Process for producing crosslinkable materials based on organic alkoxysilane-terminated polymers

Abstract

This invention relates to a method for producing a crosslinkable material (M), the method comprising mixing (A) 100% by weight of Y-[(CR 1 2) b -SiR a (OR 2 ) 3‑a ] x (I) a compound, wherein the groups and indices have the definitions specified in claim 1; (B) 0.1 to 75% by weight of at least one thixotropic agent selected from fatty acid amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, polyesteramides, polyureas, oxidized polyethylene, and metal soaps, and other optional components; optionally, other subsequent process steps; and subsequent storage of the mixture (M) obtained by this method. The invention is characterized in that the time from the start of the mixing step of (A) and (B) to the end of the storage process of the crosslinkable material (M) is at least 7 days, and during this period, all process steps are carried out at a temperature below 80°C.

Description

Technical Field

[0001] This invention relates to a method for producing crosslinkable compositions, preferably single-component crosslinkable compositions, of polymers end-capped with organoalkoxysilanes, and the use of said crosslinkable compositions as adhesives and sealants, particularly as low-modulus sealants. Background Art

[0002] Polymer systems with reactive alkoxysilanes have been known for a long time. These alkoxysilane-terminated polymers are able to condense with each other, even at room temperature, upon contact with water or atmospheric moisture, while simultaneously eliminating the alkoxy groups. One of the most important applications of such materials is in the manufacture of adhesives and sealants.

[0003] For example, adhesives and sealants based on alkoxysilane crosslinked polymers exhibit not only good adhesion to some cured substrates but also good mechanical properties, demonstrating sufficient tensile strength and high elasticity for many applications. Another advantage of silane crosslinked systems compared to several other adhesive and sealant technologies (e.g., isocyanate crosslinking systems) is the toxicological safety of the prepolymers.

[0004] In many applications, one-component systems that cure upon contact with atmospheric moisture (1K systems) are preferred. A key advantage of one-component systems is their immediate applicability, as the user does not need to mix different adhesive components. Besides saving time / work and reliably avoiding potential dosage errors, one-component systems also eliminate the need to process adhesives / sealants within a typically very narrow time window, unlike multi-component systems that require mixing two components.

[0005] There are many variations of adhesive and sealant systems based on silane crosslinked prepolymers.

[0006] The first specific variant includes prepolymers using so-called α-silane-terminated polymers. These have reactive alkoxysilyl groups linked to adjacent urethane units via methylene spacers. These compounds are highly reactive and do not require tin catalysts, strong acids, or strong bases to achieve high curing rates upon air exposure. Commercially available α-silane-terminated prepolymers are from Wacker Chemie AG. STP-E10 or -E30.

[0007] For example, EP 2 744 842 A describes a second specific variant of the adhesive of particular interest, which contains phenyl silicone resin in addition to the silane crosslinking polymer. Suitable resin additives can also produce an adhesive that, once fully cured, exhibits significantly improved hardness and tensile shear strength.

[0008] For example, a third specific variant of sealant based on silane crosslinked polymers of particular interest is described in EP 3 149 095 A. In this variant, a conventional, preferably linear silane crosslinked polymer having crosslinkable silane functionality at both ends of its chain is mixed with a silane crosslinked polymer having a reactive silane group at only one end of its chain.

[0009] For many applications, both in the fields of adhesives and sealants, there is a need for formulations with high thixotropy, i.e., formulations with low viscosity at high shear rates, so that they can be applied from a cylinder or other container with small or at least moderate force. Conversely, at low shear rates, they have high viscosity and ideal stability, allowing the applied adhesive or sealant to remain in place after application until it cures. This property is essential, especially for sealants that can also be used to seal vertical joints.

[0010] The desired thixotropy is typically achieved by adding a thixotropic agent, with polyamide waxes or their derivatives being particularly suitable. Such thixotropic agents and their use in formulations based on silane crosslinked polymers have been described extensively, especially in EP1767 584A.

[0011] However, a disadvantage of using such thixotropic agents is that they typically must be activated by heat treatment of the formulation, which results in at least partial melting of the thixotropic agent. This heat treatment can be performed during or immediately after mixing of the formulation components, or, as described in EP 1 767 584 A, only after the finished formulation has been filled into a canister or other application container.

[0012] However, regardless of the chosen procedure, the requirement for heat treatment is an additional process step. If this is done during or immediately after the mixing step, which typically takes place in a large-volume mixer, it results in a significant increase in plant uptime, leading to significantly higher production costs. On the other hand, if heat treatment is performed solely by heating the corresponding final vessel, it involves considerable additional logistical work and requires additional heating chambers and / or other technical equipment, which in many cases are unavailable. Summary of the Invention

[0013] Therefore, the object of this invention is to develop a method that no longer has the disadvantages of the prior art.

[0014] This invention relates to a method for producing a crosslinkable composition (M), the method comprising mixing the following components (A), component (B), and optionally other components:

[0015] (A) 100 parts by weight of compound (I)

[0016] Y-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I)

[0017] in

[0018] Y is an x-valent polymer group linked by nitrogen, oxygen, sulfur, or carbon.

[0019] R can be the same or different, and is an optional substituted monovalent hydrocarbon group.

[0020] R 1 They can be the same or different, and can be hydrogen atoms or optional monovalent hydrocarbon groups that can be attached to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, or carbonyl groups.

[0021] R 2 They can be the same or different, and can be hydrogen atoms or optionally substituted monovalent hydrocarbon groups.

[0022] x is an integer from 1 to 10, preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0023] a can be the same or different, and can be 0, 1, or 2, preferably 0 or 1.

[0024] b can be the same or different, and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, especially 1, and

[0025] (B) 0.1 to 75 parts by weight of at least one thixotropic agent selected from fatty acid amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, polyesteramides, polyureas, oxidized polyethylene, and metal soaps.

[0026] Optional subsequent process steps and subsequent storage of the resulting mixture (M) may be performed.

[0027] The invention is characterized in that the time from the start of the mixing step of components (A) and (B) to the end of the storage of the crosslinkable composition (M) is at least 7 days, and during this period, all process steps are carried out at a temperature below 80°C.

[0028] The start of the mixing step of (A) and (B) is defined here as the point in time at which parts or totals of (A) and (B) are first combined. During this period, mixing occurs and / or occurs simultaneously.

[0029] The end of storage for the crosslinkable composition (M) is defined as the point in time when the composition (M) is removed from the container (GB) for crosslinking purposes.

[0030] Examples of containers (GB) are cartridges, pipes, buckets, hoses, or large containers such as cans or drums, wherein containers (GB) are preferably cartridges.

[0031] Other process steps following the mixing of components according to (A) and (B) of the invention and optionally other components may include any other treatment steps of the mixture, such as heat treatment, degassing, or other mixing steps following heat treatment and / or degassing.

[0032] The storage method according to the invention preferably further includes filling and decanting the crosslinkable composition (M) into a container (GB), wherein filling can be performed directly after mixing the individual components according to the invention, or at any later point during storage. During storage, a transfer step can also be performed from one container (GB) to another container (GB). The final container (GB) is used for the final application, such as as an adhesive, sealant, or coating material.

[0033] Preferably, all process steps of the method of the present invention are carried out at temperatures below 69°C, particularly preferably below 59°C, and especially below 49°C, starting from the mixing of components (A) and (B), optional further process steps, and storage, wherein the finished composition (M) can be filled, packaged, and transported during the storage period according to the present invention until it is intended for use.

[0034] In the method according to the invention, mixing can be carried out in any manner known per se, such as by methods commonly used to prepare moisture-curing compositions. The order in which the components are mixed can be varied as needed.

[0035] The method according to the invention can be carried out at the pressure of the surrounding atmosphere, i.e., about 900 to 1100 hPa. Furthermore, in order to remove volatile compounds and / or air, the pressure can be temporarily or permanently reduced to an absolute pressure of, for example, 30 to 500 hPa.

[0036] Preferably, according to the invention, when mixing components (A) and (B) and optionally other components, the mixture is stirred for a maximum of 3 hours, particularly preferably a maximum of 2 hours, especially a maximum of 1 hour, optionally heated by a heating device at a temperature below 80°C, preferably below 69°C, particularly preferably below 59°C, especially below 49°C.

[0037] In a particularly preferred embodiment, the mixing of components (A) and (B) according to the invention, as well as other optional components, is heated only by frictional heat inevitably released during the mixing process, rather than by a heating device.

[0038] In the method of the present invention, the period from when components (A) and (B), and optionally other components, are mixed together until the end of storage of the crosslinkable composition (M) is preferably at least 10 days, particularly preferably at least 15 days, and especially at least 20 days. Storage can be in any form, i.e., it can also be the final packaging for the final application. Preferably, storage is carried out at least partially in the final packaging for the final application.

[0039] Storage according to the invention is preferably carried out at a temperature of -20 to 45°C, especially 0 to 35°C.

[0040] The method according to the invention is preferably carried out under conditions where (atmospheric) moisture is removed.

[0041] This invention is based on a surprising discovery that heat treatment for activating thixotropic agents can be replaced by long-term storage according to the invention. This saves the time-consuming and energy-intensive process step of separate heat treatment. Since the material can obviously be packaged, transported, and delivered to intermediaries or even end users during the long-term storage period according to the invention, as long as it is not used, the method with a long storage period according to the invention is generally more advantageous for the production of adhesives or sealants than conventional methods for providing heat activation of thixotropic agents.

[0042] Examples of group R are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; hexyl, such as n-hexyl; heptyl, such as n-heptyl; octyl, such as n-octyl, isooctyl, and 2,2,4-trimethylpentyl; nonyl, such as n-nonyl; decyl, such as n-decyl; dodecyl, such as n-dodecyl; octadecyl groups, such as n-octadecyl groups; cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; alkenyl groups, such as vinyl, 1-propenyl, and 2-propenyl; aryl groups, such as phenyl, naphthyl, anthracene, and phenanthrene; alkylaryl groups, such as o-, m-, and p-tolyl; xylyl and ethylphenyl; and aralkyl groups, such as benzyl, α-, and β-phenylethyl.

[0043] Examples of substituted groups R include alkyl halides such as 3,3,3-trifluoropropyl, 2,2,2,2',2',2'-hexafluoroisopropyl and heptafluoroisopropyl, and aryl halides such as ortho, meta and para chlorophenyl.

[0044] Preferably, group R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, which is optionally substituted with halogen atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms, especially a methyl group.

[0045] Group R 1 Examples of R include hydrogen atoms, groups specified for R, and optionally substituted hydrocarbon groups connected to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups.

[0046] Group R 1 Preferably, it contains hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, especially hydrogen atoms.

[0047] Group R 2 An example of this is a hydrogen atom, and an example of the group R is given.

[0048] Group R 2 Preferably, it is a hydrogen atom or an alkyl group having 1-10 carbon atoms, and particularly preferably an alkyl group having 1-4 carbon atoms that is optionally substituted with a halogen atom, especially methyl or ethyl.

[0049] In the context of this invention, it should be understood that the polymer on which the polymer group Y is based refers to all polymers in which at least 50%, preferably at least 70%, particularly preferably at least 90% of all bonds in the main chain are carbon-carbon, carbon-nitrogen, or carbon-oxygen bonds.

[0050] Examples of polymer group Y are polyester, polyether, polyurethane, polyalkylene and polyacrylate groups.

[0051] The polymer group Y is preferably an organic polymer group, comprising polyoxyethylene as a polymer chain, such as polyoxyethylene, polyoxypropylene, polyoxybutene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutene copolymer; hydrocarbon polymers, such as polyisobutylene and copolymers of polyisobutylene and isoprene; chloroprene rubber; polyisoprene; polyurethane; polyester; polyacrylate; polymethacrylate; vinyl polymers or polycarbonate, and preferably via -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR'-C(=O)-NH-,NH-C(=O)-NR'-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O )-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, -NR'- attached to the group -[(CR 1 2) b -SiR a (OR 2 ) 3-a ], where R' can be the same or different and has the definition specified for R, or the group -CH(COOR”)-CH2-COR”, where R” can be the same or different and has the definition specified for R.

[0052] The group R' is preferably a -CH(COOR”)-CH2-COOR” group or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms optionally substituted with halogen atoms.

[0053] Examples of group R' are cyclohexyl, cyclopentyl, n-propyl and isopropyl, n-butyl, isobutyl and tert-butyl, pentyl, hexyl or heptyl, and phenyl.

[0054] The group "R" is preferably an alkyl group having 1 to 10 carbon atoms, and is particularly preferably methyl, ethyl or propyl.

[0055] Component (A) may have the group -[(CR) 1 2) b -SiR a (OR 2 ) 3-a The group is attached to any location on the polymer in a manner described, such as dangling and / or terminal.

[0056] Particularly preferably, the group Y in formula (I) is an x-valent organic polymer group linked by nitrogen, oxygen, sulfur, or carbon, said group comprising polyurethane or polyoxyethylene as a polymer chain, particularly having a terminal linking group -[(CR 1 2) b -SiR a OR 2 ) 3-a The polyurethane group or having a terminal linker group -[(CR 1 2) b -SiR a OR 2 ) 3-a The polyoxyethylene group, wherein the groups and indices have the definitions given above. The groups Y are preferably linear or have 1 to 3 branch points. They are particularly preferred to be linear.

[0057] The polyurethane group Y preferably has its chain end attached to the group -[(CR)O-, -NH-C(=O)-NH-, -NR'-C(=O)-NH- or -NH-C(=O)-NR', especially via -OC(=O)-NH- or -NH-C(=O)-NR'-. 1 2) b -SiR a OR 2 ) 3-aThose groups and indices, wherein all groups and indices have one of the definitions specified above. The polyurethane group Y is preferably produced from linear or branched polyoxyethylene, particularly from polypropylene glycol and diisocyanate or polyisocyanate. The average molar mass Mn (number mean) of group Y is preferably from 400 to 30000 g / mol, more preferably from 4000 to 20000 g / mol. Suitable methods for preparing the corresponding component (A) and examples of the component (A) itself are described in EP 1 093 482B1 (paragraphs

[0014] -

[0023] ,

[0039] -

[0055] and Example 1 and Comparative Example 1) or EP 1 641 854 B1 (paragraphs

[0014] -

[0035] , Examples 4 and 6 and Comparative Examples 1 and 2), which are included in the disclosure of this application.

[0058] Average molar mass M n In the context of this invention, it was determined by volume exclusion chromatography (SEC), which was performed on a Styragel HR3-HR4-HR5-HR5 column from Waters Corp., USA, at a flow rate of 1.2 ml / min at 60°C with an injection volume of 100 μL of THF relative to the polystyrene standard, and detected by RI (refractive index detector).

[0059] The polyoxyolefin group Y is preferably a linear or branched polyoxyolefin group, particularly preferably a polyoxypropylene group, the chain end of which is preferably connected to -[(CR)-NH- or -O- via -OC(=O)-NH- or -O-. 1 2) b -SiR a (OR 2 ) 3-a ], wherein the group and the index have one of the definitions given above. Preferably, at least 85%, particularly preferably at least 90%, especially at least 95% of all chain ends are linked to the group -[(CR)- through -OC(=O)-NH-. 1 2) b -SiR a (OR 2 ) 3-a The polyoxyolefin group Y preferably has an average molar mass M of 4000 to 30000 g / mol, more preferably 8000 to 20000 g / mol. n Suitable methods for preparing the corresponding component (A) and examples of the component (A) itself are described in EP 1 535 940 B1 (paragraphs

[0005] -

[0025] and Examples 1-3 and Comparative Examples 1-4) or EP 1 896 523 B1 (paragraphs

[0008] -

[0047] ), which are included in the disclosure of this application.

[0060] The end groups of the compound (A) used according to the present invention are preferably those shown in the following general formula:

[0061] -NH-C(=O)-NR'-(CR 1 2) b -SiR a (OR 2 ) 3-a (IV)

[0062] -OC(=O)-NH-(CR 1 2) b -SiR a (OR 2 ) 3-a (V) or

[0063] -O-(CR 1 2) b -SiR a (OR 2 ) 3-a (VI),

[0064] The groups and indices have one of the definitions given above.

[0065] If compound (A) is a polyurethane (which is preferred), it preferably has one or more of the following end groups:

[0066] -NH-C(=O)-NR'-(CH2)3-Si(OCH3)3,

[0067] -NH-C(=O)-NR'-(CH2)3-Si(OC2H5)3、

[0068] -OC(=O)-NH-(CH2)3-Si(OCH3)3 or

[0069] -OC(=O)-NH-(CH2)3-Si(OC2H5)3、

[0070] R' has the above definition.

[0071] If compound (A) is polypropylene glycol (which is particularly preferred), then they preferably have one or more of the following end groups:

[0072] -O-(CH2)3-Si(CH3)(OCH3)2、

[0073] -O-(CH2)3-Si(OCH3)3、

[0074] -OC(=O)-NH-(CH2)3-Si(OC2H5)3、

[0075] -OC(=O)-NH-CH2-Si(CH3)(OC2H5)2、

[0076] -OC(=O)-NH-CH2-Si(OCH3)3、

[0077] -OC(=O)-NH-CH2-Si(CH3)(OCH3)2 or

[0078] -OC(=O)-NH-(CH2)3-Si(OCH3)3,

[0079] The latter two end groups are particularly preferred.

[0080] The average molecular weight M of compound (A) n Preferably at least 400 g / mol, particularly preferably at least 4000 g / mol, especially at least 10000 g / mol, and preferably at most 30000 g / mol, particularly preferably at most 20000 g / mol, especially at most 19000 g / mol.

[0081] The viscosity of compound (A) is preferably at least 0.2 Pas, more preferably at least 1 Pas, particularly preferably at least 5 Pas, and more preferably at most 700 Pas, more preferably at most 100 Pas, measured at 20°C in each case.

[0082] In the context of this invention, the viscosity of the polymer (A) used according to this invention was determined according to ISO 2555 after heating to 23°C at 2.5 rpm using a DV 3P rotational viscometer based on the A.Paar (Brookfield system) with spindle 5.

[0083] The compound (A) used in this invention is a commercially available product or can be prepared by standard chemical methods.

[0084] Polymer (A) can be prepared by known methods, such as addition reactions, for example, hydrosilylation, Michael addition, Diels-Alder addition, or reactions between isocyanate functional compounds and compounds having isocyanate reactive groups.

[0085] The component (A) used according to the invention may contain only one type of compound of formula (I) or a mixture of compounds of different types of formula (I). Component (A) may contain only compounds of formula (I), wherein more than 90%, preferably more than 95%, particularly preferably more than 98% of all silyl groups attached to group Y are identical. However, a component (A) containing at least a portion of compounds of formula (I) may also be used, wherein different silyl groups are attached to group Y. Finally, a mixture of different compounds of formula (I) may also be used as component (A), wherein at least two different types of silyl groups attached to group Y are present, but wherein all silyl groups attached to the respective group Y are identical.

[0086] Examples of metallic soaps (B) are calcium stearate and aluminum stearate.

[0087] Preferably, component (B) is a thermally activated thixotropic agent selected from fatty amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil, and hydrogenated castor oil derivatives, wherein fatty amides, polyamide waxes, and polyamide wax derivatives are particularly preferred. Component (B) is particularly preferred to be a polyamide wax or a polyamide wax derivative, especially a polyamide wax.

[0088] The melting point of the thixotropic agent (B) is preferably from 40°C to 200°C, particularly preferably from 50°C to 150°C, especially preferably from 60°C to 150°C, at 1013 mbar in each case.

[0089] In the method according to the invention, all process steps beginning with the mixing of components (A) and (B), optionally the simultaneous or subsequent mixing of other components, and optionally further process steps, and the storage of the final composition (M), including its transport until its use, are preferably carried out at a temperature of at least 30°C, particularly preferably at a temperature at least 40°C, especially at least 50°C, below the melting point of the component (B) used, wherein, if two or more thixotropic agents (B) are used, this description refers to the thixotropic agent (B) with the highest melting point. All process steps are preferably carried out at a temperature of at least -20°C, regardless of the melting temperature of component (B). Except for storage, all process steps are preferably carried out at a temperature of at least 0°C, particularly preferably at least 10°C, and especially preferably at least 15°C.

[0090] Examples of suitable commercially available thixotropic agents (B) include those with the trade name […]. 6500 (a polyamide wax with a melting point of approximately 123°C from Kusumoto Chemicals Ltd.) SLT (a polyamide wax from Arkema with a melting point of 117-127°C) or Thixotropic agent of SLX (a polyimide wax from Arkema with a melting point of 117-127°C).

[0091] The amount of component (B) is preferably 1 to 50 parts by weight, particularly preferably 3 to 40 parts by weight, in each case based on 100 parts by weight of component (A).

[0092] In addition to components (A) and (B) used, the composition (M) produced according to the present invention may include all other substances that have been used to date in crosslinkable compositions and are different from components (A) and (B), such as those selected from nitrogen-containing organosilicon compounds (C), non-reactive plasticizers (D), fillers (E), organosilicon resins (F), catalysts (G), tackifiers (H), water removers (I), additives (J) and adjunct materials (K).

[0093] The optional component (C) is preferably an organosilicon compound containing a unit of formula (II):

[0094] D e Si(OR 4 ) d R 3 c O (4-c-d-e) / 2 (II),

[0095] in,

[0096] R 3 It can be the same or different, and is an optional substituted SiC-bonded, nitrogen-free monovalent organic group, R 4 They can be the same or different, and can be hydrogen atoms or optionally substituted hydrocarbon groups.

[0097] D can be the same or different, and is a SiC-bonded monovalent group having at least one nitrogen atom not bonded to a carbonyl group (C=O).

[0098] c can be 0, 1, 2, or 3, preferably 0 or 1.

[0099] d is 0, 1, 2, or 3, preferably 1, 2, or 3, particularly preferably 2 or 3, and

[0100] e can be 0, 1, 2, 3, or 4, preferably 1.

[0101] The conditions are that the sum of c+d+e is less than or equal to 4 and each molecule contains at least one group d.

[0102] The organosilicon compound (C) optionally used according to the present invention can be either a silane, i.e. a compound of formula (II) where c+d+e=4, or a siloxane, i.e. a compound containing a unit of formula (II) where c+d+e<3, preferably a silane.

[0103] Group R3 The instances are those given for R.

[0104] Group R 3 Preferably, it is a hydrocarbon group having 1 to 18 carbon atoms that is optionally substituted with halogen atoms, and particularly preferably a hydrocarbon group having 1 to 5 carbon atoms, especially a methyl group.

[0105] Optionally substituted hydrocarbon group R 4 The examples are given for the group R.

[0106] Group R 4 Preferably, it is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms that is optionally substituted with a halogen atom, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, especially methyl or ethyl.

[0107] Examples of group D are groups of the following formula and reaction products of primary amino groups in the following formula with compounds containing double bonds or epoxide groups that react with primary amino groups: H2N(CH2)3-, H2N(CH2)2NH(CH2)3-, H2N(CH2)2NH(CH2)2NH(CH2)3-, H3CNH(CH2)3-, C2H5NH(CH2)3-, C3H7NH(CH2)3-, C4H9NH(CH2)3-, C5H 11 NH(CH2)3-, C6H 13 NH(CH2)3-, C7H 15 NH(CH2)3-, H2N(CH2)4-, H2N-CH2-CH(CH3)-CH2-, H2N(CH2)5-, cyclo-C5H9NH(CH2)3-, cyclo-C6H 11 NH(CH2)3-, phenyl-NH(CH2)3-, (CH3)2N(CH2)3-, (C2H5)2N(CH2)3-, (C3H7)2N(CH2)3-, (C4H9)2N(CH2)3-, (C5H 11 )2N(CH2)3-、(C6H 13 )2N(CH2)3-、(C7H 15 )2N(CH2)3-, H2N(CH2)-, H2N(CH2)2NH(CH2)-, H2N(CH2)2NH(CH2)2NH(CH2)-, H3CNH(CH2)-, C2H5NH(CH2)-, C3H7NH(CH2)-, C4H9NH(CH2)-, C5H 11 NH(CH2)-, C6H 13 NH(CH2)-, C7H 15 NH(CH2)-, cyclic -C5H9NH(CH2)-, cyclic -C6H11 NH(CH2)-, phenyl-NH(CH2)-, (CH3)2N(CH2)-, (C2H5)2N(CH2)-, (C3H7)2N(CH2)-, (C4H9)2N(CH2)-, (C5H 11 )2N(CH2)-、(C6H 13 )2N(CH2)-、(C7H 15 )2N(CH2)-, (CH3O)3Si(CH2)3NH(CH2)3-, (C2H5O)3Si(CH2)3NH(CH2)3-, (CH3O)2(CH3)Si(CH2)3NH(CH2)3-, and (C2H5O)2(CH3)Si(CH2)3NH(CH2)3-.

[0108] Group D is preferably H2N(CH2)3-, H2N(CH2)2NH(CH2)3- or cyclo-C6H 11 NH(CH2)3- group.

[0109] Examples of silanes of formula (II) optionally used according to the present invention are H2N(CH2)3-Si(OCH3)3, H2N(CH2)3-Si(OC2H5)3, H2N(CH2)3-Si(OCH3)2CH3, H2N(CH2)3-Si(OC2H5)2CH3, H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OCH3 ... )3-Si(OCH3)2CH3, H2N(CH2)2NH(CH2)3-Si(OC2H5)2CH3, H2N(CH2)2NH(CH2)3-Si(OH)3, H2N(CH2)2NH(CH2) 3-Si(OH)2CH3, H2N(CH2)2NH(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)2NH(CH2)3-Si(OC2H5)3, Ring-C6H 11 NH(CH2)3-Si(OCH3)3, cyclo-C6H 11 NH(CH2)3-Si(OC2H5)3, cyclo-C6H 11 NH(CH2)3-Si(OCH3)2CH3, cyclo-C6H 11 NH(CH2)3-Si(OC2H5)2CH3, cyclic C6H 11 NH(CH2)3-Si(OH)3, ring-C6H 11NH(CH2)3-Si(OH)2CH3, phenyl-NH(CH2)3-Si(OCH3)3, phenyl-NH(CH2)3-Si(OC2H5)3, phenyl-NH(CH2)3-Si(OCH3)2CH3, phenyl-NH(CH2)3-Si(OC2H5)2CH3, phenyl-NH(CH2)3-Si(OH)3, phenyl-NH(CH2)3-Si(OH)2CH3, HN((CH2)3-Si(OCH3)3)2, HN((CH2)3-Si(OC2H5)3)2HN((CH2)3-Si(OCH3)2CH3)2, HN((CH2)3-Si(OC2H5)2CH3)2, cyclic-C6H 11 NH(CH2)-Si(OCH3)3, cyclo-C6H 11 NH(CH2)-Si(OC2H5)3, cyclo-C6H 11 NH(CH2)-Si(OCH3)2CH3, cyclo-C6H 11 NH(CH2)-Si(OC2H5)2CH3、cyclo-C6H 11 NH(CH2)-Si(OH)3, ring-C6H 11 NH(CH2)-Si(OH)2CH3, phenyl-NH(CH2)-Si(OCH3)3, phenyl-NH(CH2)-Si(OC2H5)3, phenyl-NH(CH2)-Si(OCH3)2CH3, phenyl-NH(CH2)-Si(OC2H5)2CH3, phenyl-NH(CH2)-Si(OH)3 and phenyl-NH(CH2)-Si(OH)2CH3 and their partial hydrolysis products, preferably H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, cyclo-C6H 11 NH(CH2)3-Si(OCH3)3, cyclo-C6H 11 NH(CH2)3-Si(OC2H5)3 and cyclo-C6H 11 NH(CH2)3-Si(OCH3)2CH3 and, in each case, their partial hydrolysis products, and particularly preferably H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, and cyclo-C6H 11 NH(CH2)3-Si(OCH3)3, cyclo-C6H 11NH(CH2)3-Si(OCH3)2CH3 and, in each case, their partial hydrolysis products.

[0110] The organosilicon compound (C) optionally used according to the invention may also function as a curing catalyst or co-catalyst in the composition (M) produced according to the invention.

[0111] Furthermore, the organosilicon compound (C) optionally used according to the present invention can be used as an adhesion promoter and / or a water remover.

[0112] The organosilicon compound (C) optionally used according to the present invention is a commercial product or can be produced by standard chemical methods.

[0113] If the composition (M) produced according to the invention comprises component (C), then in each case, based on 100 parts by weight of component (A), the amount of component (C) is preferably 0.1 to 25 parts by weight, particularly preferably 0.2 to 20 parts by weight, and especially 0.5 to 15 parts by weight. Component (C) is preferably used in the method according to the invention.

[0114] The optional non-reactive plasticizer (D) can be any non-reactive plasticizer that has been used to date in crosslinkable organopolysiloxane compositions.

[0115] The non-reactive plasticizer (D) is preferably an organic compound selected from the following:

[0116] • Fully esterified aromatic or aliphatic carboxylic acids,

[0117] • Fully esterified derivatives of phosphoric acid

[0118] · Fully esterified derivatives of sulfonic acid,

[0119] • Branched or unbranched saturated hydrocarbons,

[0120] Polystyrene

[0121] Polybutene,

[0122] Polyisobutylene,

[0123] Polyester, or

[0124] Polyether.

[0125] The non-reactive plasticizer (D) optionally used according to the present invention is preferably a plasticizer that does not react with water or components (A) and (B) at a temperature of <80°C, is liquid at 20°C and 1013hPa, and has a boiling point >250°C at 1013hPa.

[0126] Examples of carboxylic acid esters (D) are phthalates, such as dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and teicosyl phthalate; fully hydrogenated phthalates, such as diisononyl 1,2-cyclohexanedicarboxylate and dioctyl 1,2-cyclohexanedicarboxylate; adipates, such as dioctyl adipate; benzoates; trimellitic esters, ethylene glycol esters; esters of saturated alkyl diols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0127] Examples of polyethers (D) are polyethylene glycol, polyTHF, and polypropylene glycol, with a preferred molar mass of 200 to 20,000 g / mol.

[0128] The plasticizer (D) used (if it is a polymeric plasticizer) is preferably of molar mass M. n The molar mass or average molar mass Mn is preferably at most 200 g / mol, particularly preferably at most 500 g / mol, and especially at most 900 g / mol.

[0129] In a preferred embodiment of the invention, the component (D) used is a phthalate-free plasticizer, such as fully hydrogenated phthalates, trimellitic esters, polyesters, or polyethers. The plasticizer (D) is particularly preferably a polyether, especially polyethylene glycol, polyTHF, and polypropylene glycol, with polypropylene glycol being especially preferred. The preferred molar mass of the polyether (D) is preferably from 400 to 20,000 g / mol, particularly preferably from 800 to 12,000 g / mol, and especially from 1,000 to 8,000 g / mol.

[0130] If a non-reactive plasticizer (D) is used according to the invention, the amount involved is preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, especially 20 to 150 parts by weight, based on 100 parts by weight of component (A) in each case. The plasticizer (D) is preferably used in the method according to the invention.

[0131] The filler (E) optionally used according to the present invention can be any filler known to date.

[0132] An example of filler (E) is a non-reinforced filler, i.e., with a BET surface area preferably up to 50 m². 2Fillers of / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite, metal oxide powders such as oxides of aluminum, titanium, iron or zinc or mixed oxides thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder; reinforcing fillers, i.e., BET surface area greater than 50m². 2 Fillers of / g, such as fumed silica, precipitated silica, precipitated chalk and mixed silica-alumina oxides, carbon black, such as furnace black and acetylene black with a large BET surface area; aluminum hydroxide, hollow spherical fillers, such as ceramic microspheres, elastic plastic beads, glass beads or fibrous fillers. The fillers can be hydrophobically modified, for example, by treatment with organosilanes or organosiloxanes or with stearic acid or by etherifying hydroxyl groups to alkoxy groups.

[0133] The filler (E) used optionally is preferably calcium carbonate, magnesium carbonate and / or mixed calcium and magnesium carbonates, talc, aluminum hydroxide, and silica. Preferred grades of calcium carbonate are ground or precipitated, and optionally surface-treated with fatty acids such as stearic acid or its salts. Preferred silica is fumed silica.

[0134] The moisture content of the optional filler (E) is preferably less than 1% by weight, and particularly preferably less than 0.5% by weight.

[0135] If filler (E) is used according to the invention, the amount involved is preferably 10 to 1000 parts by weight, particularly preferably 40 to 500 parts by weight, especially 80 to 300 parts by weight, based on 100 parts by weight of component (A) in each case. Filler (E) is preferably used in the method according to the invention.

[0136] In a particularly preferred embodiment of the method according to the invention, calcium carbonate, magnesium carbonate, and / or a calcium-magnesium mixed carbonate are used as filler (E1) in an amount of 10 to 900 parts by weight, particularly preferably 40 to 450 parts by weight, especially 80 to 280 parts by weight, based on 100 parts by weight of component (A) in each case. In addition to filler (E1) (preferably in the stated amounts), other fillers (E2) different from (E1) may also be present. The same materials as the filler (E) described above can be used as filler (E2), provided that these materials are not defined as (E1). The preferred total amount of fillers (E1) and (E2) corresponds to the preferred amount of filler (E) described above.

[0137] The silicone resin (F) optionally used in the composition (M) according to the invention is preferably a phenyl silicone resin.

[0138] The silicone resin (F) optionally used according to the invention is particularly preferably one containing at least 50% by weight, preferably at least 70% by weight, and especially at least 90% by weight of T units as shown in the following formula: PhSiO3 / 2 PhSi(OR) 5 )O 2 / 2 PhSi(OR) 5 )2O 1 / 2 MeSiO 3 / 2 MeSi(OR) 5 )O 2 / 2 and / or MeSi(OR) 5 )2O 1 / 2 Where Ph is phenyl, Me is methyl, and R 5 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted with halogen atoms, preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, based on the total number of units in each case. These resins preferably consist of at least 30% by weight, particularly preferably at least 40% by weight, of the above three PhSi functional units.

[0139] The silicone resin (F) optionally used according to the invention is particularly preferably those containing at least 50% by weight, preferably at least 70% by weight, and especially at least 90% by weight of T units represented by the following formula: PhSiO 3 / 2 PhSi(OR) 5 )O 2 / 2 and / or PhSi(OR) 5 )2O 1 / 2 All variables in the above definition are defined.

[0140] The average molar mass (number average) of the silicone resin (F) optionally used according to the present invention is M n Preferably at least 400 g / mol, particularly preferably at least 600 g / mol. The average molar mass M of the silicone resin (F) n Preferably, it is up to 400,000 g / mol, particularly preferably up to 10,000 g / mol, and especially up to 3,000 g / mol.

[0141] The silicone resin (F) optionally used according to the invention can be solid or liquid at 23°C and 1000 hPa, with the silicone resin (F) preferably being liquid. In each case, at 25°C, the viscosity of the silicone resin (F) is preferably from 10 to 100,000 mPas, more preferably from 50 to 50,000 mPas, and especially from 100 to 20,000 mPas.

[0142] Silicone resin (F) can be used in pure form or as a mixture in a suitable solvent, although pure form is preferred.

[0143] Examples of phenyl silicone resins that can be used as component (F) are commercially available products, such as various types from Wacker Chemie AG. Type, such as IC 368, IC 678 or IC 231 and SY231.

[0144] If resin (F) is used to prepare the composition (M) according to the invention, its amount is preferably at least 1 part by weight, particularly preferably at least 5 parts by weight, especially at least 10 parts by weight, and preferably at most 1000 parts by weight, particularly preferably at most 500 parts by weight, especially at most 300 parts by weight, based on 100 parts by weight of component (A) in each case.

[0145] The catalyst (G) optionally used in the composition (M) according to the invention can be any catalyst known to date for compositions cured by silane condensation.

[0146] Examples of metal-containing curing catalysts (G) are organotitanium and tin compounds, such as titanates like tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetraacetylacetonate; and tin compounds like dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin acetylacetonate, and the corresponding dioctyltin compounds.

[0147] Examples of metal-free curing catalysts (G) 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, 1,1,2,2-tetramethylguanidine, 1,1,2,3-tetramethylguanidine, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylaniline, and N-ethylmorpholine.

[0148] Acidic compounds can also be used as catalysts (G), such as phosphoric acid and its partially esterified derivatives, toluenesulfonic acid, sulfuric acid, nitric acid or other organic carboxylic acids, such as acetic acid and benzoic acid.

[0149] If a catalyst (G) is used according to the invention, the amount involved is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of component (A) in each case.

[0150] In one embodiment of the invention, the catalyst (G) optionally used is a metal-containing curing catalyst, preferably a tin-containing catalyst. This embodiment of the invention is particularly preferred when component (A) consists entirely or at least partially, i.e., at least 90% by weight, preferably at least 95% by weight, of a compound of formula (I), wherein b is not equal to 1.

[0151] To prepare the composition (M) according to the invention, if component (A) consists entirely or at least partially of a compound of formula (I), i.e., contains at least 10% by weight, preferably at least 20% by weight of a compound of formula (I), it is preferable not to use a metal-containing catalyst (G), particularly a tin-containing catalyst, in formula (I) where b equals 1 and R 1 The definition includes hydrogen atoms. The embodiment of this invention that does not contain a metal catalyst, particularly a tin catalyst, is especially preferred.

[0152] The adhesion promoter (H) optionally used according to the invention can be any adhesion promoter previously described for systems cured by silane condensation.

[0153] Examples of adhesion promoters (H) are epoxy silanes, such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmethyldiethoxysilane, 2-(3-triethoxysilylpropyl)maleic anhydride, N-(3-trimethoxysilylpropyl)urea, N-(3-triethoxysilylpropyl)urea, N-(trimethoxysilylmethyl)urea, N-(methyldimethoxysilylmethyl)urea, N-(3-triethoxysilylmethyl)urea, N-(3-methyldiethoxysilylmethyl)urea, and O-methylcarbamate methylmethyldimethoxysilane. (hylmethyldimethoxysilane), O-methylcarbamate methyltrimethoxysilane, O-ethylcarbamate methylmethyldiethoxysilane, O-ethylcarbamate methyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethylmethyldimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, acryloyloxymethyltrimethoxysilane, acryloyloxymethyldimethoxysilane, acryloyloxymethyldiethoxysilane, acryloyloxymethyldiethoxysilane and some of their condensates.

[0154] If an adhesion promoter (H) is used in the method according to the invention, its amount is preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the crosslinkable composition (M) in each case.

[0155] The water scavenger (I) optionally used in the method according to the invention can be any water scavenger described for use in systems cured by silane condensation.

[0156] Examples of water scavengers (I) are silanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, tetraethoxysilane, methyl O-carbamate methylmethyldimethoxysilane, methyl O-carbamate methyltrimethoxysilane, ethyl O-carbamate methylmethyldiethoxysilane, ethyl O-carbamate methyltriethoxysilane and / or their partial condensates and ortho-esters, such as 1,1,1-trimethoxyethane, 1,1,1-triethoxyethane, trimethoxymethane and triethoxymethane, preferably vinyltrimethoxysilane.

[0157] If the composition (M) produced according to the invention contains a water scavenger (I), the amount used is preferably 0.5 to 30 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the crosslinkable composition (M) in each case. The water scavenger (I) is preferably used in the method according to the invention.

[0158] The additive (J) optionally used according to the present invention can be a typical additive for silane crosslinking systems known to date.

[0159] The additives (J) optionally used according to the invention are compounds different from the components mentioned so far, preferably antioxidants, UV stabilizers such as so-called HALS compounds, fungicides, commercially available defoamers (e.g. from BYK (D-Wesel)), commercially available wetting agents (e.g. from BYK (D-Wesel)) or pigments.

[0160] If the additive (J) is used to prepare the composition (M) according to the invention (which is preferred), its amount is preferably 0.01 to 30 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A) in each case.

[0161] The optional auxiliary material (K) used according to the present invention is preferably a tetraalkoxysilane, such as tetraethoxysilane and / or a partial condensate thereof, a reactive plasticizer, a rheology modifier different from component (B), a flame retardant or an organic solvent.

[0162] Preferred reactive plasticizers (K) are compounds comprising an alkyl chain having 6 to 40 carbon atoms and having a group that reacts with compound (A). Examples are isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.

[0163] All typical flame retardants in adhesive and sealant systems can be used as flame retardants (K), preferably halogenated compounds and (partial) esters of phosphoric acid and their derivatives, especially (partial) esters of phosphoric acid.

[0164] Examples of organic solvents (K) are low molecular weight ethers, esters, ketones, aromatics and aliphatic compounds, and optionally halogenated hydrocarbons and alcohols, with the latter being preferred.

[0165] Preferably, no organic solvent (K) is added to the composition (M) according to the invention.

[0166] If one or more components (K) are used to prepare the composition (M) according to the invention, the amount of each component is preferably 0.5 to 200 parts by weight, particularly preferably 1 to 100 parts by weight, especially 2 to 70 parts by weight, based on 100 parts by weight of component (A) in each case.

[0167] In a preferred embodiment of the method according to the invention, the following components are mixed together:

[0168] (A) 100 parts by weight of compound (I),

[0169] (B) 0.1 to 50 parts by weight of a thixotropic agent,

[0170] (C) 0.1 to 25 parts by weight of an organosilicon compound containing a (II) unit,

[0171] Optional (D) non-reactive plasticizer,

[0172] Optional (E) packing material,

[0173] (F) silicone resin is optional.

[0174] The (G) catalyst is optionally present.

[0175] Optional (H) adhesion promoter,

[0176] Optional (I) water scavenger,

[0177] Optional (J) additives and

[0178] Optional (K) additional materials;

[0179] The resulting mixture is then stored for at least 7 days, with all process steps carried out at temperatures below 80°C.

[0180] In another preferred embodiment of the method according to the invention, the following components are mixed together:

[0181] (A) 100 parts by weight of compound (I),

[0182] (B) 1 to 40 parts by weight of thixotropic agent

[0183] (C) 0.1 to 25 parts by weight of an organosilicon compound containing a (II) unit,

[0184] Optional (D) non-reactive plasticizer,

[0185] (E) 10 to 1000 parts by weight of filler,

[0186] (F) silicone resin is optional.

[0187] The (G) catalyst is optionally present.

[0188] Optional (H) adhesion promoter,

[0189] Optional (I) water scavenger,

[0190] Optional (J) additives and

[0191] Optional (K) additional materials;

[0192] The resulting mixture is then stored for at least 7 days, with all process steps carried out at temperatures below 80°C.

[0193] In a particularly preferred embodiment of the method according to the invention, the following components are mixed together:

[0194] (A) 100 parts by weight of compound (I),

[0195] (B) 1 to 40 parts by weight of thixotropic agent

[0196] (C) 0.1 to 25 parts by weight of an organosilicon compound containing a (II) unit,

[0197] (D) 10 to 300 parts by weight of non-reactive plasticizer,

[0198] (E) 10 to 1000 parts by weight of filler,

[0199] (F) silicone resin is optional.

[0200] The (G) catalyst is optionally present.

[0201] Optional (H) adhesion promoter,

[0202] Optional (I) water scavenger,

[0203] Optional (J) additives and

[0204] Optional (K) additional materials;

[0205] The resulting mixture is then stored for at least 7 days, with all process steps carried out at temperatures below 80°C.

[0206] In another particularly preferred embodiment of the method according to the invention, the following components are mixed together:

[0207] (A) 100 parts by weight of compound (I),

[0208] (B) 1 to 40 parts by weight of thixotropic agent

[0209] (C) 0.1 to 25 parts by weight of an organosilicon compound containing a (II) unit,

[0210] (F) 10 to 200 parts by weight of plasticizer,

[0211] (E1) 10 to 800 parts by weight of calcium carbonate, magnesium carbonate and / or mixed calcium and magnesium carbonates

[0212] Choose any filler (E2) that is different from component (E1).

[0213] (F) silicone resin is optional.

[0214] The (G) catalyst is optionally present.

[0215] Optional (H) adhesion promoter,

[0216] Optional (I) water scavenger,

[0217] Optional (J) additives, and

[0218] Optional (K) additional materials;

[0219] The resulting mixture is then stored for at least 7 days, with all process steps carried out at temperatures below 80°C.

[0220] The components used according to the invention may each be one type of such component, or a mixture of at least two types of the corresponding components.

[0221] In the method according to the invention, it is preferable not to use components other than components (A) to (K).

[0222] The composition (M) produced according to the invention is preferably a paste composition. After being stored at 23°C for 21 days, these compositions preferably have a viscosity of 100 to 100,000 Pas, particularly preferably 1,000 to 50,000 Pas, and especially 2,000 to 30,000 Pas, as measured according to DIN 54458, at 25°C and 0.1% deformation.

[0223] In the method according to the invention, it is preferred to fill at a time when the viscosity of the composition (M), measured according to DIN 54458, is at least 1.5 times lower, preferably at least 2 times lower, and particularly preferably at least 3 times lower, than the viscosity of the same composition (M) measured under the same conditions after storage at 23°C for 21 days following preparation.

[0224] In another preferred variant of the method according to the invention, the filling is carried out at a time when the viscosity of the composition (M), measured according to DIN 54458, is at least 2 times lower, preferably at least 3 times lower, particularly preferably at least 4 times lower, and especially preferably at least 5 times lower than the viscosity of the same composition (M) measured under the same conditions after being stored at 23°C for 21 days following preparation.

[0225] Preferably, after being filled into the container (GB), the crosslinkable composition (M) is heated to a temperature of up to 69°C or below, particularly preferably up to 59°C or below, and especially preferably up to 49°C or below.

[0226] In a preferred embodiment of the invention, after being filled into a container (GB), the crosslinkable composition (M) is not heated to a temperature above 45°C by any heating device, particularly preferably above 35°C, and especially above 25°C.

[0227] However, in this preferred embodiment, if the above-mentioned limit is reached without a heating device, for example due to high external and / or ambient temperatures during storage and / or transportation, storage temperatures exceeding the said limit may occur.

[0228] The method according to the invention can be performed continuously or discontinuously.

[0229] The composition (M) produced according to the present invention is preferably a single-component crosslinkable composition. However, the composition (M) produced according to the present invention may also be part of a two-component crosslinking system, wherein an OH-containing compound, such as water, is added to the second component.

[0230] If water is excluded, the composition (M) produced according to the present invention can be stored, and if water is allowed to enter, it can be crosslinked.

[0231] The composition (M) prepared according to the present invention can be used for all purposes for which crosslinkable compositions based on organosilicon compounds have been used to date, such as for the production of molded articles by crosslinking and for the production of material composites.

[0232] The normal water content in air is sufficient for the composition (M) prepared according to the invention to crosslink. The compositions (M) of the invention are preferably crosslinked at room temperature. If desired, they can also be crosslinked at temperatures above or below room temperature, for example, at -5°C to 15°C or 30°C to 50°C and / or using a water concentration exceeding the normal water content of air.

[0233] The molded articles produced according to the invention preferably have a tensile strength of at least 1.0 MPa, particularly preferably at least 1.5 MPa, measured in each case according to DIN EN 53504-S1.

[0234] The molded articles produced according to the invention preferably have an elongation at break of at least 100%, particularly preferably at least 200%, as measured in each case according to DIN EN 53504-S1.

[0235] The molded articles produced according to the present invention can be any molded article, such as seals, pressed articles, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminates or adhesive layers.

[0236] Examples include joint sealing, coating, potting, production of molded articles, composite materials, and composite molded parts. Composite molded parts should be understood herein as homogeneous molded articles made of composite materials comprising a crosslinked product of the composition (M) according to the invention and at least one substrate, such that a strong, permanent bond exists between the two parts.

[0237] In the production of composite materials, the composition (M) produced according to the present invention can also be hardened between at least two identical or different substrates, such as in the case of bonding, lamination or encapsulation.

[0238] Examples of substrates that can be bonded or sealed according to the present invention include plastics (including PVC), metals, concrete, wood, mineral substrates, glass, ceramics, and painted surfaces.

[0239] The composition (M) prepared according to the present invention can be used for all purposes, wherein the composition can be used to obtain an elastomer by excluding water and crosslinking when water enters at room temperature.

[0240] The advantage of the method according to the invention is that the composition (M) according to the invention is easy to prepare, and is particularly fast and energy-efficient since the heating step is no longer necessary.

[0241] Another advantage of the method according to the invention is that the composition (M) can be rapidly filled into the appropriate container for end use, as this filling can be carried out at a viscosity significantly lower than that required for the corresponding end use. This is particularly advantageous if the end use requires, or at least demands, a composition with high viscosity and / or high thixotropy.

[0242] The advantages of the crosslinkable compositions (M) prepared according to the present invention are that they are characterized by very high storage stability and high crosslinking rate.

[0243] Furthermore, the crosslinkable compositions (M) prepared according to the present invention have the advantage of having excellent adhesive properties.

[0244] Furthermore, the crosslinkable composition (M) produced according to the present invention has the advantage of being easy to process. Detailed Implementation Plan

[0245] Unless otherwise stated, all steps in the following examples were performed at ambient atmospheric pressure, i.e., 1013 hPa, and at room temperature, i.e., 23°C, or at the temperature generated when the reactants combine at room temperature, without additional heating or cooling. Crosslinking of composition (M) was performed at 50% relative humidity. Furthermore, unless otherwise stated, all reported components and percentages are by weight.

[0246] Example 1: Preparation of Elastic Adhesive Formulation

[0247] In a laboratory planetary mixer from PC-Laborsystem equipped with a cross-arm mixer and a dissolver, 180 g of silane-terminated polypropylene glycol (with an average molar mass of 18000 g / mol) was mixed. n The end groups of the formula -OC(=O)-NH-(CH2)3-Si(OCH3)3 are commercially available from Wacker Chemie AG, D-Munich, under the trade name... STP-E35 was homogenized for 2 minutes at 200 rpm in a cross-arm mixer at approximately 25°C, using 250 g of diisoundecyl phthalate as a plasticizer, and 224 g of precipitated chalk coated with fatty acids having an average particle size (D50%) of approximately 0.07 μm (commercially available from ShiraishiOmya GmbH, AT-Gummern, trade name: STP-E35). 224g of calcium carbonate (CCR S10) coated with stearic acid with an average particle size (D50%) of approximately 2.0μm (commercially purchased) CCR S10 (trade name Omyabond520), 40g of titanium dioxide with TiO2 content >92.0%, classified according to DIN EN ISO 591 R2 standard, color index Pigment White 6, bulk density 3.9 kg / L, oil absorption 19g / 100g (based on...). 2360 (purchased from Kronos in Dallas, USA) and 40 grams of micronized polyamide wax with a melting point of 117-127°C (in the form of...) The name SLX was purchased from Arkema, France. The mixture was then stirred for 15 minutes at 600 rpm (horizontal arm mixer) and 1000 rpm (dissolver). Due to the introduced stirring energy, the mixture was heated to approximately 43°C. It was then cooled again to 25°C.

[0248] Then, 10g of a stabilizer mixture containing hindered amine light stabilizer (HALS) and UV absorber (commercially available from Wacker Chemie AG, D-Munich, trade name: [Brand Name]) was added. Stabilizer F), 20g vinyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich, trade name: Stabilizer F), XL 10) and 2 g of dioctyltin dilaurate (commercially available from TIB Chemicals AG, D-Mannheim, trade name TIB Kat 216) were stirred for 2 minutes using a horizontal arm mixer at 600 rpm and a dissolver at 1000 rpm. No significant temperature rise was observed in the mixture. Finally, 10 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich, trade name...) was added. GF 9) Stir for 2 minutes using a horizontal arm mixer at 600 rpm and a dissolver at 1000 rpm. There was no significant temperature rise in the mixture at this point.

[0249] Finally, homogenize the mixture and stir it for 1 minute at 600 rpm without bubbles using a cross-arm mixer, and then stir it for 1 minute at 200 rpm without bubbles using a cross-arm mixer at a pressure of about 100 mbar.

[0250] The resulting composition was filled into a 310 ml PE cylinder, sealed, and stored at 23°C for 3 weeks prior to testing.

[0251] Example 2

[0252] The steps are as described in Example 1, except that the finished cylinder is stored at 8°C for 3 weeks before testing.

[0253] Comparative Example 1 (C1)

[0254] The steps are as described in Example 1, except that the obtained bubble-free stirring material is used directly in the experiment described in Example 3 without any storage.

[0255] Comparative Example 2 (C2)

[0256] The steps are as described in Example 1, except that the finished cylinder is stored at 23°C for 24 hours before the test described in Example 3.

[0257] Comparative Example 3 (C3)

[0258] The steps are as described in Example 1, except that before testing, the finished cylinder is first stored at 80°C for 3 hours, and then stored at 23°C for 3 weeks.

[0259] Comparative Example 4 (C4)

[0260] The steps are as described in Example 1, except that before testing, the finished cylinder is first stored at 110°C for 3 hours, and then stored at 23°C for 3 weeks.

[0261] Comparative Example 5 (C5)

[0262] The steps are as described in Example 1, except that polyamide is added ( The first mixing step after SLX involves heating the mixture to 80°C using an external heater and holding it at that temperature for 15 minutes. All other steps are the same, and in this case, the finished product cylinder is stored at 23°C for 3 weeks.

[0263] Example 3: Determination of properties of samples from Examples 1 and 2 and Comparative Examples (C1)-(C4)

[0264] Time to Formation (SFT)

[0265] To determine the skin formation time, the crosslinkable composition obtained in the examples was applied as a 2 mm thick layer onto a PE film and stored under standard conditions (23°C and 50% relative humidity). Skin formation was tested every 5 minutes during the curing process. For this purpose, a dry laboratory spatula was carefully placed on the sample surface and pulled upwards. If the sample stuck to a finger, skin formation had not yet occurred. If no sample stuck to a finger, skin formation had occurred, and the time was recorded. The results are shown in Table 1.

[0266] Mechanical properties

[0267] The compositions were dispersed on a milled polytetrafluoroethylene plate to a depth of 2 mm and cured for 2 weeks at 23°C and 50% relative humidity.

[0268] Shore A hardness is determined according to DIN EN 53505.

[0269] Tensile strength was determined according to DIN EN 53504-S1.

[0270] Elongation at break was determined according to DIN EN 53504-S1.

[0271] 100% modulus was determined according to DIN EN 53504-S1.

[0272] The results are shown in Table 1.

[0273] Rheological properties

[0274] The viscosity at 0.1% deformation was determined according to DIN 54458 at 25°C.

[0275] Viscosity at 100% deformation was determined according to DIN 54458 at 25°C.

[0276] The results are shown in Table 1.

[0277] Table 1

[0278] Components of the embodiment 1 2 C1 C2 C3 C4 C5 SFT[min] 14 13 14 15 12 12 13 Shore A hardness 45 47 46 45 44 47 46 <![CDATA[Tensile strength [N / mm 2 > 1.7 1.6 1.7 1.7 1.7 1.6 1.7 Elongation at break [%) 229 238 231 266 245 238 243 100% Modulus [MPa] 1.1 1.0 1.1 1.1 1.0 1.0 1.1 Viscosity at 0.1% deformation [Pas] 8930 5170 550 650 8780 7610 1860 Viscosity at 100% deformation [Pas] 93 72 18 20 94 94 38

[0279] It has been shown that the compositions of the present invention exhibit thixotropic properties during the long storage period of the present invention, even without heat treatment, which are in no way inferior to, and in some cases even superior to, the properties of heat-treated compositions.

[0280] Meanwhile, the results of comparative examples C1 and C2 show that when the material of the present invention is filled into a container (e.g., a barrel) for final application within 24 hours after production, its viscosity at filling (under high and low shear) is significantly lower than its viscosity at application, and its application is only carried out after the storage period according to the present invention.

[0281] Example 4: Preparation of low-modulus sealant formulation

[0282] In a laboratory planetary mixer from PC-Laborsystem equipped with a cross-arm mixer and a dissolver, 100 g of silane-terminated polypropylene glycol (with an average molar mass of 18000 g / mol) was mixed. n The end groups of the formula -OC(=O)-NH-(CH2)3-Si(OCH3)3 are commercially available from Wacker Chemie AG, D-Munich, under the trade name... STP-E35 was homogenized for 2 minutes at 200 rpm in a cross-arm mixer at approximately 25°C, using 223 g of diisononyl cyclohexane-1,2-dicarboxylate as a plasticizer (commercially available from BASF SE; D-Ludwigshafen, trade name "HexamollDINCH"), 261 g of stearic acid-coated calcium carbonate with an average particle size (D50%) of approximately 2.0 μm (commercially available from Omya, D-Cologne, trade name Omyabond 520), and 261 g of fatty acid-coated ultrafine calcium carbonate with a primary particle size of approximately 30 μm (commercially available from ShiraishiOmya GmbH, A-Gummern, trade name...). 30), 30g of micronized polyamide wax with a melting point of 117-127℃ (commercially available from Arkema, France, A-Gummern, trade name: (SLX). The mixture was then stirred for 15 minutes at 600 rpm (horizontal arm mixer) and 1000 rpm (dissolver). Due to the introduced stirring energy, the mixture was heated to approximately 41°C. It was then cooled again to 25°C.

[0283] Then, the average molar mass (M) of 100g was... n Polypropylene glycol with a concentration of 5000 g / mol and end groups of the formula -OC(=O)-NH-(CH2)3-Si(OCH3)3, single-sided silane-terminated (commercially available from Wacker Chemie AG, D-Munich, trade name: [trade name missing]). XM 25), 5g of a stabilizer mixture containing hindered amine light stabilizer (HALS) and UV absorber (commercially available from Wacker Chemie AG, D-Munich, trade name XM 25). Stabilizer F), 15g vinyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich, trade name: [trade name missing]) XL 10) and 2g of dioctyltin-silane complex (CAS No.: 870-08-6, commercially available from TIB Chemicals AG, D-Mannheim, trade name TIB Kat417) were stirred at 600 rpm (horizontal arm stirrer) and 1000 rpm (dissolver) for 2 minutes. No significant temperature rise was observed in the mixture. Finally, 3g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich, trade name) was added. GF 9) was stirred for 2 minutes at 600 rpm (horizontal arm mixer) and 1000 rpm (dissolver). There was no noticeable temperature rise in the mixture at this point.

[0284] Finally, homogenize the mixture and stir at 600 rpm (horizontal arm mixer) for 1 minute without bubbles, then stir at 200 rpm (horizontal arm mixer) for 1 minute without bubbles, at a pressure of 100 mba.

[0285] The resulting composition was filled into a 310 ml PE cylinder, sealed, and stored at 23°C for 3 weeks prior to testing.

[0286] Comparative Example 6 (C6)

[0287] The steps are as described in Example 3, except that polyamide is added ( In the first mixing step after SLX, the mixture is heated to 80°C using an external heater and held at that temperature for 15 minutes. All other steps are the same, and in this case, the finished product cylinder is stored at 23°C for 3 weeks.

[0288] Example 5: Property determination of samples from Example 4

[0289] As described in Example 3, the epidermal formation time, mechanical properties, and rheological properties were measured. The results are shown in Table 2.

[0290] Table 2

[0291] Components of the embodiment 4 C6 SFT[min] 36 31 Shore A hardness 24 19 <![CDATA[Tensile strength [N / mm 2 > 0.9 0.9 Elongation at break [%) 622 669 100% Modulus [MPa] 0.3 0.4 Viscosity at 0.1% deformation [Pas] 5940 5970 Viscosity at 100% deformation [Pas] 78 80

[0292] This again demonstrates that the composition of the present invention in Example 3 exhibits thixotropic properties even without heat treatment during the long storage period according to the present invention, which is in no way inferior to the properties of the heat-treated composition in Comparative Example C6.

Claims

1. A method for producing a crosslinkable composition (M), the method comprising mixing the following components (A), component (B), and optionally other components: (A) 100 parts by weight of the compound of formula (I), Y-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I) in Y is an x-valent polymer group linked by nitrogen, oxygen, sulfur, or carbon. R can be the same or different, and is an optional substituted monovalent hydrocarbon group. R 1 They can be the same or different, and can be hydrogen atoms or optional substituted monovalent hydrocarbon groups that can be linked to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, or carbonyl groups. R 2 They can be the same or different, and can be hydrogen atoms or optionally substituted monovalent hydrocarbon groups. x is an integer from 1 to 10. a can be the same or different, and can be 0, 1, or 2. b can be the same or different, and is an integer from 1 to 10. (B) 0.1 to 75 parts by weight of at least one thixotropic agent selected from the following: fatty acid amides, polyamide waxes, polyamide wax derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, polyesteramides, polyureas, oxidized polyethylene, and metal soaps. Optional subsequent process steps and subsequent storage of the resulting mixture may be performed. Its features are, The time from the start of the mixing step of components (A) and (B) to the end of the storage of the crosslinkable composition (M) is at least 7 days, and during this period, all process steps are carried out at a temperature below 49°C.

2. The method according to claim 1, characterized in that, The storage is carried out at a temperature of -20 to 45°C.

3. The method according to any one of claims 1 to 2, characterized in that, Component (B) is a polyamide wax or a polyamide wax derivative.

4. The method according to any one of claims 1 to 2, characterized in that, Component (B) is a polyamide wax.

5. The method according to any one of claims 1 to 2, characterized in that, All process steps are carried out at a temperature at least 30°C below the melting point of the component (B) used, wherein if two or more thixotropic agents (B) are used, this specification applies to the thixotropic agent (B) with the highest melting point.

6. The method according to any one of claims 1 to 2, characterized in that, Mix the following components together: (A) 100 parts by weight of the compound of formula (I), (B) 0.1 to 50 parts by weight of a thixotropic agent, (C) 0.1 to 25 parts by weight of an organosilicon compound containing a (II) unit, D e Si(OR 4 ) d R 3 c O (4-c-d-e) / 2 (II) in R 3 They can be the same or different, and are optionally substituted monovalent organic groups bonded to nitrogen-free SiC. R 4 They can be the same or different, and can be hydrogen atoms or optionally substituted hydrocarbon groups. D can be the same or different, and is a monovalent group with SiC bonds having at least one nitrogen atom not attached to a carbonyl group (C=O). c can be 0, 1, 2, or 3. d is 0, 1, 2 or 3, and e is 0, 1, 2, 3, or 4. The conditions are that the sum of c + d + e is less than or equal to 4 and each molecule contains at least one group D. Optional (D) non-reactive plasticizer, Optional (E) packing material, Optional (F) silicone resin, The (G) catalyst is optionally present. Optional (H) adhesion promoter, Optional (I) water scavenger, Optional additives (J) are selected from antioxidants, UV stabilizers, fungicides, defoamers, wetting agents, or pigments and Optional additional materials (K) may be selected from tetraalkoxysilanes and / or their partial condensates, reactive plasticizers, rheology modifiers different from component (B), flame retardants, or organic solvents. The resulting mixture was then stored for at least 7 days, with all process steps carried out at temperatures below 49°C.

7. The method according to any one of claims 1 to 2, characterized in that, Filling should be performed at a time when the viscosity of the composition at 100% deformation, measured according to DIN 54458, at 25°C, is at least 1.5 times lower than the viscosity of the same composition (M) measured under the same conditions after storage at 23°C for 21 days following its preparation.

8. The method according to any one of claims 1 to 2, characterized in that, Filling is performed at such a time that the viscosity of the composition at 0.1% deformation, measured according to DIN54458 at 25°C, is at least twice as low as the viscosity of the same composition (M) measured under the same conditions after storage at 23°C for 21 days following its preparation.