DE1594096A1 - Method for gluing adjacent surfaces - Google Patents

Description

DR.-ING. WALTER ABIT2 DR. DIETER MORF

Patent attorneys

8 Munich 27, Pienzenauerstraße 28 Telephone 483225 and 480415 Telegrams: Chemindus Munich

15th March 1966 A-52 238-DiVo

LOCTITE CORPORATION 705 North Mountain Road, 11 Newington, Connecticut, V.St.A.

Method of gluing adjacent surfaces

The invention relates to a method for accelerated gluing Adjacent surfaces under exclusion of air Use of a mixture of polymerizable compounds the general formula

H ₂ C

CH ₂ ,

in which R is a hydrogen atom, a CH ₃ -, C ₂ H ₅ -, CH ^ OH group or the remainder

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-CH ₂ -0-CC-CB ₂ 9

R ¹

R ^{1 is} a hydrogen or chlorine atom or a methyl or ethyl group, R "is a V / aerator atom, a hydroxyl group or the remainder

- ο - c - σ «OB ₂ »

m is an integer with the minimum value 1 »e.g. from 1 to 8 or more, for example from 1 to 4 einsohliesalloh, η an integer with the minimum value 1? z »B. from 1 to 20 or more and ρ has the value 0 or 1 with peroxide catalysts and a separately applied accelerator.

In US Pat. No. 2,895,950, an aerosol curing compound is bee dir Leben made from monomers of Make use of the above formula and if air or oxygen is excluded in the presence of certain organic hydroperoxide catalysis, they will quickly and spontaneously result in polymerization passes the solid state. In addition to the hardening ability under the exclusion of air, these agents offer another advantage long shelf life in a liquid state as long as it is with Are in contact with air, which is particularly valuable for

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ben adjacent surface »let the adhesive last for longer Periods of time in the presence of air can be kept without polymerizing o However, if it is between two adjacent ones Areas is brought, takes place as a result of the air exclusion Polymerization with the formation of a strong bond between the neighboring surfaces.

As described in the cited patent, can conventional accelerators such as tertiary amines, ascorbic acid, phosphorous acid esters and quaternary ammonium salts, be added to reduce the required amount of hydroperoxide catalyst or the use of catalysts to enable lower oxygen content ο Such accelerators have proven to be advantageous and enjoy widespread use o

As a result of the increasing use of these resinous adhesives in the production of various pieces of equipment on the production line, there has been an increasing demand for adhesives which, after the parts are joined together, cure quickly and, in particular, without the application of heat. Although the mixtures described in the cited US AP & Λ ent writing, if they are modified by adding various accelerators customary up to now, c.-ir. rapid hardening after

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have to assemble the parts without heating, there is a need for nooh faster curing adhesives, which in the Period of outlines after joining without application provide high strength from heat

It is an object of the invention to provide an air-curing resinous adhesive in which the mixture of resin and catalyst does not exist in the presence of air polymerizes, but very fast in the absence of air hardened to form a strong bond between adjacent surfaces.

According to the invention, a polyamino compound of the general formula is used as the accelerator

R ² B ¹ K ²

tj / L

R ²

in which the radicals R are hydrogen atoms or unsubstituted alkyl groups, the best R ^{2 is} hydrogen atoms, alkyl groups or substituted alkyl groups and η has the value 2 or 3 separately applied to one or both of the mutually bonding surfaces, with a subsequently applied coating of « A mixture of catalyst and monomers, as described in the patent specification mentioned

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ben 1st, hardens very quickly in contact with the surfaces to be bonded.

Eb was further found »that the accelerating effect These polyamino compounds can be greatly increased by adding certain amounts of an organic acid ο

By applying the components of the system separately according to the invention, the desired mixing takes place Place on the spot without affecting the shelf life of the catalyst and monomers! existing binder is impaired.

The preferred embodiment of the invention consists in the use of an accelerator mixture which contains the polyamino compound in a volatile organic carrier, which expediently at the same time has good cleaning properties for the surfaces of the parts to be joined. The preferred accelerator mixtures are made durable for longer periods of time by adding a small amount of a dihydric alcohol and preferably contain in interest its highest effectiveness an organic acid. They can also contain a heavy metal ion for activation.

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Examples of monomers which can be used as binders in the process according to the invention are following diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di (pentamethylene glycol) dimethacrylate, tetraethylene glycol diacrylate, Tetraethylene glycol di-chloroacrylate), diglycerin aiacrylate, diglycerin tetramethacrylate, tetramethylene dimethacrylate and Ethylene dimethacrylate. These monomers do not need to be in a pure state, but can be of technical grade and contain inhibitors or stabilizers.

Im'allgemeinen system need only O _t 1 percent to contain # hydroperoxide catalyst. however, depending on the activity of the monomer, amounts of about 0.5 to 8.0% by weight are preferably used in order to achieve the highest curing rate and the greatest durability. Amounts of catalyst of more than 20% by weight do not provide any additional advantage, but only act as a diluent for the hardened material.

The polyamino compounds used as accelerators in the process according to the invention already have amounts of 0.01 wt. # Of that consisting of the monomer unit and the catalyst

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Binder has a clear effect, and it can even be used in amounts of 10.0% by weight, although in the case of some monomers and accelerators hardening occurs almost instantaneously. VorBUgsweise to handling ie after the activity of the mixture of monomer and catalyst, and after the activity of the relevant polyamine ranging from 0.1 to 2.0 percent, the amount of purposes as accelerators serving polyamino achieve the highest activity and ease. £ of Bindemittelaystems lie.

The effect of the change in concentration of the polyamino compound serving as an accelerator is shown in Table Io. The values relate to tests in which a few drops of a mixture of 7 wt. Nuts and bolts are applied and these are then tightened feet, whereupon the binder is allowed to harden at room temperature within the specified time periods. Then the predominant torque developed by various mixtures is determined according to the method described below _o

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Tabel I. Predominantly a
Drelmomenfe,
mkg Crowd of accelerated,
Gew "- ^ this binder-
ey stars Hardening ~
Time,
There. 0.138 0.1 20th 0.830 0.1 35 1.037 0.5 20th 1.74-2 0.5 35 1.452 1.0 20th

Rerbindangen Examples of erfindungBgemäss eu Polyamina used are 1,2-Proiandis "In, 1, 3-propanediamine, Jf, If-M-ethyl ~ i, 3-propandiauin, tetraethylenepentamine, Triäthylentetranin, I- (3-Aminoprcpan) -1, 3-propanediamine _t ithylendianin and H (2-ithanol) -äthy3endiaBin.

The aforementioned polyamino compounds of the above general In the interest of the highest activity, formulas are those for which η «= 2. Bceondsre examples include 1,2-propanedifinine and Äthylerdiania

It has also been found that the accelerating rate of the polynmino compound is still greatly increased if an organic acid is exuded. Even small amounts of acid, that is, 10% of the acid equivalent m of the polyamine, produce a distinct effect. Ss is assumed that the

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organic acid kit de «Auiin forms an ammonium salt» what τοπ. Let the advantage, because the toxicity and volatility are thereby vuroinc.ert, which is particularly important when the accelerator already tented longer before joining is applied to the surfaces of the parts concerned so that a film forms on the surface to be bound » The acid can be used in amounts of up to three acid equivalents Folyamino part binding cannot be used.

In general, that caused by the organic acid increases Increase in acceleration sharply until a great acid equivalent of the polyamide bond is present} a further However, increasing the Siuremenga no longer brings about any appreciable increase in acceleration and can even eu Trouble caused by corrosion.

Accordingly, the organic acid is preferably used in amounts of about 0.5 to 1.5 acid equivalents of the polyamino bond to achieve the best effectiveness. The effect of various amounts of organic acid tu FelTaainoTerbind results from Table II. In these experiments the nuts and bolts are first washed in a "suug" the changing amounts of SXL 1,2-Iropmndiamine and 2-ethylcaproic acid _t dissolved in; K) Isopre ^ glalkehol rmd 61 ml of trichlorethylene, contains. the

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Nuts and bolts are dried, and then are a few drops of a binding agent is sprayed on the crew passageways, which contains 7.0 wt .- $ 4 Ouaolhydroperosyd, 2.0 wt .- ^ triethylaaia and tetraethyleaglylcoldiiietheorylat, whereupon the nuts and bolts are put together. After the specified time, the predominant torque of the Binder determined.

Accelerator, ToI. ^

0.35 *

0.35 *

0.35

0.35

0.75

0.75

T able II

Sutrients, acid equivalents

1 1 1 2

Time,
Min. Torque, 5 0.138 10 0.346 5 1.244 10 2.074 5 2.005 5 2.469

* Accelerator (no acid) dissolved in srichlorethylene mi 100 al chne alcohol.

Example of organic satires that can be used in accordance with the invention are 2-ityloaproic acid, formic acid, BssigsSnre, propionic acid, oaproic acid, 2-methlyloaproic acid, 5-methylcaproic acid, Vaphthenic acid, lauric acid, linoleic acid and butyric acid.

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The polyamines are dissolved in a suitable organic carrier, which evaporates easily and leaves a thin film of the polyamine. When using a solvent that dissolves fat as at least one part of the carrier, the organic carrier simultaneously fulfills the task of cleaning the surface of the parts. This is particularly advantageous, since a film of grease or dirt can seriously impair the subsequent polymerization of the binder.

It has been found that small amounts of dihydric alcohols (glycols) greatly improve the stability of the solution of the polyamino compound in the organic carrier. Even quantities ν chi about 0.25 wt _o # cause a significant increase in stability. Amounts of more than about 10.0% by weight lead to the deposition of a non-volatile film of such thickness on the parts to be treated that the spread of the subsequently applied binder on the adjacent surfaces is disturbed and consequently the hardening in contact with d -sn underlying metal surfaces is impaired. Accordingly, the accelerator mixture preferably contains 0.5 to 7.5% by weight, in particular 1.0 to 5.0% by weight, of dihydric alcohols (glycols).

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Ethylene glycol and 1,2-propylene glycol are all special proven beneficial; however, higher glycols such as butylene glycol, polyethylene glycol and pentanediol can also be used will.

Although the mode of action of dihydric alcohol has not yet been elucidated theoretically, it is assumed »that he forms a coordination complex compound with the amino groups of the polyamino compound and thereby beaohränkt their reactivity with impurities in the Accelerator mixture are contained or are introduced afterwards. The dihydric alcohols have sioh as Proven particularly effective when the accelerator mixture a heavy metal salt and the organic carrier contains a halogen-containing ε lubricating grease solvent.

It has also been found that low molecular weight monohydric alcohols increase the wetting power of the accelerator mixture and also appear to increase the consistency of the mixture. The monohydric alcohols also increase

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the solubility of dihydric alcohols in various organic solvents such as halogenated hydrocarbons open ο

The monohydric alcohols offer a clear advantage in amounts as low as 1.0% by weight and can even be used if necessary form practically the entire organic carrier · The preferred genes contain at least 10.0% by weight and preferably at least 20.0 wt. # of monohydric alcohol.

Since the organic carrier should evaporate quickly, should the monohydric alcohols have a low molecular weight »In this regard, alcohols with 1 to 5 carbon atoms have each other in the molecule, such as methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n ~ butanol, isobutanol, tert-butanol, Isopentanol and tert-pentanol, proved to be satisfactory. If butanols and pentanols are used, they should be used in amounts less than about 50 wt. #, And the remainder of the carrier is said to be a rapidly evaporating solvent exist so that the volatility of the mixture is large enough. For some purposes, methanol can be used in Given its high flammability, high volatility

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Furthermore, it was found that the low molecular weight monohydric alcohols increase the irritability of the beach accelerator mixture and also to increase the stability of the mixture desire. The monohydric alcohols also increase the solubility of the dihydric alcohols in various organic Solvents such as haie generated hydrocarbons.

They monovalent alcohols have a distinct advantage already in Hengsn τοη 1.0 wt. flG and can even, if necessary, practically form the whole organic carrier. The preferred chemicals contain at least 10.0% by weight and, in some cases, at least 20.0% by weight of monohydric alcohol.

Sa, the organic vehicle is to rerdampfen sehaell, are the monohydric alcohols never eirj Ir Ige β molecular weight have * In this respect alcohols habet having 1 to 5 carbon atoms in the molecule, never iethylfvlkohol, ethyl alcohol, a-PropaDol, Teopropanoli n-butanol _r laobutanol, tert-butanol, isopentanol and tert-pentanol were found to be satisfactory. If butanols and pentanols are used, they should be used in amounts less than about 50 wt Methaftol can be used for some applications in view of: its easy batflammability, high escape rate

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kf.it and toxicity may be undesirable.

To be able to achieve the best dissolving power for greases and other favorable properties such as the most favorable volatility, low cost and low flammability highly active and volatile Sehmierfettlöeungaalttel form a substantial proportion of the nasty mixture. The preferred Grease solvents are non-flammable and they include halogenated hydrocarbons such as trichlorethylene. Perohlorethylene, tetrachlorethylene, tetrachlorethylene uad methylene chloride; however, flammable solvents such as mineral spirits, e.g. Stoddard 'see β solvents (Siod range 93 to 204 ° C) and aromatic hydrocarbons such as xylene are used.

The stability of the mixtures with different proportions of alcohol to chlorinated lubricating grease solvent is shown in Table III. With these Mixtures containing 1.36 al 1,2-propanediamine, 3.0 ml of 2-ethyloaproic acid and 0.37 ml of basic cupricarbonate contained in various organic carriers, iM Oven aged at 60 ° C. With this accelerated retirement corresponds to a shelf life of one day of about 16 days at room temperature.

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Table III Organizational carrier

3 _t 3 ml trichlorethylene 2 »O B1 propylene glycol

93 »3 ml trichlorethylene 2.0 ml propylene glycol

90.0 ml trichlorethylene 5.0 ml propylene glycol

190.0 ml trichlorethylene 5.0 ml propylene glycol

385.0 ml T.richlorethylene 10.0 ml propylene glycol

* 385.0 ml of trichlorofithylene 1O ₉ O ml of propylene glycol

96.0 al triehlor & ethylene 4.0 ml propylene glycol

86.0 ml trichlorethylene 10.0 ml butanol 4.0 ml propylene glycol

76.0 ml trichlorethylene 20.0 ml butanol 4.0 ml propylene glycol

66.0 ml trichlorethylene 30.0 al butanol 4.0 ml propylene glycol Shelf life, days to teraagen

58

67

16

42

Goes black in 37 days; forms precipitation for days "

Will turn black after 55 days, however no precipitation and no separation »

No par-banding or tere-worsening aaeh 55 days

* Without baelsehee copper carbonate

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The PolyaminoYerMnaung is best used in low concentration in such organic carriers because concentrated solutions apparently form a relatively thick piIa that protects the metal surface and the Curing speed decreases as soon as the mixture of monomer and catalyst is subsequently in contact with the surface Is brought into contact. The polyamino compound already has a clear effect in concentrations tor 0.05 (Jew · - ^ and can also nc cn in concentrations τοη 10.0 Grew · -? » can be applied. They contain preferred solutions 0.5 to 2.5% by weight of a polyamino compound together with an organic acid.

The effect of different concentrations of polyamino compound in such pretreatment can be seen Table 17. In these attempts the nuts and Screws first washed by Lusurgen, which contained the specified amounts of 1,2 ~ FropanAiaiLin and 2-ithylcaproic acid ic. Triohloräthylec contained, whereupon a few drops of the stuff apart from the fionoaeren and dwi catalysts according to Tables I and II has been applied.

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159A096

A-52 258 Table IT t I acid _r ToI. Torque mkg Accelerator, Toi. -4 10.0 0.864 5.0 5.0 1.797 2.5 2.5 2.143 1.25

It can be advantageous, apart from the polyamine and the orga- ' In addition to the acid, a polyvalent heavy metal ion has to be added as an activator. Although most metals catalyze the hardening of the binder, certain metals especially cadmium and zinc, not always catalytic Effect. Accordingly, the addition of a polyvalent metal ion to the gate treatment solution can be reduced in a small amount Quantities τοη 0.05 to 1, C wt .- ^ τοη be part of the gate. Belong to the connections that can be used in this sense Copper carbonate, pearl chloride as well as cobalt, manganese, blue, Copper and Sisenseifex. · The addition of such compounds reduces the resistance of the accelerator solution, and »β It may therefore be necessary to use larger amounts of dihydric alcohol in this case than in those Mixtures that do not contain meiallion.

Below is a particular composition for a '3e-

ech accelerigergeKiseh specified for door treatment, the sisi as

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exceptionally effective in combination with the mixture of monomers! and catalyst according to the above-mentioned USA patent.

Components Amount, al

1.2 ~ propanediamine 0.5

2-ethylcaproic acid 1,4

Butanol 30.0

1,2-propylene glycol 3.0

Trichlorethylene 65.1

100.0

If the abovementioned coating agent is to be used without any activator, add 0.18 g of basic cupric carbonate

This door treatment can be applied to one or both of the surfaces to be joined by dipping, brushing or spraying, followed by allowing the parts to dry for a few minutes. Eich aerosol atomizers have proven to be particularly effective for application. You pre-treated Parts can be used immediately after drying or stored for later use. Although sometimes the Effectiveness of the accelerator in the film formed somewhat wears off, the parts that have been treated can in general

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without significant loss of effectiveness for several days " to be preserved "

This can be seen from Table 7, which reports on associations in which the nuts and bolts were initially treated with the preferred solution given above. Some of the nuts and bolts were taken out immediately with the help of the Gemisohee Monomers and catalyst combined, others were stored in the air at tree temperature for 3 days and only then with the said Gemisoh put together.

Table Y Main torque, mkg

Hardening time, min. Assembled immediately Stored 5 0.622 1.106

10 1.037 1.037

20 1.866 1.936

If the polyamine compound serving as all accelerators is in The door treatment solution is applied, other acceleration ± £; he in the one consisting of the mononeren and the catalyst. Component of the system applied to a However, in this case it can have a double effect the activity is reduced by some types of accelerators] !. Ss can also be of advantage to read the sole

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Reduce the shear strength produced by the system by the use of suitable diluents, especially when working with softer metals such as aluminum and copper, or when the mesh ratio is high.

The mixture of the catalyst and the monomer can «was usually applied in the way that you can use it «Wipe the surfaces that are already in contact with one another and which are already in contact with each other, thanks to the penetration of the capillary action leaves; however, the penetration of the mixture becomes duroh the almost instant hardening on contact old the accelerator is greatly impaired, so that the biadring depth is often greatly reduced. Preferably the mixture is therefore applied before the parts are joined by applying a few drops of it to the surface and letting the mixture spread, or by applying the binding agent by dipping or spraying. In general, it is advantageous to use a thin, low viscosity oil which gives good capillary action, including binding precisely to surfaces that mate with one another or binding parts that have already been joined together duroh penetration or entanglement «wipe the surfaces that are in contact with each other However, mixtures of high viscosity are preferred here.

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Several simple test methods are available for measuring the activity of the adhesive system. According to one method a few drops of the adhesive? stems between the two oblong plates made of glass or metal or made of glass and metal are introduced, the gate in part form a right angle with each other · As soon as the two flats, if nan one Sound her in hand, behave as if she were consist of a stick, the polymerisation of the adhesive has taken place. A more quantitative test is that the plates are not subjected to shear stress determines the shear strength of the bond.

According to another test specimen, the strength of the bond is determined between organs screwed together, iniam you put a few drops of the adhesive system into each other introduces engaging threads of a nut and a screw, tightening the nut up to a certain torque and allowing the adhesive to harden, generally at tree temperature. In some cases this becomes the Breakaway required '' Torque determined, usually however, the prevailing or predominant torque is used as a measure for the strength of the bond. To the predominant To determine the torque of the binding, one takes the mean value of the torques that are required to achieve the Screw or nut on several, usually four or

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five, points after overcoming the torque required to break loose to turn up to a great turn. E.g. one measures the torques required for 1/4, 1/2, 3/4 and a full turn and takes the mean value. Technically, a screw adhesive that develops a torque τοη τοη 0.138 mkg for a 9.525 mm full nut, is considered to be satisfactory.

example 1

An accelerator is prepared by mixing 0.5 ml of 1,2-propanediamine, 1.4 "1 2-ethyleapronic acid, 3.0 ml of 1,2-propylene glycol, 30.0 ml of butanol and 65.1 ml of trichlorethylene". This accelerator solution is made by heating it up Aged 60 ° C and shows no discoloration, precipitation or other signs of spoilage even after 60 days Heating, which results in a long shelf life at room tea temperature. The solution is sprayed onto the thread τοη 9 * 525 mn nuts and bolts and dried for 20 minutes calmly.

": - * i contains triethylamine and Tetraäthyleng] yfcoldimethajrylat, roxyd, 2.0 percent & Cumolhydrope w .-?." Grounded on the threads of dried nuts and Schrauban applied a few drops of GeraiBchee which 7.0 G. Then the kut-

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tern and screws put together and at room temperature ditched. After 5 minutes the predominant torque is 0.830 mkg, after 10 minutes 1.065 mkg and after 20 minutes 1.687 mkg.

If the same mixture of acrylate, hydroperoxide and triethylamine is applied to screws and bolts that are not with the accelerator solution have been pretreated, so developed

After 3 »10 and 20 minutes there is no torque at all, while the predominant torque after 3 hours is 1.383 mkg.

Example 2

Two further accelerator mixtures according to Example 1 are used manufactured; however, the butanol in one mixture is replaced by a corresponding amount of methanol in the other replaced by a corresponding amount of propanol.

After heat aging at 60 ° C, the mixture containing the methanol shows no color change or other signs for deterioration even after 60 days. The mixture containing the propanol becomes chattered after 40 days however, after 60 days there is no precipitation or other signs of deterioration and is fully active. keep.

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These two mixtures are made according to Example 1 by spraying onto the threads of 9 »525 mm nuts and Screwing and subsequent application of the binder according to Example 1 investigated.

The ethanol mixture develops a predominant torque of 1.244 mkg after 5 minutes and one after 10 minutes of 1.272 mkg and after 20 hours one of 1.535 mkg.

With the propanol mixture, the predominant torque is after 5 minutes 1.590 mkg, after 10 minutes 1.452 mkg and after 20 minutes 1.452 mkg.

Example 3

Sin accelerator mixture is made by mixing 0.75 al 1,2-propanedianine, 4,4 »1 2-ethyloaproic acid, 30.0 ml isopropyl alcohol and 65» 0 ml trichlorethylene. That Mixture is used as a bath, in which * 9 »525 om-Huttern and screws next to be washed, whereupon you sis lets dry.

Then a few drops of a mixture, which is 7.0 96 wt

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Bolts and nuts put together and at room temperature be left standing.

Haoh 15 minutes is the mean predominant torque 2.489 mkgο

Example 4

An accelerator mixture is made by mixing 0.375 ml 1,2-propanediamine, 1.1 ml 2-ethyloaproic acid, 15> 0 ml isopropyl alcohol and 83.5 ml of trichlorethylene produced »

In the test according to example 1, this is predominant Torque after 5 minutes 1.244 mkg and after 15 minutes 2 * 074 mkg.

Example 5

It is e.tn accelerator mixture by mixing 0.25 ml Triethylenetetramine and 25 ml of trichlorethylene produced. Screws and nuts (9.525 mm) are washed with the solution, then dried and treated according to example 1 «

After 10 minutes the predominant torque is 1.625 ffkg.

Example 6

A chicken mixture is made from 0.25 ml of 3,3'-diaminodipropylamine, 0.5 ml of 2-ethylcaproic acid and 25 ml of triohlorethylene prepared.

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Bolts and nuts are washed with the solution and then treated with the binder. The predominant torque is after 20 minutes 0.415 mkg.

Example 7

A similar mixture is made from 0.25 ml of 1,3-propanediamine, 1.0 ml 2-Ethylcaproic acid and 25.0 ml of trichlorethylene produced =

After washing with this solution, screws and nuts are assembled with the aid of the aorylate gemisohes according to Example 1 « Da3 predominant torque is 0.277 mkg after 10 minutes and after 20 minutes 0.691 mkg,

Ex iel 8

A similar mixture is made from 0.25 ml of ethylenediamine and 23.0 ml Trichlorethylene-made nuts and bolts are made with Treated this mixture and then put together with the binder. The predominant torque is 0.415 mkg after 10 minutes.

A separate sample of the above mixture is mixed with 1.0 ml of 2-ethyleapronic acid = this results in a predominant one Torque of 0.968 mkg after 10 minutes.

Example Q ^ ~ ^ °

Ee will offer a number of mixtures with different proportions Tetraethylene pentamine in trichlorethylene was used as an accelerator represents. 909840/1543

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After pre-washing the nuts and bolts with the L5-eung and assembly according to Example 1, the following predominant torques result after curing for 20 minutes t

Accelerator, torque *

ToI.-jfe mkg

20 0.277

10 0.415

5. 0.553

Example 10

£ s is a mixture of 1.23 g of Te traäthylenpentanin and 100 al Trichlorethylene produced.

Part of this solution is diluted to 100 pounds with trichlorethylene.

20 al of the diluted solution are mixed with 1.0 ml of 2-ethylpronic acid vareetat.

Ahh de 'method of Examples 1 obtained after 5 th Minn long "hardening with the first mixture a vorwiegendem torque of 0.415 mkg, such mkg with the sweiten Gemisoh one such" 0.760 mkg and the third mixture of 1.244.

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The above description and the examples show that the invention is a new »strongly accelerated, with the exclusion of air; provides hardening β adhesive system,
which obvious advantages for the rapid binding of
Tin -j am Quantity joined surfaces together, especially for working on the! Moving belt, offers »

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Claims (1)

Claims Verfrhrer, for gluing adjacent surfaces through separate application of a mixture of a monomer of the general formula H ₂ C If σ - σ I ¹ - ο (CH ₉ ) 2'm in dt »r R a hydrogen ptom, a CH--, CpH, - odor CHgOH group or the rest 0-C-C = the radicals R 'Waesersöoff' or chlorine atoms, methyl or ethyl groups, R ^w a hydrogen atom, a hydroxyl group or the radical -0-C-C = m is an integer with the minimum value 1, e.g. from 1 to 8 or more, for example, from 1 to 4 inclusive, - 30 - 909840/1543 BAD OR! G; η is an integer with de: n minimum value 1, z * B. from 1 to 20 or more, "and ρ is 0 or 1, with a lower one, for polymerizing the monomer at room temperature a sufficient amount of less as 20 wt, # of a hydroperoxide catalyst and one Amine as an accelerator, characterized in that an accelerator is used "which is a small amount of not more than 10 Ge - * <, # of a polyamine compound of the general formula H C H HH
! £ C-N-i E ¹ ! S ² N - IT in which the radicals R are hydrogen or unsubstituted alkyl « ρ
groups which mean radicals R Wanseretoff, alkyl groups or oxy or aminoalkyl groups, η has the value 2 or 3 and m is 0.2 or 3, dissolved in a volatile organic ir ^ ger, contains 2 · Method according to claim Ί ^ characterized in that nan in accelerate ?. ' an organic Sahire in amounts corresponding to 0.1 to 4.0 Sii-ureäquivelenter the polyamino compound .> used. 3. The method according to claim 1 and / or 2 "characterized in that the accelerator mpn} * eiiie small amount of a ssweiwertigen alcohol in amounts of at least 0.1 wt% Bi # -. * Applies ver ~ · - 31 9098A0 / 1543 BAD DRSGlNAt dot 4. Method n ^ oh one or more of claims 1 to 5? characterized in that there is at least a small percentage of a low molecular weight monovalent in the accelerator Alcohol used " 5 »Method according to one or more of claims 1 to 4 _f, characterized in that the polyamirto compounds are used in amounts of 0.01 to 10.0 Grew, # * 909840/1 543 BATH ORIGINAL