DE2009620A1 - Polyene compounds and their use - Google Patents

Description

Polyene Compounds and Their Use The invention relates to certain Polymers, namely compounds that have an -en or -in functionality of at least 2 have. Compounds that combine a polymer according to the invention with a polythiol can be contained, for example, by exposure to solid polythioethers cure, so that they can be used as an adhesive for connecting surfaces together are.

The main group of currently used adhesives, in particular for bonding metals, they are epoxy.

refrigerants, which have various disadvantages.

One of the main disadvantages is that the hardening speed even at higher temperatures of, for example, more than 120 ° C for various practical uses is not short enough. Often times are curing times of 1 hour and more at temperatures of 120 ° C and higher are required to achieve a to achieve a hard and fully cured adhesive layer. Another disadvantage is that most epoxy adhesives insufficient flexibility own. It is therefore necessary to use the polymerizable monomeric epoxy compound a monoglycidyl derivative of a long chain aliphatic compound such as a monoglycidyl derivative to add a polyamide, polysulfide or a long-chain aliphatic diamine, which are generally compatible with common epoxy resins, but many the desired physical or chemical properties, e.g. impact resistance and the thermal stability of the polymerizable mixture and thus the hardened one Affect the resin.

The present invention relates to certain new chemical compounds which are obtained in the first stage from epoxy and which can be cured rapidly at various temperatures between room temperature and 150 ° C (generally below 120 ° C) and which give adhesives with a satisfactory flexibility, without the need for the additives specified above, which were previously used to increase flexibility. The new compounds according to the invention are polyene compounds with a molecular weight of 150 to 20,000 and an -en- or -in functionality of at least 2, which are obtained by a) an organic epoxy with at least two Reacts groups with hydrazine, a primary or secondary amine or a salt of a tertiary amine, an organic alcohol or thioalcohol or an organic acid, which are polymerizable and contain at least one ethylenically or acetylenically unsaturated group or b) a polymerizable organic epoxide with at least one ethylenic or acetylenically unsaturated group with hydrazine or an organic compound which contains at least two radicals with a hydrogen atom that can react with an epoxy group of the epoxy and which correspond to one of the following formulas: In addition to the novel polyenes, the invention proposes a composition which contains a polyene of the above definition together with a polythiol. The invention also relates to a method for connecting surfaces to one another, in which a layer of a compound is provided between the two surfaces, which is the polyene / polythiol compound according to the invention, which is then cured by means of a free radical initiator Polyene / polythiol compositions according to the invention can also be used as light-curing compositions in photographic processes, for example for the production of printing plates.

The polyenes according to the invention have a viscosity from 0 to 20 million cP at 130 ° C. If they are not liquid at room temperature (250C), they can be mixed with a dispersing agent or plasticizer, so that a composition is obtained whose viscosity in liquid form is indicated Area lies; in this form the polyenes can always be combined with the polythiols will.

The polyenes normally have a viscosity of 0 at 130 ° C up to 20 million cP or you can with a dispersion or a plasticizer be mixed to obtain a mass whose viscosity is in the specified Area lies; As a rule, the polyenes are liquid at 25 ° C.

The polyenes are obtained from compounds that have the oxirane (epoxy) group They are obtained by reacting the oxirane groups with compounds which contain active hydrogen atoms that open the ring, namely in one of the following two ways: a) a di- or polyfunctional epoxy compound is reacted with an unsaturated, active hydrogen-containing compound or b) a di- or polyfunctional, active hydrogen-containing compound is reacted with an unsaturated epoxy compound.

These two possible reactions can be explained by the following equations using specific examples: Diepoxide (I) unsaturated amine (II) Polyene (III) Diol (IV) unsaturated epoxy (V) Polyene (VI) The starting compounds can have any molecular weight, that is to say either monomeric or polymeric, with the only restriction that the polyene must not have such a high molecular weight that it can no longer be processed into a composition with the viscosity indicated above leaves. Furthermore, the starting compounds can differ in their individual functionality within a considerable range, the only restriction in this case being that the -en- or -in functionality of the polyene product must be at least two.

Various other examples of compounds containing epoxy groups, which are analogous to the compounds I and V given above can be found in the chapters 2, 3 and 4 and its appendix in Henry's Handbook of Epoxy Resins Lee and Kris Neville, McGraw-Hill Book Co., 1967, compare pages in particular 2-1 and 2-33. Such epoxy group-containing compounds are for production of the compounds according to the invention can be used.

Several other examples of active hydrogen containing compounds, which react with the oxirane groups with ring opening are in chapter 5 of the above cited Handbook of Epoxy Resins, especially in Appendix 5-1, pages 5-32 to 5-40. Such active hydrogen-containing compounds are for manufacture of the compounds according to the invention useful The one used in the present context The term "polythiols" includes simple or complex organic compounds with at least two -SH groups, which are in the middle or at the end of the molecule (im Average) can be bound. Usually they have a viscosity of 0 to 20 million cP at 700C (measured in a Brookfield viscometer), if necessary after mixing with an inert solvent, in an aqueous dispersion or after Addition of a plasticizer to produce a composition having the specified Viscosity. The polyenethiols normally have a molecular weight of 50 until 20,000, preferably from 100 to 10,000 and have the general formula R8 - (SH) n, in which n is at least 2 and R8 is a polyvalent organic radical which does not contain any reactive unsaturated carbon bonds. Accordingly, R8 can also contain cyclic groups and smaller amounts of hetero atoms, such as N, S, P or 0, but has mainly carbon-hydrogen, Carbon-oxygen, or silicon-oxygen bonds and is free from unsaturated carbon-carbon bonds.

Under "reactive" unsaturated carbon-carbon bonds carbon double or triple bonds are understood, which when exposed to of free radicals on the polythio) could lead to auto-polymerization.

Such double bonds would likely trigger the reaction between interfere with the polyene and the polythiol during curing, either due to a Autopolymerization or because of a copolymerization with the unsaturated bonds in the polyenes.

One class of suitable polythiols are esters of the following general formula in which B9 and B10 denote organic radicals which contain no reactive unsaturated carbon-carbon bonds, and where n is at least 2. The esters can be derived from acids of the general formula HS-R9-COOH containing thiol groups and polyhydroxy compounds of the general formula R10 # (OH) n, where R9, R10 and n have the meaning given above.

Certain polythiols, such as the aliphatic monomeric polythiols (e.g. Ethanedithiol, hexamethylene dithiol, decamethylene dithiol and tolylene-2,4-dithiol) and some polymeric polythiols (e.g., ethylcyclohexyldimerecaptan polymers terminated with Thiol groups and similar polythiols), which can be easily produced and which are technically obtained are, in spite of their repulsive smell useful, but many of the end products thus obtained are of practical use and for commercial reasons only applicable to a limited extent. Examples of connections with Thiolglycolic acid esters have a relatively less unpleasant odor HS-CH2COOH, the α-mercaptopropionic acid HS-CH (CH3) -COOH and the ß-mercaptopropionic acid HS-CH2CH2COOH with polyhydroxy compounds such as glycols, triols, tetraols, pentols or hexols. Specific examples of preferred polythiols are ethylene glycol bis (thioglycolate), Ethylene glycol bis (ß-mercaptopropionate), trimethylolpropane tris (thioglycolate) Trimethylolpropane tris (ß-mercaptorpropionate). Pentaerythritol tetrakis (thioglycolate) and pentserythritol tetrakis (ß-mercapto propionate), which are on the market without exception. A specific example of a preferred one polymeric polythiol is polypropylene ether glycol bis (ß-mercaptopropionate), which is made of Poly (propylene ether) glycol (e.g. "Pluracol P 2010" from Wyandotte Chemical Corporation) and β-mercaptopropionic acid can be produced by esterification.

The preferred polythiol compounds are characterized by a weak one mercaptan-like odor both before implementation and after implementation with the polyene and result in practically odorless polythioethers, which are commercially available are useful and suitable adhesives for both indoor and outdoor use represent.

The term "functionality" used in the present context refers to the average number of -en- or -in groups per molecule of the polyene or of thiol groups per molecule of the polyhiol. So is for example a triene is a polyene with an average of three reactive unsaturated carbon-carbon bonds per molecule and thus has a functionality of ton 3u A dithiol is a polythiol with average two thiol groups per Molkül, thus one Has functionality of 2.

It should also be pointed out in the present context that that with such definitions the functionality of the polyenes and the polythiols usually expressed in whole numbers, although the functionality did is actually a fraction of a decimal, for example, a polyene has a nominal Functionality of 2 (derived solely from theoretical considerations) actually an effective functionality of -slightly less than 2.

In an attempt to produce a diene from a diepoxide, whereby the implementation would run 100% of the theory completely (provided that the use of 100% pure starting compounds) a functionality of 2.0 can be achieved. However, if the implementation only has a degree of implementation of 90% of the Reached theory, about 10% of the molecules present would only be functional -en group and there could also be traces of compounds which have no -en-functional group at all. About 90% of the molecules however, would have the desired diene structure and the product as a whole in this case actually a functionality of 1.9. One such polyene is usable in the context of the present invention and falls under those in the foregoing connection used term of a functionality of 2.

The aforementioned polyenes and polythiols can be used if desired formed or generated in situ and cured rapidly by the method according to the invention will.

To achieve maximum strength, solvent resistance, a low tendency to creep, an optimal thermal stability and a low The polyenes and polythiols which form the reaction components become tacky combined according to the invention in such amounts that a solid, crosslinked, polymeric Polythioether with three-dimensional linkage is obtained after curing. Around To achieve the formation of such a network, the individual polyenes must and polythiols each have a functionality of at least two. Mixtures of Polyenes and the polythiols having the required functionality can be used Those according to the invention to be hardened, that is to be converted into solid resins or elastomers Masses can optionally contain further additives, such as ¢ BO antioxidants » Accelerators for a radical reaction, dyes, inhibitors for a radical reaction Reaction, activators, Fillers, pigments, antistatic agents, Flame retardants, light scattering agents, thickeners, thixotropic agents, surfactants, viscosity modifying agent stretchers, plasticizers and tack improvers. Such additives are generally added to the polyene or polythiol prior to mixing the latter two components.

added. Usable fillers are natural and synthetic Resins, soot, glass fibers, sawdust, clay, silica, aluminum oxide, carbonates, oxides, Hydroxides, silicates, glass flakes, glass beads, borates, phosphates, diatomaceous earth, Talc, kaolin, barium sulfate, calcium sulfate, calcium carbonate and antimony oxide. the The aforementioned additives can be used in amounts up to 500 parts by weight or more, usually 0.005 to 500 parts by weight and preferably 0.005 to 300 parts by weight per 100 Parts by weight of polymer be present, The polyene and polythiol containing blends contain no less than 2% (based on the weight of polyene and polythiol) the respective component; the ratio of polyene to polythiol is preferred approximately stoichiometric for the hardening reaction to form the polythio äthers0 Tuesday Hardening between the novel polyenes and the polythiols is caused by free radicals triggered, e.g.

by a dissociation of the hydrogen atom initiated by free radicals the -SH group or another radical mechanism, and preferably two under normal conditions. In many cases it is possible to use the polyene / polythiol mixture simply exposure to atmospheric conditions (atmospheric oxygen is an initiator) and thus a cured test elastomeric or resinous polythioether product to obtain. Azo compounds or peroxides (with or without amine as accelerator), which decompose under normal conditions are also considered to generate free radicals Medium suitable. Actinic electromagnetic radiation, e.g., ultraviolet light (with or without the help of photosensitizers) or certain forms an ionizing radiation are also suitable means of generating free Radical.

The curing time can be less than 1 minute up to 33 days or more be. Conventional free radical generating reaction initiators or accelerators, which are suitable within the scope of the invention are at for example Oxygen, organic or inorganic peroxides, hydroperoxides, peracids, persulfates, Azo compounds such as azo-bis-isovaleronitrile, ultraviolet light (with or without appropriate sensitizers) »High-energy radiation such as X-rays, ß-rays, electron beams, γ-rays and the like, ozone, oxidizing agents, like lead dioxide and benzoyl peroxide or cyclohexanone peroxide with dimethylaniline. Usual Inhibitors or retarders for the radical reaction, which are used can include hydroquinone, p.-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, Phenotiazine, N-phenyl-2-naphthylemin, inert gases such as helium, argon, nitrogen and Carbon dioxide; carrying out the reaction also acts in the same direction Negative pressure or vacuum.

The mixing of the polyene with the polythiol can be done in various ways Way. For example, the polyene, the polythiol and the others inert additives mixed together under an inert atmosphere and combined into one oxygen-free container, e.g. an aerosol can, a metal bucket, a tube or a cartridge can be filled. When the mixture escapes into the air under normal conditions hardening of the mixture occurs 0 Another suitable way of working consists in being in atmospheric conditions but in the absence of a mixture of actinic radiation is produced using a conventional mixing technique, those made from a polyene, a polymerization inhibitor (which is an antioxidant acts) to prevent spontaneous hardening induced by oxygen, a polythiol, and preferably a UV photosensitizer (among which everyone is popular Sensitizer that initiates or accelerates hardening on irradiation with UV light is to be understood) and possibly other inert additives. This mass can be stored in the dark for a long time, but it hardens when exposed to actinic acid Radiation (e.g. the UV light from sunlight) in a controllable manner and in very short time to solid polythioethers, the polyene and the polythiol can can also be stored separately packaged, with the polyene among such Conditions are maintained that self-polymerization of the polyene does not occur while the polythiol is packaged separately therefrom; the ratio of polyene in the first pack to polythiol in the second pack should be about the required correspond to the stoichiometric ratio that is required for the curing reaction is, so that the end user, if the instructions for use are followed correctly both packs are completely used up.

The polyene in the first pack must be oxygen free and preferably in a container that is impermeable to UV light and other ionizing radiation Be packaged or the package must contain a sufficient amount of a polymerization inhibitor which prevents noticeable polymerisation of the polyene. The polythiol pack may contain a UV sensitizer and / or accelerator for curing Various photosensitizers can be used. Examples include Benzophenone, acetophenone, acensphthenchinon, methyl ethyl ketone, valerophenone, hexanophenone, γ-phenyl butyrophenone, p-morpholilnopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4'-morpholinodecxybenzoin, p-diacetylbenzo, 4-aminobenzene phenone, 4'-methoxyacetophenone, Benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indenone, 1,3,5-triacetylbenzene, Thioxanthen-9-one, xanthen-9-one, 7-H-benz [de] -anthracen 7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, Fluoren-9-one, 1'-acetonaphthone, 2'-acetonaphthone and 2,3-butanedione. These connections enable in general.

a significant reduction in curing times and are therefore special valuable if the hardening can be achieved with the help of high-energy radiation target. The photosensitizers are usually used in an amount up to 50% by weight, preferably from 0.005 to 25% by weight based on the mass forming the polythioether, used.

The molecular weight of the polyenes according to the invention can be determined by means of different conventional methods, e.g. based on viscosity in solution, due to osmotic pressure, or by gel permeation chromatography. Furthermore, the molecular weight can be derived from the known molecular weight of Calculate output connections.

The viscosity of the polyenes was measured using a Brookfield.

Viscometer at 130 ° C according to the instructions given for the device measured.

To further explain the present invention, the following are intended Examples are used in which all data in parts and% relate to weight, unless otherwise stated.

Example 1 1 mol of bisphenol A diglycidyl ether with a molecular weight ranging from 370 to 384 ("Epon 828" from Shell Chemical Company) and 2 moles of allythydrazine were dissolved in 500 ml of benzene in a beaker at room temperature (25 ° C). The reaction was continued with stirring for 18 hours with an exotherm Reaction took place and the reaction temperature was kept below 800C0 then the benzene was removed under reduced pressure. 1 mole of the obtained liquid Polyens was obtained with @ o @ pentaerythritol tetrakis (ß-mercaptopropionate) ("Q 43" from Carlisle Chemical Company) mixed together with 2.0 g of acetophenone, a UV photosensitizer. A 10 g portion of the liquid mass was placed on a small aluminum plate and irradiated with a 275 watt RS type daylight lamp, the distance of the lamp was 22.5 cm from the liquid surface.

Within 5 minutes the mixture hardened into a solid, self-supporting one Dimensions.

Example 2 Example 1 was repeated, but this time 2 mol Allylamine was used in place of the 2 moles of allyl hydrazine. That way Liquid polyene obtained resulted after UV curing with the pentaerythritol tetrakis (ß-mercaptor propionate) and the acetophenone of Example 1 a cured solid within 3 minutes Mass, Example 3 Example 1 was repeated, but instead of the 2 moles of allyl hydrazine 2 moles of diallylamine were used.

In this case, no solvent was used for the synthesis. The resulting liquid polyene yielded upon curing with the polythiol and the UV sensitizer of Example 1 within 5 minutes when exposed to UV radiation 275 watt high-altitude sun a hard, hardened solid mass 0 Example 4 Example 1 was repeated, except that 2 moles of N, N-dimethyl N-allylammonium-p toluenesulfonate found instead of the 2 moles of allyl hydrazine of Example 1 use. The received liquid polyene gave under the curing conditions of Example 1 within 5 minutes etne hardened solid mass. It has been observed that this polyene is present was very soluble in water after hardening.

Example 5 Example 3 was repeated, except that 2 moles of allyl alcohol found instead of the 2 moles of diallylamine use.

The liquid polyene obtained gave when cured as in Example 3 solid cured within less than 2 hours when irradiated at 50 ° C Dimensions.

Example 6 Example 9 was repeated, but using 2 moles of allylacetic acid instead of the 2 moles of diallylamine were used. The obtained liquid polyene was cured as in Example 3 and gave within 15 minutes on irradiation a solid hardened mass at 60 ° C.

Example 7 2 moles of allyl glycidyl ether were added dropwise with stirring to 1 mole of hydrazine in 200 ml of tetrahydrofuren as a solvent in a beaker added and stirring continued for 18 hours. The temperature was kept below 80 ° C. during the reaction. After removing the solvent in vacuo 1 mol of the resulting liquid polyene with 0.5 mol of pentaerythritol tetrakis (ß-mercaptopropionate) mixed. 50 g of this mixture were along with 1.0 g of benzophenone put in a glass mold as a UV sensitizer. The mold was preheated to 50 ° C and then placed under a 275 watt ES type daylight lamp. Within after 5 minutes the mixture hardened to a solid self-supporting mass.

Examples 8 to 13 Example 7 was repeated, except that the hydrazine replaced in each case by 1 mol of another starting compound given below became. In each case, the liquid polyene was cured in the example 7 obtained a solid hard mass within 5 minutes.

Example No. Compound 8 used in place of hydrazine is n-butylamine 9 N, N'-dimethylethylenediamine 10 di- (p-toluenesulfonic acid salt) of N, N, N ', N'-tetramethylethylenediamine 11 ethylene glycol 12 succinic acid 13 tetramethylene dithiol example 14 Example 3 was repeated, except that the polyene / polythiol mixture was not used UV sensitizer was added.

The mixture hardened to a solid mass within less than 14 minutes if the UV irradiation took place in a heated mold at 6o0C irradiation at room temperature resulted in hardening of the sample into one self-supporting solid mass required 30 minutes.

Example 5 was repeated, however, curing at room temperature carried out with 5.0 g of benzoyl peroxide and 5.0 g of dimethylaniline instead of acetophenone became. The liquid polyene / polythiol mixture hardened within 10 minutes Absence of UV radiation to a solid self-supporting mass.

Example 16 The polyene and polythiol of Example 1 were in the same amounts as stated there, used. The hardening has been achieved putting the polyene / polythiol mixture under the electron beam of a Van de Graaf Accelerator was carried out until a total radiation dose was absorbed by 2Megarads. It became a hardened solid self-supporting Mass received.

Example 17 The polyene and polythiol of Example 1 were used together used with 0.075 g of iron (III) acetylacetonate. The hardening took place under atmospheric conditions Conditions. Within 15 minutes a solid cured self-supporting Mass received.

Example 18 Example 17 was repeated, except that 10.0 g of one Oxime ester, namely quinone dioxime di-n-hetanoate, was added to the mixture. Within of 4 minutes became a solid self-supporting under atmospheric conditions Mass received.

Example 19 The polyene and polythiol of Example 1 were found together with 7.5 g of benzilic acid as free radicals, the agent is used. Within of 60 minutes became a solid cured self-supporting under atomic spherical conditions Mass received.

Example 20 The polyene and polythiol of Example 1 were used. The polyene / polythiol mixture was affected by γ-radiation within 48 hours hardened from a cobalt-60 source to a self-supporting mass, the absorbed Dose was 2 megarads.

Example 21 1 mole of a polyoxypropylenetriamine having a molecular weight of about 400 ("POPTA 403" from Jefferson Chemical Company) and 3 moles of allyl glycidyl ether were mixed together in a beaker at room temperature.

The reaction was continued with stirring for 18 hours, whereby the temperature was kept below 50 ° C.

1 mole of the resulting liquid polyene was tris (ß-mercaptopropionate) with 1 mole of trimethylolpropane ("P33" from Carlisle Chemical Company) and 2.0 g of dibenzosuberone as a UV sensitizer put together. A 10 g portion of the liquid mass was poured into a small aluminum teller and the mixture was irradiated with a 275 watt RS type daylight lamp A solid, cured, self-supporting polythio ether received.

Example 22 1 mol of the liquid polyene according to Example 1 was used with 0.5 mol of pentaerythritol tetrakis (ß-mercaptopropionate) and 0.5% by weight (based on the Adhesive mixture) mixed with dibenzosuberone as an accelerator. The glue mix was placed on an area of two ordinary sheet glass sections with the dimensions 15 cm x 15 cm x 3 wan applied in a layer thickness of 50μ. The two glass sections were brought together with the adhesive layer in between and 2 minutes long exposed to UV radiation from a 275 watt daylight lamp, so that the The radiation density in the adhesive layer was 4,000 microwatts / cm². The hardened one Safety glass was tested by smashing it with a hammer. It broke Although the glass is divided into many parts, the parts adhere to the one in between Adhesive layer.

Example 23 A layered product was obtained from a piece 125 μm thick Wrapping paper, a 250µ thick piece of aluminum foil »a 1.5 mm thick piece of glass and a 0.76 mm thick piece of steel and a block made of ash concrete Each layer was with the adhesive composition of Example 21 (without dibenzosuberone) coated in an application thickness of 50 µ. The individual layers became clamped together under pressure and with a 3 MeV dynamite electron accelerator (manufactured by Radiation Dynamitron, Inc.) with a beam current of 5 mA and a 25 cm slot at a dose of 1.0 megarad. One try, separating the individual layers from one another showed that the layer product in never broke apart at the adhesive seam.

Claims (1)

Claims 1. A process for the preparation of polyene compounds with a molecular weight of 150 to 20,000 and an -en- and -in functionality of at least 2, characterized in that a) an organic epoxide with at least two Reacts groups with hydrazine, a primary or secondary amine or a salt of a tertiary amine, an organic alcohol or thioalcohol or an organic acid, which are polymerizable and contain at least one ethylenically or acetylenically unsaturated group or b) a polymerizable organic epoxide with at least one ethylenic or acetylenically unsaturated group reacts with hydrazine or an organic compound »which contains at least two radicals with a hydrogen atom, which can react with an epoxy group of the epoxy and which correspond to one of the following formulas: 2. Compounds of the general formula: in which n is zero or an integer corresponding to a molecular weight of not more than 20,000. 3. Connections of the general formal: in which n is zero or an integer corresponding to a molecular weight of not more than 20,000. 4. Compounds of the general formula 50 compounds of the general formula: in which n is zero or an integer corresponding to a molecular weight of not more than 20,000 and X is one or two anions with a negative charge of 2 in total. 6. Compounds of the general formula: in which the sum of x + y + z is at least 3 with a molecular weight not exceeding 20,000 and R is a hydrogen atom or a lower alkyl radical. 70 A mass suitable for obtaining solid polythioether, marked by a content of a) a liquid polyene compound prepared according to the The method of claim 1 or claims 2 to 6 and b) a polythiol with a molecular weight of 50 to 20,000 of the general formula R8 # (SH) n, in R8 a polyvalent organic radical without reactive unsaturated carbon-carbon bonds (as defined above) and n is at least 2, the ratio of polyene to polythiol in bulk is such that initiated by a free radical Reaction between the polyene and the polythiol obtained a solid polythioether will. 8. Composition according to claim 7, characterized in that it also contains a UV photosensitizer. 90 Process for making a solid polythioether, thereby characterized in that a) a liquid polyene compound according to the claims 2 to 6 or prepared by the process of claim 1 with b) a polythiol with a molecular weight of 50 to 20,000 of the general formula R8 # (SH) n where R8 is a polyvalent organic radical that is not reactive contains unsaturated carbon-carbon bonds, and n is at least 2, or mixed with a mixture of such polythiols and then the polyene / polythiol mixture subject to free radical initiation. 10. The method according to claim 9, characterized in that the radical initiator is added to the mass and that the mass is used for initiation exposed to the radical reaction of the atmosphere. 11. The method according to claim 9, characterized in that the radical reaction initiated by exposure to UV light. 12. A method for connecting two surfaces, characterized in that that between the two surfaces a layer of the mass according to claim 7 or 8 provides and this mass by means of a free radical initiator hardens. 13. The method according to claim 12, characterized in that one to harden the mass of this a free @@ d @@@ le forming initiator or a Source of ionizing radiation clogs. 14. The method according to claim 12, characterized in that at least one of the surfaces is permeable to actinic radiation and that the mass can pass through Exposure to actinic radiation cures.