EP3743454A1

EP3743454A1 - Curable composition comprising an acetal plasticizer

Info

Publication number: EP3743454A1
Application number: EP19700970.7A
Authority: EP
Inventors: Andreas Kramer; Urs Burckhardt; Rita Cannas
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2018-01-26
Filing date: 2019-01-24
Publication date: 2020-12-02
Also published as: CN111655748A; WO2019145420A1; JP2021510744A; US20210163667A1; AU2019212195A1

Abstract

The present invention relates to curable compositions comprising at least one organic polymer which contains silane groups and/or isocyanate groups, at least one compound which contains acetal groups and has a molecular weight of at least 280 g/mol, and at least one basic catalyst. The composition according to the invention is particularly storage-stable and can be readily processed. Using moisture the composition cures rapidly, and with very little residual tackiness, to form a resilient material that has good adhesive and mechanical properties, in particular a high level of malleability and elasticity, is heat resistant and exhibits hardly any odour formation or migration effects. In particular, said composition has very consistent product properties during storage in respect of viscosity, curing rate and odour.

Description

HARDENABLE COMPOSITION WITH ACETAL SOFT MAKER

Technical area

The invention relates to curable compositions which are particularly suitable as elastic adhesives, sealants or coatings.

State of the art

At room temperature, moisture-curable compositions based on silane group and / or isocyanate group-containing polymers play an important role in many industrial applications, in particular as elastic adhesives, sealants or coatings. To improve the application properties and to increase the elasticity, so-called plasticizers are usually added to such compositions. These are low volatility organic substances that are not covalently bound into the polymer matrix during curing. Conventional plasticizers are esters of aromatic or aliphatic di- or tricarboxylic acids, in particular phthalates such as diisononyl phthalate or diisodecyl phthalate, hydrogenated phthalates or 1,2-cyclohexanedicarboxylates, terephthalates, trimellitates, adipates, sebacates, succinates, citrates or similar esters.

In particular, in compositions based on silane-group-containing organic polymers, which are also referred to as "silane-functional polymers", "silane-modified polymers" (SMP) or "silane-terminated polymers" (STP), such plasticizers often lead to the composition of the storage changes over time. This manifests itself in particular in the form of an excessive increase in viscosity and / or altered curing characteristics after storage. Increased viscosity makes it more difficult to apply the composition, since it requires higher pressing forces, makes the material less pumpable or has lower stability. A change in the hardening characteristics can be seen in a shortening or lengthening of the skin formation time and / or the hardening time. Such storage-dependent changes are highly undesirable as they lead to large fluctuations in the pro- cause the product to become unpredictable at the processor. They are particularly pronounced when the composition contains basic catalysts such as amines, amidines or guanidines. In addition to altered application and curing properties, interfering odors may also result from storage due to low molecular weight decomposition products gassed from the composition.

Because of widespread skepticism about phthalates, there is also a desire for phthalate-free products. However, many compounds which are used as an alternative to phthalate plasticizers, such as, in particular, adipates or 1,2-cyclohexanedicarboxylates, are only insufficiently compatible with the polymer matrix and tend to migrate. This leads to undesirable effects such as "bleeding", staining, in particular in the case of porous substrates, softening, cracking, discoloration or loss of adhesion of the substrate or of a lacquer or lacquer applied over it coat of paint.

Acetals are known in principle, for example from EP 959 086 or EP 1 318 179, where bis (2-phenoxyethyl) is formally used as a thinner in two-component polyurethane coatings. From these documents, however, it is not clear that such acetals are also used as plasticizers for moisture-curing elastic sealants or adhesives based on isocyanate- and / or silane-functional organic polymers which contain basic catalysts, and thereby can take over the softening function of conventional phthalates, without causing problems with storage stability. Two- or more-functional acetal-capped polyether polyols are known, for example from US Pat. No. 3,923,744, where they are used as latent, moisture-releasable polyols in coatings containing isocyanate groups.

Presentation of the invention

The object of the present invention is therefore to provide a curable composition which avoids the disadvantages of the prior art. with regard to the storage stability of moisture-curing compositions containing plasticizers and basic catalysts.

This object is achieved by a curable composition as described in claim 1. The composition is surprisingly diluted and elasticized by the acetal group-containing compound without increasing migration effects. Surprisingly, it does not show any significant changes in product properties during storage, as observed in phthalate compositions. In particular, it has a very constant viscosity and curing speed over the storage period and does not develop any disturbing odors. In addition, the stability of the cured composition to heat stress is surprisingly not only equal, but even better compared to compositions containing phthalate plasticizers such as DIDP or DINP. The basic catalyst stabilizes the acetal group-containing compound so that no moisture is cleaved back to the alcohol when moisture is added.

The composition according to the invention is particularly storage-stable and easy to process. With moisture, it hardens quickly and with very little residual tackiness to form an elastic material which has good adhesion and mechanical properties, in particular a high extensibility and elasticity, is heat-resistant and hardly shows any odor formation or migration effects. In particular, the composition has very constant product properties during the storage period in terms of viscosity, curing rate and odor.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

Ways to carry out the invention

The invention relates to a curable composition comprising - at least one silane group and / or isocyanate group-containing organic polymer, at least one acetal group-containing compound having a molecular weight of at least 280 g / mol, and

- At least one basic catalyst.

A "curable" is a composition which hardens by crosslinking reactions of reactive groups contained in it or can obtain a state of increased mechanical strength.

The term "silane group" denotes a silyl group bonded to an organic radical having one to three, in particular two or three, hydrolyzable alkoxy radicals on the silicon atom.

As "silane" are both Organoalkoxysilane, which carry one to three organic substituents on each silane group, as well as Tetraalkoxysilane called. Silanes which have one or more hydroxyl, isocyanato, amino or mercapto groups on an organic radical in addition to the silane group are termed "hydroxysilane", "isocyanatosilane", "aminosilane" or "mercaptosilane".

The term "acetal group" refers to the geminal diether group of an acetal. The term "acetal" refers to geminal diethers, ie compounds having two alkoxy or aryloxy groups on the same carbon atom. Acetals are also referred to as ketals.

"Molecular weight" refers to the molar mass (in grams per mole) of a molecule or moiety. By "average molecular weight" is meant the number average molecular weight (M _n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecular moieties. It is usually determined by means of gel permeation chromatography (GPC) against polystyrene as standard.

Substance names beginning with "poly", such as polyamine, polyol or polyisocyanate, refer to substances which formally contain two or more of the functional groups occurring in their name per molecule.

"Stable in storage" or "storable" is a composition which is cured at room temperature in a suitable container for a prolonged period of time, typically for at least 3 months to 6 months and more. can be maintained without altering their application or use properties by storage to an extent that is relevant to their use.

A dashed line in the formulas in this document represents the bond between a substituent and the associated moiety.

The term "room temperature" refers to a temperature of approx. 23 ° C.

The curable composition preferably hardens with moisture, preferably atmospheric moisture. Such a composition is also called "moisture-curing".

The silane group- and / or isocyanate-group-containing organic polymer preferably has an average molecular weight, determined by GPC against polystyrene as standard, in the range from 1 Ό00 to 30Ό00 g / mol, in particular from 2Ό00 to 20Ό00 g / mol.

It is preferably liquid at room temperature.

It preferably contains on average from 1.1 to 4, preferably from 1.2 to 3, more preferably from 1.5 to 3, in particular from 1.7 to 2.8, silane groups and / or isocyanate groups per molecule.

It preferably has fractions of polyether structural units, in particular predominantly polyoxypropylene structural units. Such a composition is particularly elastic and elastic.

In a preferred embodiment, the silane group- and / or isocyanate-group-containing organic polymer is free of isocyanate groups. Such a curable composition thus contains at least one silane-containing organic polymer. Such a polymer is also referred to as a "silane-modified polymer" (SMP) and such a composition is also referred to as an SMP composition. The silane group-containing organic polymer preferably has silane groups of the formula on,

in which

R ^{a is} a linear or branched, monovalent hydrocarbon radical having 1 to 5 C atoms, in particular methyl or ethyl,

R ^{b is} a linear or branched, monovalent hydrocarbon radical having 1 to 8 C atoms, in particular methyl, and

x is a value of 0 or 1 or 2, preferably 0 or 1, in particular 0.

Methoxysilane groups have the advantage that they are particularly reactive. Ethoxysilane groups have the advantage that they are toxicologically advantageous and particularly stable on storage.

Particular preference is given to trimethoxysilane groups, dimethoxymethylsilane groups or triethoxysilane groups.

Most preferred are trimethoxysilane groups or triethoxysilane groups.

A preferred silane-containing organic polymer is a polyolefin or a polyester or a polyamide or a poly (meth) acrylate or a polyether or a mixed form of these polymers. The silane groups can be located laterally in the chain or terminally and are bound to the organic polymer via a carbon atom.

The silane-group-containing organic polymer is particularly preferably a silane-containing polyether.

As a "silane-containing polyether" are organic polymers containing at least one silane group referred to the polymer chain mainly polyether units, in particular 1, 2-oxypropylene units having. In addition to the polyether units, urethane groups, urea groups, thiourethane groups, ester groups or amide groups can also be present in particular. The silane-group-containing polyether preferably contains at least 50% by weight, in particular at least 70% by weight, particularly preferably at least 80% by weight, of 1,2-oxypropylene units.

Processes for the preparation of suitable silane-containing polyethers are known to the person skilled in the art.

In a preferred process, silane-containing polyethers are obtainable from the reaction of allyl-containing polyethers with hydrosilanes, optionally with chain extension with, for example, diisocyanates.

In a further preferred process, silane-functional polyethers are obtainable from the copolymerization of alkylene oxides and epoxysilanes, optionally with chain extension with, for example, diisocyanates.

In a further preferred process, silane-containing polyethers are obtainable from the reaction of polyether polyols with isocyanatosilanes, optionally with chain extension with diisocyanates.

In a further preferred method, silane-containing polyethers are obtainable from the reaction of isocyanate-group-containing polyethers with aminosilanes, hydroxysilanes or mercaptosilanes. Silane-group-containing polyethers from this process are particularly preferred. This method makes it possible to use a large number of commercially available, cost-effective starting materials, with which different polymer properties can be obtained, in particular a high ductility, a high strength, a low elastic modulus, a low glass transition point or a high weather resistance.

The silane-group-containing polyether is particularly preferably obtainable from the reaction of isocyanate-group-containing polyethers with aminosilanes and / or hydroxysilanes and / or mercaptosilanes.

Suitable isocyanate group-containing polyethers are in particular obtainable from the reaction of polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, preferably polyoxypropylene diols or polyoxypropylene triols, with a greater than stoichiometric amount of polyisocyanates, in particular diisocyanates.

The reaction between the polyisocyanate and the polyether polyol is preferably carried out with exclusion of moisture at a temperature of 50.degree. C. to 160.degree. C., if appropriate in the presence of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups are proportionate to the hydroxyl groups of the Polyols are present in stoichiometric excess. In particular, the excess of polyisocyanate is chosen so that after the reaction of all hydroxyl groups, a content of free isocyanate groups of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight, based on the entire polymer remains.

Preferred diisocyanates are the same as those mentioned for the preparation of isocyanate group-containing polymers. Particularly preferred is IPDI or TDI. Most preferred is IPDI. This silane-containing polyethers are obtained with particularly good light fastness.

Particularly suitable as polyether polyols are polyoxypropylene diols having a degree of unsaturation lower than 0.02 meq / g, in particular lower than 0.01 meq / g, and an average molecular weight in the range of 400 to 25Ό00 g / mol, in particular 1 Ό00 to 20Ό00 g / mol.

In addition to polyether polyols, it is also possible proportionally to use other polyols, in particular polyacrylate polyols, and low molecular weight diols or triols.

Suitable aminosilanes for the reaction with an isocyanate group-containing polyether are primary and secondary aminosilanes. Preference is given to 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3- aminopropyltrimethoxysilane, adducts of primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and Michael acceptors such as acrylonitrile, (Meth) acrylic acid esters, (meth) acrylic acid amides, maleic acid or fumaric diesters, citraconic diesters or itaconic diesters, in particular N- (3-trimethoxysilylpropyl) -anninobemsteinsäuredinnethyl- or -diethylester. Likewise suitable are analogs of said aminosilanes with ethoxy groups instead of the methoxy groups on the silicon.

Suitable hydroxysilanes for the reaction with an isocyanate-containing polyether are in particular obtainable from the addition of aminosilanes to lactones or to cyclic carbonates or to lactides.

Preferred hydroxysilanes obtained in this way are N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, N- (3-trimethoxysilylpropyl) -2-hydroxypropanamide, N- (3-triethoxysilylpropyl) -4-hydroxypentanamide, N - (3-triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -5-hydroxyde- canamidamide or N- (3-triethoxysilylpropyl) -2-hydroxypropylcarbamate.

Further suitable hydroxysilanes are obtainable from the addition of aminosilanes to epoxides or from the addition of amines to epoxysilanes.

Preferred hydroxysilanes obtained in this manner are 2-morpholino-4 (5) - (2-trimethoxysilylethyl) cyclohexan-1-ol, 2-morpholino-4 (5) - (2-triethoxysilylethyl) cyclohexan-1-ol or 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.

Suitable mercaptosilanes for the reaction with an isocyanate group-containing polyether are in particular 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

Also suitable as silane-group-containing polyethers are commercially available products, in particular the following: MS Polymer ™ (ex Kaneka, in particular the types S203H, S303H, S227, S810, MA903 and S943); MS Polymer ™ or Silyl ™ (from Kaneka, especially the types SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951); Excestar ^® (of Asahi Glass, in particular the types S2410, S2420, S3430, S3630); SPUR + ^* (by Momen- tive Performance Materials, in particular the types 101 OLM, 1015LM, 1050MM); Vorasil ™ (from DowDuPont, especially types 602 and 604); Desmoseal ^® (of Covestro, in particular the types S XP 2458 S XP 2636, S XP 2749, S XP 2774 and S XP 2821), TEGOPAC ^® (from Evonik, in particular the types Seal 100, bond 150, bond 250), Polymer ST (by Hanse

Chemie / Evonik, especially types 47, 48, 61, 61 LV, 77, 80, 81);

Geniosil ^® STP (from Wacker, in particular types E10, E15, E30, E35).

The silane-group-containing polyether is particularly preferably obtained from the reaction of at least one isocyanate-group-containing polyether with at least one aminosilane and / or hydroxysilane and / or mercaptosilane.

The aminosilane and / or hydroxysilane and / or mercaptosilane is preferably selected from the group consisting of N- (3-trimethoxysilylpropyl) -aminosuccinic acid dimethyl ester, N- (3-trimethoxysilylpropyl) -aminobutyric acid diethyl ester, N- (3-triethoxysilylpropyl) -aminosuccinic acid dimethyl ester, N N- (3-trimethoxysilylpropyl) -2-hydroxypropanamide, N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

The preferred embodiments of the silane group-containing organic polymer enable compositions having good storage stability, rapid curing and particularly good mechanical properties, in particular high elasticity and ductility with good strength, and high heat resistance.

In a further preferred embodiment, the composition contains at least one isocyanate group-containing polymer. Such a composition is also referred to as a polyurethane composition.

A suitable isocyanate group-containing polymer is obtained in particular from the reaction of at least one polyol with a superstoichiometric amount of at least one polyisocyanate. The reaction is preferably carried out with exclusion of moisture at a temperature in the range of 50 carried out to 160 ° C, optionally in the presence of suitable catalysts. The NCO / OH ratio is preferably in the range of 1.3 / 1 to 2.5 / 1. The polymer obtained preferably has a content of free isocyanate groups in the range from 0.5 to 10% by weight, in particular from 1 to 5% by weight, particularly preferably from 1 to 3% by weight. Optionally, it is prepared with the concomitant use of plasticizers or solvents, wherein the plasticizers or solvents used contain no isocyanate-reactive groups.

Preferred polyisocyanates are aliphatic or cycloaliphatic diisocyanates, in particular 1,6-hexamethylene diisocyanate (HDI), 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), cyclohexane-1,3 or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'-or 4,4'-diphenylmethanediisocyanate ( HMDI), 1, 3- or 1, 4-bis (isocyanatomethyl) cyclohexane, m- or p-xylylene diisocyanate (XDI), or mixtures thereof, in particular HDI, IPDI, HMDI, or mixtures thereof.

Also suitable as the polyisocyanate are aromatic diisocyanates, in particular 2,4- or 2,6-toluene diisocyanate or any desired mixtures of these isomers (TDI), 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or any mixtures thereof. of these isomers (MDI), 1, 3-phenylene diisocyanate or 1, 4-phenylene diisocyanate, or mixtures thereof, in particular TDI or MDI.

Particularly preferred are aliphatic or cycloaliphatic diisocyanates, in particular HDI or IPDI or mixtures thereof.

Suitable polyols are commercially available polyols or mixtures thereof, in particular

Polyetherpolyols, in particular polyoxyalkylenediols and / or polyoxyalkylenetriols, in particular polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, these with the aid of a starter molecule with two or more active hydrogen atoms can be polymerized, in particular a starter molecule such as water, ammonia or a Compound having a plurality of OH or NH groups, such as 1, 2-ethanediol, 1, 2- or 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, Heptanediols, octanediols, nandi- nandiols, decanediols, undecanediols, 1,3- or 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or Aniline, or mixtures of the aforementioned compounds. Also suitable are polyether polyols with polymer particles dispersed therein, in particular those with styrene-acrylonitrile particles (SAN) or polyurea or polyhydrazodicarbonamide particles (PHD).

Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-capped) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene mixed polyols which are obtained, in particular, in that polyoxypropylene diols or triols are further alkoxylated after conclusion of the polypropoxylation reaction with ethylene oxide and thus finally have primary hydroxyl groups.

Preferred polyether polyols have a degree of unsaturation of less than 0.02 meq / g, especially less than 0.01 meq / g.

Polyester polyols, also called oligoesterols, prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or lactones or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. Preference is given to polyester diols from the reaction of dihydric alcohols, in particular 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol , Glycerol,

1, 1, 1-trimethylolpropane or mixtures of the abovementioned alcohols, with organic dicarboxylic acids or their anhydrides or esters, in particular succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, Terephthalic acid or hexahydrophthalic acid or mixtures of the abovementioned acids, or polyester polyols derived from lactones, in particular especially e-caprolactone. Particular preference is given to polyesterpolyols of adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentylglycol.

Polycarbonate polyols, as obtainable by reacting, for example, the abovementioned alcohols used to form the polyester polyols, with dialkyl carbonates, diaryl carbonates or phosgene.

At least two OH-group-carrying block copolymers which have at least two different blocks having a polyether, polyester and / or polycarbonate structure of the type described above, in particular polyetherpolyesterpolyols.

Polyacrylate or polymethacrylate polyols.

Polyhydroxy-functional fats or oils, for example natural fats and oils, in particular castor oil; or obtained by chemical modification of natural fats and oils - so-called oleochemical - polyols, for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols Epoxypoly- ester or epoxy polyether, or obtained by flydroformylation and Flydrierung unsaturated oils polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, the resulting degradation products or derivatives thereof obtained polyols. Suitable degradation products of natural fats and oils are, in particular, fatty acids and fatty alcohols and also fatty acid esters, in particular the methyl esters (FAME), which can be derivatized, for example by hydroformylation and hydrogenation, to hydroxy fatty acid esters.

Polyhydrocarbyl polyols, also called oligohydrocarbonols, such as in particular polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprene; polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example as produced by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1, 3-butadiene, which may in particular also be prepared from anionic polymerization; Polyhydroxy-functional copolymers of dienes such as 1, 3-butadiene or diene mixtures and vinyl monomers such Styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, in particular polyhydroxy-functional acrylonitrile / butadiene copolymers, in particular from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (for example commercially available under the name Hypro ^® CTBN or CTBNX or ETBN from Emerald Performance Materials); or hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

Also suitable are, in particular, mixtures of polyols.

Preference is given to polyether polyols, polyester polyols, polycarbonate polyols, poly (meth) acrylate polyols or polybutadiene polyols.

Particular preference is given to polyether polyols, in particular polyoxyalkylene polyols.

Most preferred are polyoxypropylenedi- or -triols or ethylene oxide-terminated polyoxypropylenedi- or -triols.

Preference is given to polyols having an average molecular weight in the range from 400 to 20Ό00 g / mol, preferably from 1 Ό00 to 15Ό00 g / mol.

Preference is given to polyols having an average OH functionality in the range from 1.6 to 3.

Preference is given to polyols which are liquid at room temperature.

In the preparation of an isocyanate group-containing polymer, it is also possible to use fractions of difunctional or polyfunctional alcohols, in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propane - diol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 3-pentanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, Dibromneopentylglykol, 1, 2 Hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1 , 3- or 1,4-cyclohexanedimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, dimer fatty acid alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylol propane, Glycerol, pentaerythritol, sugar alcohols such as in particular xylitol, sorbitol or mannitol or sugar in particular sucrose or alkoxylated derivatives of said alcohols or mixtures of said alcohols.

The isocyanate group-containing polymer preferably has an average molecular weight in the range from 1'500 to 20Ό00 g / mol, in particular 2Ό00 to 15Ό00 g / mol.

The isocyanate group-containing polymer preferably has a content of isocyanate groups in the range from 1 to 5% by weight, preferably 1 to 3% by weight.

The isocyanate group-containing polymer preferably has aliphatic isocyanate groups. Such a composition, together with the basic catalyst, has good storage stability, hardens rapidly and has the advantageous properties described.

In addition to an isocyanate group-containing polymer, the composition may contain at least one diisocyanate and / or an oligomer or polymer of a diisocyanate, in particular an IPDI isocyanurate or a TDI oligomer or a mixed isocyanurate based on TDI / HDI or an HDI Oligomer or a liquid at room temperature form of MDI.

A liquid form of MDI which is liquid at room temperature represents liquefied 4,4'-MDI either by partial chemical modification-in particular carbodiimidization or uretonimine formation or adduct formation with polyols-or it is a mixture of selectively brought about by blending or conditioned by the precipitation process 4,4'-MDI with other MDI isomers (2,4'-MDI and / or 2, 2'-MDI), and / or MDI oligomers and / or MDI flomologists (polymeric MDI or PMDI).

If the composition contains an isocyanate group-containing polymer, the composition preferably has a content of free isocyanate groups in the range from 0.2 to 2% by weight. Such a composition has a high elasticity and elasticity. Most preferably, the organic polymer contained in the composition is free of isocyanate groups. Such a composition is toxicologically particularly advantageous and particularly critical with respect to constant curing rate during the storage period.

Furthermore, the curable composition contains at least one acetal group-containing compound having a molecular weight of at least 280 g / mol.

The acetal group-containing compound is typically liquid at room temperature.

The acetal group-containing compound preferably has a molecular weight in the range from 280 to 10Ό00 g / mol, more preferably 280 to 5Ό00 g / mol, particularly preferably 280 to 2500 g / mol, in particular 280 to 1500 g / mol , on.

The acetal group-containing compound preferably contains one to three, in particular one or two, acetal groups.

Such preferred acetal group-containing compounds dilute the curable composition well without migrating or diffusing out of the composition to a high degree after the application, and they improve the mechanical properties of the cured composition, in particular they lower the elastic modulus and increase the elasticity.

The acetal group-containing compound is preferably a compound of the formula (I),

in which

R ¹ and R ² independently of one another are each H or an alkyl, cycloalkyl, aralkyl or aryl radical having 1 to 7 C atoms, R ^{3 is} an optionally ether-containing alkyl, cycloalkyl or aralkyl radical having 1 to 30 C atoms or a monohydric polyoxyalkylene radical having an average molecular weight in the range from 300 to 2Ό00 g / mol,

R ^{4 is} an optionally ether-containing n-valent alkyl, cycloalkyl or aralkyl radical having 4 to 30 C atoms or an n-valent polyoxyalkylene radical having an average molecular weight in the range from 300 to 4Ό00 g / mol, and

n is 1 or 2 or 3,

where R ¹ and R ² together can also stand for an unbranched or branched alkylene radical having 4 to 12 C atoms and R ² and R ^{3 together} also represent an unbranched or branched alkylene radical having 3 to 8 C atoms can stand,

and wherein the compound of formula (I) has a molecular weight of at least 280 g / mol.

The compound of the formula (I) preferably has a molecular weight in the range from 280 to 5Ό00 g / mol, more preferably 280 to 2500 g / mol, in particular 280 to 1'500 g / mol.

Preferably, n is 1 or 2.

Preferably, R ^{1 is} Fl or methyl, especially Fl.

Preferably, R ^{2 is} Fl or an alkyl radical having 1 to 7 C-atoms, in particular methyl.

R ³ is preferably an alkyl, cycloalkyl or aralkyl radical having 1 to 15 C atoms having one or two ether groups, in particular methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, flexyl, 2-ethylhexyl, Allyl, cyclohexyl, benzyl or phenyl, isononyl, isodecyl, lauryl, 2-phenoxyethyl, 2-phenoxypropyl, 2-benzyloxyethyl, 1- (2-methoxy-1-methylethoxy) -2-propyl, 1- (2 - Methoxypropoxy) -2-propyl, 1- (2-butoxy-1-methylethoxy) -2-propyl, 1- (2-butoxypropoxy) -2-propyl.

Further preferably, R ^{3 is} a monohydric polyoxypropylene radical having an average molecular weight in the range of 300 to 2Ό00 g / mol.

In the event that R ¹ and R ² together are an alkylene radical, they are preferably 1,4-butylene or 1, 5-pentylene, in particular 1, 5-pentylene.

In the event that R ² and R ³ together represent an alkylene radical, they are preferably 1, 3-propylene or 1, 4-butylene, in particular 1, 4-butylene.

Preferably, R ^{4 is} an alkyl, cycloalkyl or aralkyl radical having from 4 to 15, in particular 8 to 15, C atoms having one or two ether groups. Furthermore, R ⁴ is preferably an n-valent polyoxyalkylene radical having an average molecular weight in the range from 300 to 4Ό00 g / mol, preferably from 300 to 2Ό00 g / mol.

The polyoxyalkylene radicals are preferably polyoxypropylene radicals or polyoxypropylene radicals which additionally have oxyethylene units, in particular for polyoxypropylene radicals.

Such a compound of the formula (I) is particularly well tolerated with polymers which themselves have polyoxypropylene units and does not cause increased hydrophilicity of the composition.

The polyoxyalkylene radicals preferably contain at least 50% by weight, in particular at least 70% by weight, particularly preferably at least 80% by weight, of 1,2-oxypropylene units.

A monovalent polyoxyalkylene radical preferably has an ether group as end group, in particular a butyl ether group. Such compounds of the formula (I) are derived from alcohol-initiated, in particular butanol-initiated, polyoxyalkylene monols. In a preferred compound of the formula (I), n is 1, R ¹ and R ^{2 are} each the same for Fl and R ³ and R ⁴ are the same radicals.

Here, R ³ and R ⁴ are each preferably an optionally one or two ether groups having alkyl, cycloalkyl or Aral kyl radical having 6 to 15, in particular 8 to 15, carbon atoms. Such a compound of the formula (I) is particularly easy to access and dilutes the composition particularly well.

Furthermore, R ³ and R ⁴ are each preferably a monohydric, optionally ethylene oxide units containing polyoxypropylene radical having an average molecular weight in the range of 300 to 2Ό00 g / mol. Such a compound of the formula (I) is particularly easy to access and particularly compatible in the composition.

Particularly preferably, R ³ and R ⁴ each represent identical radicals selected from isononyl, isodecyl, lauryl, 2-phenoxyethyl, 2-phenoxypropyl, 2-benzyloxyethyl, 1- (2-methoxy-1-methylethoxy) -2 propyl, 1- (2-methoxypropoxy) -2-propyl, 1- (2-butoxy-1-methylethoxy) -2-propyl, 1- (2-butoxypropoxy) -2-propyl and a 1-butanol-started polyoxypropylene Rest with an average molecular weight in the range of 300 to 2Ό00 g / mol. In particular, R ³ and R ^{4 are} each 2-phenoxyethyl. Such a compound of the formula (I) enables particularly low-viscosity compositions

subsidence. She has the formula

on.

In particular, R ³ and R ⁴ furthermore each represent a 1-butanol-initiated polyoxypropylene radical having an average molecular weight in the range from 300 to 2Ό00 g / mol. Such a compound of the formula (I) enables curable compositions having particularly low migration effects. She has the formula wherein Y is 1, 2-propylene and m is an integer in the range of 3 to 35.

In a further preferred compound of the formula (I), n is 1, R ^{1 is} Fl, R ^{4 is} a 1-butanol-initiated polyoxypropylene radical having an average molecular weight in the range from 650 to 2Ό00 g / mol and either R ² and R ³ together for 1,3-propylene or 1,4-butylene or R ² for methyl and R ³ for methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, flexyl, 2-ethylhexyl, allyl, cyclohexyl , Benzyl or phenyl, preferably methyl, ethyl, isopropyl, butyl or isobutyl, in particular isobutyl.

Such a compound of the formula (I) enables curable compositions with particularly few migration effects. In particular, it has the formula

or wherein Y is 1, 2-propylene and m is an integer in the range of 9 to 35.

In a further preferred compound of the formula (I), n is 2, R ^{1 is} H, R ^{4 is} a polyoxypropylene radical having an average molecular weight in the range from 650 to 4Ό00 g / mol, in particular 650 to 2Ό00 g / mol, and either R ² and R ³ together are 1,3-propylene or 1,4-butylene or R ^{2 is} methyl and R ^{3 is} methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2- Ethylhexyl, allyl, cyclohexyl, benzyl or phenyl, preferably methyl, ethyl, isopropyl, butyl or isobutyl, in particular isobutyl.

Such a compound of the formula (I) is particularly easy to access and enables curable compositions with particularly few migration effects. In particular, it has the formula

or wherein Y is 1, 2-propylene and m is an integer in the range of 10 to 35.

The acetal group-containing compound of the formula (I) is formally obtainable from the condensation of at least one aldehyde or ketone of the formula (II) with at least one alcohol of the formula (III) and at least one alcohol of the formula (IV).

In the formulas (II), (III) and (IV), R ¹ , R ² , R ³ , R ⁴ and n have the meanings already mentioned.

Preferred as aldehyde or ketone of the formula (II) is formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, flexanal, 2-ethylhexanal, cyclohexylcarboxaldehyde or benzaldehyde, or acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or acetophenone, especially formaldehyde or acetaldehyde.

For compounds of the formula (I) in which n is 1 and R ³ and R ^{4 are} each the same, the alcohols of the formula (III) and (IV) used are preferably in each case the same alcohol, in particular isononanol, isodecanol, lauryl alcohol , 2-phenoxyethanol, 2-phenoxypropanol, 2-benzyloxyethanol, dipropylene glycol methyl ether, dipropylene glycol butyl ether or alcohol-initiated polyoxypropylene monols having an average molecular weight in the range from 300 to 2Ό00 g / mol. Butanol-initiated polyoxypropylene monols are commercially available, for example play Ucon LB ^® 65 or Synalox 100-20B ^®, ^® Synalox 100-40B or Synalox 100-85B ^® (all from DowDuPont). Compounds of the formula (I) in which R ³ and R ^{4 are} not identical radicals can be prepared in particular by reacting at least one alcohol of the formula (IV) with at least one vinyl ether of the formula (V)

in which

R ¹ 'is H or methyl,

R ² 'is an alkylidene radical having 1 to 7 C atoms,

R ³ 'is an alkyl or aryl radical having 1 to 8 C atoms,

where R ¹ 'and R ² ' together can also be an optionally substituted 1,4-butylidenediyl or 1,5-pentylidenediyl radical and R ² 'and R ³ ' are also together for a 1,3-propylidenediyl or 1 , 4-Butylidendiyl residue can stand.

R ² 'is preferably an alkylidene radical having 1 to 4 C atoms, in particular methylidene, or R ² ' and R ³ 'together are 1, 3-propylidenediyl or 1, 4-butylidenediyl.

Particularly suitable alcohols of the formula (IV) are butanol-initiated polyoxypropylene monols having an average molecular weight in the range from 650 to 2,000 g / mol, or polyoxypropylene diols having an average molecular weight in the range from 650 to 4,000 g / mol, in particular 650 to 2Ό00 g / mol, or trimethylolpropane or glycerol started Polyoxypropylentriole having an average molecular weight in the range of 1 Ό00 to 4Ό00 g / mol. Suitable vinyl ethers of the formula (V) are, in particular, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert. Butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, 1-propenyl methyl ether, 1-propenyl ethyl ether, isopropenyl methyl ether, isopropenyl ethyl ether, isopropenyl propyl ether, isopropenyl isopropyl ether, isopropenyl butyl ether, isophenylphenyl ether, 1-methoxycyclopentene (cyclopentenyl methyl ether), 1 Ethoxycyclopentene (cyclopentenylethyl ether), 1-methoxycyclohexene (cyclohexenylmethyl ether), 1-ethoxycyclohexene (cyclohexenylethyl ether), 2,3-dihydro-furan, 3,4-dihydro-2H-pyran or 4-methyl-3,4-dihydro- 2H-pyran.

Preference is given to methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, isopropenyl methyl ether, isopropenyl ethyl ether, 2,3-dihydrofuran or 3,4-dihydro-2H-pyran.

Most preferred is isobutyl vinyl ether, 2,3-dihydrofuran or 3,4-dihydro-2H-pyran.

From the reaction with isobutyl vinyl ether, compounds of the formula (I) are obtained in which R ^{1 is} H, R ^{2 is} methyl and R ^{3 is} isobutyl.

From the reaction with 2,3-dihydrofuran or 3,4-dihydro-2H-pyran compounds of the formula (I) are obtained in which R ^{1 is} H and R ² and R ³ together for 1, 3-propylene or 1, 4-butylene stand.

Also possible is the preparation of compounds of formula (I) by

R ¹

R'O OR ³

Transacetalization of at least one acetal of the formula R ² with at least one alcohol of the formula (IV), or by transacetalization of

at least one acetal of the formula with at least one alcohol of the formula (III) and at least one alcohol of the formula (IV), wherein the alcohol ROH is liberated and preferably removed by distillation. there R ¹ and R ^{2 have} the meanings already mentioned. R 'is preferably methyl or ethyl.

Particularly suitable acetal for a transacetalization is dimethoxymethane or diethoxymethane.

The reaction is preferably carried out so that the resulting reaction product is finally free of hydroxyl groups.

The reaction is preferably carried out in the presence of an acid as a catalyst, in particular hydrochloric acid, sulfuric acid, phosphoric acid or a sulfonic acid, optionally in the form of an acidic ion exchange resin.

The curable composition further contains at least one basic catalyst. The basic catalyst preferably has a pK _a value of the conjugated acid of at least 9, more preferably at least 10, in particular at least 1. Such a catalyst is able to accelerate very well the curing of silane and / or isocyanate group-containing organic polymers.

Preferred basic catalysts are nitrogen or phosphorus compounds having a pKa of the conjugated acid of at least 9, particularly preferably at least 10, in particular at least 1, in particular amines, amidines, guanidines, biguanides, phosphines, phosphites, phosphazene bases or Phosphatrane.

Preferred as a basic catalyst

tertiary amines, in particular triethylamine, triisopropylamine, N, N, N ', N'-tetramethylalkylenediamine, tris (3-dimethylaminopropyl) amine, 1,4-diazabicyclo [2.2.2] octane (DABCO), dimethylcyclohexylamine, 4 Dimethylaminopyridine 1, 3,5-tris (3- (dimethylamino) propyl) hexahydrotriazine or tris-2, 4,6-dimethylaminomethylphenol,

Amines having primary and / or secondary amino groups, in particular butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, cyclohexylamine, octylamine, 2-ethylhexylamine, laurylamine, stearylamine, ethylenediamine, Butylenediamine, hexamethylenediamine, polyether amines such as 2-aminopropyl terminated glycols such as ^® are available amine, for example under the tradename Jeff- (from Huntsman), or aminosilanes such especially 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-amino nopropyltriethoxysilan, 3- Aminopropyldiethoxymethylsilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane or N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine, wherein primary and / or secondary amines are used Amino groups are suitable as catalyst only for isocyanate-free compositions,

In particular 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene, N, N'-di-n-hexylacetamidine (DHA), 2-methyl-1, 4,5,6-tetrahydropyrimidine, 1, 2 Dimethyl-1, 4,5,6-tetrahydropyrimidine, 2,5,5-trimethyl-1, 4,5,6-tetrahydropyrimidine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-triethoxysilylpropyl ) -4,5-dihydroimidazole, 1- (3-dimethylaminopropyl) -2-methyl-1, 4,5,6-tetrahydropyrimidine, 1- (3-aminopropyl) -2-methyl-1, 4,5,6- tetrahydropyrimidine or reaction products thereof,

Guanidines, in particular 1-butylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,1,3,3-tetramethylguanidine (TMG), 2- (3- (trimethoxysilyl) -propyl) -1, 1 , 3,3-tetramethylguanidine, 2- (3- (methyldimethoxysilyl) propyl) -

1, 1, 3,3-tetramethylguanidine, 2- (3- (triethoxysilyl) propyl) -1, 1, 3,3-tetramethyl-guanidine, 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 7-cyclohexyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1-phenylguanidine, 1 - (o-tolyl) guanidine (OTG), 1, 3-diphenylguanidine, 1, 3-di (o-tolyl) - guanidine, 2-guanidinobenzimidazole or guanidines from the reaction of monoamines, polyamines or Aminosilanes with carbodiimides, in particular dicyclohexylcarbodiimide or diisopropylcarbodiimide,

Biguanides, in particular biguanide, 1-butylbiguanide, 1,1-dimethylbiguanide, 1-butylbiguanide, 1-phenylbiguanide or 1- (o-tolyl) biguanide (OTBG),

Phosphazene bases such as, in particular, the commercially available tert-butylimino-tris (dimethylamino) phosphorane (phosphazene base Pi-t-Bu), tert-butyl-imino-tripyrrolidinophosphorane (BTPP), tert-octylimino-tris (dimethylamino) no) phosphorane (phosphazene base Pi-t-Oct), 1-ethyl-2, 2,4,4, · 4-pentakis (dimethylamino) -2A ⁵ , 4A ^5- catenadi (phosphazene) (phosphazene base P2-Et), 1 - tert-butyl-2,2,4,4,4-pentakis (dinnethylannino) -2A ^5, 4A, ⁵ -catenadi (phosphazene) (phosphazene base P2-t-Bu) or 2-tert .Butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,2,2-diazaphosphorin (BEMP).

The basic catalyst is particularly preferably an amidine or a guanidine, in particular DBU, 1- (3-dimethylaminopropyl) -2-methyl-1,5,5,6-tetrahydropyrimidine, 1- (3-aminopropyl) -2 -methyl-1, 4,5,6-tetrahydropyrimidine or reaction products thereof, or a guanidine from the reaction of monoamines, polyamines or aminosilanes with dicyclohexylcarbodiimide or diisopropylcarbodiimide. Such a catalyst is readily available and especially active.

The curable composition preferably additionally contains one or more further constituents, in particular selected from fillers, adhesion promoters, drying agents and further catalysts.

Suitable fillers are, in particular, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barytes, quartz flours, quartz sands, dolomites, wollastonites, kaolins, calcined kaolins, phyllosilicates, such as mica or talc, zeolites, Aluminum hydroxides, magnesium hydroxides, silicic acids including finely divided silicas from pyrolysis processes, industrially produced carbon black, graphite, metal powder, for example of aluminum, copper, iron, silver or steel, PVC powder or floc balls.

Preference is given to ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, calcined kaolins or industrially produced carbon blacks, as well as combinations of the aforementioned fillers.

The composition preferably has a content of fillers in the range from 10 to 60% by weight, in particular from 20 to 50% by weight. Particularly suitable adhesion promoters are aminosilanes, in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxynethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldinnethoxymethylsilane, N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediannine or its analogues with ethoxy instead of methoxy groups, furthermore N-phenyl-, N-cyclohexyl- or N-alkylaminosilanes, mercaptosilanes, epoxysilanes, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes , Alkylsilanes or iminosilanes, oligomeric forms of these silanes, adducts of primary aminosilanes with epoxysilanes or (meth) acrylosilanes or anhydridosilanes, amino-functional alkylsilsesquioxanes, in particular amino-functional methylsilsesquioxane or aminofunctional propylsilsesquioxane, or titanates.

Epoxy silanes such as, in particular, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms of these silanes are suitable as fl uid mediators for isocyanate group-containing composition.

Suitable drying agents for compositions containing silane-containing polymers are, in particular, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or organoalkoxysilanes which have a functional group in the a position to the silane group, in particular N- (methyldimethoxysilylmethyl) -0-methylcarbamate, (methacryloxymethyl ) silanes, methoxymethylsilanes, orthoformic acid esters, calcium oxide or molecular sieve powder.

Suitable drying agents for compositions containing isocyanate groups are, in particular, molecular sieve powders, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, monomeric diisocyanates or ortho-formic acid esters.

Suitable further catalysts are in particular metal catalysts for the crosslinking of silane groups, in particular compounds of tin, titanium, zirconium, aluminum or zinc. Preference is given to diorganotin (IV) compounds, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dicodecanoate, dibutyltin (IV) bis (acetylacetonate) or dioctyltin (IV) dilaurate, furthermore titanium (IV) or zirconium (IV) or aluminum (III) or zinc (II) complexes with in particular Al koxy, carboxylate, 1, 3-diketonat, 1, 3-Keto esterat- or 1, 3-ketoamidate ligands, in particular organotitanates.

Suitable further catalysts are further catalysts for the reaction of isocyanate groups, in particular organotin (IV) compounds such as in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, complex compounds of bismuth (III) or Zirconium (IV), in particular with ligands selected from alcoholates, carboxylates, 1,3-diketonates, oxinate, 1,3-ketoesterates and 1,3-keto amides, or so-called "delayed action" catalysts, which are modifications of known metal oxides. or amine catalysts.

The curable composition may contain other ingredients, in particular the following auxiliaries and additives:

additional plasticizers, in particular carboxylic esters, such as phthalates, in particular dioctyl phthalate, bis (2-ethylhexyl) phthalate, bis (3-propylheptyl) phthalate, diisononyl phthalate or diisodecyl phthalate, terephthalates, trimellitates, diesters of ortho-cyclohexanedicarboxylic acid, in particular diisononyl-1, 2-cyclohexanedicarboxylate, adipates, in particular dioctyl adipate, azelates, sebacates, succinates or citrates, ethers or monocarboxylic esters of alcohols or glycols, in particular methyl ether, 2-ethylhexanoates or benzoates, furthermore fatty acid methyl or ethyl ester, also called "biodiesel", natural or modified Vegetable oils, in particular rapeseed oil, soybean oil, epoxidized soybean oil or castor oil, organic phosphoric or sulphonic acid esters, sulphonic acid amides, urethanes, high-boiling hydrocarbons, polybutenes, polyisobutylenes, polystyrenes or chloroparaffins;

- solvents;

Crosslinking agents, in particular latent hardeners for isocyanate group-containing polymers, in particular ketimines, aldimines or oxazolidines; Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, synthetic fibers such as polyamide fibers or polyethylene fibers, or natural fibers such as wool, cellulose, hemp or sisal;

- dyes;

Pigments, in particular titanium dioxide or iron oxides;

Rheology modifiers, in particular urea compounds, phyllosilicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, fumed silicas, cellulose ethers or hydrophobically modified polyoxyethylenes;

- natural resins, fats or oils such as rosin, shellac, linseed oil, ricinus oil or soybean oil;

non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP) , Polyisobutylenes, ethylene vinyl acetate copolymers (EVA) or atactic poly-α-olefins

(APAO);

Flame retardant substances, in particular the abovementioned fillers aluminum hydroxide or magnesium hydroxide, and in particular organic phosphoric acid esters, in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris (1,3-dichloro-2-propyl) phosphate , Tris (2-chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris (isopropylphenyl) phosphates of different isopropylation degree Resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) or ammonium polyphosphates;

- Additives, in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides;

as well as other commonly used in curable compositions

Substances. It may be useful to chemically or physically dry certain ingredients before mixing into the composition. The curable composition is preferably free of phthalates.

The curable composition is preferably substantially free of solvents, solvents being volatile organic compounds having a boiling point below 250 ° C at atmospheric pressure and / or a vapor pressure of at least 10 Pa at 20 ° C and atmospheric pressure. The composition preferably contains less than 2% by weight, in particular less than 1% by weight, of solvent. Particularly preferably, the composition is completely free of solvents. Such a composition is particularly advantageous from a toxicological and ecological point of view.

The curable composition preferably contains a content of acetal group-containing compounds having a molecular weight of at least 280 g / mol, in particular compounds of the formula (I), in the range from 1 to 50% by weight, particularly preferably 2 to 45% by weight -%, especially 5 to 40% by weight, most preferably 10 to 35% by weight.

Such a composition is easy to process and has elastic properties.

The curable composition is preferably prepared and stored in the absence of moisture. In particular, it is storage-stable in a suitable packaging or arrangement, such as in particular a bottle, a can, a bag, a bucket, a drum or a cartridge, to the exclusion of moisture.

The curable composition can be present in the form of a one-component or in the form of a multicomponent, in particular two-component, composition.

A "one-component" is a composition in which all constituents of the composition are present in the same container and which as such is storage-stable. "Two-component" refers to a composition in which the constituents of the composition are present in two different components, which are stored in separate containers and mixed together only shortly before or during the application of the composition.

The curable composition is preferably one-component. It is storage stable with suitable packaging and storage, typically for several months to a year or more.

When applying the composition, the process of curing begins. As a result, the cured composition is formed.

In the case of a one-component composition, it is applied as such and begins to cure under the influence of moisture or water. To accelerate the curing, the composition can be mixed with an accelerator component which contains or releases water and / or a catalyst during application, or the composition can be brought into contact with such an accelerator component after its application , Such a composition is also referred to as "moisture-curing".

In the case of a two-component composition, this is applied after mixing the two components and begins to cure by internal reaction, wherein the curing is optionally completed by the action of external moisture. The mixing of the components can be carried out continuously or batchwise with dynamic mixers or static mixers.

When hardened, silane groups react with each other under the influence of moisture. Upon contact with moisture they can hydrolyze to silanol groups (Si-OFI groups). Further silane groups can condense with silanol groups to form siloxane groups (Si-O-Si groups). On curing, isocyanate groups react under the influence of moisture with one another and / or with further reactive groups optionally present in the composition, in particular hydroxyl groups or free amino groups. In the event that additional latent hardeners are present, they react under the influence of moisture with isocyanate groups.

As a result of these reactions, the composition eventually cures.

When curing by means of atmospheric moisture, the composition cures from the outside to the inside, wherein first a skin is formed on the surface of the composition. The so-called skin-forming time represents a measure of the curing rate of the composition. The rate of curing is generally determined by various factors, such as the availability of water, the temperature and the existing catalysts and other ingredients.

The moisture required for curing can additionally or completely also come from one or more substrates to which the composition has been applied into the composition and / or originate from an accelerator component which is admixed with the composition during application or after application is brought into contact with this, for example by brushing or spraying.

The composition is preferably applied at ambient temperature, in particular in the range of about 0 to 50 ° C, preferably in the range of 5 to 40 ° C.

The curing of the composition is preferably carried out at ambient temperature.

The curable composition has good processability and storage stability due to the acetal group-containing compound. That is, the compound of the formula (I) does not dissolve in the composition any reactions that result in limited utility, and also shows no propensity to segregation. paration during storage in the container. In particular, the acetal group-containing compound does not cause significantly altered skin formation time and unpleasant odors during storage of the composition, as is often observed with curable SMP compositions of the prior art. After curing of the composition, the acetal group-containing compound remains in the composition where it exerts an elasticizing effect, is not prone to migration effects and causes no problems with odor or fogging.

The composition is suitable for a variety of uses.

Preferably, the composition is an elastic adhesive or sealant or an elastic coating.

As an elastic adhesive and / or sealant, the composition is suitable for adhesive and sealing applications, in particular in the construction and manufacturing industries or in vehicle construction, in particular for parquet bonding, attachment bonding, cavity sealing, assembly, module bonding, car body adhesion, windshield bonding or joint sealing ,

Elastic adhesive bonds in vehicle construction are, for example, the adhesion of parts such as plastic covers, trim strips, flanges, bumpers, cabs or other attachments, to the painted body of a vehicle, or the gluing of discs in the body, the vehicles especially automobiles, Represent lorries, buses, rolling stock or ships.

As a sealant, the composition is particularly suitable for the elastic cal sealing joints, seams or cavities of all kinds, especially joints in construction such as dilation joints or connecting joints between components. In particular, for the sealing of dilatation joints on structures, a sealant with soft elastic properties is particularly suitable.

As an elastic coating, the composition is suitable for protecting floors or walls, in particular as a coating for balconies, terraces, squares, bridges, parking decks, or for sealing roofs, in particular special flat roofs or slightly inclined roof areas or roof gardens, or inside buildings for waterproofing, for example under tiles or ceramic plates in wet rooms or kitchens, or as floor covering in kitchens, industrial halls or production rooms, or as a seal in catch basins, canals, Shafts or waste water treatment plants, or for protecting surfaces as a lacquer or seal, or as a casting compound for cavity sealing, as a seam seal or as a protective coating for, for example, pipes.

It can also be used for repair purposes as a seal or coating, for example, from leaky roof membranes or inadequate floor coverings or, in particular, as a repair compound for highly reactive spray-on seals.

For use as an elastic adhesive or sealant, the composition at room temperature preferably has a pasty consistency with structure-viscosity properties. Such a paste-like sealant or adhesive is applied in particular from commercially available cartridges, which are operated manually, by means of compressed air or battery, or from a barrel or hobbock by means of a feed pump or an extruder, optionally by means of an application robot on a substrate.

For use as an elastic coating, the composition preferably has a liquid at room temperature consistency with self-leveling properties. If necessary, it is slightly thixotropic, so that the coating can be applied to sloping to vertical surfaces without immediately flowing away. It is in particular applied by means of a roller or brush or by pouring and distributing by means of, for example, a roller, a scraper or a dental trowel. In this case, a layer thickness in the range of 0.5 to 3 mm, in particular 1.0 to 2.5 mm, is typically applied in one operation.

Suitable substrates which can be glued or sealed or coated with the composition are, in particular - glass, glass ceramic, concrete, mortar, fiber cement, in particular fiber cement slabs, brick, brick, plaster, in particular gypsum boards, or natural stones such as granite or marble;

- repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

- metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-refined metals or alloys such as galvanized or chromium-plated metals;

- asphalt or bitumen;

- leather, textiles, paper, wood, wood-based materials bonded with resins such as phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites;

- Plastics such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma , Corona or flames;

- Fiber reinforced plastics such as Carbon Fiber Reinforced Plastics (CFRP), Glass Fiber Reinforced Plastics (GRP) and Sheet Molding Compounds (SMC);

- insulating foams, in particular of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);

coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

- paints or varnishes, in particular automotive finishes.

If necessary, the substrates can be pretreated prior to application, in particular by physical and / or chemical cleaning methods or the application of an activator or a primer.

Two similar or two different substrates can be bonded and / or sealed.

After curing of the composition, a cured composition is obtained. Another object of the invention is a cured composition from the curing of the described curable composition with water, in particular in the form of humidity.

The cured composition is elastic and has a high extensibility. It preferably has an elongation at break of at least 50%, in particular at least 100%, determined on dumbbell-shaped test specimens having a length of 75 mm, a web length of 30 mm and a web width of 4 mm at a thickness of 2 mm according to DIN EN 53504 a pulling speed of 200 mm / min, as described in the examples.

From the application and curing of the composition, an article is obtained which is glued or sealed or coated with the composition. This article may be a building or a part thereof, in particular a building of civil engineering, a bridge, a roof, a staircase or a facade, or it may be an industrial good or a consumer good, in particular a window Pipe, a rotor blade of a wind turbine, a household machine or a transport such as in particular a car, a bus, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an attachment thereof.

Examples

In the following, exemplary embodiments are listed which are intended to explain the described invention in more detail. Of course, the invention is not limited to these described embodiments.

The term "standard climate" ("NK") refers to a temperature of 23 + 1 ° C and a relative humidity of 50 + 5%.

The chemicals used were from Sigma-Aldrich unless otherwise specified. 1.) Preparation of acetal group-containing compounds:

The viscosity was measured with a Rheotec RC30 thermo-conical cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10 s ^-1 ).

Infrared (FT-IR) spectra were measured as undiluted films on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a diamond crystal horzontal ATR measuring unit. The absorption bands are given in wavenumbers (cm ^-1 ).

Compound V-1: butanol-initiated polypropylene glycol having l- (isobutoxy) -ethoxy end group and average molecular weight of about 850 g / mol

300.00 g butanol-initiated polyoxypropylene monol with a medium molecular weight 750 g / mol (Synalox 100-20B ^® from DowDuPont) and 12:17 g of methane sulfonic acid (anhydrous) were charged to a round bottom flask under Stickstoffatmos- phere. Then 41.16 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were slowly added dropwise with stirring, so that the temperature of the reaction mixture did not rise above 70 ° C, and then stirred at 70 ° C under a nitrogen atmosphere until, by IR and GC spectrometry no flydroxyl groups were detectable. Subsequently, 0.07 g of sodium methylate was added and stirred, followed by 0.06 g of acetic acid. Then, first at 80 ° C and 5 mbar and then at 100 ° C and 2 mbar vacuum, the volatiles were removed from the reaction mixture. There was obtained a clear, yellowish liquid with a viscosity of 97 mPa s at 20 ° C.

FT-IR: 2969, 2931, 2868, 1455, 1372, 1343, 1296, 1257, 1099, 1012, 924, 905, 867, 831.

Compound V-2: Butanol-initiated polypropylene glycol having tetrahydropyran-2-oxy end group and average molecular weight of about 840 g / mol

Compound V-2 was prepared as described for compound V-1 but using 34.57 g of 3,4-dihydro-2F-pyran instead of 41.16 g of isobutyl vinyl ether. There was obtained a clear, colorless liquid having a viscosity of 77 mPa s at 20 ° C. FT-IR: 2967, 2931, 2867, 1454, 1372, 1343, 1297, 1260, 1099, 1021, 997, 925, 906, 869, 814.

Compound V-3: Butanol-initiated polypropylene glycol having tetrahydrofuran-2-oxy end group and average molecular weight of about 830 g / mol

Compound V-3 was prepared as described for compound V-1, but using 28.81 g of 2,3-dihydrofuran instead of 41.16 g of isobutyl vinyl ether. There was obtained a clear, colorless liquid having a viscosity of 64 mPa s at 20 ° C.

FT-IR: 2969, 2931, 2867, 1455, 1372, 1343, 1296, 1258, 1099, 1035, 1010,

919, 865, 836.

Compound V-4: butanol-initiated polypropylene glycol having l- (isobutoxy) -ethoxy end group and average molecular weight of about T200 g / mol

300.00 g butanol-initiated polyoxypropylene monol vinyl ethers with moderate molecular weight T100 g / mol (Synalox 100-40B ^® from DowDuPont) and 28.16 g of isobutyl (stabilized with 0.1% potassium hydroxide) was sodium methoxide using 0.08 g as described for compound V-1 described implemented. A clear, yellowish liquid with a viscosity of 207 mPa s at 20 ° C. was obtained.

FT-IR: 2969, 2931, 2868, 1455, 1372, 1344, 1296, 1257, 1099, 1012, 924, 906, 867, 831.

Compound V-5: Butanol-initiated polypropylene glycol having l- (isobutoxy) -ethoxy end group and average molecular weight of about T900 g / mol

300.00 g butanol-initiated polyoxypropylene monol vinyl ethers with moderate molecular weight T800 g / mol (Synalox 100-85B ^® from DowDuPont) and 17:33 g of isobutyl (stabilized with 0.1% potassium hydroxide) was sodium methoxide using 0.09 g as described for compound V-1 described implemented. A clear, yellowish liquid with a viscosity of 533 mPa s at 20 ° C. was obtained.

FT-IR: 2969, 2930, 2867, 1455, 1372, 1344, 1296, 1257, 1099, 1012, 924, 867, 832. Compound V-6: Butanol-initiated polypropylene glycol having tetrahydropyran-2-oxy end group and average molecular weight of about 1 '890 g / mol

300.00 g butanol-initiated polyoxypropylene monol with a medium molecular weight 1 '800 g / mol (Synalox 100-85B ^® from DowDuPont) and 14:55 g of 3,4-di- hydro-2H-pyran in place of isobutyl vinyl ether were prepared using 0.11 g of sodium methylate as described for compound V-1. A clear, yellowish liquid with a viscosity of 412 mPa s at 20 ° C. was obtained.

FT-IR: 2969, 2931, 2867, 1454, 1372, 1344, 1296, 1259, 1097, 1020, 925, 908, 869, 834.

Compound V-7: Butanol-initiated polypropylene glycol having tetrahydrofuran-2-oxy end group and average molecular weight of about 1 '880 g / mol

300.00 g butanol-initiated polyoxypropylene monol with a medium molecular weight 1 '800 g / mol (Synalox 100-85B ^® from DowDuPont) and 12.13 g of 2,3-di- hydro-2FI-furan instead of isobutyl vinyl ether were prepared using 0.11 g of sodium methylate as described for compound V-1, wherein the temperature of the reaction mixture was kept at the addition of 2,3-dihydro-2F-furan but below 50 ° C and then stirred at 50 instead of 70 ° C. A clear, yellowish liquid with a viscosity of 347 mPa s at 20 ° C. was obtained.

FT-IR: 2969, 2930, 2867, 1455, 1372, 1344, 1296, 1257, 1097, 1011, 922, 866, 834.

Compound V-8: Polypropylene glycol with two 1- (isobutoxy) ethoxy end groups and average molecular weight of about T200 g / mol

300.00 g of polyoxypropylene diol having an average molecular weight 1Ό00 g / mol (Vo- ranol ^® P 1010 from DowDuPont) and 61.90 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were reacted using 0.07 g of sodium methoxide as described for compound V -1. There was obtained a clear, yellowish liquid with a viscosity of 711 mPa s at 20 ° C. FT-IR: 2970, 2931, 2869, 1454, 1372, 1343, 1296, 1257, 1099, 1013, 984, 924 903, 867, 830.

Compound V-9: Polypropylene glycol with two 1- (isobutoxy) ethoxy end groups and average molecular weight of about 2,200 g / mol

300.00 g of polyoxypropylene diol having an average molecular weight 2Ό00 g / mol (Vo- ranol ^® 2000 L, of DowDuPont) and 39.95 g of isobutyl vinyl ether (stabilized with 0.1% potassium hydroxide) were reacted using 0.08 g of sodium methoxide as described for compound V -1. There was obtained a clear, yellowish liquid having a viscosity of 1149 mPa s at 20 ° C.

FT-IR: 2970, 2930, 2868, 1454, 1372, 1343, 1296, 1257, 1099, 1012, 924, 906, 867, 831.

2.) used commercial substances and abbreviations thereof:

DPEF: Di (2-phenoxyethyl) formal (Desavin ^{®, manufactured} by Covestro)

DIDP: diisodecyl phthalate (Palatinol ^® 10-P, from BASF)

DINP: diisononyl phthalate (Palatinol ^® N from BASF)

DINCFI: diisononyl 1, 2-cyclohexanedicarboxylate (Flexamoll ^® DINCFI,

from BASF)

DOA: Di (2-ethylhexyl) adipate (Adimoll ^® DO, from Lanxess)

TXIB: 1-isopropyl-2,2-dimethyltrimethylene diisobutyrate (Eastman

TXIB ™, from Eastman Chemical)

IsoSDE: isosorbide diester (Polysorb ^® ID-37, Roquette Freres of)

DPGDB: dipropylene glycol (Benzoflex ^® 9-88, Eastman

Chemical)

PAS: Cio-C2i-Alkylsulfonsäurephenylester (Mesamoll ^® , from

Lanxess)

TOF: tris (2-ethylhexyl) phosphate (TOF Disflamoll ^® from Lanxess)

DPO: 2-ethylhexyl (Disflamoll ^® DPO, of

Lanxess)

BBSA: N-butylbenzenesulfonamide (Proviplast ^® 024, from Proviron)

ESBO: Epoxidized soybean oil (ESBO Merginat® ^® from HOBUM

Oleochemicals) PPG 400: polypropylene glycol having an average molecular weight of about 400 g / mol (Voranol ^® P 400, of DowDuPont)

Ricinusöl: castor oil (Alberdingk ^® castor oil DIN quality, from

Alberdingk Boley)

DME500: polyethylene glycol dimethyl ether with a mean molecular weight of about 500 g / mol (Polyglycol DME 500, ex Clariant)

Ibay: bis (ethylacetoacetato) diisobutoxy-titanium (IV) (Tyzor ^® ibay,

from village Ketal)

DBU: 1, 8-diazabicyclo [5.4.0] undec-7-ene (Lupragen ^® N 700, from

BASF)

AMMO 3-aminopropyltrimethoxysilane (Silquest ^® A-1110, from

Momentive)

DAMO 3- (2-aminoethyl) aminopropyltrimethoxysilane (Silquest ^® A-1120 from Momentive)

Chalk: Omyacarb ^® 5-GU (Omya)

Russ: ^Monarch® 570 (by Cabot)

Silica fumed silica (Aerosil ^® R 972, from Evonik)

acid:

3.) Preparation of Silane Group and / or Isocyanate Group-Containing Organic Polymers:

Polymer P1: (silane-group-containing polyether)

Absence of moisture, 1000 g of polyol Acclaim ^® 12200 (poly oxypropylendiol with low degree of unsaturation, by Covestro; OFI number 11.0 mg KOFI / g); ((Vestanat ^® IPDI, by Evo nik IPDI) and 0.1 g of bismuth tris, 43.6 g of isophorone diisocyanate neodecanoate) (10 wt .-% in diisodecyl phthalate) with constant stirring to 90 ° C and left at this temperature until the titrimetrically determined content of free isocyanate groups had reached a stable value of 0.7 wt .-%. Subsequently, 63.0 g of diethyl N- (3-trimethoxysilylpropyl) amino-succinate (adduct of 3-aminopropyltrimethoxysilane and diethyl maleate prepared as described in US Pat. No. 5,364,955) were mixed in and the mixture was stirred at 90.degree. C. until filtered by means of FT-IR. Spectroscopy no free isocyanate was detected. The resulting trimethoxysilane-containing polyether was cooled to room temperature and stored with exclusion of moisture. Polymer P2: (silane-containing polyether)

Absence of moisture, 720.0 g of Acclaim ^® 12200, 34.5 g isophorone diisocyanate (IPDI Vestanat ^® from Evonik), 80.0 g of diisononyl 1, 2-cyclohexane-dicarboxylate (DINCH ^® Hexamoll, from BASF) and 0.5 g of bismuth tris (neodecanoate) - Solution (10% by weight in diisononyl-1,2-cyclohexanedicarboxylate) was heated to 90 ° C. with constant stirring and kept at this temperature until the titrimetrically determined content of free isocyanate groups had reached a stable value of 0.73% by weight. Subsequently, 49.1 g of N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, prepared as described below, were added and the mixture was stirred under nitrogen atmosphere at 80 ° C. until no isocyanate groups were detectable by IR spectroscopy (about 2 hours ). The triethoxysilane group-containing polyether thus obtained was cooled to room temperature and stored with exclusion of moisture.

N- (3-triethoxysilylpropyl) -2-hydroxypropanamide was prepared by mixing 20.00 g of 3-aminopropyltriethoxysilane and 6.71 g (46.6 mmol) of L-lactide and stirring under nitrogen atmosphere for 3 h at 80 ° C, until no by IR spectroscopy Reaction progress was detected more, and the crude product was then post-treated for 15 min at 60 ° C and 10 mbar. A colorless liquid product was obtained.

Polymer P3: (isocyanate group-containing polymer)

With exclusion of moisture, 590 g Acclaim ^® were 4200 (polyoxypropylene diol, of Covestro; OFI number 28.5 mg KOFI / g), 1180 g Caradol ^® MD34-02 (poly oxypropylenpolyoxyethylentriol, of Shell; number OFI 35.0 mg KOFI / g) and 230 g of isophorone diisocyanate (Vestanat ^® IPDI, Evonik) according to a known method at 80 ° C converted to a liquid at room temperature, the NCO-terminated poly- urethane polymer having a free isocyanate group content of 10.2% by weight. 4. Preparation of curable compositions:

Compositions Z1 to Z16: (SMP compositions)

For each composition, the ingredients listed in Table 1 were mixed in the stated amounts (in parts by weight) by means of a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc.) with exclusion of moisture for one minute at 3000 rpm and stored with exclusion of moisture.

Each composition was tested for fluffing time and viscosity, fresh (one hour after Fierstellung) and after a storage period of 7 days in a sealed container in a heated to 60 ° C convection oven. The skin formation time is a measure of the curing rate, and a low Viskosiät allows good application properties.

To determine the skin formation time (HBZ), a few grams of the composition in a layer thickness of about 2 mm were applied to cardboard and determined in standard climate, the time until lightly tapping the surface of the composition by means of a pipette of LDPE for the first time no residues left more on the pipette. The skin formation time was determined in the fresh state and in the stored state. A change of less than 25% was rated as "good", from 25 to 100% as "medium" and more than 100% as "poor".

The viscosity was measured as described above at 20 ° C in the fresh state and in the stored state. A change of less than 100% was rated as "good", 100 to 200% as "medium" and more than 200% as "bad".

The results are shown in Table 1.

The compositions marked (Ref.) Are comparative examples.

Table 1: Composition (in parts by weight) and properties of Z1

to Z16.

Table 1: (continued)

Compositions Z17 to Z24: (SMP compositions)

For each composition were 25.1 parts by weight of (GT) polymer P1, 25.1 GT of the plasticizer indicated in Table 2, 1.0 part of vinyltrimethoxysilane, 12.4 GT of precipitated stearate-coated chalk, 35.1 GT of chalk, 1.0 GT of DAMO, 0.2 GT DBU and 0.05 GT IBAY as for Composition Z1 described mixed and stored with exclusion of moisture.

Each composition was tested for fluffing time and viscosity as described for Composition Z1. When changing the viscosity, a change of less than 50% was rated as "good", 50 to 100% as "medium" and more than 100% as "poor".

The smell of the uncured material was tested in the fresh state and after storage in a sealed container for 7 days at 60 ° C by smelling the nose at a distance of 10 cm. He is indicated as "weak", "medium" or "strong".

To determine the mechanical properties of each composition was applied to a PTFE-coated film to a film of 2 mm thickness, stored for 7 days in standard climate, some dumbbells with a Length of 75 mm with a web length of 30 mm and a web width of 4 mm punched out of the film and this according to DIN EN 53504 at a tensile speed of 200 mm / min on tensile strength (breaking strength), elongation at break and modulus 50% ( at 0.5-50% elongation) tested. These results are given as "NK".

The resistance to heat in the cured state was tested by, during 7 days in NK cured films of 2 mm thickness, prepared as described above, stored for 7 days in a convection oven at 60 ° C or at 100 ° C and then the tensile strength , Elongation at break and modulus 50% were determined as already described. These results are reported as "7d 60 ° C" and "7d 100 ° C", respectively.

Further, the aspect of these films was visually evaluated before and after storage at 60 ° C, designated "NK" and "7d 60 ° C", respectively. As "beautiful" was a regular film with non-sticky surface called without bubbles. The term "greasy" referred to a film on the surface of which had formed an oily film due to plasticizer migration.

The results are shown in Table 2.

The compositions marked (Ref.) Are comparative examples.

Table 2: Composition and properties of Z17 to Z24.

1 not measurable, depolymerized

Table 2: (continued)

Compositions Z25 to Z33: (SMP compositions)

For each composition, the ingredients listed in Table 3 were mixed in the indicated amounts (in parts by weight) using a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc.) with exclusion of moisture for one minute at 3000 rpm and stored in the absence of moisture.

Each composition was tested as follows:

The rate of cure (HBZ) was determined as the measure of the cure rate. For this purpose, a few grams of the composition were applied in a layer thickness of about 2 mm on cardboard and determined in the standard climate for a period of time until lightly tapping the surface of the composition For the first time, no residues were left on the pipette by means of a pipette made of LDPE.

To determine the mechanical properties, each composition was applied to a PTFE-coated film to form a film of 2 mm thickness, stored for 7 days under standard conditions and then as described for composition Z17 to tensile strength (breaking strength), elongation at break, Modulus 5% (at 0.5-5% strain) and modulus 50% (at 0.5-50% strain) tested.

The smell of the uncured material was tested in the fresh state and after storage in a sealed container for 7 days at 60 ° C by smelling the nose at a distance of 10 cm. It is given as "black", "medium" or "strong".

The aspect was visually evaluated on the produced films. The term "beautiful" was used to describe a regular film with a non-sticky surface without bubbles.

As a measure of the plasticizer migration, the horizontal staining on cardboard was determined. For this purpose, each composition was applied to a piece of cardboard so that it had a round base of 15 mm in diameter and a height of 4 mm and then stored for 7 days under standard conditions and then for 12 hours in a convection oven at 100 ° C. Around each composition there was a dark oval spot on the cardboard. Its dimensions (height and width) were measured and indicated as migration (horizontal).

The results are shown in Table 3.

The compositions marked (Ref.) Are comparative examples.

Table 3: Composition (in parts by weight) and properties of Z-25

to Z-33.

Compositions Z34 to Z40: (polyurethane compositions)

For each composition, the ingredients listed in Table 4 were mixed in the indicated amounts (in parts by weight) using a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc.) with exclusion of moisture for one minute at 3000 rpm and with exclusion of moisture kept.

Each composition was tested as follows:

Flushing time (HBZ), tensile strength, elongation at break, modulus of elasticity 5%, E-modulus 50%, aspect and odor were tested as described for composition Z25.

As a measure of the plasticizer migration, the vertical staining on paper was determined. For this purpose, 30 g of the composition in a round, open-top vessel of 45 mm diameter were filled (filling height about 17 mm) and then a piece of printer paper, rolled to a cylinder, 26 mm in diameter and 100 mm high, was placed in the fresh composition with the round side so that the rolled paper touched the bottom of the vessel and protruded from the top of the composition. This arrangement was stored under standard conditions and after 3, 7 and 14 days it was observed whether there was staining by liquid absorbed in the paper. The height of the annular spot was measured and as

Migration (vertical) indicated.

The results are shown in Table 4.

The compositions marked (Ref.) Are comparative examples.

Table 4: Composition (in parts by weight) and properties of Z-34

to Z-40.

¹ 1 - (3-dimethylaminopropyl) -2-methyl-1, 4,5,6-tetrahydropyrimidine (prepared as amidine A3 in WO 2016/166336), 25% by weight in xylene

Claims

claims:

1. comprising curable composition

at least one organic group containing silane groups and / or isocyanate groups,

at least one acetal group-containing compound having a molecular weight of at least 280 g / mol, and

- At least one basic catalyst.

2. A composition according to claim 1, characterized in that the organic polymer has an average molecular weight, determined by GPC against polystyrene as standard, in the range of 1 Ό00 to 30Ό00 g / mol.

3. A composition according to any one of claims 1 or 2, character- ized in that the organic polymer is free of Isocyanatgrup- pen.

4. A composition according to claim 3, characterized in that the organic polymer is a silane-containing polyether.

5. A composition according to any one of claims 1 or 2, character- ized in that the organic polymer contains isocyanate groups and the composition has a total content of free isocyanate groups in the range of 0.2 to 2% by weight.

6. A composition according to any one of claims 1 to 5, character- ized in that the acetal group-containing compound has a molecular weight in the range of 280 to 10Ό00 g / mol.

7. A composition according to any one of claims 1 to 6, character- ized in that the acetal group-containing compound is a compound of formula (I),

in which

R ¹ and R ² independently of one another are each H or an alkyl, cycloalkyl, aralkyl or aryl radical having 1 to 7 C atoms,

R ^{3 is} an optionally ether-containing alkyl, cycloalkyl or aralkyl radical having 1 to 30 C atoms or a monohydric polyoxyalkylene radical having an average molecular weight in the range from 300 to 2Ό00 g / mol,

n is 1 or 2 or 3,

where R ¹ and R ² together can also stand for an unbranched or branched alkylene radical having 4 to 12 C atoms and R ² and R ³ together also represent an unbranched or branched alkylene radical having 3 to 8 C atoms can stand,

and wherein the compound of the formula (I) has a molecular weight of at least 280 g / mol.

8. A composition according to claim 7, characterized in that n for 1, R ¹ and R ² each for H and R ³ and R ^{4 are} each the same radicals.

9. A composition according to claim 7, characterized in that n is 1, R ^{1 is} H, R ^{4 is} a polybutylene radical started with a mean molecular weight in the range from 650 to 2Ό00 g / mol and either R ² and R ² for a 1-butanol ³ together for 1,3-propylene or 1,4-butylene or R ² for methyl and R ³ for methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, allyl, cyclohexyl, benzyl or phenyl stand.

10. A composition according to claim 7, characterized in that n is 2, R ^{1 is} H, R ^{4 is} a polyoxypropylene radical having a mean molecular weight in the range of 650 to 4Ό00 g / mol and either R ² and R ³ together for 1, 3-propylene or 1, 4-butylene or R ² for methyl and

R ^{3 is} methyl, ethyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, allyl, cyclohexyl, benzyl or phenyl.

11. A composition according to any one of claims 1 to 10, character- ized in that the basic catalyst is a nitrogen or phosphorus compound having a pKa value of the conjugated acid of at least 9.

12. A composition according to any one of claims 1 to 11, characterized in that it has a content of fillers in the range of 10 to

60% by weight

13. A composition according to any one of claims 1 to 12, character- ized in that it is one-component.

14. A composition according to any one of claims 1 to 13, character- ized in that it is an elastic adhesive or sealant or an elastic coating.

15. Cured composition obtained from the curing of the composition according to any one of claims 1 to 14 with water.