Silane-terminated polymers with improved color stability

Abstract

The invention relates to silane-terminated polymers having a polyoxyalkylene-based backbone, which exhibit improved color stability when they are transported, e.g. shipped, and / or stored for a period of several weeks or months prior to compounding into an adhesive or sealant or a coating.

Description

[0001] Wal2430S / Mk

[0002] Silane-terminated polymers with improved color stability

[0003] The invention relates to silane-terminated polymers with a polyoxylalkylene-based backbone that exhibit improved color stability when transported, e.g. by shipping, and / or stored for a period of several weeks or months prior to compounding into an adhesive, sealant, or coating.

[0004] Moisture-crosslinkable preparations are well known. They are widely used as adhesives and sealants, as well as in coatings. Silyl-functionalized polyoxyalkylenes or silyl-functionalized polyurethanes represent an important moisture-reactive binder for such products. Among these, those with terminal alkoxysilyl groups are preferred, as the breakdown products are non-corrosive and toxicologically harmless in the low concentrations released.

[0005] Corresponding alkoxysilane-terminated polyoxyalkylenes and polyurethanes have long been state of the art and are commercially available, for example, under the trade names GENIOSIL® STP-E (Wacker Chemie AG), MS-Polymer® or SAX®-Polymers (Kaneka), DESMOSEAL® (Covestro AG) or SPUR (Momentive).

[0006] The silyl-functionalized polyoxyalkylenes and polyurethanes are prepared using known methods. A common approach involves reacting hydroxyl-terminated polyoxyalkylenes or hydroxyl-terminated polyoxyalkylene-based polyurethanes with isocyanatoalkyl-alkoxysilanes. Another method involves reacting the aforementioned polyoxylalkylenes with di- or polyisocyanates, the latter being used in excess, such that in Wal2430S / Mk

[0007] 2

[0008] In this first reaction step, isocyanate-functional polyoxylalkylene-based polyurethanes are produced. These are then reacted in a second reaction step with alkoxysilanes possessing an alkyl-bound isocyanate-reactive group, in particular with N-substituted aminoalkylalkoxysilanes. A third method involves the reaction of an alkenyl-terminated, especially allyl-terminated, polyoxylalkylene with a silane that, in addition to hydrolyzable groups, possesses a silicon-bound hydrogen atom. In this reaction, also called hydrosilylation, the H-Si function adds to the double bond, forming a Si-C bond.

[0009] The reaction of hydroxyl-functional polymers with isocyanates such as the aforementioned isocyanatoalkylalkoxysilanes, di- or polyisocyanates is preferably carried out in the presence of catalysts, since only in this way can sufficiently high reaction rates be achieved in the corresponding reaction step for the economical production of the alkoxysilane-terminated polymers. Numerous compounds are known as silane condensation catalysts, such as dialkyltin(IV) compounds, like dibutyltin dilaurate or dioctyltin dilaurate, bismuth(III) compounds, like bismuth(III) decanoate or bismuth(III) ethylhexanoate, as well as various metal complex compounds (chelates and carboxylates), e.g., of titanium, zirconium, amines and their salts, and other known acidic and basic catalysts.

[0010] The reaction of alkenyl-functional polymers with H-Si functions is also preferably carried out in the presence of catalysts, preferably platinum-containing complex compounds. Wal2430S / Mk

[0011] 3

[0012] Furthermore, catalysts are also used in the production of polyoxyalkylene precursors. These can be basic alkali metal salts, but are usually so-called DMC catalysts.

[0013] A disadvantage of using all of the above catalysts, whether they were used to produce the silane-terminated end products or the polyoxyalkylene intermediates, is the fact that they usually remain completely or at least partially in the end product, the silane-functional polymer, which can have a negative impact on its storage stability.

[0014] All of the above-mentioned reactions for the synthesis of silane-terminated polymers with a polyoxylalkylene-based backbone are carried out at elevated temperatures to ensure a sufficiently high reaction rate and the most complete conversion possible. Typical reaction temperatures are in the range of 70–100 °C.

[0015] For many applications, silane-terminated polymers with a polyoxylalkylene-based backbone are compounded into colorless and usually transparent or at least translucent end products. Colorless and transparent adhesives have the advantage that any adhesive residue that might be squeezed out of the adhesive joint when the substrates to be bonded are virtually invisible. Colorless and translucent formulations are also desired by end customers for many coating applications.

[0016] For the production of colorless end products, especially for colorless and transparent or translucent end products, it is of course necessary that the individual components Wal2430S / Mk

[0017] 4

[0018] Including the silane-terminated polymers, they must also be colorless and transparent, or at least translucent. This is especially important if the corresponding end products are sold in transparent containers, such as cartridges, for marketing reasons. Since light has to travel a relatively long distance through such a transparent container, even the smallest discolorations are immediately noticeable.

[0019] Unfortunately, polyoxylalkylenes have a general problem with storage stability, as they form peroxides in the presence of traces of air, which can undergo numerous subsequent reactions. Silane-terminated polymers with a polyoxylalkylene-based backbone are no exception; on the contrary, they are particularly susceptible because, as already mentioned, they contain potentially critical traces of catalyst and have already been exposed to elevated temperatures during their production, which can result in "pre-damage" to individual structural elements. Therefore, during prolonged storage and / or transport, silane-terminated polymers with a polyoxylalkylene-based backbone tend to discolor, especially yellowing.

[0020] It is generally known that polyoxylalkylenes can be stabilized by adding stabilizers such as antioxidants or HALS (Hindered Amine Light Stabilizer). However, a disadvantage of this method is that while it can prevent or at least slow down the degradation of the polyoxylalkylene backbone, so that the mechanical properties of the final product remain largely unchanged, the aforementioned discolorations usually still occur. Wal2430S / Mk

[0021] 5

[0022] The object of the invention was therefore the development of products, i.e., silane-terminated polymers with a polyoxyalkylene-based backbone, which exhibit significantly reduced discoloration even during prolonged storage and / or transport.

[0023] The subject of the present invention is a formulation (M) containing

[0024] at least 90 wt. - [%] of at least one silane-terminated polymer (A) of formula ( I ), based on the total weight of the formulation (M),

[0025] YX- [ (CR b-SlRa (OR 2 ) 3-a ] x ( I ),

[0026] where

[0027] Y means an x-valent polymer residue consisting of at least 90 wt. - [%] polyoxyalkylene units,

[0028] X oxygen or a divalent bonding group selected from non- or N-substituted urethane or urea group means,

[0029] R can be the same or different and represents a monovalent, substituted or unsubstituted, SiC-bonded hydrocarbon residue,

[0030] R 1may be the same or different and represent a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon residue which may be bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or a carbonyl group,

[0031] R 2 can be the same or different and represent a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon residue,

[0032] x is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2, Wal2430S / Mk

[0033] a can be the same or different and 0, 1 or 2, preferably 0 or 1, is and

[0034] 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

[0035] 10 to 1200 ppm of at least one stabilizer (B) according to formula ( II ), based on the total weight of the formulation (M),

[0036]

[0037] where

[0038] R 3 can be the same or different and represents an n-valent, optionally substituted hydrocarbon residue with 1 to 40 carbon atoms, which can be branched or unbranched and can also have cyclic units, wherein the carbon chains can be interrupted by oxygen atoms, ester, amide, urethane or urea units, and n can be the same or different and is 1 to 10, preferably 1 to 4.

[0039] Preferably, the formulation (M) contains at least 95% wt. - [%], particularly preferably at least 97% wt. - [%] silane-terminated polymer (A) of formula (I), in each case based on the total weight of the formulation (M).

[0040] In particular, formulation (M) is preferred to contain at least 99% by weight of the formulation Wal2430S / Mk.

[0041] (M) from the components (A) of formula (I) and (B) of formula (II) •

[0042] Preferably, the formulation (M) contains, in addition to components (A) of formula (I) and (B) of formula (II), 1 to 5000 ppm, preferably 5 to 1000 ppm, and particularly preferably 10 to 500 ppm, each based on the total weight of the formulation (M), at least one catalyst (K) or (K') used to prepare component (A). The formulation (M) also preferably contains 1 to 5000 ppm, preferably 5 to 1000 ppm, and particularly preferably 10 to 500 ppm, each based on the total weight of the formulation (M), of at least one further catalyst (K'') or products of its deactivation, wherein the catalyst (K'') was used to prepare the polyoxyalkylene segments contained in the polymers (A).

[0043] In the present invention, it was completely surprising that only the use of the very specific stabilizers (B) according to the invention, in the quantities specified according to the invention, not only leads to the protection of the polymers (A) against oxidative degradation and thus to the protection against deterioration of the mechanical properties of the cured products produced from the polymers (A) thus stored, but also significantly improves the color stability of the formulation (M) according to the invention. It was particularly surprising that only the very small quantities of stabilizers according to the invention lead to particularly good color stability, whereas the color stability deteriorates when larger quantities of stabilizers are used, although a person skilled in the art would expect precisely the opposite: even better stabilization. Wal2430S / Mk

[0044] 8

[0045] Component (A)

[0046] In a preferred embodiment of the invention, the silane-terminated polymers (A) are polymers (Aa) of formula (aa)

[0047] Y- [ZC (=0) -NR 4 - (CR b-SiRa (OR 2 ) 3-a ] x ( la),

[0048] where

[0049] R 4 can be the same or different and hydrogen atom, a monovalent, substituted or unsubstituted hydrocarbon residue, a group - (CRM b-SiR a (OR 2 ) 3-a or a group -CH (COOR' ) -CH2-COOR' means and

[0050] Z can be the same or different and NH means an oxygen atom and

[0051] R' can be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon residue and

[0052] Y, X, R, R 1 , R 2 , x, a, and b have the meaning mentioned above in formula ( I ).

[0053] Examples of R groups are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl groups; hexyl groups, such as n-hexyl; heptyl groups, such as n-heptyl; octyl groups, such as n-octyl, isooctyl, and 2,2,4-trimethylpentyl; nonyl groups, such as n-nonyl; decyl groups, such as n-decyl; dodecyl groups, such as n-dodecyl; and octadecyl groups, such as n-octadecyl. 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, anthryl, and phenanthryl; alkaryl groups, such as o-, Wal2430S / Mk

[0054] 9

[0055] m-, p-tolyl groups; xylyl groups and ethylphenyl groups; and aralkyl groups, such as the benzyl group, the a- and the β-phenylethyl group.

[0056] Examples of substituted residues R are haloalkyl residues, such as the 3,3,3-trifluoro-n-propyl residue, the 2,2,2,2,2',2',2'-hexafluoroisopropyl residue and the heptafluoroisopropyl residue, and haloaryl residues, such as the o-, m- and p-chlorophenyl residue.

[0057] Preferably, the residue R is a monovalent hydrocarbon residue with 1 to 6 carbon atoms, optionally substituted with halogen atoms, particularly preferably an alkyl residue with 1 or 2 carbon atoms, especially the methyl residue.

[0058] Examples of residues R 1 are hydrogen atoms, the residues specified for R, and, if necessary, substituted hydrocarbon residues bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group.

[0059] Preferably, the remainder is R. 1around hydrogen atoms or hydrocarbon residues with 1 to 20 carbon atoms, especially around hydrogen atoms.

[0060] Examples of remainder R 2 are hydrogen atoms or the examples given for residue R.

[0061] Preferably, the remainder is R. 2 Alkyl groups with 1 to 10 carbon atoms substituted with hydrogen atoms or optionally with halogen atoms, particularly preferably with alkyl groups with 1 to 4 carbon atoms, especially with the methyl or ethyl group. Wal2430S / Mk

[0062] 10

[0063] Examples of residues R 4 are these hydrogen atoms, a

[0064] Group -CH (COOR' ) -CJR-COOR' or the residues specified for R, in particular cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl, the various steroidal isomers of the pentyl, hexyl or heptyl residue and the phenyl residue.

[0065] With the remainder R 4preferably a hydrogen atom, a group -CH (COOR' ) -CH2-COOR', a group

[0066] - (CR b-SiRa (OR 2 ) 3-a with R, R', R 1 , R 2 , a and b equal to one of the meanings given in formula ( I ) or an optionally substituted hydrocarbon residue with 1 to 20 carbon atoms, preferably around a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms or around an optionally halogen-substituted aryl group with 6 to 20 carbon atoms, particularly preferably around a linear, branched or cyclic alkyl group with 1 to 8 carbon atoms.

[0067] The R' groups are preferably alkyl groups with 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl groups.

[0068] If the variable Z represents an oxygen atom, then R 4 preferably for a hydrogen atom.

[0069] If the variable Z represents an NH group, then R represents 4 preferably one of the above meanings other than hydrogen atom.

[0070] The residues Y preferably have number-average molar masses M n of at least 200 g / mol, particularly preferably of at least 500 g / mol, and especially of at least 2000 g / mol. The residues Y preferably have number-average molar masses M n of at most Wal2430S / Mk

[0071] 11

[0072] 40,000 g / mol, in particular of at most 25,000 g / mol, in particular of at most 20,000 g / mol.

[0073] The number-average molar mass M n Within the scope of the present invention, size exclusion chromatography (SEC) is used to measure the size of a polystyrene standard in THF at 60°C and a flow rate of [missing information].

[0074] 1.2 ml / min and detection with RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA with an injection volume of 100 pl.

[0075] The polymer residues Y are preferably polyester, polyoxyalkylene, or polyurethane residues, wherein the polyester and / or polyurethane residues consist of at least 90 wt. [%] polyoxyalkylene units. Polyurethane or polyoxyalkylene residues are particularly preferred, especially polyoxyalkylene residues, with polyoxypropylene residues being even more preferred, provided that their number-average molecular mass is 200 to 40,000 g / mol, particularly preferably 2,000 to 25,000 g / mol.

[0076] Component (B)

[0077] The stabilizers (B) are preferably compounds (Ba) according to formula (Ila)

[0078]

[0079] where Wal2430S / Mk

[0080] 12

[0081] R 5 can be the same or different and represents an n-valent substituted or unsubstituted hydrocarbon residue with 1 to 37 carbon atoms, which can be branched or unbranched and may also contain cyclic units,

[0082] W represents an oxygen atom or an NH group, and n can be the same or different and is 1 to 10, preferably 1 to 4, and particularly preferably 1.

[0083] Preferably, the remainder R 5 a branched or unbranched hydrocarbon residue with 1 to 30, particularly preferably with 4 to 20 carbon atoms. Preferably the residue is R 5 not substituted.

[0084] Preferably, the remainder W is an oxygen atom.

[0085] Examples of commercially available stabilizers (B) or (Ba) are Irganox® 1135, Irganox® 1010, Irganox® 1098 or Irganox® 1076 from BASF (D, Ludwigshafen).

[0086] Preferably the concentration of component (B) or preferably (Ba) is 20 to 1000 ppm, particularly preferably 50 to 500 ppm and especially preferably 50 to 250 ppm, in each case based on the total weight of the formulation (M).

[0087] A further object of the invention is a method for producing the formulation (M) according to the invention, characterized in that the starting materials for the production of the compounds (A) or preferably (Aa) are reacted in the presence of 10 to 1200 ppm of at least one component (B) or (Ba), respectively, or 10 to 1200 ppm of at least one component (B) or (Ba) are added after its reaction. Preferably, the production is carried out using Wal2430S / Mk

[0088] 13

[0089] of the compounds (A) or preferably (Aa) in the presence of at least one component (B) or (Ba).

[0090] Preferably, the amounts of stabilizers (B) or (Ba), wherein (Ba) is preferably used, are 20 to 1000 ppm, particularly preferably 50 to 500 ppm and particularly preferably 50 to 250 ppm, each based on the total weight of the formulation (M).

[0091] If the production of compound (A), or preferably (Aa), is a multi-stage process, component (B) may be present in all process stages or only in the last process stage. Preferably, however, it is present in all process stages.

[0092] The process according to the invention is preferably carried out at temperatures between 20°C and 180°C, particularly preferably between 40°C and 150°C, and especially between 50°C and 120°C. If the process according to the invention is carried out in several reaction steps, each individual step is preferably carried out in the aforementioned preferred temperature ranges.

[0093] The method according to the invention is preferably carried out at a pressure of 100 to 2000 hPa, particularly preferably at 900 to 1100 hPa.

[0094] The process according to the invention is preferably carried out in a protective gas atmosphere, preferably argon or nitrogen.

[0095] The process according to the invention can be carried out continuously, e.g. in one or more Wal2430S / Mk tubular reactors.

[0096] 14

[0097] or loop reactors, in cascades of several stirred reactors connected in series, or even just in a single stirred reactor to which new reactants are continuously supplied while reaction mixture is continuously withdrawn. Combinations of several reactor types are also conceivable.

[0098] Likewise, the process according to the invention can also be carried out discontinuously, e.g. in a stirred reactor in which all reactants are added either simultaneously or in quick succession or in several process steps that are clearly separated from each other in time.

[0099] A preferred subject matter of the invention is a process (process variant 1) for the production of silane-terminated polymers (Ab) of formula (Ib)

[0100] Y- [NH-C (=0) -NR 4 - (CR b-SiRa (OR 2 )3-a] ( Ib),

[0101] by implementing

[0102] (al) at least one hydroxyl-functional polymer consisting of more than 90 wt. - [%] polyoxylalkylene units, (bl) at least one di- and / or polyisocyanate and

[0103] (cl ) at least one aminosilane of the formula

[0104] HNR 4 - (CR b-SiRa (OR 2 ) 3-a ( III )

[0105] as well as, where applicable, other components different from (al), (bl), and (cl).

[0106] where Y, R, R 1 , R 2 , R 4 , a, b and x have the meanings given in formula ( I ) and ( aa) respectively. Wal2430S / Mk

[0107] 15

[0108] Preferably, in the production of the silane-terminated polymers of formula (Ib) no further components are used other than the components (al) , (bl) and (cl) and a catalyst (K).

[0109] In the process variant 1 according to the invention, the proportions of the components (al ), (bl ) and (cl ) are preferably selected such that per mole of isocyanate groups from component (bl ), 0.5 to 1.5 mol, particularly preferably 0.8 to 1.3 mol, in particular 0.95 to 1.2 mol, isocyanate-reactive groups from the components (al ) and (cl ) are used.

[0110] The polyols (al ) used according to the invention are preferably branched or unbranched polyoxyl alkyl polyols, particularly preferably polyoxypropylenes, especially unbranched polyoxypropylenes or polyoxypropylenes with a branching point.

[0111] The polyols (al) used according to the invention have an average molar mass M n Preferably from 200 to 30,000 g / mol, particularly preferably from 600 to 24,000 g / mol, and especially from 900 to 20,000 g / mol. These are preferably unbranched.

[0112] Preferably, the polyols (al ) used according to the invention have a viscosity of 10 to 1,000,000 mPas at 23°C, particularly preferably of 1,000 to 300,000 mPas.

[0113] Within the scope of the present invention, the viscosity is determined after tempering to 23°C using a DV 3 P rotational viscometer from A. Paar (Brookfield Systems), with spindle 5 at 2.5 rpm according to ISO 2555. Wal2430S / Mk

[0114] 16

[0115] The polyols ( al ) used according to the invention are commercially available products or can be produced according to methods commonly used in polymer chemistry.

[0116] The component (al) can also be a mixture of different polyols, in particular mixtures of unbranched and simply branched polyols. Preferably, however, only unbranched polyols are used.

[0117] The di- and / or polyisocyanates (bl) used according to the invention are preferably common diisocyanates or polyisocyanates, such as diisocyanatodiphenylmethane (MDI), both in the form of crude or technical grade MDI and in the form of pure 4,4' or 2,4' isomers or mixtures thereof, tolylene diisocyanate (TDI) in the form of its various regioisomers, in particular 2,4- and 2,6-TDI, as well as mixtures of these regioisomers, diisocyanatonaphthalene (NDI), isophorone diisocyanate (IPDI), or hexamethylene diisocyanate (HDI). Examples of polyisocyanates are polymeric MDI (p-MDI), triphenylmethane triisocyanate, or trimerisates (biurethe or isocyanurates) of the above-mentioned diisocyanates. Mixtures of different di- and / or polyisocyanates can also be used.

[0118] The isocyanates (bl) used according to the invention are commercially available products or can be produced using methods commonly used in chemistry.

[0119] The component ( cl) used according to the invention is preferably a

[0120] HN[(CH2)3-Si(OCH3)3]2, HN[(CH2)3-Si(OC2H5)3]2,

[0121] HN[(CH2)3-Si(OCH3)2CH3]2, HN[(CH2)3-Si(OC2H5)2CH3]2,

[0122] HN [ ( CH2) -S i ( OCH3) 3 ] 2, HN [ ( CH2) -S i ( OC2H5 ) 3 ] 2, Wal2430S / Mk

[0123] 17

[0124] HN[(CH2)-Si(OCH3)2CH3]2, HN[(CH2)-Si(OC2H5)2CH3]2,

[0125] cyclo-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, cyclo-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, Phenyl-NH (CH2) 3-Si (OCH3) 3, Phenyl-NH (CH2) 3-Si (OC2H5) 3,

[0126] Phenyl-NH(CH2)3-Si(OCH3)2CH3, Phenyl-NH(CH2)3-Si(OC2H5)2CH3, Phenyl-NH(CH2)-Si(OCH3)3, Phenyl-NH(CH2)-Si(OC2H5)3,

[0127] Phenyl-NH(CH2)-Si(OCH3)2CH3, Phenyl-NH(CH2)-Si(OC2H5)2CH3, Alkyl-NH(CH2)3-Si(OCH3)3, Alkyl-NH(CH2)3-Si(OC2H5)3,

[0128] Alkyl-NH (CH2) 3-Si (OCH3) 2CH3, Alkyl-NH (CH2) 3-Si (OC2H5) 2CH3, Alkyl-NH (CH2) -Si (OCH3) 3, Alkyl-NH (CH2) -Si (OC2H5) 3,

[0129] Alkyl-NH (CH2) -Si (OCH3) 2CH3 oder Alkyl-NH (CH2) -Si (OC2H5) 2CH3, besonders besprecht um cyclo-C6H 11 NH(CH2)3-Si(OC2H5)3,

[0130] cyclo-C6H 11 NH(CH2)3-Si(OCH3)2CH3, cyclo-C6H 11 NH(CH2)3-Si(OC2H5)2CH3, cyclo-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, Phenyl-NH(CH2)3-Si(OCH3)3, Phenyl-NH(CH2)3-Si(OC2H5)3,

[0131] Phenyl-NH (CH2) 3-Si (OCH3) 2CH3, Phenyl-NH (CH2) 3-Si (OC2H5) 2CH3, Phenyl-NH (CH2) -Si (OCH3) 3, Phenyl-NH (CH2) -Si (OC2H5) 3,

[0132] Phenyl-NH (CH2) -Si (OCH3) 2CH3, Phenyl-NH (CH2) -Si (OC2H5) 2CH3, Alkyl-NH (CH2) 3-Si (OCH3) 3, Alkyl-NH (CH2) 3-Si (OC2H5) 3,

[0133] Alkyl-NH (CH2) 3-Si (OCH3) 2CH3, Alkyl-NH (CH2) 3-Si (OC2H5) 2CH3, Alkyl-NH (CH2) -Si (OCH3) 3, Alkyl-NH (CH2) -Si (OC2H5) 3,

[0134] Alkyl-NH (CH2) -Si (OCH3) 2CH3 or Alkyl-NH (CH2) -Si (OC2H5) 2CH3, wherein "alkyl" preferably represents ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and the various steroidal isomers of the pentyl, hexyl, heptyl or octyl residue.

[0135] According to the inventive process variant 1, the silane-terminated polyurethanes of formula (Ib) can be produced by a simultaneous reaction of all components (al), (bl), and (cl). However, a multi-stage Wal2430S / Mk is often used.

[0136] 18

[0137] A preferred process involves first reacting the hydroxy-functional polymer (al) with an excess of a di- or polyisocyanate (bl) before reacting with the silanes (cl). This minimizes side reactions in which the hydroxy-functional polymer (al) reacts with the silyl groups of the silane (cl) and substitutes a previously Si-bound alkoxy group, forming a polymer-O-Si bond.

[0138] The multi-stage process described above can also be carried out continuously or discontinuously. The former takes place in several reactors connected in series, in which the different reaction steps are carried out, whereas in the discontinuous process, the stepwise reaction is achieved by a correspondingly controlled, successive addition of the reactants.

[0139] Component (B), or preferably (Ba), is preferably present in all process steps. It is particularly preferably added together with the polyoxylalkylene (al₂) or directly before or after the addition of the polyoxylalkylene (al₂) to the reaction mixture. It is especially preferably added dissolved in the polyoxylalkylene (al₂) to the reaction mixture.

[0140] Another preferred subject matter of the invention is a process (process variant 2) for the production of silane-terminated polymers (Ac)

[0141] Y- [OC (=0) -NH- (CR b-SiRa (OR 2 )3-a] ( Ic),

[0142] by implementing Wal2430S / Mk

[0143] 19

[0144] ( a2 ) at least one x-valent polymer consisting of more than 90 wt. - [ % ] polyoxylalkylene units

[0145] (b2) at least one di- and / or polyisocyanate and

[0146] (c2) at least one isocyanatosilane of the formula

[0147] OCN- (CR b-SiRa (OR 2 ) 3-a ( IV)

[0148] as well as, if applicable, other components different from ( a2 ), (b2 ) and ( c2 ),

[0149] where Y, R, R 1 , R 2 , a, b and x have the meaning given in formula (I).

[0150] Preferably, in the production of the silane-terminated polymers of formula (Ic) no further components are used other than the components (a2), (b2) and (c2) and a catalyst (K).

[0151] In the process variant 2 according to the invention, the proportions of the components (a2), (b2) and (c2) are preferably chosen such that per mol I isocyanate groups from component (b2) and (c2), 0.5 to 1.5 mol, particularly preferably 0.8 to 1.3 mol, in particular 0.85 to 1.2 mol, hydroxyl groups from the components (a2) are used.

[0152] The polyols (a2) preferably used according to the invention are the same polyols that have already been described above as preferred or particularly preferred polyols (al).

[0153] The di- and / or polyisocyanates (b2) preferably used according to the invention are the same di- and / or polyisocyanates already mentioned above as preferred or particularly Wal2430S / Mk

[0154] 20

[0155] preferred di- and / or polyisocyanates (bl ) were described.

[0156] Preferably, component (c2) is

[0157] OCN (CH2) 3-Si (OCH3) 3, OCN (CH2) 3-Si (OC2H5) 3, OCN (CH2)3-Si (OCH3)2CH3, OCN (CH2) 3-Si (OC2H5)2CH3, OCN (CH2) -Si (OCH3) 3, OCN (CH2) -Si (OC2H5) 3, OCN (CH2) -Si (OCH3)2CH3 or OCN (CH2) -Si (OC2H5)2CH3, wherein OCN (CH2)3-Si (OCH3)3 or OCN (CH2) -Si (OCH3)2CH3 are particularly preferred.

[0158] According to the inventive process variant 2, the silane-terminated polyurethanes of formula (Ic) can be produced by a simultaneous reaction of all components (a2), (b2), and (c2). However, a multi-stage process is often preferred here as well, in which the hydroxyl-functional polymer (a2) is first reacted with di- or polyisocyanate (b2) before the reaction with the silane (c2) takes place.

[0159] The crucial difference to the production of silane-terminated polyurethanes according to process variant 1 described above is that the isocyanate component is used in a deficit rather than an excess in the first reaction step. This results in a hydroxyl-terminated polyurethane, which is then reacted with the isocyanate-functional silane (c2) in a subsequent step.

[0160] This procedure, like the one already described in procedure variant 1, can also be carried out continuously or discontinuously.

[0161] In a particularly preferred embodiment of process variant 2, a hydroxyl-functional polyurethane is produced by a reaction of components (a2 ) and (b2 ), which is then combined with an excess of an isocyanate-functional silane Wal2430S / Mk

[0162] 21

[0163] (c2 ) is reacted. In this reaction, preferably 1.01 to 2.00 mol, particularly preferably 1.05 to 1.40 mol, and especially 1.05 to 1.25 mol, of isocyanate-functional silanes (c2 ) are used per mol of hydroxyl groups contained in the polyurethane intermediate. This achieves not only rapid but also largely complete termination of all previously hydroxyl-functional chain ends.

[0164] Since unreacted isocyanate-functional silanes (c2) can remain in the reaction mixture during this procedure, they are preferably quenched after completion of the polymer synthesis by adding an isocyanate-reactive compound. In principle, this isocyanate-reactive compound can be any compound that possesses at least one group reactive towards isocyanates. Amines or alcohols are preferred, particularly alcohols, especially low-molecular-weight alcohols such as methanol, ethanol, propanol, isopropanol, butanol, or isobutanol, or short-chain polyoxylalkylenes, preferably polyoxyethylenes or polyoxypropylenes, which have only one chain end terminated with a hydroxyl group and one chain end terminated with an alkyl group. These short-chain polyoxylalkylenes preferably have a molar mass of 300–2000 g / mol.

[0165] In a batch process, quenching can be carried out by simply adding the isocyanate-reactive compound after completion of the synthesis of the polymers of formula (Ib). If the process is carried out continuously, the quenching step is also preferably carried out continuously by continuously adding the isocyanate-reactive compound to the Wal2430S / Mk after the preparation of the silane-terminated polymers.

[0166] 22

[0167] The reaction mixture is mixed in and, if necessary, reacted in a separate reactor.

[0168] Just like the reaction according to the invention itself, the quenching step is preferably carried out at temperatures between 20°C and 180°C, particularly preferably between 40°C and 150°C, and especially between 50°C and 120°C.

[0169] In this variant of the process, component (B) or preferably (Ba) is also preferably present in all process steps. It is particularly preferably added together with the polyoxylalkylene (a2) or directly before or after the addition of the polyoxylalkylene (a2) to the reaction mixture. It is especially preferably added dissolved in the polyoxylalkylene (a2) to the reaction mixture.

[0170] Another preferred subject matter of the invention is a process (process variant 3) for the production of silane-terminated polymers (Ad) of formula (Id)

[0171] Y-[OC(=O)-NH-(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (Id),

[0172] by implementing

[0173] (a3) an x-valent polymer consisting of at least 90 wt. - [%] polyoxylalkylene units, and

[0174] (c3) at least one isocyanatosilane of formula ( IV)

[0175] OCN-(CR 1 2) b -SiR a (OR 2 ) 3-a (IV),

[0176] where Y, R, R 1 , R 2 , a, b and x have the meaning given in formula (I). Wal2430S / Mk

[0177] 23

[0178] Preferably, in the production of the silane-terminated polymers of formula (Id) no further components are used other than components (a3) ​​and (c3) and a catalyst (K).

[0179] In the process variant 3 according to the invention, the proportions of components (a3) ​​and (c3) are preferably chosen such that 0.5 to 2.0 mol, particularly preferably 0.8 to 1.4 mol, in particular 0.95 to 1.25 mol, isocyanate groups from component (c3) are used per mol of hydroxyl groups from component (a3).

[0180] The polyols (a3) ​​preferably used according to the invention are the same polyols that have already been described above as preferred or particularly preferred polyols (al ).

[0181] The isocyanate functional silanes (c3) preferably used according to the invention are the same silanes that have already been described above as preferred or particularly preferred silanes (c2).

[0182] In a particularly preferred embodiment, the hydroxyl-functional polymer (a3) ​​is reacted with an excess of isocyanate-functional silane (c3). That is, the proportions of components (a3) ​​and (c3) are preferably chosen such that for each mole of hydroxyl groups from component (a3), 1.01 to 2.00 mol, particularly preferably 1.05 to 1.40 mol, and especially 1.05 to 1.25 mol, of isocyanate groups from component (c3) are used. In this way, not only rapid but also largely complete termination of all chain ends is achieved. Wal2430S / Mk

[0183] 24

[0184] Since unreacted isocyanate-functional silanes (c3) may remain in the reaction mixture during such a procedure, these are preferably quenched after completion of the polymer synthesis by adding an isocyanate-reactive compound. The quenching step is preferably carried out in the same way as already described in process variant 2.

[0185] The inventive method variant 3 can also be carried out continuously or discontinuously.

[0186] In this variant of the process, component (B), or preferably (Ba), is also preferably present in all process steps. It is particularly preferably added together with the polyoxylalkylene (a3) ​​or directly before or after the addition of the polyoxylalkylene (a3) ​​to the reaction mixture. It is especially preferably added dissolved in the polyoxylalkylene (a3) ​​to the reaction mixture.

[0187] Another preferred subject matter of the invention is a process (process variant 4) for the production of silane-terminated polymers (Ae) of formula ( le)

[0188] Y[-O-(CR 1 2)3-SiR a (OR 2 ) 3-a ] x (I),

[0189] by implementing

[0190] (a4 ) a polymer of formula (V), and

[0191] Y[-O-(CR 1 2)-CR 1 =CR 1 2] x (V)

[0192] (c4 ) at least one silane of formula (VI ) Wal2430S / Mk

[0193] 25

[0194] H-SiRa (OR 2 ) 3-a (VI )

[0195] as well as, if applicable, other components different from (a4) and (c4),

[0196] where Y, R, R 1 , R 2 , a and x have the meaning given in formula ( I ).

[0197] Preferably, in the production of the silane-terminated polymers of formula ( le) no further components are used except for the components (a4 ) and (c4 ) and a catalyst (K ' ).

[0198] The inventive method variant 4 can also be carried out continuously or discontinuously.

[0199] In this variant of the process, component (B) or preferably (Ba) is also preferably present in all process steps. It is particularly preferably added together with the polyoxylalkylene (a4) or directly before or after the addition of the polyoxylalkylene (a4) to the reaction mixture. It is particularly preferably added dissolved in the polyoxylalkylene (a4) to the reaction mixture.

[0200] In process variants 1-3, all catalysts that accelerate reactions between isocyanate groups and hydroxyl groups can be used as catalysts (K).

[0201] Preferred examples of catalysts (K) are tin compounds such as dialkyltin (IV) compounds, such as dibutyltin dilaurate or dioctyltin dilaurate, bismuth (III) compounds, such as bismuth (III) decanoate or bismuth (III) ethylhexanoate, as well as various metal complex compounds (chelates and carboxylates), Wal2430S / Mk

[0202] 26

[0203] e.g. titanium, zirconium, amines and their salts and other known acidic and basic catalysts.

[0204] Particularly preferred examples of catalysts (K) are bismuth-containing catalysts such as bismuth carboxylates like bismuth (2-ethylhexanoate), bismuth neodecanoate or bismuth tetramethylhep-tanedionate. Catalysts containing other metals besides bismuth, especially bismuth-zinc mixed catalysts, are particularly preferred examples of catalysts (K). Examples of commercially available catalysts (K) include Borchi® Kat 22, Borchi® Kat VP 0243, Borchi® Kat VP 0244 or OMG 315 (all OMG-Borchers), TIBKAT® 716 from TIB Chemicals AG, Bi-Neodecanoate from Chemos or American Elements, Reaxis MSA 70 or Reaxis C 719 from Reaxis, BICAT® catalysts (The Shepherd Chemical Company, USA) and K-Kat® K-348 (KING INDUSTRIES, INC., USA).

[0205] In particular, the catalysts (K) are preferably carboxylates of bismuth, e.g. bismuth (2-ethylhexanoate), bismuth neodecanoate or mixtures thereof.

[0206] In process variant 4, all catalysts that accelerate reactions involving Si-H functions and vinyl groups can be used as catalysts (K ' ).

[0207] Preferred examples of catalysts (K ' ) are platinum complexes.

[0208] The formulations (M) according to the invention have the advantage that they are extremely stable during storage under exclusion of moisture and exhibit very high color stability. Wal2430S / Mk

[0209] 27

[0210] The formulations (M) according to the invention also have the advantage that they can be produced quickly and easily, using readily available raw materials as starting materials.

[0211] Another advantage of the formulations (M) according to the invention is that they can be used directly in further applications, e.g. in the production of crosslinkable masses.

[0212] The formulations (M) according to the invention can be used wherever silane-terminated polymers have previously been used.

[0213] A further aspect of the present invention is the use of the formulation (M) according to the invention in crosslinkable materials, in particular room-temperature curable adhesives and sealants, as well as coatings. The production of silane-crosslinking coatings, adhesives, and sealants from corresponding polymers has already been described extensively in the literature, e.g., in EP1535940 (corresponding to US2005119436), EP2785755 (corresponding to US2014311674), EP2744842 (corresponding to US2014155545), or EP2561024 (corresponding to US2013029037).The moisture-curing formulations based on silane-terminated polymers described in these documents, the additional ingredients used therein, and the processes described therein for the production of corresponding formulations are to be considered part of the disclosure content of this description, as are the applications described therein for the finished coatings, adhesives and sealants.

[0214] The process according to the invention has the advantage of being quick and easy to carry out, using readily available raw materials as starting materials. Wal2430S / Mk

[0215] 28

[0216] Another advantage of the process according to the invention is that, depending on the availability of the equipment, it can be carried out in many different ways, e.g. as a discontinuous batch process in simple stirred tanks or as a particularly cost-effective continuous process in appropriately suitable plants.

[0217] The examples described below are not to be considered limiting to the present invention. All viscosity values ​​in the examples refer to a temperature of 20°C, unless otherwise stated. Unless otherwise stated, the following examples are carried out at atmospheric pressure, i.e., at approximately 1000 hPa, and room temperature, i.e., at approximately 20°C, or at a temperature that occurs when the reactants mix at room temperature without additional heating or cooling.

[0218] Example aa (not according to the invention)

[0219] In a 1000 ml reaction vessel equipped with stirring, cooling and heating facilities, 500.0 g of a hydroxy-terminated polypropylene glycol with an average molar mass M are reacted. n A polyol containing 12,000 g / mol and no stabilizer was prepared and dried for 2 hours at 80°C and 1 mbar with stirring. A distinct foaming during the first 30-40 minutes of drying indicates the evaporation of trace amounts of moisture from the polyol.

[0220] The vacuum is then broken with argon. The entire subsequent reaction is carried out under an argon protective gas atmosphere.

[0221] To carry out the silane termination, 16.1 g of isocyanatomomethyl Wal2430S / Mk are first added to the dried polyoxylalkylene at 80°C.

[0222] 29

[0223] Methyldimethoxysilane (GENIOSIL® XL 42 from Wacker Chemie AG, Munich, Germany) was added dropwise, followed by 0.075 g of OMG catalyst 315 (a bismuth neadecanoate-containing catalyst from OMG Borchers) using an Eppendorf pipette. This corresponds to a catalyst concentration of 150 ppm based on the total weight of the reaction mixture. Immediately after the catalyst was added, the reaction mixture was heated to 84–85°C. It was then stirred at a temperature of 80°C.

[0224] After 60 min, at unchanged temperature, 15.00 g of a mono-butoxy- and mono-hydroxy-terminated polypropylene glycol with a number-average molar mass M are added. nApproximately 600 g / mol of polyglycol (commercially available from Clariant under the name Polyglycol B01 / 10) was added. The mixture was then stirred for a further 60 minutes at 80 °C. A sample was then taken from the reaction mixture and analyzed by IR for any remaining isocyanatosilane residues. The sample was isocyanate-free. The viscosity, measured according to the method described, was 7700 mPas.

[0225] Example lb (according to the invention)

[0226] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n 0.100 g (200 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0227] Example lc (according to the invention)

[0228] The procedure is the same as in example aa, with the only difference being that the hydroxy-terminated polypropylene glycol Wal2430S / Mk

[0229] 30

[0230] with a mean molar mass M n 0.200 g (400 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0231] Example ld (not according to the invention)

[0232] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n0.400 g (800 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0233] Example le (according to the invention)

[0234] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n 0.500 g (1000 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0235] Example lf (not according to the invention)

[0236] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n of 12,000 g / mol after drying and before the addition of the isocyanatosilane and the catalyst 0.700 g (1400 ppm) 3- (3,5-Di-tert-butyl-4-hydroxy- Wal2430S / Mk

[0237] 31

[0238] phenyl ) -propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added using an Eppendorf pipette.

[0239] Example 2: Investigation of color stability

[0240] 50 g of each of the polymer mixtures obtained in examples aa-f are placed in a 100 ml screw-top vial, which is then carefully sealed airtight. These samples are stored at 60 °C for 8 weeks, with visual inspections after 1 week, 2 weeks, 4 weeks, and at the end of the 8-week storage period. For colorless or only slightly discolored samples—that is, for all samples that cannot be immediately assessed as not color-stable—the Hazen color number is also determined.

[0241] The determination of the Hazen color numbers (APHA) is carried out according to DIN ISO 6271. The results obtained are shown in Table 1:

[0242] Table 1:

[0243] FormulationAdditional Amount Color Number Color Number Color Number Color Number from Irganox® (APHA) (APHA) (APHA) (APHA) Example 1135 after 1 W after 2 W after 4 W after 8 W ala — light gray dark gray dark gray dark gray lb 200 ppm colorless colorless colorless colorless Color Number 16 Color Number 19 Color Number 22 Color Number 22 1c 400 ppm colorless colorless colorless colorless Color Number 23 Color Number 21 Color Number 24 Color Number 28 Id 800 ppm colorless colorless colorless light yellow Color Number 20 Color Number 24 Color Number 29 Color Number 43 le 1000 ppm colorless colorless light yellow light yellow Color Number 23 Color Number 24 Color Number 35 Color Number 46 lf 1400 ppm colorless light yellow yellow yellow Color Number 23 Color Number 38 color number 54 color number 63

[0244]

[0245] Wal2430S / Mk

[0246] 32

[0247] Example 3a (according to the invention)

[0248] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M.n 0.100 g (200 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octadecyl ester (commercially available under the name Irganox® 1076 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0249] Example 3b (not in accordance with the law)

[0250] The procedure is the same as in example aa, with the sole difference that 0.100 g (200 ppm) of a HALS stabilizer (bis-(2,2,6,6-tetramethyl-l-octyloxypiperidin-4-yl)-1,10-decanedi-oate) (commercially available under the name TINUVIN® 123 from BASF, D., Ludwigshafen) are added to the hydroxy-terminated polypropylene glycol with an average molar mass Mn of 12,000 g / mol using an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0251] Example 4: Investigation of color stability

[0252] The storage and colorimetric determinations of the samples from Examples 3a and 3b were carried out as described in Example 2. The results obtained are shown in Table 2:

[0253] Table 2:

[0254] Formulation Stabiliser Color number Color number Color number Color number from tortype (APHA) (APHA) (APHA) (APHA) Example 200 ppm after 1 W after 2 W after 4 W after 8 W 3a Irganox® colorless colorless colorless light yellow 1076 Color number 15 Color number 15 Color number 22 Color number 28 3b TINUVIN® light yellow deep yellow deep yellow deep yellow 123 Color number 38

[0255]

[0256] Wal2430S / Mk

[0257] 33

[0258] Example 5a (not according to the invention)

[0259] In a 1000 ml reaction vessel equipped with stirring, cooling and heating facilities, 500.0 g of a hydroxy-terminated polypropylene glycol with an average molar mass M are reacted. nA polyol containing 12,000 g / mol and no stabilizer was prepared and dried for 2 hours at 80°C and 1 mbar with stirring. A distinct foaming during the first 30-40 minutes of drying indicates the evaporation of trace amounts of moisture from the polyol.

[0260] The vacuum is then broken with argon. The entire subsequent reaction is carried out under an argon protective gas atmosphere.

[0261] To carry out the silane termination, 20.5 g of isocyanatopropyl trimethoxysilane (GENIOSIL® GF 60 from Wacker Chemie AG, Munich, Germany) are first added dropwise to the dried polyoxylalkylene at 80°C, followed by 0.075 g of OMG catalyst 315 (a bismuth neadecanoate-containing catalyst from OMG Borchers) using an Eppendorf pipette. This corresponds to a catalyst concentration of 150 ppm based on the total weight of the reaction mixture. Immediately after the catalyst addition, the reaction mixture is heated to approximately 84°C. It is then stirred at a temperature of 80°C.

[0262] After 60 min, at unchanged temperature, 15.00 g of a mono-butoxy- and mono-hydroxy-terminated polypropylene glycol with a number-average molar mass M are added. nApproximately 600 g / mol of polyglycol (commercially available from Clariant under the name Polyglycol B01 / 10) is added. The mixture is then stirred for a further 60 minutes at 80 °C. A sample is then taken from the reaction mixture and analyzed by IR for any remaining isocyanatosilane residues. The sample is isocyanate-free. The Wal2430S / Mk

[0263] 34

[0264] Viscosity, measured according to the method mentioned in the description, is 7900 mPas.

[0265] Example 5b (according to the invention)

[0266] The procedure is the same as in Example 5a, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n0.100 g (200 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0267] Example 5c (according to the invention)

[0268] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n 0.200 g (400 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0269] Example 5d (according to the invention)

[0270] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n 0.400 g (8000 ppm) of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, Ludwigshafen, Germany) are added using an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst. Wal2430S / Mk

[0271] 35

[0272] Example 5e (according to the invention)

[0273] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n0.500 g (1000 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0274] Example 5f (not in accordance with the invention)

[0275] The procedure is the same as in example aa, with the sole difference being that the hydroxy-terminated polypropylene glycol has an average molar mass M. n 0.700 g (1400 ppm) of 3-(3,5-Di-tert-butyl-4-hydroxyphen-nyl)-propionic acid n-octyl ester (commercially available under the name Irganox® 1135 from BASF, D., Ludwigshafen) are added by means of an Eppendorf pipette after drying and before the addition of the isocyanatosilane and the catalyst.

[0276] Example 6: Investigation of color stability

[0277] The storage and colorimetric determinations of the samples from Examples 3a and 3b were carried out as described in Example 2. The results obtained are shown in Table 3: Wal2430S / Mk

[0278] 36

[0279] Table 3:

[0280] Formula Additional amount Color number Color number Color number from Irganox® (APHA) (APHA) (APHA) (APHA) Example 1135 after 1 week after 2 weeks after 4 weeks after 8 weeks 5a — Light gray grayish yellow deep gray deep grayish yellow yellow

[0281] 5b 200 ppm colorless colorless colorless colorless Color number 19 Color number 21 Color number 24 Color number 23 5c 400 ppm colorless colorless colorless light yellow Color number 18 Color number 24 Color number 29 Color number 43 5d 800 ppm colorless colorless light yellow light yellow Color number 20 Color number 24 Color number 35 Color number 46 5e 1000 ppm colorless light yellow yellow yellow Color number 23 Color number 38 Color number 54 Color number 63 5f 1400 ppm light yellow yellow yellow deep yellow Color number 35 Color number 54 Color number 79

[0282]

Claims

Wal2430S / Mk 37 Patent claims 1. Formulation (M) containing at least 90 wt. - [%] of at least one silane-terminated polymer (A) of formula ( I ), based on the total weight of the formulation (M), YX- [ (CR b-SiRa (OR 2 ) 3-a] ( I ), where Y means an x-valent polymer residue consisting of at least 90 wt. - [%] polyoxyalkylene units, X oxygen or a divalent bonding group selected from non- or N-substituted urethane or urea group means, R can be the same or different and represents a monovalent, substituted or unsubstituted, SiC-bonded hydrocarbon residue, R 1may be the same or different and represent a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon residue which may be bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or a carbonyl group, R 2 can be the same or different and represent a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon residue, x is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2, a can be the same or different and 0, 1 or 2, preferably 0 or 1, is and 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 Wal2430S / Mk 10 to 1200 ppm of at least one stabilizer (B) according to formula ( II ), based on the total weight of the formulation (M) ( II ), where R 3 may be the same or different and represent an n-valent, substituted or unsubstituted hydrocarbon residue with 1 to 40 carbon atoms, which may be branched or unbranched and may also have cyclic units, wherein the carbon chains may be interrupted by oxygen atoms, ester, amide, urethane or urea units, and n can be the same or different and is 1 to 10, preferably 1 to 4.

2. Formulation according to claim 1, characterized in that it contains at least 97 wt. - [%] of at least one silane-terminated polymer (A) of formula ( I ), based on the total weight of the formulation (M).

3. Formulation according to claim 1 or 2, characterized in that (A) is a polymer (Aa) of formula (aa). Y- [ ZC (=0) -NR 4 - (CR b-SiRa (OR 2 )3-a] ( la), where Wal2430S / Mk 39 R 4 can be the same or different and hydrogen atom, a monovalent, possibly substituted hydrocarbon residue, a group - (CR b-SiR a (OR 2 ) 3-a or a group -CH (COOR' ) -CH2-COOR' means and Z can be the same or different and NH means an oxygen atom and R' can be the same or different and represents a monovalent, possibly substituted, hydrocarbon residue and Y, X, R, R 1 , R 2 , x, a, and b have the meaning mentioned above in formula ( I ).

4. Formulation according to one of claims 1 to 3, characterized in that (B) are compounds (Ba) according to formula (Ha) where R 5may be the same or different and represents an n-valent substituted or unsubstituted hydrocarbon residue with 1 to 37 carbon atoms, which may be branched or unbranched and may also have cyclic units, W represents an oxygen atom or an NH group, and n may be the same or different and is 1 to 10. Wal2430S / Mk 40 5. Formulation according to any one of claims 1 to 4, in that it contains 20 to 1000 ppm based on the total weight of the formulation (M) of at least one stabilizer (B) or (Ba).

6. Formulation according to any one of claims 1 to 4, in that it contains 50 to 500 ppm based on the total weight of the formulation (M) of at least one stabilizer (B) or (Ba).

7. Formulation according to any one of claims 1 to 4, in that it contains 50 to 250 ppm based on the total weight of the formulation (M) of at least one stabilizer (B) or (Ba).

8. Method for producing the formulation (M) according to any one of claims 1 to 7, characterized in that the starting materials for the production of the compounds (A) or (Aa) are reacted in the presence of 10 to 1200 ppm, in each case based on the total weight of the formulation (M) of at least one component (B) or (Ba), or the corresponding amounts of at least one component (B) or (Ba) are added after its reaction.

9. Method (method variant 1) according to claim 8 for producing the formulation (M), with the proviso that (A) represents a silane-terminated polymer (Ab) of formula (Ib) Y- [NH-C (=0) -NR 4 - (CR b-SiRa (OR 2 )3-a] ( Ib), and through the implementation of (al) at least one hydroxyl-functional polymer consisting of more than 90 wt. - [%] polyoxylalkylene units, (bl) at least one di- and / or polyisocyanate and (cl ) at least one aminosilane of formula ( III ) Wal2430S / Mk 41 HNR 4 - (CR b-SiRa (OR 2 ) 3-a (HI) as well as, if applicable, other components different from ( al ), (bl ) and ( cl ), will be received where Y, R, R 1 , R 2 , R 4 , a, b and x have the meaning given in formula ( I ) or ( la ).

10. Method (method variant 2) according to claim 8 for producing the formulation (M), wherein (A) is a silane-terminated polymer (Ac) of formula (Ic). Y- [ 0-C (=0) -NH- ( CR b-SiRa ( OR 2 ) 3-a ] x ( Ic ), and through the implementation of ( a2 ) at least one x-valent polymer consisting of more than 90 wt. - [ % ] polyoxylalkylene units (b2) at least one di- and / or polyisocyanate and (c2) at least one isocyanatosilane of formula (IV) OCN- ( CRM b-SiRa ( OR 2 )3-a ( IV) as well as, if applicable, other components different from ( a2 ), (b2 ) and ( c2 ), will be received where Y, R, R 1 , R 2 , R 4 , a, b and x have the meaning given in formula ( I ).

11. Method (method variant 3) according to claim 8 for producing the formulation (M), wherein (A) is a silane-terminated polymer (Ad) of formula (Id). Y- [ 0-C (=0) -NH- ( CR b-SiRa ( OR 2 )3-a ] ( Id), Wal2430S / Mk and through the implementation of (a3) an x-valent polymer consisting of at least 90 wt. - [%] polyoxylalkylene units, and (c3) at least one isocyanatosilane of formula (IV) OCN- ( CR b-SlRa ( OR 2 ) 3-a ( IV) and possibly other components different from ( a3 ) and ( c3 ), where Y, R, R 1 , R 2 , a, b and x have the meaning given in formula (I).

12. Method (method variant 4) according to claim 8 for producing the formulation (M), wherein (A) is a silane-terminated polymer (Ae) of formula (le). Y [ -O- ( CR 3-SiRa ( OR 2 ) 3-a ] x ( le ), and through the implementation of ( a4 ) a polymer of formula (V), and Y [ -O- ( CR -CR 1= CR x (V) (c4) at least one silane of formula (VI) H-SlRa ( OR 2 ) 3-a (VI ) and possibly other components different from ( a4 ) and ( c4 ), Wal2430S / Mk 43 where Y, R, R 1 , R 2 , a and x have the meaning given in formula ( I ).

13. Use of the formulation (M) according to any one of claims 1-7 in crosslinkable masses.

14. Use according to claim 13, characterized in that the crosslinkable masses are adhesives and sealants as well as coatings that can be cured at room temperature.

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