EP2922894A1

EP2922894A1 - Specific aminoalkyl-functional alkoxysiloxane-oligomer mixtures, processes for producing same and use of same

Info

Publication number: EP2922894A1
Application number: EP13770452.4A
Authority: EP
Inventors: Thomas Schlosser; Ingo Kiefer; Jürgen FRITZ; Regina KRAUSE; Svenja Schütt
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2012-11-22
Filing date: 2013-09-25
Publication date: 2015-09-30
Also published as: US20150299540A1; CN104854169A; BR112015011520A2; DE102012221379A1; RU2015123806A; JP2016506423A; KR20150087328A; WO2014079614A1

Abstract

The present invention relates to specific mixtures containing straight-chain aminopropyl-functional alkoxysiloxanes of the general formula I and/or cyclic aminopropyl-functional alkoxysiloxanes of the general formula II (R)₃Si-O-[Si(R)₂-O]_m-Si(R)₃ (I), (II), in which the groups R are composed mutually independently of (i) aminopropyl-functional groups of the formula -(CH₂)₃-NH₂, -(CH₂)₃-NH(CH₂)₂-NH₂ and/or -(CH₂)₃-NH(CH₂)₂-NH(CH₂)₂-NH₂, (ii) methoxy and/or ethoxy groups and (iii) optionally butyl or octyl groups, m is an integer from 2 to 30 and n is an integer from 3 to 30, where there is at most one aminoalkyl-functional group bonded to a silicon atom of a compound of the formula I and/or II, and where the quotient calculated from the molar ratio of Si to alkoxy groups is at least 0.3, and a process for producing same. These have excellent suitability for application as adhesives and sealants, while featuring improved adhesion more particularly on substrates that are not easily bonded to one another.

Description

Specific aminoalkyl-functional Me alkoxysiloxane oligomer mixtures, process for their preparation and their use

The present invention relates to specific aminoalkyl-functional alkoxysiloxane oligomer mixtures, processes for their preparation and their use in adhesives and sealants.

Monomeric organofunctional silanes have been used successfully for many years to formulate adhesives and sealants. Especially in moisture crosslinking, so-called reactive adhesives and sealants, such. In silicones or in (alkoxysilane) -terminated polymers, such as polyurethanes or polyethers, amino-functional alkoxysilanes have proven to be efficient adhesion promoters.

Examples of post-crosslinking hot melt adhesives or sealants which cure via terminal isocyanate and / or Al koxysilangruppen and contain the aminosilanes functionalized polymers can be found in

DE 38 40 220 A1. When using amino-functional alkoxysilanes as

Adhesion agents succeed in improving the adhesion to the substrate to be bonded / sealed. At the same time, the cohesion within the adhesive and sealant is increased. For the sealing / gluing of generally difficult

To seal or difficult to stick substrates, such as aluminum and plastics, such as polymethyl methacrylate ("PMMA") and polycarbonate ("PC"), provide standard used, amino-functional alkoxysilanes, such as aminopropyltrimethoxysilane (Dynasylan ^® AMMO), usually only a basic liability , Therefore, in various applications with so-called primers

(to be prepared.

EP 0 997 469 A2 and EP 1 304 345 A2 generally disclose aminoalkylalkoxysiloxane-containing mixtures. Thus, EP 0 997 469 A2 discloses two specific examples of a 3-aminopropyl / n-propyl / methoxy-siloxane oligomer mixture and an N-aminoethyl-3-aminopropyl / n-propylmethoxysiloxane oligomer mixture and EP 1 304 345 A2 the specific examples starting from tetraethoxysilane and aminopropyltrimethoxysilane; Tetraethoxysilane, propyltriethoxysilane and aminopropyltrimethoxysilane; Methyltrimethoxysilane, propyltrimethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane; Propyltrimethoxysilane and N- (n-butyl) -2-aminopropyltrimethoxysilane; Methyltriethoxysilane, propyltriethoxysilane and aminopropyltrimethoxysilane; Phenyltrimethoxysilane, propyltrimethoxysilane and aminopropyltrimethoxysilane and vinyltrimethoxysilane, propyltrimethoxysilane and aminopropyltrimethoxysilane.

Object of the present invention is to provide an additive for

Compositions that can be used in particular as adhesives and sealants that are easy to use and dose, and the bonds and

Seals with a significantly improved adhesion to a variety of

Substrates, for example, metals and plastics result. Surprisingly, it has been found that the use of a mixture based on specific aminopropyl-functional alkoxysiloxane oligomers, as they emerge in particular from claims 1, 7 and 10, in combination with silane-modified polymers advantageous for improving the adhesion of adhesives keitsvernetzenden from adhesive and Sealants, such. As silicones or silane-modified polyurethanes or silane-modified polyethers, to a variety of substrates, eg. B. on aluminum or plastic surfaces leads.

The present invention thus relates to a mixture containing at least chain-like aminopropyl-functional alkoxysiloxanes of the general formula I and / or cyclic aminopropyl-functional alkoxysiloxanes of the general formula II R- R

(I) (") in which the groups R independently of one another

(i) aminopropyl functional groups of the formulas

- (CH ₂ ) 3 _{-NH 2j} - (CH ₂ ) 3 -NH (CH ₂ ) 2 -NH 2 and / or - (CH ₂ ) 3 -NH (CH ₂ ) ₂ -NH (CH ₂ ) 2 -NH ₂ ,

(ii) methoxy and / or ethoxy groups and

(iii) optionally butyl or octyl groups exist,

m is an integer from 2 to 30 and n is an integer from 3 to 30,

wherein at least one aminopropyl functional group is bonded to a silicon atom of a compound of formula I and II, and

wherein the quotient of the molar ratio of Si to alkoxy groups is at least 0.3, preferably> 0.4, in particular> 0.5.

The individual groups R in the compounds of the formulas I and II are preferably selected independently of one another from the group of the radicals 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl, N- [N '- (2-aminoethyl) -2 aminoethyl] -3-aminopropyl, methoxy, ethoxy, i -butyl, n -butyl, i -octyl, n-octyl.

In particular, mixtures according to the invention are characterized in that the individual groups R in the compounds of the formulas I and II of a mixture of the aminopropyl-functional alkoxysiloxane oligomers, the radicals

3-aminopropyl and methoxy,

3-aminopropyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl and ethoxy,

3-aminopropyl, i-butyl and methoxy, 3-aminopropyl, i-butyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, i-butyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, i-butyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl, i-butyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl, i-butyl and ethoxy,

3-aminopropyl, n-butyl and methoxy,

3-aminopropyl, n-butyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, n-butyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl-n-butyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-butyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-butyl and ethoxy,

3-aminopropyl, i-octyl and methoxy,

3-aminopropyl, i-octyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, i-octyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, i-octyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, i -octyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, i -octyl and ethoxy,

3-aminopropyl, n-octyl and methoxy,

3-aminopropyl, n-octyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, n-octyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, n-octyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-octyl and methoxy or

- N - [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-octyl and ethoxy.

Furthermore, mixtures according to the invention contain chain-shaped aminopropyl-functional alkoxysiloxanes of the general formula I and / or cyclic ones

Aminopropyl-functional alkoxysiloxanes of the general formula II advantageously have a boiling point at 1 atm pressure of greater than 200 ° C. In addition, mixtures according to the invention comprising chain-shaped aminopropyl-functional alkoxysiloxanes of the general formula I and / or cyclic aminopropyl-functional alkoxysiloxanes of the general formula II

Flash point of greater than 100 ° C on.

As a rule, mixtures according to the invention are essentially based on

chain-shaped aminopropyl-functional alkoxysiloxanes of the formula I and / or cyclic aminopropyl-functional alkoxysiloxanes of the general formula II, wherein the content of alkoxy groups preferably between 0.1 and 70 wt .-%, particularly preferably 0.5 to 60 wt .-% and most preferably 5 to 50 wt .-%, and the content of free alcohol in the mixture, in particular methanol and / or ethanol, <5 wt .-%, preferably 0.001 to 3 wt .-%, particularly preferably 0.01 to 1 Wt .-%, based on the weight of the aminopropyl functional alkoxysiloxane oligomer mixture is.

Further object of the present invention is a process for the preparation of a mixture, which is characterized in that

as component A, at least one 3-aminopropyl-functional trialkoxysilane, at least one N- (2-aminoethyl) -3-aminopropyl-functional trialkoxysilane and / or at least one N- [N '- (2-aminoethyl) -2-aminoethyl] -3- aminopropyltrialkoxysilane and optionally as component B at least one

Butyltrialkoxysilane or an octyltrialkoxysilane, where alkoxy is in each case methoxy or ethoxy,

the components A and B optionally in succession or in a mixture using 0.7 to 1.2 mol of water per 1 mol of Si and 0.1 to 0.5 times

Weight of methanol or ethanol, based on the used

Alkoxysilanes, hydrolyzed specifically at a temperature of 60 to 80 ° C and condensed or co-condensed and

- Subsequently, the alcohol used and released during the reaction at atmospheric pressure or under reduced pressure and a bottom temperature to

90 ° C removed by distillation from the product mixture. Preference is given to the process according to the invention as components A and optionally B

3-aminopropyltrimethoxysilane (AMMO),

3-aminopropyltriethoxysilane (AMEO),

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (DAMO),

N- (2-aminoethyl) -3-aminopropyltriethoxysilane (DAEO),

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane (TRIAMO),

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane,

3-aminopropyltrimethoxysilane and i-butyltrimethoxysilane (IBTMO),

3-aminopropyltriethoxysilane and i-butyltriethoxysilane (IBTEO),

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and i-butyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and i-butyltriethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane and i-butyltrimethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and i-butyltriethoxysilane,

3-aminopropyltrimethoxysilane and n-butyltrimethoxysilane,

3-aminopropyltriethoxysilane and n-butyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and n-butyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and n-butyltriethoxysilane

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane and n-butyltrimethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and n-butyltriethoxysilane,

3-aminopropyltrimethoxysilane and i-octyltrimethoxysilane (OCTMO),

3-aminopropyltriethoxysilane and i-octyltriethoxysilane (OCTEO),

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and i-octyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and i-octyltriethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane and i-octyltrimethoxysilane, N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and i-octyltriethoxysilane,

3-aminopropyltrinnethoxysilane and n-octyltrimethoxysilane (OCTMO),

3-aminopropylthethoxysilane and n-octyltriethoxysilane (OCTEO),

N- (2-aminoethyl) -3-aminopropylthioethoxysilane and n-octyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and n-octylthethoxysilane

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrin-triethoxysilane and n-octylthymethoxysilane

or

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and n-octyltriethoxysilane

one.

Advantageously, in the process according to the invention, the components A and B are used in a molar ratio of 1 to 0 to 1 to 7, for example 10 to 1 to 1 to 6, in particular 9 to 1, 8 to 1, 7 to 1, 6 to 1 , 5 to 1, 4 to 1, 3 to 1, 2 to 1, 1 to 1, 1 to 2, 1 to 3, 1 to 4, 1 to 5 - to name but a few advantageous feed ratios. In general, the process according to the invention is carried out as follows:

As a rule, component (s) A and, optionally, component B are initially introduced. It is also possible to submit a mixture of the components concerned. In addition, however, one or both components can also be initially introduced and hydrolyzed, preferably partially hydrolyzed, and then the remaining amounts of the other component (s) added and the hydrolysis continued. The present alkoxysilane mixture is thus advantageous with the addition of 0.1 to 0.5 times the amount by weight, preferably 0.1 to 0.3 times the amount by weight of methanol and / or ethanol, based on the alkoxysilanes used over a period of up to about 30 Diluted in minutes. In this case, the metered amount of alcohol may be aqueous and the reaction mixture is advantageously mixed. In addition, the total calculated for the implementation, if necessary still missing amount of water, suitably with good mixing, for example with stirring, and also over a period of time up to about 30 minutes. Thus, in total, it is advantageous to use 0.7 to 1.2 mol, preferably 0.75, 0.8, 0.85, 0.9, 0.95, 1, 0, 1, 05, 1, 1, 1, 15 mol, to name just a few of the intermediate values, of water per 1 mol of Si of the alkoxysilanes used. Advantageously, it is possible to heat the reaction mixture before and / or after the alcohol, alcohol / water and / or water metering, preferably to 60 to 80 ° C., preferably 60, 62, 64, 66, 68, 70, 72, 74, 76 , 78 ° C - just to name a few of the intermediate values; the heating can also be gradual or continuous. Subsequently, the mixture is allowed to after-react for a period of 15 minutes to 5 hours, preferably for 2 to 4 hours, with thorough mixing. However, the reaction can also in the presence of a hydrolysis and condensation catalyst, such as. an addition of HCl conc. or aqueous hydrochloric acid or sulfuric acid, to name only one suitable catalyst, preferably in an amount of 0 to 0.5, preferably 0.01 to 0.3, particularly preferably 0.05 to 0.2, in particular 0.1 wt. % HCl, based on the amount of component (s) A or A used and optionally B, ie A and B, are carried out. The catalyst can be added, for example, together with the diluent, the diluent / water mixture and / or the water. After the reaction, the product mixture thus obtained is worked up by distillation in a particularly gentle manner. In this case, the present proportion of methanol and / or ethanol is usually almost completely separated. Preference is given to carrying out the workup by distillation of the product mixture at a bottom temperature of up to 90 ° C., preferably at 50 to 85 ° C., more preferably at 60 to 80 ° C., under normal pressure, ie atmospheric pressure, or under reduced pressure, preferably at a pressure of 400 mbar down to 10 mbar, by.

By the present method of preparation can be produced according to the invention advantageously aminopropyl-functional alkoxysiloxane oligomer mixtures, which in the case of cocondensates, for example, a statistical Distribution or block distribution of different functional [(R) ₂ Si (O) _2/2 ] units and terminal units [-Oi ₂ Si (R) 3] have. Moreover, a mixture of the invention and also branched siloxane oligomers with units [(R) Si (O-) _3/2] contain, ie siloxane oligomers which also contain T-structures besides sg M- and D-structures.

The definition of M, D, T and Q structures usually refers to the number of bound oxygens, as exemplified below by means of silylic units:

M = monofunctional units [-Oi ₂ Si (R) 3]

D = difunctional units [(R) 2Si (O-) _2/2]

T = trifunctional units [(R) Si (O-) _3/2]

Q = tetrafunctional units [Si (O-) _{_4/2]} Thus, it is possible to describe silicones and siloxanes or silane oligomers illustrative, rather than an idealized formulaic description on the M, D, T and Q structures resorted. For a more detailed nomenclature of the naming of such siloxane structures, reference should be made to the "Römpp Chemielexikon" - Keyword: Silicones - For example, only dimers with M ₂ can be formed from units M. Compositions of units D and M are required for building chains, so that trimers ( M ₂ D), tetramers (M ₂ D ₂ ) and so forth can be built up to linear oligomers with M ₂ D _n To form cyclic oligomers, building units D are required In this way, for example, rings with D ₃ , D, . D be established ₅ or higher branched or crosslinked structure elements, including spiro compounds are expected to be obtained when units T and / or Q are present together Possible cross-linked structures may be used as T _n (n>4);. _n D T _m (m <n); D _n T _m (n >>m); D ₃ T ₂ ; MQ; DQ and so on, to name only a few conceivable possibilities. Units of construction M are also referred to as stoppers or controllers , while D units are referred to as chain or ring former and the T and possibly also the Q units as network formers. So The use of tetraalkoxysilanes due to the four hydrolyzable groups and access of water or moisture units Q and thus the formation of a network (space-crosslinked) effect. In contrast to fully hydrolyzed trialkoxysilanes branches, ie T units [-Si (-O-) _3/2], condition in a structural element, for example MD3TM2 for an oligomer having a degree of oligomerization n = 7, wherein in these structural representations of the respective functionalities the free valences of the silyloxy be defined. Further details on the understanding of nomenclature of M-, D-, T- and Q-structures as well as related investigation methods are:

"Structural Investigations of Oligomeric and Polymeric Siloxanes by High Resolution ²⁹ Si Nuclear Magnetic Resonance", H.-G. Horn, H. Ch. Marsmann, Die

Markromolecular Chemistry 162 (1972), 255-267;

"About the ¹ H, ¹³ C and ²⁹ Si NMR Chemical Shifts of Some Linear, Branched and Cyclic Methyl Siloxane Compounds", G. Engelhardt, H. Jancke, J. Organometal Chem 28 (1971), 293-300;

- "Chapter 8 - NMR spectroscopy of organosilicone compounds", Elizabeth A.

Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd, 51 1 -533. The content of M, D, T or Q structures is generally determined by a method known per se to the person skilled in the art, preferably by means of ²⁹ Si NMR.

The present process is particularly selective and gentle on the product for the preparation of the specific mixtures according to the invention of homocondensed or co-condensed aminopropyl-functional alkoxysiloxane oligomers, as they can be found idealized formulas I and II. Compared to a mixture consisting of monomeric Aminoalkyltrialkoxysilanen contains a mixture according to the invention of aminopropyl-functional alkoxysiloxanes significantly less volatile organic compounds (VOC = volatile organic compounds), which in addition in the application in adhesives and sealants as Environmentally friendly and last but not least from an occupational medical point of view is advantageous.

Thus, the specific mixtures according to the invention with their advantageous application properties are obtainable by the process according to the invention with its selected measures.

Likewise provided by the present invention is the use of a mixture according to the invention in adhesives and / or in sealants, d. H. especially in corresponding moisture-curing adhesive or sealant compositions.

It is advantageous to use mixtures according to the invention in adhesive or sealant compositions, preferably for bonding wood, glass, metals, plastics, painted surfaces and / or mineral substrates, in particular for bonding metal and plastic parts, bonding of several plastic parts, bonding of wood and plastic parts, bonding of glass and metal and / or plastic parts, bonding of mineral substrates and metals and / or plastic parts, very particularly preferably adhesions in which aluminum is used as the metal and as a plastic polyolefin, polycarbonate and / or poly ( meth) acrylate, polyvinyl chloride, polycarbonate and / or polymethylmethacrylate.

Also particularly advantageous is the use of such adhesive or sealant compositions for bonding in the interior and exterior, especially for applications in vehicle, container, apparatus and shipbuilding, in the interior of real estate and in window and door construction, and also particularly advantageous for the gluing in the production of protective glazing, Sandwichverklebungen, lamp covers, lamp holders, switch parts, control knobs and in window construction. In addition, such adhesive and sealant compositions are very stable on storage in the absence of moisture and harden after application to the substrates to be bonded under the influence of moisture. As a rule, the humidity is sufficient to cause the crosslinking of the adhesives and sealants.

Said adhesives and sealants are very good and easy to process. After application to the substrates skin formation occurs. At 23 ° C and 50% relative humidity, skin typically forms within 1 to 200 minutes. The duration of the curing depends inter alia on the thickness of the desired adhesive bond. Typically, through-curing takes place in a layer of 1 to 5 mm within 24 hours.

The bonds produced are also characterized by excellent mechanical properties and excellent adhesion. Through-hardened bonds typically have moduli of elasticity of 0.2 to 10 N / mm ² , as well as tensile strengths of 1 to 10 N / mm ² , ultimate elongations of 100 to 1000% and Shore A hardnesses of 20 to 90.

Thus, mixtures of the invention are surprisingly particularly advantageous in the improvement of adhesives and sealants.

Examples:

In the following application examples, silane-modified polyurethane (ST61 and ST75 from Evonik Hanse GmbH) and a silane-modified polyether (MS polymer S303H from Kaneka Corp.) were used. ST61 was developed for high modulus applications and had a dynamic viscosity of 35,000 mPas (at 25 ° C). It was aliphatic polyurethane that was clear and colorless. Example 1A:

Synthesis of an Aminopropyl-Functional Methoxysiloxane Oligomer (Oligomer 1) To a 2-liter stirred glass reactor equipped with vacuum, dosing and distillation equipment was charged 716 g of 3-aminopropyltrimethoxysilane (Dynasylan® AMMO and 108 g of methanol 72 g of water and 80 g of methanol were added dropwise within 10 to 30 minutes, during which the reaction mixture warmed slightly, and then the mixture was heated to about 70 ° C. and stirred for 2 hours after distilling off the alcohol in vacuo (bottom temperature 50-70 ° C, pressure 400 mbar falling to 10 mbar), 532 g of a clear, colorless to slightly yellowish liquid (oligomer 1) were obtained.

This oligomer was used to prepare a test formulation with the silane-terminated polyurethane adhesive ST 61. The ingredients are shown in the next table.

Example 1 B:

Preparation of adhesive compositions

In a planetary mixer base polymer a) and plasticizer b) were mixed together for 5 minutes. Thereafter, the chalk c) was stirred in portions within 10 minutes in the mass, and this homogenized for 40 minutes (heat generation). Subsequently, component d) was introduced in portions within 10 minutes with stirring and mixed for a further 20 minutes. This premix was then cooled to about 40 ° C under vacuum (about 30 mbar) and reduced stirring power. After addition of component e) and further mixing (15 minutes), the mass was degassed at 30 mbar for 5 minutes to give the so-called masterbatch. For the individual performance tests, 100 g of this so-called masterbatch with 1.12 g of component f) and 0.06 g of component g) were mixed for 30 seconds in a rotary mixer (SpeedMixer ™). The final formulated adhesive was transferred to a cartridge. The application tests were carried out from the cartridge.

Application testing (test methods)

The adhesive was tested on the basis of DIN EN ISO 527 and DIN EN 1465 (tear strength, elongation at tear strength, tensile shear strength Lapshear)

Example 1 C:

Use of a homo-oligomer prepared from 3-aminopropyltrimethoxysilane to improve adhesion on aluminum surfaces

A siloxane oligomer of 3-aminopropyltrimethoxysilane was used, which was prepared with 1.0 mol of water / mol of silicon according to Example 1A (= oligomer 1). This led in the STPU adhesive formulation according to Example 1 B to an improved adhesion to the substrate aluminum of about 30% compared to the market standard Dynasylan® AMMO. Other important mechanical properties of the adhesive, such as tensile strength and elongation at break, were not adversely affected.

The 180 ° tensile strength of the aluminum / aluminum adhesive bond in the presence of oligomer 1 in the adhesive was 4.77 N / mm ² , while the comparative strength when using Dynasylan® AMMO in the adhesive was 3.71 N / mm ² . Examples 2A to 6A:

In analogy to the procedure of Example 1 A further aminopropyl-functional siloxane oligomers were prepared. The materials used and the procedure are listed in the table below.

In the case of oligo-template addition addition reaction-extraction time, distillation prey

No. [min] duration [g]]

2A 2 178.4 g iso-40 g 5 70 ° C bottom: 50-579.1 butyltrimeth-water, 4 h 70 ° C oxysilane, 13.3 g 40 g pressure: 400

Water, 0.72 g methanol mbar (on

HCl (conc), 40 g 10 mbar

Methanol, falling 537.2) g AMMO

3A 3 716 g AMMO 86.4 g 10-30 70 ° C Bottom: 50- 495.2

108 g methanol water, 2 h 70 ° C.

80 g pressure: 400

Methanol mbar (on

Dropping 10 mbar)

4A 4 178.4 g iso-13.3 g 5 70 ° C bottom: 50- 289.0 butyltrimethoxy-water, 4 h 70 ° C silane, 13.3 g 20 g pressure: 400

Water, 0.72 g methanol mbar (on

HCl (conc), 40 g 10 mbar

Methanol, falling 179.0) g AMMO 5A 5 889.6 g N- 86.4 g 10-30 70 ° C Bottom: 50-668.8

Aminoethyl-3-water 2 h 70 ° C aminopropyltri- 80 g pressure: 400 methoxysilane), methanol mbar (on

132 g of methanol 10 mbar

falling)

6A 6 178.4 g iso-13.3 g fast 70 ° C. bottom: 50-332.7 butyltrimethoxy-water, 4 h 70 ° C. silane, 13.32 g 20 g pressure: 400

Water, 0.72 g methanol mbar (on

HCl (conc), 20 g 10 mbar

Methanol, 222.4 dropping) g of amino-ethyl-3-amino-propyltrimethoxysilane

These oligomers were used to prepare test formulations with the silane-terminated polyurethane adhesive ST 61 in analogy to Example 1B. The ingredients are shown in the next table.

Examples 2B to 6B:

Preparation of adhesive compositions

The masterbatch and the final formulated adhesive of Examples 2B to 6B were prepared as described in Example 1B. The performance tests were carried out from the cartridge containing the respective adhesive formulations. Examples 2C to 6C:

Application engineering experiments

In analogy to Example 1 C performance tests were carried out. The results are shown in the following tables.

Example Adhesive adhesion on AI Elongation at break on Al Tensile strength on AI No. or PC or or PC or or PC or

PMMA ^* 'PMMA ^* ' PMMA ^* '

2C 2B 20% improves 20% less No change

opposite AMMO opposite AMMO AMMO (on AI) (on AI) (on AI)

3C 3B 32% improved No change No change

compared to AMMO over AMMO AMMO (on PC) (on PC) (on PC)

4C 4B improved 7% improved 25% improved 8%

compared to AMMO over AMMO AMMO (on PC) (on PC) (on PC)

5C 5B 165% improved No change No change

compared to AMMO versus AMMO AMMO (on (on PMMA) (on PMMA)

PMMA)

6C 6B 25% improved 7% improved No change

compared to AMMO versus AMMO AMMO (on (on PMMA) (on PMMA)

PMMA) Example adhesive / 180 ° tensile shear elongation tensile strength

Adhesive Strength (According to the Invention / (Inventive) Bond (According to the Invention in the Presence / in the Presence

/ in the presence of AMMO) of AMMO) of AMMO)

2C 2B / AI / AI 4,37 N / mm ² /200% / 3,34 N / mm ² /

3.71 N / mm ² 172% 3.16 N / mm ²

3C 3B / 3.59 N / mm ² /157% / 3.56 N / mm ² /

PC / PC 2.73 N / mm ² 172% 3.16 N / mm ²

4C 4B / 2.91 N / mm ² /215% / 3.41 N / mm ² /

PC / PC 2.73 N / mm ² 172% 3.16 N / mm ²

5C 5B / 3,29 N / mm ² / not determined not determined

PMMA / 1, 25 N / mm ²

PMMA

6C 6B / 1, 54 N / mm ² /183% / 3,23 N / mm ² /

PMMA / 1, 25 N / mm ² 172% 3.16 N / mm ²

PMMA

'AI = aluminum; PC = polycarbonate; PMMA = polymethyl methacrylate

Examples 7A to 17A:

Furthermore, in analogy to the procedure of Example 1A, cf. also Examples 2A to 6A, further inventive aminopropyl-functional siloxane oligomers (co-oligomers) prepared; the molar ratios of the alkoxysilanes used in each case are listed in the table below. Example Oligomer No. Component A Component B Molar Feed No. ratio A to B

7A 7 AMMO OCTMO 1 to 1

8A 8 AMMO OCTMO 3 to 1

9A 9 AMMO IBTMO 1 to 1

10A 10 AMMO IBTMO 3 to 1

1 1A 1 1 DAMO OCTMO 1 to 1

12A 12 DAMO OCTMO 3 to 1

13A 13 TRIAMO OCTMO 3 to 1

14A 14 DAMO IBTMO 1 to 1

15A 15 DAMO IBTMO 3 to 1

16A 16 DAMO OCTMO 1 to 6.5

17A 17 TRIAMO OCTMO 1 to 6.5

Examples 7C to 10C:

In further performance experiments, the adhesion of STPU adhesive formulations PC / PC was tested on the basis of Example 1 C, wherein these were prepared in analogy to Example 1 B and thereby in place of oligomer 1 in each case an oligomer from the series 7 to 10 as well as for comparison with AMMO (monomer) were used as standard. The results are summarized in the following table:

Example silane or 180 ° tensile shear strength

No. Oligomer No. [N / mm ² ]

Standard AMMO 2.73

7C 7 3.36

8C 8 3,18

9C 4 3.07

10C 5 3,48 Examples 11 C to 15 C:

In further performance experiments, the adhesion of STPU adhesive formulations was tested on adhesive PMMA / PMMA, based on Example 1 C, which were prepared in analogy to Example 1 B and thereby in place of oligomer 1 in each case an oligomer from the series 1 1 to 15 and for comparison with AMMO (monomer) were used as standard. The results are summarized in the following table:

EXAMPLES 16C and 17C: In further performance experiments, the adhesion of STPU sealant formulations to PC / PC adhesive bonds was tested on the basis of Example 1C, these being prepared in accordance with Example 1B and in each case one oligomer from the series 16 to 17 and used as a standard for comparison with an oligomer starting from AMMO and PTMO according to EP 0 997 469 A2; the composition of the STPU sealant formulations is shown in the table below; Furthermore, the results of the related performance tests are summarized in the following table: Starting materials for STPU sealant formulation weight [g]

Polymer ST 75 101, 02

Phthalate plasticizer 40.6

Chalk coated with stearic acid 131, 32

Dynasylan ^® VTMO 4.2

AMMO / PTMO oligomer as

2.8

Comparative Example or Oligomer 16 or 17

Dibutyltin dineodecanoate 0,056

Examples 18C to 22C:

In further performance experiments, the adhesion of MS adhesive formulations on PC / PC adhesive bonds was tested on the basis of Example 1 C, which were prepared in accordance with Example 1 B and in each case an oligomer from the series 8, 9, 1 1, 1 2, 15 and for comparison with AMMO (monomer) were used as standard; the composition of the MS adhesive formulations is shown in the table below; Furthermore, the results of the related performance tests are summarized in the following table: Starting materials for MS-adhesive formulation weight [g]

MS polymer S303H 65.1

Phthalate plasticizer 47.3

Chalk coated with stearic acid 124.98

AEROSIL ^® R 202 15,6

Dynasylan ^® VTMO 2.6

Dynasylan® AMMO as a comparative example or

3.9

oligomer

Dibutyltin dineodecanoate 0.52

The present application examples prove in particular the surprising, advantageous use of functional alkoxysiloxane oligomer mixtures according to the invention, as can be seen from Examples 1A to 17A.

Claims

claims:

1 . Mixture comprising chain-shaped aminopropyl-functional alkoxysiloxanes of the general formula I and / or cyclic aminopropyl-functional alkoxysiloxanes of the general formula II

(R) ₃ Si-O- [Si (R) ₂ -O] _m -Si (R) ₃ (I), (R) i (R) ₂ ] _n (II), in which the R groups are independent of each other

(i) aminopropyl functional groups of the formulas

- (CH ₂ ) 3 -NH _2j - (CH ₂ ) ₃ -NH (CH ₂ ) ₂ -NH ₂ and / or - (CH ₂ ) ₃ -NH (CH ₂ ) ₂ -NH (CH ₂ ) ₂ -NH _2y

(ii) methoxy and / or ethoxy groups and

(iii) optionally butyl or octyl groups exist,

m is an integer from 2 to 30 and n is an integer from 3 to 30, wherein to a silicon atom of a compound of formula I and II at most one aminopropyl functional group is bound, and wherein the quotient of the molar ratio of Si to Alkoxy groups is at least 0.3.

2. Mixture according to claim 1, characterized in that the individual

Groups R in the compounds of the formulas I and II are independently selected from the group of the radicals 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl, N- [N '- (2-aminoethyl) -2-aminoethyl ] -3-aminopropyl, methoxy, ethoxy, i -butyl, n -butyl, i -octyl, n -octyl.

3. Mixture according to claim 1 or 2, characterized in that the individual groups R in the compounds of formulas I and II of a mixture of aminoalkyl-functional siloxane oligomers, the radicals

3-aminopropyl and methoxy,

3-aminopropyl and ethoxy, N- (2-aminoethyl) -3-anninopropyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl and ethoxy,

3-aminopropyl, i-butyl and methoxy,

3-aminopropyl, i-butyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, i-butyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, i-butyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl, i-butyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-anninopropyl, i-butyl and ethoxy,

3-aminopropyl, n-butyl and methoxy,

3-aminopropyl, n-butyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, n-butyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl-n-butyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-butyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-butyl and ethoxy,

3-aminopropyl, i-octyl and methoxy,

3-aminopropyl, i-octyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, i-octyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, i-octyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, i -octyl and methoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, i -octyl and ethoxy,

3-aminopropyl, n-octyl and methoxy,

3-aminopropyl, n-octyl and ethoxy,

N- (2-aminoethyl) -3-aminopropyl, n-octyl and methoxy,

N- (2-aminoethyl) -3-aminopropyl, n-octyl and ethoxy,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-octyl and methoxy or

- N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyl, n-octyl and ethoxy. Mixture according to claim 1 or 2, characterized in that the mixture has a boiling point at 1 atm pressure of greater than 200 ° C.

Mixture according to claim 1 or 2, characterized in that the mixture has a flash point of greater than 100 ° C.

Mixture according to Claim 1 or 2, characterized in that the aminoalkyl-functional siloxane oligomers comprise a mixture substantially

chain-like siloxanes and / or branched siloxanes of the general formulas I or II are based, wherein the content of alkoxy groups between 0.1 and 70 wt .-%, particularly preferably 0.5 to 60 wt .-% and most preferably 5 and 50 Wt .-%, and the content of free alcohol in the mixture, in particular methanol and / or ethanol, <5 wt .-%, preferably 0.001 to 3 wt .-%, particularly preferably 0.01 to 1 wt .-%, based on the weight of the siloxane-oligomer mixture is.

Process for the preparation of a mixture according to one of Claims 1 to 6, characterized in that

as component A, at least one 3-aminopropyl-functional trialkoxysilane, at least one N- (2-aminoethyl) -3-aminopropyl-functional trialkoxysilane and / or at least one N- [N '- (2-aminoethyl) -2-aminoethyl] 3-aminopropyltrialkoxysilane and optionally as component B at least one Butyltrialkoxysilan or an octyltrialkoxysilane, where alkoxy is in each case methoxy or ethoxy,

- the components A and B optionally in succession or in mixture below

Use of 0.7 to 1, 2 moles of water per 1 mol of Si and 0.1 to 0.5 times the amount by weight of methanol and / or ethanol, based on the alkoxysilanes used, selectively hydrolyzed at a temperature of 60 to 80 ° C. as well as condensed or co-condensed, optionally in the presence of a hydrolysis or condensation catalyst, and - subsequently the alcohol used and released during the reaction at atmospheric pressure or under reduced pressure and a

Bottom temperature to 90 ° C by distillation removed from the product mixture.

8. The method according to claim 7, characterized

that as components A and optionally B

3-aminopropyltrimethoxysilane,

3-aminopropyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane,

3-aminopropyltrimethoxysilane and i-butyltrimethoxysilane,

3-aminopropyltriethoxysilane and i-butyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and i-butyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and i-butyltriethoxysilane,

3-aminopropyltrimethoxysilane and n-butyltrimethoxysilane,

3-aminopropyltriethoxysilane and n-butyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and n-butyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and n-butyltriethoxysilane

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and n-butyltriethoxysilane

3-aminopropyltrimethoxysilane and i-octyltrimethoxysilane,

3-aminopropyltriethoxysilane and i-octyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and i-octyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane and i-octylthethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropylthmethoxysilane and i-octylthmethoxysilane,

N- [N '- (2-aminoethyl) -2-aminoethyl] -3-aminopropyltriethoxysilane and i-octyltriethoxysilane,

3-aminopropyltrinnethoxysilane and n-octyltrimethoxysilane,

3-aminopropylthethoxysilane and n-octyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and n-octyltrimethoxysilane,

N- (2-aminoethyl) -3-aminopropyltriethoxysilane and n-octylthethoxysilane

or

starts.

9. The method according to claim 7 or 8, characterized in that the

Components A and B are used in a molar ratio of 1 to 0 to 1 to 7.

10. The method according to any one of claims 7 to 9, characterized in that as the hydrolysis or condensation catalyst hydrogen chloride (HCl) preferably in an amount of 0 to 0.5 wt .-% HCl, based on the amount of components A and optional B, uses.

1 1. Mixture according to one of claims 1 to 6 obtainable according to one of claims 7 to 10.

12. Use of a mixture according to any one of claims 1 to 6 or prepared according to any one of claims 7 to 10 or obtainable according to claim 1 1 in

Adhesives and / or in sealants.

13. Use according to claim 12, characterized in that bonds of wood, glass, metals, plastics, painted surfaces and / or mineral substrates are produced, in particular bonding of metal and plastic parts, bonding of several plastic parts, bonding of wood and plastic parts , Bonding of glass and metal and / or plastic parts, bonding of mineral substrates and metals and / or plastic parts, most preferably

Bonding in which aluminum is used as metal and as plastic polyolefin, polycarbonate and / or poly (meth) acrylate, polyvinyl chloride,

Polycarbonate and / or polymethylmethacrylate.

14. Use according to claim 12, characterized in that the

Indoor and outdoor bonding, in particular for applications in vehicle, container, apparatus and shipbuilding, in the interior construction of

Real estate as well as in window and door construction done

15. Use according to claim 12, characterized in that the

Bonding in the production of protective glazing, sandwich gluing, luminaire covers, lampholders, switch parts, control knobs and window construction.