EP1343841A1

EP1343841A1 - Odour-reduced sulphur cross-linked rubber masses

Info

Publication number: EP1343841A1
Application number: EP01989588A
Authority: EP
Inventors: Peter Born; Ralf Sauer; Thomas Zahn
Original assignee: Henkel Teroson GmbH
Current assignee: Henkel Teroson GmbH
Priority date: 2000-12-16
Filing date: 2001-12-07
Publication date: 2003-09-17
Also published as: DE10062861A1; AU2002227999A1; WO2002048252A1

Abstract

The invention relates to hot-setting, reactive compositions of natural and/or synthetic elastomers containing olefinic double bonds, based on liquid polyenes and optionally solid rubbers, vulcanisation systems, comprising sulphur and one or several organic accelerators and/or metal oxides and one or several heterocyclic compounds with at least two nitrogen atoms in the ring. Said compositions are vulcanised by sulphur and sulphur compounds with an avoidance or marked reduction of odour nuisance. Said compositions are suitable as adhesives, sealants, or coating agents, in particular in automobile construction.

Description

"Odor-reduced sulfur-crosslinking rubber compounds"

The present invention relates to heat-curing, reactive compositions based on natural and / or synthetic rubbers and sulfur-containing vulcanizing agents which cause little to no odor nuisance during curing. Furthermore, this invention relates to the use of such compositions, their production and a method for connecting metal parts and / or sealing joints between metal parts.

In modern manufacturing methods for connecting metallic components in machine, vehicle or device construction, especially in automobile construction, the classic fastening methods such as riveting, screwing or welding are increasingly being replaced by gluing. Spot welding in particular, as a source of future corrosion, is suppressed as far as possible or used in combination with structural adhesives. For this reason, there is an increasing need for high-strength structural adhesives and sealing flexible materials. For manufacturing reasons, these adhesives have to be used in automobile manufacture in the so-called bodyshell, ie, these adhesives are generally applied to the unpurified metal surface. These surfaces are often coated with a wide variety of corrosion protection or drawing oils, so that the adhesives used there must not be impaired in their function by these oils. Furthermore, these adhesives must be resistant to the various washer baths and systems, preferably without pre-gelling, and must be able to withstand the high temperatures of up to approximately 240 ° C of the stoving ovens for electrocoating without damage and harden in this temperature range. Furthermore, these adhesives / sealants must have good aging-resistant adhesion on the various galvanized steels such as, for example, electrolytically galvanized, hot-dip galvanized as well as the corresponding thermally post-treated galvanizations or galvanized and subsequently phosphated steel sheets as well as non-galvanized steels and aluminum. Structural adhesives for this Applications must still have a minimum strength of around 15 MPa. Sealing and sealing materials as well as relining adhesives have strengths between 0.2 and 3 MPa. For reasons of the simple workflow, only one-component materials that can be conveyed by pumps and that can be applied by machine are suitable.

Because of the high strength requirements, one-component heat-curing epoxy adhesives were predominantly used for these applications in the past. In addition to the advantages of high tensile strength, epoxy adhesives have a number of decisive disadvantages. The pasty, heat-curing one-component epoxy adhesives do not have sufficient wash-out resistance in the scrubbing and phosphating baths, so that these bonds usually have to be pre-gelled by induction heating or special ovens. However, this means an additional step. Attempts have been made to circumvent this by developing one-component, thermosetting, epoxy adhesives with a hotmelt character, but these require special application systems, since these adhesives have to be applied hot. Another general disadvantage of epoxy adhesives is their tendency to absorb water under the influence of high atmospheric humidity, which can lead to signs of corrosion and weakened adhesion in the adhesive joint. Epoxy adhesives are characterized by a high tensile strength, but their elongation at break is generally very low, even the epoxy adhesives made flexible by the addition of rubber only have an elongation at break of less than 5%. In addition, the use of epoxy adhesives based on low molecular weight epoxy compounds (molecular weight <700) is undesirable for reasons of occupational hygiene, since these low molecular weight epoxy compounds can trigger allergic or sensitizing reactions in contact with skin.

As an alternative, compositions based on vulcanizable rubbers have been used for some time. EP-B-97394 describes an adhesive mixture based on a liquid polybutadiene rubber, powdered sulfur, organic accelerators and, if appropriate, solid rubber. BD Ludbrook, Int. J. Adhesion and Adhesives Vol. 4, No.4, S. 148-150, states that such adhesives based on liquid polybutadienes can achieve strength values which are equivalent to those of flexible epoxy adhesives by appropriate selection of the amount of sulfur and accelerators. While these formulations have good hardening properties and good aging resistance and show reasonably useful adhesion even on normal oiled steel sheet, their use for the various galvanized steel sheets is unsatisfactory, and the elongation at break of these high-strength rubber adhesives is very low.

To improve the adhesion, DE-C-3834818 proposes to use OH-terminated polybutadienes for the liquid rubber. According to EP-B-441244, as functional rubber polymer, in addition to hydroxy-functional homopolymers or copolymers, those having thiol, amino, amido, carboxyl, epoxy, isocyanate, anhydride or acetoxy groups can also be used, but the cured one Adhesive mixture has an elongation at break that does not exceed 15%.

According to EP-B-309903 and DE-C-4027064, polyfunctional epoxy compounds can be added to the adhesive mixtures based on liquid rubbers in order to improve the adhesion or to improve the tensile shear strength. Apart from the fact that it is undesirable to use epoxy resin-containing adhesive compositions for the reasons mentioned above, the adhesive compositions described in the latter two publications are not suitable as structural adhesives since they only achieve a very low strength level of at most 3 MPa.

WO 96/23040 describes high-strength structural raw rubber-based adhesives which are equivalent in strength to epoxy resin adhesives. With these compositions, tensile shear strengths of over 15 MPa can be achieved, the elongation at break being clearly above 15%, very often above 20%.

The abovementioned rubber compositions are preferably used in automobile construction; overall, they have an excellent one The range of properties, disadvantageous and very disruptive is that of

Curing unpleasant smell that is suspected of

Sulfur compounds comes from the vulcanizing agents. Some of the writings of the aforementioned prior art and in particular also the WO

9818853 disclose rubber-based compositions that

Use vulcanizing agents that are free of elemental sulfur. So do vulcanization systems based on peroxides, quinones or

Quinone dioximes also make less smelly products in the

Hardening, however, these compositions are significantly more expensive than sulfur-containing vulcanization systems and sometimes more difficult to handle in production and storage.

Based on this prior art, the object of the present invention was to further develop heat-curing, reactive compositions based on natural and / or synthetic rubbers and the technically evaluated sulfur-containing vulcanizing agents in such a way that the formation of odors during curing is eliminated or at least drastically is reduced.

The solution to the problem according to the invention can be found in the patent claims; it essentially consists in providing heat-curing, reactive compositions based on natural and / or synthetic rubbers (i.e. elastomers containing olefinic double bonds) and vulcanizing agents which

a) 0-10% by weight solid rubber (e) with a molecular weight of 100,000 or higher b) 5-50% by weight liquid (s) polyen (e) with a molecular weight below 20,000 c) a vulcanization system consisting of sulfur and one or more organic Accelerator (s) and / or metal oxide (s) d) one or more heterocyclic compounds with at least two nitrogen atoms in the ring contain.

Another object of the present invention is the use of heterocyclic compounds with at least two nitrogen atoms in the ring to eliminate or reduce the formation of odors during the vulcanization of the thermosetting rubber compositions with sulfur-containing vulcanizing agents, and a method for producing these rubber compositions.

Another object of the present invention is a method for connecting metal parts and / or sealing joints between metal parts, in which

at least one surface of a part is coated with the aforementioned rubber compositions,

- the parts to be connected are assembled,

- and the joined parts, if necessary with mechanical fixation, are heated to cure the reactive composition without unpleasant odors.

The adhesive / sealant compositions according to the invention contain at least one of the following substances:

one or more liquid rubbers and / or solid rubbers or elastomers,

- fine-particle powders made of thermoplastic polymers,

- vulcanizing agents, vulcanization accelerators, catalysts,

- fillers,

- tackifiers and / or adhesion promoters,

- blowing agent,

- extender oils,

- anti-aging agents,

- rheology aids, - Heterocyclic compounds with at least two nitrogen atoms in the ring.

Liquid rubbers or elastomers can be selected from the following group of homo- and / or copolymers:

Polybutadienes, in particular the 1, 4- and 1, 2-polybutadienes, polybutenes, polyisobutylenes, 1,4- and 3,4-polyisoprenes, styrene-butadiene copolymers, butadiene-acrylonitrile copolymers, these polymers being terminal and / or (statistically distributed ) may have lateral functional groups. Examples of such functional groups are hydroxyl, amino, carboxyl, carboxylic anhydride or epoxy groups. The molecular weight of these liquid rubbers is typically below 20,000, preferably between 900 and 10,000. The proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical properties of the cured composition. The proportion of liquid rubber or elastomer normally varies between 5 and 50% by weight of the total formulation. It has proven expedient to use mixtures of liquid rubbers of different molecular weights and different configurations with respect to the remaining double bonds. In order to achieve optimal adhesion to the various substrates, a proportion is used in the particularly preferred formulations

Liquid rubber component with hydroxyl groups or acid anhydride groups used. At least one of the liquid rubbers should contain a high proportion of cis-1,4 double bonds, another one a high proportion of vinyl double bonds.

Suitable solid rubbers have a significantly higher molecular weight (MW = 100,000 or higher) compared to the liquid rubbers. Examples of suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4-double bonds (typically over 95%), styrene-butadiene rubber, Butadiene acrylonitrile rubber, synthetic or natural isoprene rubber, butyl rubber or polyurethane rubber. The addition of finely divided thermoplastic polymer powders brings a significant improvement in tensile shear strength while maintaining a very high elongation at break, which was previously unusual for structural adhesives. This enables tensile shear strengths of over 15 MPa to be achieved, with the elongation at break being clearly over 15%, very often over 20%. The high-strength structural adhesives commonly used to date were based on epoxy resins, which even as flexible adhesive formulations only have elongations at break of less than 5%. The combination of high tensile shear strength values paired with high elongation at break is attributed to the addition of thermoplastic polymer powders according to the invention. According to the invention, a large number of thermoplastic polymer powders are suitable as an additive, for example vinyl acetate, either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives, polyvinyl chloride, vinyl chloride Λ / inyl acetate copolymers, styrene copolymers, as described, for example, in DE A-4034725 are described, polymethyl methacrylate and its copolymers with other (meth) acrylic acid esters and functional comonomers, as described for example in DE-C-2454235, or polyvinyl acetals such as polyvinyl butyral. Although the particle size or particle size distribution of the polymer powders does not appear to be particularly critical, the average particle size should be less than 1 mm, preferably less than 350 μm, very particularly preferably between 100 μm and 20 μm. Polyvinyl acetate or copolymers based on ethylene vinyl acetate (EVA) are very particularly preferred. The amount of thermoplastic polymer powder added depends on the desired strength range, it is between 2 and 20% by weight, based on the total composition, a particularly preferred range is 10 to 15%. Since the crosslinking or curing reaction of the rubber composition has a decisive influence on the tensile shear strength and on the elongation at break of the cured adhesive composition, the vulcanization system must be selected and coordinated with particular care. A large number of vulcanization systems based on elemental sulfur as well as vulcanization systems without elemental sulfur are suitable, the latter being the vulcanization systems based on thiuram disulfides. Vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds are particularly preferred. The powdered sulfur is used in amounts of 1 to 15% by weight, based on the total composition, and amounts of between 4 and 8% are particularly preferably used. Suitable organic accelerators are the dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (for example hexamethylene tetramine) and guanidine accelerators; dibenzothiazyl disulfide (MB) is very particularly preferred ). These organic accelerators are used in amounts of between 2 and 8% by weight, based on the overall formulation, preferably between 3 and 6%. In the zinc compounds acting as accelerators, a choice can be made between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide. The content of zinc compounds is in the range between 1 and 10% by weight, preferably between 3 and 7% by weight. In addition, other typical rubber vulcanization aids such as, for example, fatty acids (for example stearic acid) can be present in the formulation.

Although the compositions according to the invention generally already have very good adhesion to the substrates to be bonded due to the content of liquid rubber with functional groups, if necessary, tackifiers and / or adhesion promoters can be added. Suitable for this purpose are, for example, hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyamino amides, anhydrides and copolymers containing anhydrides. The addition of polyepoxide resins in small amounts (<1% by weight) can also improve the adhesion on some substrates. For this purpose, however, the solid epoxy resins with a molecular weight of significantly more than 700 are preferably used in finely ground form, so that the formulations are nevertheless essentially free of epoxy resins, in particular those with a molecular weight of less than 700. If tackifiers or adhesion promoters are used, their nature depends and amount of the Polymer composition of the adhesive / sealant, on the desired strength of the cured composition and on the substrate to which the composition is applied. Typical tackifying resins (tackifiers) such as the terpene phenol resins or resin acid derivatives are normally used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or resorcinol derivatives are used in the range between 0.1 and 10% by weight.

In principle, all conventional blowing agents can be used to achieve foaming during the curing process, but organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonylhydrazides or sulfonylsemicarbazides are preferred. Examples of the azo compounds to be used according to the invention include azobisisobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitroso-pentamethylenetetramine is mentioned, from the class of sulfohydrazides 4,4'-oxybis (benzenesulfonic acid hydrazide), diphenyl sulfone 3,3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of the semicarbazides the p-toluenesulfonylsemicarbazide. In place of the aforementioned blowing agents, the so-called expandable microspheres, i.e. Unexpanded thermoplastic polymer powders occur that are soaked or filled with low-boiling organic liquids. Such "microspheres" are described, for example, in EP-A-559254, EP-A-586541 or EP-A-594598. Although not preferred, hollow microspheres which have already been expanded can also be used or also used. If necessary, these expandable / expanded hollow microspheres can be combined in any quantity ratio with the above-mentioned "chemical" blowing agents. The chemical blowing agents are used in foamable compositions in amounts between 0.1 and 3% by weight, preferably between 0.2 and 2% by weight, the hollow microspheres between 0.1 and 4% by weight, preferably between 0.2 and 2% by weight .% used.

The compositions according to the invention are preferably free from plasticizers for the thermoplastic polymer. In particular, they are free from phthalic acid esters. However, it may be necessary to determine the rheology of the uncured composition and / or the mechanical properties of the to influence hardened composition by the addition of so-called extender oils, ie aliphatic, aromatic or naphthenic oils.

However, this influence is preferably effected by the appropriate one

Selection of low molecular weight liquid rubbers or by using low molecular weight polybutenes or polyisobutylenes. If extender oils are used, amounts in the range between 2 and 15% by weight are used.

The fillers can be selected from a large number of materials, in particular chalks, naturally ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, heavy spar, graphite and carbon black. Also flaky fillers, e.g. Vermiculite, mica, talc or similar layered silicates are suitable as fillers. It may be expedient that at least some of the fillers have been surface-pretreated, in particular a coating with stearic acid has proven to be expedient for the various calcium carbonates or chalks in order to reduce the moisture introduced and to reduce the sensitivity to moisture of the cured composition. In addition, the compositions according to the invention generally contain between 1 and 20% by weight, preferably between 8 and 15% by weight. Calcium oxide. The total proportion of fillers in the formulation can vary between 10 and 70% by weight, the preferred range is between 25 and 60% by weight.

Against the thermal, thermooxidative or ozone depletion of the compositions according to the invention, conventional stabilizers such as sterically hindered phenols or amine derivatives are used, typical quantity ranges for these stabilizers are 0.1 to 5% by weight.

Although the rheology of the compositions according to the invention can normally be brought into the desired range by the selection of the fillers and the quantitative ratio of the low-molecular liquid rubbers, conventional rheological aids such as, for example, pyrogenic silicas, bentones or fibrillated or pulp short fibers can be used in the range between 0.1 and 7% are added. In addition, other conventional auxiliaries and additives can be used in the compositions according to the invention.

Examples of suitable heterocyclic compounds are imidazole compounds, pyrazole compounds, thiadiazole compounds,

Pyrimidine compounds, pyriddizine compounds, pyrazine compounds and tiadiazine compounds and mixtures thereof. Specific examples are imidazole and its N-alkyl derivatives or C-alkyl derivatives and alkyl dimercapto-1, 3,4-thiadiazoles.

Alkylated 2,5-dimercapto-1,4-thiadiazoles are known from WO 94/17164 for use as sulfur scavengers in hydraulic oil compositions. This document does not, however, indicate that these compounds are also suitable as sulfur scavengers in sulfur-containing vulcanization systems for heat-curing rubber compositions.

As mentioned at the beginning, a preferred field of application for the 1-component heat-curing adhesive / sealant compositions according to the invention is the body-in-white in the automotive industry, so that the curing of the compositions in a temperature range between 80 and 240 ° C. in about 10 to 35 minutes. to be held. Temperatures between 160 and 200 ° C are preferably used in the shell. A decisive advantage of the compositions according to the invention is that they have all the advantages of the rubber-based adhesives / sealants known per se, ie they have a so-called "laundry resistance" immediately after the adhesives have been applied. This means that they do not require any pre-gelling, such as epoxy adhesives, to be stable in the various washing and phosphating baths in the body shop. They have the good aging-resistant adhesion required at the outset on the various galvanized steels such as, for example, electrolytically galvanized, hot-dip galvanized and the corresponding thermally post-treated galvanizations or galvanized and subsequently phosphated steel sheets, as well as non-galvanized steels and aluminum, even if the substrates still contain the various corrosion protection and / or deep drawing oils are provided. Across from the previously known sulfur-vulcanized, thermosetting rubber -

Compositions have the advantage that no or a drastically reduced odor nuisance occurs during curing.

The compositions according to the invention can be used both for a large number of structural adhesive applications and for adhesive / sealing functions in the automotive sector. Examples include seam sealing of spot welds, (high-strength) structural adhesives, flat coatings for stiffening and / or acoustic damping, pumpable or profiled (highly) expandable rubber foams in contact with the air space of the vehicle interior, e.g. (Pumpable) "pillar filler". According to the invention, these materials compositions have the following preferred compositions:

Gew. - Chemical name

percent

3.0-10.0 ice 1, 4 polybutadiene, solid

3.0-20 zinc oxide

2.0-20 calcium oxide

0.1-2.0 2.2 methylene-bis- (4 methyl-6-tert-butylphenol)

0.5-5.0 Russ

0-2.0 hollow microspheres

5.0-40.0 calcium carbonate

5.0-40.0 calcium carbonate, coated with stearate

5.0-20.0 polybutadiene liquid, MW approx. 1800, ice - 1, 4 approx. 72%

5.0-30.0 polybutadiene with active carboxyl groups, MW approx. 1700

2.0-40.0 low molecular weight, sterospec. Polybutadiene oil, MW 1800, vinyl

50%

1, 0-10.0 sulfur

0.2-5.0 MBTS

2.0-10.0 EVA copolymer, Tg approx. 40 ° C 0.1-5.0 alkyl dimercapto-1, 3-4 thiadiazole, or

0.2-2.0 imidazole

0-5.0 magnesium oxide

The compositions according to the invention can be prepared in a manner known per se in high-shear mixing units, these include, for example Kneaders, planetary mixers, internal mixers, so-called "Banbury mixers" and similar mixing units known to those skilled in the art.

The invention is to be explained in more detail in the following exemplary embodiments, the selection of the examples not being intended to limit the scope of the subject matter of the invention. Unless otherwise stated, all amounts in the examples below are parts by weight.

Examples:

Example 1

The following constituents were mixed in a laboratory kneader until homogeneous, so that a structural adhesive was obtained: ice 1.4 polybutadiene, solid 2.80

Zinc oxide 3.00

Calcium oxide 2.50

2.2 methylene - bis - (4 methyl-6-tert-butylphenol) 0.50

Soot 0.50

Hollow microspheres 0.20

Calcium carbonate 18.20

Calcium carbonate, coated with stearate 15.00

Polybutadiene liquid, MW ca.1800, ice -1, 4 ca.72% 7.35

Polybutadiene with active carboxyl groups, MW 1700 10.00 low molecular weight, sterospec. PB-ÖI.MW 1800, vinyl 50% 19.00

Sulfur 6.50

MBTS 0.95

Polyvinyl acetate, EVA copolymer, Tg approx. 40 ° C 8.50

Mg oxide 2.00 Hexamethylene bisthiosulfate 0.50

Alkyl dimercapto-1, 3,4-thiadiazole 2.50

Example 2 (According to the Invention)

The procedure was as in Example 1, the alkyl dimercapto

1, 3,4-thiadiazole was replaced by imidazole.

Example 3 (comparison):

The procedure was as in the previous examples, but neither

Alkyl-dimercapto-1, 3,4-thiadiazole or imidazole added.

Suitability tests were carried out with all three adhesives, with all 3 showing

Adhesives under standard curing conditions (30 min 160 ° C to 15 min

200 ° C) excellent adhesion to oiled steel sheet (St 1505), the refined

Steels ZE, ZEP, HDG, OC as well as on degreased aluminum or on pretreated aluminum (Alodine 2040, from Henkel).

On the steel substrates, all 3 adhesives were named after the above

The following tensile shear strengths are obtained:

30 min 160 ° C 6 MPa

30 min 180 ° C 13 MPa

30 min 200 ° C 15 MPa

Based on automotive-specific test standards (VAG Group PV 3900), the odor caused by the adhesives was evaluated during the spot welding of the bonded substrates, which means:

1 imperceptible,

3 clearly perceptible, but not yet disturbing,

6 unbearable

Ratings between 4 and 6 are no longer accepted in the automotive industry.

The following results were obtained:

Example 1 3.5 Example 2 3.5

Example 3 6.

From these results it can be seen that the compositions according to the invention cause a desired, significantly reduced odor nuisance than the comparative example of the prior art.

Claims

claims

1. Heat-curing reactive composition based on natural and / or synthetic olefinic double bonds containing elastomers and vulcanizing agents, characterized in that the composition a) 0-10% by weight of solid rubber (s) with a molecular weight of 100,000 or higher b) 5-50 % By weight liquid (s) polyene (s) with a molecular weight below 20,000 c) a vulcanization system consisting of sulfur and one or more organic accelerators (s) and / or metal oxide (s) d) one or more heterocyclic compounds with at least two nitrogen atoms in the Contains ring.

2. Composition according to claim 1, characterized in that at least one liquid polyene from the group consisting of 1, 2-polybutadiene, 1, 4-polybutadiene, polyisoprene, polybutene, polyisobutylene, copolymers of butadiene and / or isoprene with styrene and / or Acrylonitrile, copolymers of acrylic acid esters with dienes is selected, the molecular weight of the liquid polyene being in the range from 900 to about 10,000.

3. Composition according to claim 2, characterized in that the liquid (s) polyene (s) additionally contains terminal and / or randomly distributed carboxyl groups, carboxylic anhydride groups, hydroxyl groups, amino groups, mercapto groups or epoxy groups as functional groups.

4. Composition according to at least one of the preceding claims, characterized in that the solid rubber (s) from the group cis-1, 4-polybutadiene, styrene-butadiene rubber, synthetic isoprene rubber, natural rubber, ethylene-propylene-diene rubber (EPDM), nitrile rubber, butyl rubber, acrylic rubber is / are selected.

5. Composition according to at least one of the preceding claims, characterized in that the heterocyclic compound is selected from imidazole, pyrazole, thiadiazole, pyrimidine, pyridazine, pyrazine, thiadiazine compounds or mixtures thereof.

6. Composition according to at least one of the preceding claims, characterized in that it additionally contains a thermoplastic polymer.

7. Composition according to claim 6, characterized in that the thermoplastic polymer contains olefinic double bonds, hydroxyl groups, carboxyl groups, epoxy groups, amino groups and / or mercapto groups as functional groups.

8. Composition according to at least one of the preceding claims, characterized in that it additionally contains fillers, rheology aids, extender oils, adhesion promoters and / or anti-aging agents.

9. Use of N-heterocyclic compounds selected from imidazole, pyrazole, thiadiazole, pyrimidine, pyridazine, pyrazine, thiadiazine compounds or mixtures thereof for the preparation of low-odor vulcanizable rubber compositions according to at least one of the preceding claims.

10. Use of the composition according to at least one of the preceding claims as a one- or two-component adhesive, sealant or coating composition with vibration-damping properties.

11. Production of the thermosetting reactive composition according to at least one of the preceding claims by mixing the components under high shear.

12. A method for connecting metal parts and / or sealing joints between metal parts, characterized in that

at least one surface of a part is coated with the compositions according to at least one of the preceding claims,

- the parts to be connected are assembled,

- And the joined parts, if necessary with mechanical fixation, are heated to cure the reactive composition.

13. A method for coating components by spraying or extruding compositions according to at least one of claims 1 to 8 onto the surface of the part and heating the coated part to cure the composition.

14. A method for coating, gluing and / or sealing components, characterized in that an extruded film, an extruded cord or an extruded tape, produced from a composition according to at least one of Claims 1 to 8, is placed on at least one component, if necessary, the parts are put together and then heated to harden the composition.