 5> 60 t-butyl hydroperoxide 6 12> 180 Example A sample of the the anaerobic comparative material of Example 1 supplemented with 0.05% ferrocene, was used in combination with surface activators, containing various kinds of acids. The fixture time on glass sheets was determined in the manner described in the previous examples. In all cases the acid was applied in the form of a 2% solution in methyl chloroform. The acids used and the obtained fixing times are given in Table II.

Table II - Ptxturic time Nitrotoluenesulfonic acid Trichloroacetic acid I Tololene sulfonic acid Dichloroacetic acid Example 6 A methacrylate-terminated urethane compound was prepared by condensing a diisocyanate with hydroxyethyl methacrylate.

With this product were mixed 053% saccharin, 2.7% cumene hydroperoxide and 1% maleic acid, whereby an anaerobic adhesive was obtained. This was applied to steel nuts and bolts (dimension 3 / 8-24) which had been pretreated with a methyl chloroform solution of ferrocene (2%) or one of several different ferrocene derivatives (1%). The ferrocene polymer listed in Table III is a low molecular weight material of the formula 10 15 20 25 30 15 The torque required on average to turn the nut relative to the bolt (i.e. to break the polymer lock) measured: at different times after screwing together a series of such nuts and bolts, and the values obtained were taken as a measure of the cure rate of the anacroba material. The activators used and the results obtained are given in Table III.

Table III Torque (kpm) at different curing times Activator 5 min 15 min 20 h Ferrocene 1 0.69 1.38 2.48 Acetylferrocene 0.02 0.03 2.65 Benzoylferrocene dissolved 0.02 2.65 Hydroxyethylferrocene 0.63 1 1,85 1,1'-dibutylferrocene 1,61 1,85 2,54 Butylferrocene 1,85 1,90 2,65 Ferrocene polymer 1,73 2,54 3,11 Example 7 A polymerizable anaerobic material was prepared by preparing polyethylene glycol dimethacrylate was added with about 2% cumene hydroperoxide. The viscosity of the material was below 500 cP. Pretreatment solutions were prepared by dissolving ferrocene and the ferrocene derivatives listed below in methyl chloroform. The percentage was about 2% of the solution and the derivatives 1%. Fixture tests were performed at 0.5 mm joint width, as described in Example 2; The fixture times are given in Table IV.

All tests gave strong connections.

Table IV Activator Fixture time (min) at 0.5 mm joint width Ferrocene 2 A 18 Hydroxyethylferrocene 15 Butylferrocene _ '25 Dibutylferrocene 2 27 t ~ amylferrocene Ii 5 35 Acetylferrocene 300 Benzoylferrocene I f> 360, <1080

Claims (17)

17405281 '-3 16 PATENTKRAV An anaerobic adhesive or sealant, characterized in that it consists essentially of a polymerizable monomeric acrylic acid ester and 0.1 to 10% by weight of a hydroperoxide or perester active as a peroxy polymerization initiator capable of triggering polymerization of the monomer in absence of oxygen, partly 0.005 - 1% by weight of an activator in the form of an organic compound containing a ferrocenyl group, partly 0.1 - 5% by weight of acid, whose pKa is at most 3. Agent according to Claim 1, characterized in that the polymerizable acrylic acid ester has the formula R 20 in cIJRZ I II l _ H2c = c_nc.-o ___- xocc =, cH2 where R2 represents a hydrogen or halogen atom or a alkyl group with not more than 4 carbon atoms, Q is a positive integer and X is an organic radical with at least 2 carbon atoms and with a total binding capacity equal to q + 1. 3. An agent according to claim 2, characterized in that q is 1, 2, 3 or H. Agent according to claim 2, characterized in that the peroxy polymerization initiator is a hydroperoxide of the formula Ru (00H) 2, wherein R "represents a hydrocarbon group containing not more than about 18 carbon atoms, or a perester according to the formula A-co -oos, where- A denotes R 5 -co-ooß or a nitrogen / carbon group containing up to 10 carbon atoms, B denotes R 5 -OO-COR 6 or hydrocarbon group containing up to 10 carbon atoms, and R 5 and R 5 denote hydrocarbon groups containing up to 10 carbon atoms 10 carbon atoms V Agent according to claim 1, characterized in that the activator is ferrocene, a ferrocene containing polymer or an acyl, aryl, alkyl, hydroxyalkyl or alkenyl derivative of ferrocene or a mixture of these substances. Agent according to claim 5, characterized in that the activator is ferrocene, "Nea-w v. .O -,» '7404281-3 17 Agent according to claim 5, characterized in that the activator is a ferrocene polymer containing up to about 20 dicyclopentadienyl iron units. Agent according to claim 7, characterized in that one or both of the cyclopentadienyl groups bears substituents. Agent according to claim 5, characterized in that the activator is an acetyl, benzoyl or benzenesulfonyl derivative of ferrocene. Agent according to claim 5, characterized in that the activator is an alkyl derivative of ferrocene. Agent according to claim 5, characterized in that the activator is a hydroxyalkyl derivative of ferrocene. Agent according to claim 5, characterized in that the activator is an alkenyl derivative of the ferroe. Agent according to claim 5, characterized in that the activator is a breeding derivative of ferrocene. Agent according to any one of claims 1 to 13, characterized in that it is in the form of a two-part preparation, each part containing the polymerizable acrylic acid ester and the peroxy initiator and the other part containing the activator and the acid. Composition according to Claim 14, characterized in that the second part consists of a solution based on a volatile solvent containing 0.05 to 10% by weight of the activator and 0.1 to 5% by weight of the acid. Composition according to any one of Claims 1 to 13, characterized in that it is in the form of a two-part preparation, one part of which contains the polymerizable acrylic acid ester, the peroxyinitiator and the activator and the other part of which is a solution of the acid in a volatile solvent. Composition according to any one of Claims 1 to 13, characterized in that it is in the form of a two-part preparation, one part of which contains the polymerizable acrylic acid ester, the peroxy initiator and the acid and the other part of which consists of a solution of the activator in a volatile solvent. PROMISED PUBLICATIONS: Switzerland 440 694 (39 b: 22 / Û6) US 3 046 262 (260 ~ 89.5) Anita publications: Plaste und Kautschuk. 17 (1970): 3, pp. 182-184 (Kleinert, H).