WO2012130663A1

WO2012130663A1 - Curable mass based on organyl oxysilane-terminated polymers

Info

Publication number: WO2012130663A1
Application number: PCT/EP2012/054858
Authority: WO
Inventors: Volker Stanjek; Marko Prasse; Wolfram Schindler
Original assignee: Wacker Chemie Ag
Priority date: 2011-03-25
Filing date: 2012-03-20
Publication date: 2012-10-04
Also published as: EP2688937A1; DE102011006128A1

Abstract

The invention relates to curable masses having a viscosity of at least 20,000 mPas at 25°C comprising: (A) compounds of the formula A-[-0-C(=0)-NH-(CR¹ ₂)_b-SiR_a(OR²)_3-a]₂ (I); and (B) silanes of the formula R³ _cSi(OR⁴)_dR⁵ _4-c-d (II), and partial hydrolysates thereof, wherein the radicals and indices have the meanings given in claim 1, to the method for the production thereof, and to the use thereof as adhesives, particularly for gluing substrates.

Description

Crosslinkable compositions based on organyloxysilane erminier en polymers

The invention relates to crosslinkable compositions based on silane-crosslinking prepolymers, processes for their preparation and their use as adhesives, in particular for bonding substrates.

Polymer systems that have reactive alkoxy ilyl groups have long been known. On contact with water or atmospheric moisture, these alkoxysilane-terminated polymers are already able to condense with one another at room temperature, with elimination of the alkoxy groups. One of the most important applications of such materials is the production of adhesives, in particular elastic adhesive systems.

Adhesives based on alkoxysilane-crosslinking polymers in the cured state show not only good adhesion properties on some substrates, but also very good mechanical properties, since they can be both tear-resistant and highly elastic. Another key advantage of silane crosslinking systems over many other adhesive and sealant technologies (e.g., over isocyanate crosslinking systems) is the toxicological safety of the prepolymers.

In many applications, one-component systems (1-component systems) are preferred which cure when exposed to atmospheric moisture. The decisive advantages of single-component systems are, above all, their very easy applicability since no mixing of different adhesive components by the user is required here. In addition to the time / labor savings and the safe avoidance of any dosage errors, is at 4858

einkomonentigen systems also not given the need to process the adhesive / sealant within a usually quite narrow time window, as is the case with multi-component systems after mixing of the two components.

A disadvantage of these systems according to the prior art, as described for example in WO-A 2010126937, is in particular the low reactivity of the corresponding MS ~ or SPUR polymers to moisture, which requires aggressive catalysis. The corresponding mixtures therefore typically contain significant amounts of toxicologically harmful tin catalysts. Here, the use of so-called α-silane-terminated prepolymers is advantageous which have reactive alkoxysilyl groups which are connected by a methylene spacer to an adjacent urethane unit. This class of compounds is highly reactive and requires neither tin catalysts nor strong acids or bases to achieve high cure rates on exposure to air. Commercially available a-silane-terminated prepolymers are GENIOSIL STP-E10 or -E30 from Wacker · Chemie AG. However, silane-crosslinking adhesives generally have the disadvantage of not having sufficiently good adhesion on all materials. For example, they often show inadequate adhesion to concrete, especially wet concrete, as well as numerous plastics, especially PVC. The adhesion to wood is not optimal in many cases. This applies in particular to adhesives which have a tensile strength measured after curing according to DIN EN 14293 and / or DIN EN 53504 of at least 1 MPa. In particular, these tear solid adhesives for mechanically stressed adhesive seams high demands on the liability, as they not only do not tear when high tensile forces occur but of course not allowed to detach from the substrate.

Although the adhesion profile of tear-resistant adhesives can be improved by the addition of organofunctional silanes, in particular of silanes with a primary amino group. The o.g. described liability problems are solved in this way, however, insufficient. Also combinations of these silanes, as e.g. in EP 1 179 571 or EP 1 975 910, or the use of organic resins as described in EP 1 724 321, do not represent a sufficient improvement. An object of the invention was the development of silane-crosslinking adhesives which, after their curing have a tensile strength measured according to DIN EN 53504 of at least 1 MPa, with which the disadvantages of the prior art can be overcome.

The invention relates to crosslinkable compositions having a viscosity of at least 20,000 mPas at 25 ° C containing

(A) compounds of the formula A- [-O-C (-O) -NH- (CR ^l _a) b- S IRA {OR ²⁾ ₃ -a] 2 (I), wherein

A represents a divalent polyoxyalkylene radical,

R may be identical or different and represents a monovalent, optionally substituted, Sic-bonded hydrocarbon radical,

R ^{1 may be} identical or different and is hydrogen or a monovalent, optionally substituted hydrocarbon 12 054858

4

Is a substance residue which can be attached to the carbonator via nitrogen, phosphorus, oxygen, sulfur or carbonyl group,

R ^{2 may be the} same or different and represents hydrogenator or a monovalent, optionally substituted hydrocarbon radical,

a may be the same or different and is 0, 1 or 2, preferably 0 or 1, and

b may be identical or different and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1,

and

(B) Silanes of the formula R ³ _c Si (O ⁴ ) _d R ⁵ _4-cd {II) wherein

R ^{3 may be} identical or different and denotes a monovalent Sic-bonded hydrocarbon radical having 10 to 40 carbon atoms,

R ^{4 may be} identical or different and is hydrogen or optionally substituted hydrocarbon radicals, R ^{5 may be} identical or different and is a monovalent, Sic-bonded, hydrocarbon est having 1 or 2 carbon atoms,

c is 1, 2, 3 or 4, preferably 1, and

d is 0, 1, 2 or 3, preferably 2 or 3, more preferably 3

with the proviso that the sum of c + d is equal to 2, 3 or 4 and their partial hydrolysates.

Examples of radicals R are alkyl radicals such as methyl, ethyl, n ~ _f propyl iso-propyl, ln-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-penyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical, iso-octyl radicals and the 2, 2, -trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals such as the vinyl, 1-propenyl and 2-propenyl radicals; Aryl radicals, such as the phenyl, napthyl, anthryl and phenantryl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl radicals and ethylphenyl radicals and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radicals.

Examples of substituted radicals R are haloalkyl radicals, such as the 3, 3, 3-trifluoro-n-propyl radical, the 2, 2, 2, 2 ", 2 ', 2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as o-, m- and p-chlorophenyl radical.

Radical R is preferably monovalent hydrocarbon radicals having 1 to 6 carbon atoms which are optionally substituted by halogen atoms, more preferably alkyl radicals having 1 or 2 carbon atoms, in particular the methyl radical. Examples of radicals R ¹ are hydrogen, the radicals indicated for R and optionally substituted by nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group bonded to the carbon atom, optionally substituted hydrocarbon radicals. Radical R ¹ is preferably hydrogen atom and hydrocarbon radicals having 1 to 20 carbon atoms, in particular hydrogen atom. PT / EP2012 / 054858

6

Examples of radical R ² are hydrogen atom or the examples given for radical R.

The radicals R ^{2 are} preferably hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms optionally substituted by halogen atoms, more preferably alkyl radicals having 1 to 4 carbon atoms, in particular the methyl and ethyl radical. The polyoxyalkylene radicals A are preferably linear polyoxyalkylene radicals, particularly preferably those of the formula

- [R ⁸ 0] _e -R ⁸ - (IV), where

R ^{8 may be the} same or different and is an optionally substituted divalent hydrocarbon radical having 1 to 12 carbon atoms, which may be linear or branched, meaning and

e is an integer from 50 to 550.

Examples of radical R ⁸ are -CH ₂ -, ~CH ₂ -CH ₂ ~, -CH ₂ -CH (CH ₃ ) -, -CH ₂ - CH ₂ -CH ₂ ~, -CH ₂ -CH (-CH ₂ -CH ₃ ) ~ CH <CH ₃ ) ~ CH <CH ₃ ) -, -CH ₂ ~ CH ₂ -CH ₂ -CH ₂ - and -CH ₂ ~C {CH ₃ ) ₂ -.

Radical R ⁸ is preferably a divalent hydrocarbon est having 1 to 4 carbon atoms, particularly preferably a divalent hydrocarbon radical having 1 to 4 carbon atoms, very particularly preferably -CH ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ - and -CH ₂ -CH {CH ₃ ) -, in particular -CH (CH ₃ ) ~ CH ₂ - and ~ CH ₂ -CH (CH ₃ ) -. In particular, the polyoxyalkylene radical A is polyoxyalkylene radicals having 65 to 350 repeat units.

The polyoxyalkylene radicals A preferably have average molar masses M _n of 4,000 to 30,000 daltons, particularly preferably 8,000 to 20,000 daltons.

Examples of the component (A) used according to the invention and processes for their preparation are described inter alia in EP 1 535 940 B1 [paragraphs [0005] ~ [0025] and also examples 1-3 and comparative example 1-4) or EP 1 896 523 B1 (US Pat. Paragraphs [0008] - [0047]) which are to be included in the disclosure of the present application. Component (A) is preferably polypropylene glycols having hindered siloxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl or triethoxysilyl end groups.

The viscosity of the compounds (A) is preferably at least 0.2 Pas, preferably at least 1 Pas, more preferably at least 5 Pas, and preferably at most 700 Pas, preferably at most 100 Pas, each measured at 20 ° C.

The component (A) used according to the invention may contain only one type of compound of the formula (I) as well as mixtures of different types of compounds of the formula (I). In this case, component (A) may contain exclusively compounds of the formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98% of all silyl groups bound to the radical A are identical. However, it is then also possible to use a component (A) which contains, at least in part, compounds of the formula (I) in which different silyl groups are bonded to a radical A. Finally, you can as component (A) it is also possible to use mixtures of different compounds of the formula {1} in which a total of at least 2 different types of silyl groups bonded to radicals A are present, but all silyl groups bound to one radical A are identical.

If component (A) is a different type of compound of formula (I), mixtures comprising both compounds (AI) having end groups of formula (I) in which b = 1 and R ¹ = H and a = 0 or 1, as well as compounds (A2) having end groups of the formula (I) in which b = 3 and R is ^X = H and a = 0, are preferred, and those in which the weight ratio of (AI) to (A2) is 0.1 to 10, preferably 0.2 to 5.

The compositions of the invention preferably contain compounds (A) in concentrations of at most 60% by weight, more preferably at most 40% by weight and preferably at least 10% by weight, particularly preferably at least 15% by weight.

The radicals R ^{3 are} preferably branched, linear or cyclic alkyl radicals having 14 to 40 carbon atoms, particularly preferably branched, linear or cyclic, preferably linear, alkyl radicals having 16 to 30 carbon atoms, the alkyl radicals preferably having an even number of carbon atoms ,

Examples of the radical R ³ are the decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl radical. Preferred examples of the radical R ³ are the tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl radical. Especially the hexadecyl and octadecyl are. 8th

9

Examples of optionally substituted hydrocarbon radicals R ⁴ are the examples given for radical R.

The radicals R ⁴ are preferably a hydrogen atom and optionally with Halogenatottien substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and Kohlenwasserstof radicals having 1 to 10 carbon atoms, in particular methyl and Et yl radical. Preferably, R ⁵ is the methyl radical.

Examples of the silanes (B) used according to the invention are decyltrimethoxysilanes, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane, where the examples mentioned are preferably Alkyl silanes is. The silanes used according to the invention are commercially available products or can be prepared by processes customary in chemistry.

The compositions of the invention contain component (B) in amounts of preferably from 1 to 50 parts by weight, more preferably from 2 to 25 parts by weight, based in each case on 100 parts by weight of compound (A).

The compositions according to the invention preferably contain at least 1% by weight, more preferably at least 2% by weight and less than 10% by weight, more preferably less than 7% by weight, of the component (B), based in each case on the entire composition the crosslinkable formulation. 54858

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In addition to the components (A) and (B) used, the compositions according to the invention may contain all other substances which have hitherto been used in crosslinkable compositions and which are different from components (A) and (B), such as e.g. further silane-trained polymers (Α '), basic nitrogen-containing organosilicon compound (C), fillers (D), catalyst (E), adhesion promoter (F), water scavenger (G), additives (H) and additives (K).

The compositions according to the invention preferably contain no component (A ') or these in amounts of preferably at most 15% by weight, preferably at most 10% by weight and particularly preferably at most 5% by weight, based in each case on the total weight of the components (A ) and {A ').

Component (C) is preferably organosilicon compounds containing units of the formula D _h Si (OR ⁷ ) _g R ⁶ fO ( ₄ .fgh) / 2 (III), in which

R ^{6 may be the} same or different and a monovalent, optionally substituted SiC-bonded, of basic

Nitrogen free organic residue means

R ^{7 may be} identical or different and is hydrogen or is optionally substituted hydrocarbon radicals, D may be identical or different and represents a monovalent, SiC-bonded radical with basic nitrogen,

f is 0, 1, 2 or 3, preferably 1,

g is 0, 1, 2 or 3, preferably 1, 2 or 3, more preferably 1 or 3, and

h is 0, 1, 2, 3 or 4, preferably 1, 2 054858

I I with the proviso that the sum of f + g + h is less than or equal to 4 and at least one residue D is present per molecule.

The organosilicon compounds (C) which may optionally be used according to the invention may be both silanes, ie compounds of the formula (III) with f + g + h = 4, as well as siloxanes, ie compounds containing units of the formula (III ) with f + g + h <3, which are preferably silanes. Examples of radical R ⁶ are the examples given for R.

The radicals R ^s are preferably hydrocarbon radicals having 1 to 18 carbon atoms which are optionally substituted by halogen atoms, more preferably hydrocarbon radicals having 1 to 5 carbon atoms, in particular the methyl radical.

Examples of optionally substituted hydrocarbon radicals R ⁷ are the examples given for radical R.

The radicals R ⁷ is preferably a hydrogen atom and an optionally halogen-substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radicals.

Examples of radicals D are radicals of the formulas H ₂ N {CH ₂ ) ₃ ~,

H ₂ N (CH _a ) ₂ NH (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -, H ₃ CNH (CH ₂ ) ₃ -,

C ₂ H ₅ NH (CH ₂ ) ₃ -, C ₃ H ₇ NH (CH ₂ ) ₃ -, C ₄ H ₉ NH (CH ₂ ) ₃ -, C ₅ HnNH (CH ₂ ) ₃ -,

C ₆ H ₁₃ NH (CH ₂ ) ₃ -, C ₇ H ₁₅ NH (CH ₃ ) ₃ -, H ₂ N (CH ₂ ) ₄ -, H ₂ N-CH ₂ -CH (CH 3) - CH ₂ -, H ₂ N (CH ₂ ) ₅ -, cyclo-C ₅ H _s NH (CH ₂ ) ₃ -, cyclo-C ₆ HnNH (CH ₂ ) ₃ -, phenyl-NH (CH ₂ ) ₃ -, (CH ₃ ) ₂ N (CH ₂₎ ₃ -, (C ₂ H _5} ₂ N {CH _2} ₃ -, (C ₃ H ₇₎ ₂ NH {CH _2} ₃ -,

(C ₄ H ₉ ) ₂ NH (CH ₂ ) ₃ -, (C ₅ H ₁₁ ) ₂ NH (CH ₂ ) ₃ -, (C ₆ H ₁₃ ) ₂ NH (CH ₂ ) ₃ -, EP2012 / 054858

12

(C ₇ H ₁₅ ) ₂ NH {CH ₂ ) ₃ -, H ₂ N (CH ₂ ) -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) -,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH {CH ₂ ) -, H ₃ CNH (CH ₂ ) -, C ₂ H ₅ NH (CH ₂ ) -, C ₃ H ₇ NH {CH ₂ ) -, C ₄ H ₉ NH (CH ₂ ) -, CsH HtCHa) -, C ₆ Hi ₃ NH (CH ₂ ) -, C ₇ H ₁₅ NH (CH ₂ ) -, cyclo-C ₅ H ₉ NH (CH ₂ ) -, cyclo-CeHnNHiCHa) phenyl-NH (CH ₂ ) -, (CH ₃ ) ₂ N (CH ₂ ) -, (C ₂ H ₅ ) ₂ N (CH ₂ ) -, (C ₃ H ₇ ) ₂ NH (CH ₂ ) -, (C ₄ H ₉ ) ₂ NH (CH ₂ ) -, (C ₅ H _iX ) ₂ NH (CH ₂ ) -, (C ₆ H ₁₃ ) ₂ NH (CH ₂ ) -, (C ₇ H _{1 S)} ₂ NH (CH ₂₎ -, {CH ₃ 0) ₃ Si {CH ₂₎ ₃ NH (CH ₂₎ ₃ -,

(C ₂ H ₅ O) ₃ Si {CH ₂ ) ₃ NH (CH ₂ ) ₃ -, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ - and

(C ₂ H _s O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NH {CH ₂ ) ₃ - as well as reaction products of the abovementioned primary amino groups with compounds which contain reactive double bonds or epoxy groups relative to primary amino groups.

Preferably, radical D is the H ₂ N (CH ₂ ) ₃ -,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ - and cyclo-C ₆ HnNH (CH ₃ ) ₃ radical.

Examples of the inventively optionally used

Silanes of the formula (III) are H ₂ N (CH) ₃ -Si {OCH ₃ } ₃ ,

H ₂ N (CH ₂ ) 3-Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ,

H ₂ N (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N {CH ₂ } ₂ NH {CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ,

H ₂ N {CH ₂ } ₂ NH {CH ₂ } ₃ -Si {OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₃ ,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₂ CH _3i H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H _s ) ₃ , cycloC _e H NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cyclo -C ₆ HnNH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , cyclo- _O ₆ Η _{Χ 1} ΝΗ (CH ₂ ) ₃ -Si {OCH ₃ ) ₂ CH ₃ , cyclo-C ₆ HuNH (CH ₂ ) 3-Si (OC ₂ H ₅ ) ₂ CH ₃ , cyclo-C ₆ Hn H (CH ₂ ) ₃ -Si (OH) ₃ , cyclo-C ₆ HuNH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , Phenyl-NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , phenyl-NH (CH ₂ ) 3-Si (OC ₂ H ₅ ) ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ,

Phenyl-NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OH) ₃ , phenyl-NH {CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ) ₂ ,

HN ((CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ ) ₂ HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ) ₂ ,

HN {(CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ ) ₂ ,

(CH ₂₎ Si (OCH ₃₎ _3, C cyclo- _S H _U NH (CH ₂₎ Si (OC ₂ H _s) _3, cyclo-C ₆ H Hu (CH ₂₎ Si (OCH ₃₎ ₂ CH ₃ , cyclo C ₆ HnNH (CH ₂ ) -Si {OC ₂ H _s ) ₂ CH ₃ , cycloC ₆ H _xl NH (CH ₂ ) -Si (OH) ₃ , cycloC ₆ HnNH (CH ₂ ) -Si (OH ) ₂ CH ₃ , phenyl-NH (CH ₂ ) SiSi (OCH ₃ ) ₃ ,

Phenyl-NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₃ , phenyl-NH (CH ₂ ) -Si (OCH ₃ ) ₂ CH ₃ , phenyl-NH (CH ₂ ) -Si (OC ₂ H ₅ } ₂ CH ₃ , phenyl-NH (CH ₂ ) -Si (OH) ₃ and

Phenyl-NH (CH ₂ ) -Si (OH) ₂ CH ₃ and their partial hydrolysates, wherein H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ } ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ ,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , cyclo-C ₆ HnNH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cyclo-C ₆ HnNH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ and cycloC ₆ Hn H (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ and in each case their Teilhydrolysate preferred and

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OGH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , cycloC ₆ HnNH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cyclo-C ₆ H _{1: L} NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ and in each case their partial hydrolysates are particularly preferred.

The organosilicon compounds (C) optionally used according to the invention can also assume the function of a curing catalyst or cocatalyst in the compositions according to the invention.

Furthermore, the organosilicon compounds (C) which may optionally be used according to the invention may act as adhesion promoters and / or as water scavengers.

The organosilicon compounds (C) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.

If the compositions according to the invention comprise component (C), these are amounts of preferably 0.01 to 25 parts by weight, more preferably 0.1 to 10 parts by weight, in particular 0.5 to 5 parts by weight, in each case based on 100 parts by weight of component ( A). The compositions of the invention preferably contain component (C). EP2012 / 054858

The fillers (D) optionally used in the compositions according to the invention may be any known fillers known to date. Examples of fillers (D) are non-reinforcing fillers, ie fillers having a BET surface area of preferably up to 50 m ² / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powder, such as aluminum, titanium -, iron or zinc oxides or their

Mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders, such as polyacrylonitrile powder; reinforcing fillers, ie fillers having a BET surface area of more than 50 m / g, such as fumed silica, precipitated silica, precipitated chalk, carbon black, such as furnace and acetylene black and silicon

Mixed aluminum oxides of large BET surface area; Aluminum trihydroxide, hollow spherical fillers, such as ceramic microspheres, such as those available under the trade name Zeo spheres ™ from 3M Germany GmbH in D-Neus, elastic plastic balls, such as those available under the trade name EXPANCEL ^® in the Fa. AKZO NOBEL, Expancel in

Sundsvall, Sweden, or glass balls; fibrous fillers, such as asbestos and plastic fibers. The fillers mentioned may be rendered hydrophobic, for example by treatment with organosilanes or siloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy group.

The optional fillers (D) used are preferably calcium carbonate, talc, aluminum trihydroxide and silicic acid. Preferred calcium carbonate types are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or its salts. When the be ~ 4858

Preferred silica is preferably fumed silica.

Optionally used fillers (D) have a moisture content of preferably less than 1% by weight, more preferably less than 0.5% by weight.

If the compositions according to the invention contain fillers (D), these are amounts of preferably 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, in particular 80 to 300 parts by weight, in each case based on 100 parts by weight of component (A). The compositions of the invention preferably contain fillers (D). In a particularly preferred embodiment of the invention, the compositions according to the invention as fillers (D) comprise a combination of

a) silica, in particular fumed silica, and

b) calcium carbonate, aluminum trihydroxide and / or talc.

If the compositions according to the invention contain this particularly preferred combination of different fillers (D), they preferably contain from 1 to 80 parts by weight, more preferably from 5 to 40 parts by weight, of silica, in particular pyrogenic, diacid, and preferably from 10 to 500 parts by weight, particularly preferably from 50 to 300 Parts by weight, calcium carbonate, aluminum trihydroxide, talc or mixtures of these materials, each based on 100 parts by weight of component (A). The catalysts (E) which may optionally be used in the compositions according to the invention may be any, hitherto known catalysts for compositions which cure by silane condensation. Examples of metal-containing curing catalysts (E) are organic titanium and tin compounds, for example titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, di-butyltin oxides, and corresponding dioctyltin compounds. Examples of metal-free curing catalysts (E) are basic compounds, such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, Ν, Ν-bis- (N, N-direthyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenylamine, and N- Ethylmorpholinin.

Also, as the catalyst (E), acidic compounds such as phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid or organic carboxylic acids, e.g. Acetic acid and benzoic acid.

If the novel compositions comprise catalysts (E), these are amounts of preferably 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, based in each case on 100 parts by weight of component {A).

In one embodiment of the invention, the optionally used catalysts (E) are metal-containing curing catalysts, preferably tin-containing catalysts. This embodiment of the invention is particularly preferred when component (A) is wholly or at least partially, ie at least 90% by weight, preferably at least 95% % By weight of compounds of the formula (I) in which b is not equal to 1.

In the case of the compositions according to the invention, preference may then be given to metal-containing catalysts (E), and in particular to catalysts containing tin, if component (A) is wholly or at least partially, ie at least 10% by weight, preferably at least 20 wt .-%, consists of compounds of formula (I), in which b is 1 and R ^{1 has} the meaning of hydrogen atom. This embodiment of the invention without metal and in particular without tin-containing catalysts is particularly preferred.

The adhesion promoters (F) optionally used in the compositions according to the invention may be any adhesion promoters hitherto known to cure by silane condensation.

Examples of adhesion promoters (F) are epoxysilanes, such as glycidoxypropyltrimethoxysilanes, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmetyldiethoxysilane, 2- (3-triethoxysilylpropyl) maleic anhydride, N- {3-trimethoxysilylpropyl} urea, (3 Triethoxysilylpropyl) urea, N ~ (trimethoxysilylmethyl) urea, N- (methyldimethoxysilymethyl) urea, N- (3-triethoxysilylmethyl) urea, N- (3-triethoxysilylpropyl) urea

Methyldiethoxysilylmethyl) harnstof f, O ethylcarbamatomethyl- methyldimethoxysilane, O- ethy1carbamatomethy1 -1rimethoxysila, Q-EthyIcarbamatomethy1-methyIdiethoxysilan, O-methyl- Ethylcarbamato- riethoxysilan, 3 -Met acryloxypropyl trimethoxysilane, methacryloxymethyl trimethoxysilane, Methacryloxymethy1-methyldimethoxysilane, methacryloxymethyl triethoxysilane, Methacryloxymethyl-methyldiethoxysilane, 3-acryloxypropyltrimeth- oxysilane, acryloxymethyltrimethoxysilane, acryloxymethylmethyldimethoxysilanes, acryloxymethyltriethoxysilane and acryloxymethyl-methyldiethoxysilane, and also their partial condensates. If the compositions according to the invention comprise adhesion promoters (F), these are amounts of preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of crosslinkable composition. The water scavengers (G) optionally used in the compositions according to the invention may be any water scavengers described for systems which cure by silane condensation. Examples of water scavengers (G) are silanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyl-1-trimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, and / or their partial condensates and orthoesters such as 1, 1, 1-trimethoxyethane, 1, 1, 1-triethoxyethane, trimethoxymethane and triethoxymethane.

If the compositions according to the invention contain water scavengers (G), they are amounts of preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition. The compositions of the invention preferably contain water scavenger {G}.

The additives (H) which may be used in the compositions according to the invention may be any desired additives known hitherto for silane-crosslinking systems. The additives (H) optionally used according to the invention are preferably antioxidants, UV stabilizers, such as, for example, HALS compounds, fungicides and pigments. If the compositions according to the invention contain additives (H), these are amounts of preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A). The compositions of the invention preferably contain additives (H).

The additives {K) optionally used according to the invention are preferably tetraalkoxysilanes, e.g. Tetraethoxysilane and / or their partial condensates, plasticizers, rheology additives, flame retardants and organic solvents.

Examples of plasticizers (K) are such as phthalic acid esters (e.g., dioctyl phthalate, diisooctyl phthalate and diundecyl phthalate), perhydrogenated phthalic acid esters {e.g. 1,2-cyclohexanedicarboxylic acid isoisononyl ester and 1,2-cyclohexanedicarboxylic acid dioctyl ester), adipic acid ester (e.g., dioctyl adipate), benzoic acid ester, glycollene ester, esters of saturated alkanediols {e.g. 2, 2, 4-trimethyl-l, 3-pentanediol monoisobutyrate and 2, 2, -trimethyl-1, 3 -pentandioldi- isobutyrate), phosphoric acid esters, sulfonic acid esters, polyesters, polyethers (for example, polyethylene glycols and polypropylene glycols having molecular weights of preferably 1000 to 10,000 Dalton), polystyrenes, polybutadienes, polyisobutylenes, paraffinic hydrocarbons and high molecular weight, branched hydrocarbons, preference being given to using no plasticizers (K).

The rheology additives (K) are preferably polyamide waxes, hydrogenated castor oils or stearates. Examples of organic solvents (K) are the compounds already mentioned above as solvents, preferably alcohols. Preferably no organic solvents (K) are added to the compositions according to the invention.

If the compositions according to the invention comprise one or more components (K), they are each preferably amounts of from 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, in each case based on 100 parts by weight of component ( A).

The compositions of the invention are preferably those containing

(A) compounds of the formula (I)

(B) silanes of the formula (II),

possibly

{Ά ') silane-terminated polymers,

possibly

(C) basic nitrogen compound,

possibly

(D) fillers,

possibly

(E) catalysts,

possibly

(F) adhesion promoter,

possibly

(G) water catcher,

possibly

(H) additives and

possibly

(K) aggregates. T EP2012 / 054858

21

The compositions according to the invention preferably contain no further components apart from the components (A) to (). The components used according to the invention may in each case be one type of such a component as well as a mixture of at least two types of a respective component. The compositions according to the invention are preferably viscous to pasty compositions having viscosities of preferably from 25,000 to 1,000,000 mPas, more preferably from 30,000 to 500,000 mPas, in each case at 25 ° C. The preparation of the compositions according to the invention can be carried out in any manner known per se, such as by methods and mixing methods, as are customary for the preparation of moisture-curing compositions. The order in which the various components are mixed together can be varied as desired.

Another object of the present invention is a process for preparing the composition according to the invention by mixing the individual components in any order.

This mixing can be carried out at room temperature and the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.

If desired, however, this mixing can also take place at relatively high temperatures, for example at temperatures in the range from 30 to 130.degree. Furthermore, it is possible to mix temporarily or constantly under reduced pressure, such as at 30 to 500 hPa absolute pressure to remove volatile compounds and / or air.

The mixing according to the invention is preferably carried out with the exclusion of moisture.

The process according to the invention can be carried out continuously or batchwise. The compositions according to the invention are preferably one-component crosslinkable compositions. However, the compositions according to the invention can also be part of two-component crosslinking systems in which OH-containing compounds, such as water, are added in a second component.

The compositions according to the invention can be used for all uses for which materials which are storable with the exclusion of water and can crosslink on admission of water at room temperature to elastomeric materials can be used, in particular as adhesives.

Another object of the invention is the use of crosslinkable compositions containing

(A) Compounds of the formula (I) and

(B) Silanes of the formula (II)

and their partial hydrolysates

as an adhesive.

For the crosslinking of the compositions according to the invention, the usual content of water in the air is sufficient. The crosslinking of the compositions of the invention is preferably carried out at room temperature. It may, if desired, even at higher or lower temperatures than room temperature, for example at -5 ° to 15 ° C or at 30 ° _, 12 054858

23 to 50 ° C and / or by means of the normal water content of the air exceeding concentrations of water are performed.

Preferably, the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.

Another object of the present invention are molded articles prepared by crosslinking of the inventive masses.

The moldings according to the invention preferably have a tensile strength of at least 1 MPa, preferably of at least 1.5 MPa, more preferably of at least 2 MPa, in particular of at least 3 MPa, in each case measured according to DIN EN 53504.

The moldings according to the invention may be any shaped articles, such as, for example, gaskets, pressed articles, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers.

Another object of the invention is a method for producing composite materials, in which the composition of the invention is applied to at least one substrate and then allowed to crosslink.

Examples include the production of composite materials and composite moldings. Composite molded parts is to be understood here as meaning a uniform molded article made of a composite material which is composed of a cross-linked product of the compositions according to the invention and at least two substrates, that there is a strong, permanent connection between the substrates.

In the method according to the invention for the production of material-bound compounds, the composition according to the invention can also be vulcanized between at least two identical or different substrates, such as e.g. for gluing or laminates.

Examples of substrates which can be bonded according to the invention are plastics including PVC, concrete, wood, mineral substrates, metals, glass, ceramics and painted surfaces.

The compositions of the invention have the advantage that they are easy to prepare.

The crosslinkable compositions according to the invention have the advantage that they are distinguished by a very high storage stability and a high crosslinking rate. Furthermore, the crosslinkable compositions according to the invention have the advantage that they have an excellent adhesion profile.

Furthermore, the crosslinkable compositions according to the invention have the advantage that they are easy to process.

In the examples described below, all viscosity data refer to a temperature of 25 ° C. Unless otherwise specified, the examples below are at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature resulting from combining the reactants at room temperature without additional heating or cooling, as well performed at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.

Example 1: Method for Formulating the Adhesive

75 g of both sides silane-terminated linear polypropylene glycol having an average molecular weight (M _n ) of 12,000 daltons and end groups of the formula

-O-C (= O) -3MH-CH ₂ -SiCH ₃ (OCH ₃ ) ₂

®

(commercially available under the name GENIOSIL STP-E10 from Wacker Chemie AG, D-Munich) and 50 g of both sides silane-terminated polypropylene glycol having an average molecular weight (M _n ) of 12,000 daltons and end groups of the formula

-O-C (= O) -NH- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃

(commercially available under the name GEHIOSIL ⁹ STP-E15 from Wacker Chemie AG, D-Munich) are mixed and placed in a laboratory planetary mixer from the PC Laboratory System equipped with two beam mixers at about 25 ° C. with 10 g vinyltrimethoxysilane , 50 g of hexadecyltrimethoxysilane and 2.5 g of stabilizer

(commercially available under the name TINUVIN "123 from BASF AG, Germany, CAS No. 129757-67-1) for 2 minutes at 200 rpm, then 155 g of chalk with a BET surface area of 15 m ² / g and a d50 value of 0.45 xm (commercially available under the name "Socal U1S2" from Solvay) and 155 g of chalk having a BET surface area of 3 m ² / g and a d50 value of 0 , 45 pm (commercially available under the name "Imerseal 50" from Imerys) with stirring for one minute at 600 rpm After incorporation of the chalk, 5 g of aminopropyltrimethoxysilane are mixed for 1 minute at 200 rpm, Homogenized for 2 minutes at 600 rpm and 1 minute at 200 rpm in a partial vacuum (about 100 mbar) and stirred bubble-free. EP2012 / 054858

26

The formulation is filled into 310 ml PE cartridges and stored for 1 day at 25 ° C prior to testing.

Example 2, 3 and Comparative Example VI

The other examples are formulated analogously. The corresponding plasticizers are initially introduced together with the silane-terminated polymers. The fumed silica is incorporated after incorporation of the chalks and digested with stirring for one minute at 600 U / min.

Table 1: Composition of the adhesive formulations

Plasticizers polypropylene glycol having a M _n of 2,000 plasticizer Hexamoll DINCH (BASF)

Chalk 1 Socal U1S2 (Solvay)

Chalk 2 Imerseal 50 (Imerys)

Chalk 3 Omyacarb 5GU

Pyrogenic silica: HDK H18 from Wacker Chemie GmbH Alkyl silane: Hexadecy1-rimethoxysilane

Water scavenger: vinyltrimethoxysilane

Aminosilane: aminopropyltrimethoxysilane

Stabilizer: TINUVIN ^® 123 (BASF)

Example 4

The adhesives obtained in Examples 1 to 3 and Comparative Example 1 were allowed to crosslink and examined with regard to their skin formation, their mechanical properties and their adhesion profile. The results are shown in Table 2.

Skin formation time (HBZ)

For the determination of the skin formation time the into the

Examples of crosslinkable compositions obtained in a 2 mm thick layer applied to PE ™ film and stored under standard conditions (23 ° C and 50% relative humidity). During curing, the formation of a skin is tested every 5 min. For this purpose, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to the finger, no skin has formed yet. If no sample sticks to the finger, a skin has formed and the time is noted. Mechanical properties

The compositions were each spread on ausgefraßten Teflon plates with 2 mm depth and 2 weeks at 23 ° C, 50 rel. Humidity cured. Shore A hardness is determined according to DIN 53505.

Tensile strength is determined according to DIN 5350 -Sl.

Elongation at break is determined according to DIN 53504-S1. Liability profile:

The masses were each subjected to adhesion tests on the substrates indicated in Table 2 under the following conditions:

Storage A: A 5-7 cm thick bead is applied to the substrate and stored for 7 days at room temperature.

Storage B: A 5-7 cm thick bead is applied to the substrate and stored in water at room temperature for 7 days and also at room temperature for 2 weeks

(for wood, 2 weeks at 50 ° C and 95% relative humidity}.

Storage C: A 5-7 cm thick bead is applied to the substrate and stored in water at room temperature for 7 days and also at room temperature for 4 weeks

(for wood: 4 weeks at 50 ° C and 95% relative humidity).

After storage, a peel test is performed in which the caterpillar is cut at one end with a sharp knife over a length of about 2 cm from the substrate. Subsequently, starting from this cut, the remainder of the bead is torn from the substrate and the nature of the resulting crack (cohesive and / or adhesive) is assessed.

Table 2: Mechanical properties and adhesion of the adhesive formulations

Mass from Example 1 2 3 VI

HBZ [min] 40 55 45 35

Shore A hardness 70 58 62 67

Tear strength [N / mm ² ] 2.4 1.8 1, 9 2.3

Elongation at break [%] 170 220 200 250

Storage ABCABCABCABC EP2012 / 054858

29

Aluminum - + + + + 0 + + 0 + 0

Eloxal + + + + 0 0 + 0 0 + +

Steel 0 + + + + 0 + + 0 + ₊ -

Glass + + + + + + + + + + +

Concrete + - - ₊ - + - - +

Wood - spruce + + + + + + + + + + +

Wood - alkyd paint + + + 0 - - 0 - - + -

Polycarbonate - + - - 0 0 - 0 - -

PM A. + ~ - + 0 0 + 0 - -

PVC + 0 - + 0 + + 0 0 - -

Polystyrene + 0 - - 0 0 +

Claims

claims

1. Crosslinkable compositions having a viscosity of at least

Containing 20,000 mPas at 25 ° C

(A) Compounds of the formula

A- [-OC (-O) -NH- (CR ¹ ₂ ) _b "SiR _a (OR ² ) ₃ -a] 2 (I) where

A represents a divalent polyoxyalkylene radical,

R may be the same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon residue;

R ^{1 may be} identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group,

R ^{2 may be} identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical,

a may be the same or different and is 0, 1 or 2 and b may be the same or different and is an integer from 1 to 10,

and

(B) Silanes of the formula

R ³ _c Si {OR) _d R ⁵ _4-cd (Ii) wherein

R ^{3 may be} identical or different and denotes a monovalent SiO-bonded hydrocarbon radical having from 10 to 40 carbon atoms, R ⁴ may be the same or different and Wasserstof atom or optionally substituted hydrocarbon radicals, R ^£ may be the same or different and is a monovalent, SiC-bonded atoms hydrocarbon radical having 1 or 2 carbon atoms means,

c is 1, 2, 3 or 4 and

d is 0, 1, 2 or 3

2. Crosslinkable compositions according to claim 1, characterized in that the polyoxyalkylene radicals A are those of the formula - [R ^s O] _e -R ⁸ - (IV), where

R ^{8 may be the} same or different and is an optionally substituted divalent hydrocarbon radical having 1 to 12 carbon atoms, which may be linear or branched, and

e is an integer from 50 to 550.

3. Crosslinkable compositions according to claim 1 or 2, characterized in that e in the compositions according to the invention are those containing

(A) compounds of the formula {I),

(B) silanes of the formula (II),

possibly

(A ') silane-terminated polymers,

possibly

(C) basic nitrogen compound,

possibly (D) fillers,

possibly

(E) catalysts,

possibly

(F) adhesion promoter,

ifflls

(G) water absorber,

possibly

(H) additives and

possibly

(K) aggregates

trade . , Crosslinkable compositions according to one or more of Claims 1 to 3, characterized in that the compositions are viscous to pasty compositions having viscosities of 25,000 to 1,000,000 mPas at 25 ° C.

5. A process for the preparation of the composition according to one or more of claims 1 to 4 by mixing the individual components in any order.

6. Use of crosslinkable compositions containing

(A) Compounds of the formula (I) and

(B) Silanes of the formula (II)

and their partial hydrolysates

as an adhesive.

7. Use of the compositions according to one or more of claims 1 to 4 or produced according to claim 5 as an adhesive,

8. Shaped body produced by crosslinking of the compositions according to one or more of claims 1 to 4 or produced according to claim 5.

9. Shaped body according to claim 8, characterized in that they have a tensile strength of at least 1 MPa, measured according to DIN EN 53504.

10. A process for producing composite materials, wherein the composition according to one or more of claims 1 to 4 or prepared according to claim 5 is applied to at least one substrate and then allowed to crosslink.