ORGANYLOXYSILYL-TERMINATED POLYMERS BASED ON 1,3-DIOXOLANE COPOLYMER BUILDING BLOCKS

Description

[0001] The invention relates to crosslinkable silane-terminated polymers containing 1,3-dioxolane copolymer building blocks in their backbone, processes for their preparation, and compositions containing the polymers (P). The polymers exhibit high hydrophilicity and consequently particularly good curing properties.

[0002] Moisture-curable preparations are well-known. They are widely used as adhesives and sealants, as well as in coatings. Silyl-functionalized polymers represent an important moisture-reactive binder for such products. Among these, linear or simply branched polypropylene glycols and / or polyurethanes based on these polypropylene glycols are preferred, as they possess terminal alkoxysilyl groups at the ends of the respective polymer chains. This product group thus combines several advantages: The polymers with a polypropylene glycol backbone remain liquid even at the very long chain lengths required for this application before crosslinking. The alcohols released as breakdown products during crosslinking are non-corrosive and toxicologically harmless in the low concentrations released. The cured polymer formulations are characterized by very good mechanical properties.

[0003] Corresponding alkoxysilane-terminated polymers 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 (Kaneka), DESMOSEAL ®< (Bayer AG) or SPUR ®< (Momentive).

[0004] A disadvantage of many state-of-the-art systems, however, is the low reactivity of the polymers towards moisture, which necessitates aggressive catalysis. The corresponding mixtures therefore typically contain significant amounts of toxicologically problematic tin catalysts.

[0005] Here, the use of so-called α-silane-terminated prepolymers is advantageous. These prepolymers feature alkoxysilyl groups linked to an adjacent urethane unit via a methylene spacer. This class of compounds is highly reactive and requires neither tin catalysts nor strong acids or bases to achieve high curing rates upon contact with air. Corresponding products are commercially available under the trade name GENIOSIL® STP-E from Wacker-Chemie AG.

[0006] However, even these systems, which cure particularly quickly upon contact with humidity, still exhibit the problem of bonding large areas to non-porous substrates such as glass, metals, or plastics. The curing rate of a deep adhesive joint is limited not only by the reactivity of the crosslinkable polymers but also by the restricted availability of the water traces within the joint that are necessary for curing. And this latter factor, when bonding or sealing non-porous substrates, depends primarily on the rate at which water molecules can diffuse from the surface of the adhesive or sealant joint through the adhesive matrix into the deeper layers of the joint.

[0007] In principle, this problem can be solved by using so-called two-component systems, where the first component contains the moisture-curing polymer and the second component water. If both components are mixed together immediately before application, no diffusion of water from the air into the joint is necessary, and the adhesive or sealant cures evenly in deeper layers. However, such two-component systems are extremely user-unfriendly and difficult to work with, even for professional users. Therefore, they are only used when no single-component alternative exists for the specific application.

[0008] Therefore, in order to enable improved curing of even deep adhesive or sealant joints without the use of a 2-component system, an adhesive matrix that allows faster water diffusion would be highly desirable.

[0009] Another disadvantage of all currently available commercially available silane-crosslinking polymers is their polypropylene glycol-based backbone. Polypropylene glycols are currently produced from raw materials derived exclusively from fossil carbon sources. It would therefore be desirable to be able to use other, more ecologically sound polymer building blocks as a basis for the production of silane-crosslinkable polymers.

[0010] One way to achieve this goal is to utilize CO2 in the production of these polymer building blocks, thus integrating CO2 into the value chain not as waste, but as a starting material.

[0011] In this context, polyacetals could represent highly attractive polymer building blocks for the development of novel silane-crosslinking polymers. These can be produced via the intermediate cyclic acetals, for example, by the catalytic fixation of CO₂ with green hydrogen.

[0012] However, a problem arises because classic polyacetals, also known as polyoxymethylenes (POM), such as those obtained by polymerization of formaldehyde, trioxane (POM-H), or by ring-opening polymerization of 1,3-dioxolane (POM-C), are solid at room temperature. Therefore, they are unsuitable for the production of binders for liquid or pasty adhesives, sealants, or coatings that are intended to be applied solvent-free at room temperature and cure only during or after application.

[0013] The object of the invention was therefore the development of silane-terminated polymers based on polymer building blocks that can be produced wholly or partially from non-fossil carbon sources and that should also enable better diffusion of water molecules through the polymer matrix.

[0014] US 2005 / 119436 A1 discloses the production of alkoxysilyl-terminated polypropylene glycol polymers by reacting polypropylene glycol with isocyanate-functional silanes. The invention relates to organyloxysilyl-terminated polymers (P) with end groups of the formula (I) - (CR 1< 2 ) b -SiR a (OR 2< ) 3-a (I) , wherein R can be the same or different and represents a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon residue, R 1< can be the same or different and represents a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon residue, R 2< can be the same or different and represents a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon residue, a can be the same or different and is 0, 1 or 2, preferably 0 or 1, 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, the 1,3-dioxolane copolymer building blocks (DP) of general formula (II) in their backbone -[(O-CH 2 -O-CH 2 -CH 2 -) x1 (O-CH 2 -CH 2 -O-CH 2 -) x2 (O-CH 2 -O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH 2 )] y2 -O- (II) included, whereby R3< can be the same or different and represents hydrogen or a monovalent, unsubstituted or substituted C1 to C18 alkyl group; R4< can be the same or different and represents hydrogen or a monovalent, unsubstituted or substituted C1 to C18 alkyl group; x1+x2 values ​​from 10 to 2000; y1+y2 values ​​from 3 * (x1+x2+y1+y2) / 100 to 90 * (x1+x2+y1+y2) / 100. with the proviso that in the units [O-CH 2 -O-CHR 3 -CHR 4 -] y1 and [O-CHR 3 -CHR 4 O-CH 2 -] y2 each at least one remainder R 3 or R 4 a C 1 - to C 18 -Alkyl group means.

[0015] The 1,3-dioxolane copolymer building blocks (DP) of formula (II) have the units [O-CH 2 -O-CH 2 -CH 2 -] x1 , [O-CH 2 -CH 2 O-CH 2 -] x2 , [O-CH 2 -O-CHR 3< -CHR 4< -] y1 , [O-CHR 3< -CHR 4< O-CH 2 -] y2 , statistically distributed or in blocks.

[0016] Examples of unsubstituted 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 groups; alkenyl groups, such as vinyl, 1-propenyl and 2-propenyl groups; aryl groups, such as phenyl, naphthyl, anthryl and phenanthryl groups; alkaryl groups, such as o-, m-, p-tolyl groups; xylyl groups and ethylphenyl groups; and aralkyl groups, such as benzyl, α- and β-phenylethyl groups.

[0017] Examples of substituted residues R are haloalkyl residues and haloaryl residues, such as the o-, m- and p-chlorophenyl residue.

[0018] Preferably, the residue R is an unsubstituted or halogen-substituted monovalent hydrocarbon residue with 1 to 6 carbon atoms, particularly preferably an alkyl residue with 1 or 2 carbon atoms, especially the methyl residue.

[0019] Examples of residues R 1< are hydrogen atoms, the residues specified for R, and unsubstituted or substituted hydrocarbon residues bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group.

[0020] Preferably, the residue R 1< is a hydrogen atom and unsubstituted or substituted hydrocarbon residues with 1 to 20 carbon atoms, in particular a hydrogen atom.

[0021] Examples for residue R 2< are hydrogen atoms or the examples given for residue R.

[0022] Preferably, the residue R 2< is a hydrogen atom or unsubstituted or halogen-substituted alkyl residues with 1 to 10 carbon atoms, particularly preferably unsubstituted or halogen-substituted alkyl residues with 1 to 4 carbon atoms, especially the methyl and ethyl residues.

[0023] Examples of alkyl groups R3< and R4< are hydrogen atoms, linear and branched alkyl groups such as methyl, ethyl, i-octyl, and n-octyl groups, and cycloalkyl groups such as cyclohexyl groups. Preferably, R3< and R4< denote hydrogen atoms or C1 to C6 alkyl groups, particularly preferably hydrogen atoms, methyl, ethyl, n-propyl, or i-propyl groups.

[0024] Preferably, only one residue R 3< or R 4< in the units [O-CH 2 -O-CHR 3< -CHR 4< -] y1 and [O-CHR 3< -CHR 4< O-CH 2 -] y2 represents a C 1 - to C 18 -alkyl residue, whereas the other residue represents a hydrogen atom.

[0025] Preferably, x1+x2 represent values ​​from 20 to 1000, particularly preferably from 30 to 500, especially from 50 to 300.

[0026] Preferably, y1+y2 means values ​​from 5 * (x1+x2+y1+y2) / 100 to 50 * (x1+x2+y1+y2) / 100, particularly preferably values ​​from 10 (x1+x2+y1+y2) / 100 to 30 * (x1+x2+y1+y2) / 100, especially values ​​from 14 * (x1+x2+y1+y2) / 100 to 25 * (x1+x2+y1+y2) / 100.

[0027] The 1,3-dioxolane copolymer building blocks (DP) of formula (II) preferably have a number-average molecular weight M n between 750 and 300,000 Daltons, particularly preferably between 1,500 and 125,000 Daltons, most preferably between 4,000 and 24,000 Daltons, and particularly between 6,000 and 20,000 Daltons.

[0028] The organyloxysilyl-terminated polymers (P) can be branched, preferably having 1 to 3 branching sites and accordingly 3 to 5 chain ends. Some or all chain ends may be terminated with silane groups of formula (I). Preferably, at least 90%, and particularly preferably at least 95%, of all chain ends are terminated with silane groups of formula (I).

[0029] In a preferred embodiment, however, the polymers (P) are unbranched and thus have two chain ends. One or both chain ends can be terminated with silane groups of formula (I). Preferably, however, at least 90%, and particularly preferably at least 95%, of all chain ends are terminated with silane groups of formula (I).

[0030] The preparation of the organyloxysilyl-terminated polymers (P) is preferably carried out by a reaction of hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) of the general formula (III) H-[(O-CH 2 -O-CH 2 -CH 2 -) x1 (O-CH 2 -CH 2 -O-CH 2 -) x2 (O-CH 2 -O-CHR 3< -CHR 4< -) y1 (O-CHR 3< -CHR 4< O-CH 2 ) y2 -OH (III), wherein all variables have the meaning given in formula (II) and thus all requirements given in this formula are met.

[0031] The hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) preferably have a number-average molecular weight Mn between 750 and 300,000 Daltons, particularly preferably between 1,500 and 125,000 Daltons, most preferably between 4,000 and 24,000 Daltons, and especially between 6,000 and 20,000 Daltons. Compared to the polymer building blocks (DP) of formula (II) resulting from the use of the 1,3-dioxolane copolymers (DP-OH), the average molar mass is naturally increased by the weight of the two terminal hydrogen atoms.

[0032] In accordance with the present invention, the number-average molar mass M n is preferably determined by means of size exclusion chromatography (SEC) against a polystyrene standard in THF at 60°C, flow rate 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 µl.

[0033] The hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) preferably have a dynamic viscosity at 25 °C between 50 mPas - 500 Pas, particularly preferably between 500 mPas - 200 Pas, and especially between 1 Pas - 100 Pas.

[0034] The viscosity of non-pasty liquids is preferably determined within the scope of the present invention after tempering to 23°C using a DV 3 P rotational viscometer from A. Paar (Brookfield Systems) using spindle 6 at 5 Hz according to ISO 2555.

[0035] Numerous processes are known that are suitable for the production of organyloxysilyl-terminated polymers from hydroxyl-functional prepolymers, e.g., polypropylene glycols. All of these processes can be readily adapted for the conversion of hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) to the polymers (P) according to the invention. All process parameters, such as temperature, reaction time, catalysis, etc., can remain unchanged. The only difference is that a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) is used as the starting material, i.e., as the hydroxyl-functional polymer.

[0036] In a common process (V1), the hydroxyl-containing polymers (DP-OH) are first reacted with a compound having a hydroxyl-reactive group and a double bond, preferably allyl chloride, to form a corresponding vinyl-terminated polymer, which is then hydrosilylated with a silane of formula (IV) H-SiR a (OR 2< ) 3-a (IV), where all variables have the meanings given in formula (I). Suitable processes for carrying out this reaction are known and are described, among other places, in EP 1 566412 A1 (paragraphs

[0144] ff, method (a)). The specific instructions for carrying out the silylation of the hydroxyl-terminated polypropylene glycols used in the production examples of EP 1 566412 A1 can also be directly applied to the silylation of the hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH).

[0037] In a second, also common process (V2), the hydroxyl-group-containing polymers (DP-OH) are reacted with at least one isocyanate-functional compound. Preferably, these are di- or polyisocyanates. Examples of common diisocyanates are 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; 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 aforementioned diisocyanates.

[0038] The isocyanates can be used in a stoichiometric deficit (variant (V2-1)) or excess (variant (V2-2)) with respect to the ratio of isocyanate groups to hydroxyl groups of the hydroxyl-containing polymer (DP-OH). Variant (V2-1) results in a polyurethane polymer whose chain ends are terminated with hydroxyl groups, while variant (V2-1) results in a polymer whose chain ends consist of isocyanate groups.

[0039] The hydroxyl-functional polyurethane polymer obtained in variant (V2-1) is preferably reacted with an isocyanate-functional silane of formula (V) OCN-(CR 1< 2 ) b -SiR a (OR 2< ) 3-a (V), wherein the substituents and indices have one of the meanings given in formula (I). Suitable processes for carrying out this reaction are known and are described, inter alia, in EP 0 931 800 A (paragraphs

[0011] -

[0022] and Examples 1-5).

[0040] The isocyanate-functional polymer obtained in variant (V2-2) is preferably reacted with an isocyanate-reactive silane of formula (VI) Z-(CR 1< 2 ) b -SiR a (OR 2< ) 3-a (VI), where Z represents an isocyanate-reactive group and all other substituents and indices have a meaning given in formula (I).

[0041] The isocyanate-reactive group Z is preferably a hydroxyl group or an amino group, particularly preferably an amino group of the formula NHR', wherein R' has one of the meanings given for the residues R or stands for a group - CH(COOR")-CH 2 -COOR" in which R" can be the same or different and has a meaning given for R.

[0042] Examples of R' residues are cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl, the various stereoisomers of the pentyl, hexyl or heptyl residue, and the phenyl residue.

[0043] The residue R' is preferably a group -CH(COOR")-CH 2 -COOR" or an optionally substituted hydrocarbon residue with 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms or an optionally halogen-substituted aryl group with 6 to 20 carbon atoms.

[0044] The residues R" are preferably alkyl groups with 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl residues.

[0045] Suitable methods for carrying out the method variant (V2-2) are known and are described, among other places, in EP 1 093 482 B1 (paragraphs

[0014] -

[0023] ,

[0039] -

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

[0014] -

[0035] , Examples 4 and 6 as well as Comparative Examples 1 and 2).

[0046] In a particularly preferred process (V3), the polymers (P) according to the invention are obtained by a direct reaction of the hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) with isocyanate-functional silanes of formula (V). Suitable processes for carrying out this reaction are known and are described, inter alia, in EP 1 535 940 B1 (paragraphs

[0005] -

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

[0008] -

[0047] ), which are to be included in the disclosure scope of the present application.

[0047] The polymers of formula (VII) (RO 5< ) 3-a R 4< a Si-(CR 3< 2 ) b -NH-CO-[(O-CH 2 -O-CH 2 -CH 2 -) x1 (O-CH 2 -CH 2 -O-CH 2 -) x2 (O-CH 2 -O-CHR 3< -CHR 4< -) y1 (O-CHR 3< -CHR 4< O-CH 2 -) y2 ]-O-CO-NH-(CR 3< 2 ) b -SiR 4< a (OR 5< ) 3-a (VII) obtainable by the preferred method (V3), wherein all variables have the meanings given in formulas (I) and (II) and thus all requirements given in these formulas are met, represent a particularly preferred embodiment of the invention.

[0048] The hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) of the above general formula (III) can be prepared easily and with short reaction times.

[0049] The preparation is preferably carried out by copolymerization of 1,3-dioxolane with one or more alkyl-substituted 1,3-dioxolanes of the general formula (VII) in the presence of a Lewis or Brønsted acid, wherein the alkyl groups R 3< and R 4< have the meanings given in formula (II).

[0050] The process is a ring-opening polymerization of dioxolane monomers via cationically induced catalysis. The catalyst is a Lewis or Brønsted acid.

[0051] In the process, preferably at least 10 mol%, particularly preferably at least 20 mol%, in particular at least 30 mol% of alkyl-substituted 1,3-dioxolane of general formula II, based on the total amount of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of general formula II, are used.

[0052] The amount of alkyl-substituted 1,3-dioxolanes used is crucial for the ratio (y1+y2) / (x1+x2+y1+y2) in the hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) obtained during the copolymerization. However, it should be noted that the process usually requires slightly more alkyl-substituted 1,3-dioxolane of general formula (VII) than would be calculated, since it is less reactive than the unsubstituted 1,3-dioxolane and is therefore incorporated into the polymer chain less frequently.

[0053] Examples of acids are Lewis acids such as BF3, AlCl3, TiCl3, SnCl4, SO3, PCl5, POCl3, FeCl3 and its hydrates and ZnCl2; Brønsted acids, such as boric, tetrafluoroboric, nitric, nitrous, phosphoric, phosphorous, hypophosphorous, sulfuric, sulfurous, peroxosulfuric, hydrochloric, hydrofluoric, hydrogen iodide, hydrogen bromide, perchlorophosphoric, hexafluorophosphoric acid, aluminum chloride, zinc chloride, benzenesulfonic, p-toluenesulfonic, methanesulfonic, trifluoromethanesulfonic and carboxylic acids, such as chloroacetic, trichloroacetic, acetic, acrylic, benzoic, trifluoroacetic, citric, crotonic, formic, fumaric, maleic, malonic, gallic, itaconic, lactic, tartaric, oxalic, phthalic and succinic acid, acidic ion exchangers, acidic zeolites, acid-activated bleaching earth and acid-activated carbon black.

[0054] Boron trifluoride etherate and trifluoromethanesulfonic acid are particularly preferred.

[0055] Initiators can be used in the process. A difunctional alcohol is preferred as an initiator; ethylene glycol is particularly preferred.

[0056] The process can be carried out in the presence or absence of aprotic solvents. If aprotic solvents are used, solvents or solvent mixtures with a boiling point or boiling range of up to 120°C at 0.1 MPa are preferred.Examples of such solvents are ethers, such as dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, diisopropyl ether, diethylene glycol dimethyl ether; chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, trichloroethylene; hydrocarbons, such as pentane, n-hexane, hexane isomer mixtures, heptane, octane, white spirit, petroleum ether, benzene, toluene, xylenes; siloxanes, in particular linear dimethylpolysiloxanes with trimethylsilyl end groups with preferably 0 to 6 dimethylsiloxane units, or cyclic dimethylpolysiloxanes with preferably 4 to 7 dimethylsiloxane units, for example hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; Ketones, such as acetone, methyl ethyl ketone, di-isopropyl ketone, methyl isobutyl ketone (MIBK); esters, such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, ethyl isobutyrate; carbon disulfide and nitrobenzene, or mixtures of these solvents.

[0057] The term solvent does not mean that all reaction components must be soluble in it. The reaction can also be carried out in a suspension or emulsion of one or more reactants. The reaction can also be carried out in a solvent mixture with a miscibility gap, where at least one reactant is soluble in each of the mixed phases.

[0058] A solution of trifluoromethanesulfonic acid and an initiator is particularly preferred, with methylene chloride being used as the preferred solvent.

[0059] The amount of catalyst and initiator used determines the achievable molecular weight of the 1,3-dioxolane copolymer (DP-OH) of general formula (IV).

[0060] The process is preferably carried out at a temperature between 10 and 60 °C, particularly preferably between 15 and 40 °C, and especially between 21 and 30 °C. A reaction temperature of 23 °C is most particularly preferred.

[0061] The reaction is preferably carried out by inactivating the catalyst with a suitable base, washing with a hydrocarbon such as heptane, and subsequently removing it by distillation under reduced pressure. Pyridine, triethylamine, or aqueous sodium hydroxide are preferred bases.

[0062] The invention is based on several surprising discoveries: First, the hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH), which are composed of 1,3-dioxolane and 1,3-dioxolane substituted at the 4-position and / or 5-position, are liquid over a wide temperature range, including room temperature. This also applies when they have average molar masses of >> 10,000 Daltons. Given this surprising property, they are ideally suited as polymer building blocks (DP) for the synthesis of the polymers (P) according to the invention using one of the processes V1 to V3 and are therefore very well suited for further processing.

[0063] The polymers (P) based on the 1,3-dioxolane copolymer building blocks (DP) are highly polar and therefore hydrophilic. This makes them an ideal binder for adhesives and sealants, allowing rapid diffusion of water molecules into the deeper layers of an adhesive or sealant joint and thus ensuring particularly good, fast, and uniform curing of the respective adhesive or sealant.

[0064] The polymers (P) represent a suitable binder for adhesives and sealants, exhibiting excellent properties after curing that are largely comparable to those of a conventional silane-terminated polypropylene glycol-based polymer. This entirely new product group, whose raw material is obtained via the intermediate stage of cyclic acetals through the catalytic fixation of CO₂ with green hydrogen, thus represents an alternative with which existing products derived exclusively from fossil carbon sources can be completely or at least partially replaced.

[0065] The organyloxysilyl-terminated polymers (P) produced according to the invention can be used wherever organyloxysilyl-terminated polymers have previously been used. They are particularly suitable as components of crosslinkable compounds, i.e., as binders for adhesives, sealants, and / or coatings. Due to their improved curing properties, they are especially suitable for use in deep adhesive or sealing joints and for bonding non-porous substrates over large areas.

[0066] The invention therefore also relates to compositions which contain the organyloxysilyl-terminated polymers (P) and, depending on the specific application or the respective requirement profile, at least one further component selected from (A) nitrogen-containing organosilicon compounds, (B) silicone resins, (C) catalysts, (D) adhesion promoters, (E) water scavengers, (F) fillers, (G) additives and (H) aggregates.

[0067] The compositions according to the invention preferably contain crosslinkable masses (P) organyloxysilyl-terminated polymers (P), optionally (A) nitrogen-containing organosilicon compounds, optionally (B) silicone resins, optionally (C) catalysts, optionally (D) adhesion promoters, optionally (E) water scavengers, optionally (F) fillers, optionally (G) additives and optionally (H) aggregates.

[0068] The components (A) to (H) and their preferred quantities are described in many places, for example WO-A 2015024773 on page 12, line 24 to page 23, line 21, which is to be considered part of the disclosure content of the present application.

[0069] The compositions according to the invention are particularly preferably those containing crosslinkable masses (P) organyloxysilyl-terminated polymers, (A) nitrogen-containing organosilicon compounds, optionally (B) silicone resins, optionally (C) catalysts, optionally (D) adhesion promoters, optionally (E) water scavengers, optionally (F) fillers, optionally (G) additives and optionally (H) aggregates.

[0070] The compositions according to the invention are particularly preferably crosslinkable masses consisting of (P) organyloxysilyl-terminated polymers, (D) nitrogen-containing organosilicon compounds, optionally (B) silicone resins, optionally (C) catalysts, optionally (D) adhesion promoters, optionally (E) water scavengers, optionally (F) fillers, optionally (G) additives and optionally (H) aggregates.

[0071] The components used according to the invention can each be one type of such component or a mixture of at least two types of each component.

[0072] The adhesives, sealants, or coatings according to the invention can be produced in any known manner, such as by methods and mixing processes commonly used for the production of moisture-curing compositions. The order in which the various components are mixed can be varied as desired.

[0073] This mixing can take place at room temperature and atmospheric pressure, i.e., approximately 900 to 1100 hPa. If desired, this mixing can also be carried out at higher pressures.

[0074] Temperatures are reached, e.g.at temperatures in the range of 30 to 130°C. Furthermore, it is possible to mix temporarily or continuously under reduced pressure, as described below. e.g. at 30 to 500 hPa absolute pressure to remove volatile compounds and / or air. The mixing according to the invention preferably takes place in the absence of moisture.

[0075] The polymers (P) according to the invention have the advantage that they can be produced just as quickly and easily as conventional silane-crosslinking polymers based on polypropylene glycols.

[0076] The polymers (P) according to the invention have the advantage that they are low in viscosity and comparatively low in viscosity, so that they can be compounded excellently into finished adhesives and sealants.

[0077] The polymers (P) according to the invention have the advantage that, although they represent a completely new product group, they can be further processed into adhesives and sealants in the same way as conventional silane-crosslinking polymers based on polypropylene glycols. Neither new nor modified equipment nor new or modified processing techniques are necessary for further processing.

[0078] The polymers (P) according to the invention have the advantage that adhesives and sealants with excellent mechanical properties can be produced from them.

[0079] The polymers (P) according to the invention have the advantage that adhesives and sealants can be produced from them which exhibit a particularly fast and uniform curing.

[0080] The polymers (P) according to the invention have the advantage that the adhesives and sealants produced from them exhibit an excellent adhesion profile on countless substrates such as plastics including PVC, metals, concrete, wood, mineral substrates, glass, ceramics and painted surfaces and are therefore suitable for bonding and / or sealing all these materials.

[0081] The polymers (P) according to the invention have the advantage that they are transparent, colorless and color-stable, and are therefore also suitable for the production of transparent and crystal-clear adhesives and sealants.

[0082] The polymers (P) according to the invention have the advantage that they can be produced by fixing CO2, making them particularly climate-friendly.

[0083] The masses that can be produced from the polymers (P) according to the invention can be used for all purposes for which masses that can be stored in the absence of water and that crosslink to elastomers upon exposure to water at room temperature can be used.

[0084] The materials that can be produced from the polymers (P) according to the invention are therefore ideally suited, for example, for sealing and flexibly bonding metallic components. They can thus be used as assembly adhesives, in the automotive industry, and in the manufacture of buses, trucks, and rail vehicles. Furthermore, they are suitable for window construction, especially of skylights, structural glass bonding, or for the production of photovoltaic elements, display cases, as well as, for example, for the production of protective coatings or molded parts, and for the insulation of electrical or electronic devices.

[0085] In the examples described below, all viscosity values ​​refer to a temperature of 25°C. Unless otherwise stated, the following examples are carried out at atmospheric pressure, i.e., approximately 1000 hPa, and at room temperature, i.e., approximately 23°C, or at the temperature that occurs when the reactants are combined at room temperature without additional heating or cooling, and at a relative humidity of approximately 50%. Furthermore, all values ​​for parts and percentages refer to weight unless otherwise stated. Examples Production example 1: Preparation of a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH)

[0086] Preparation of the catalyst solution: In a Schlenk flask with septum, 150 ml of dry dichloromethane, 15 ml of ethylene glycol and 1.14 ml of trifluoromethanesulfonic acid are mixed under a nitrogen atmosphere.

[0087] 154 ml of the previously prepared catalyst solution are transferred to a laboratory reactor equipped with a KPG stirrer, thermometer, nitrogen connection, and septum, and heated to 23 °C. 1.15 kg of 4-ethyl-1,3-dioxolane (10.9 mol) and 770 ml (10.9 mol) of 1,3-dioxolane are added to this solution, and the mixture is stirred at 23 °C. The reaction mixture becomes more viscous and turns pink during the reaction time. After 5 h, approximately 20 ml of pyridine and 100 ml of dichloromethane are added until the reaction solution is decolorized. The product mixture is washed first with heptane and then with water until a pH of 7 is reached.

[0088] Finally, all volatile components are removed under vacuum (1 mbar) and a viscous oil is obtained. Production example 2: Production of a polymer according to the invention (P)

[0089] In a 1 l three-necked flask equipped with dropping funnel, KPG stirrer and thermometer, 475 g of the 1,3-dioxolane copolymer from Example 1 are placed, heated to 80 °C and dried for 2 h at a pressure of 10 mbar (vacuum).

[0090] The vacuum is broken with nitrogen, and 18.5 g of α-isocyanatomethyl methyldimethoxysilane (GENIOSIL® < XL 42, commercially available from Wacker Chemie AG, Munich, Germany) are added dropwise over 15 minutes while stirring. The temperature remains at 80 °C. Then, 0.07 g of a bismuth-containing catalyst (commercially available as "Borchi-Kat 315" from OMG-Borchers, Langenfeld, Germany) is added. This causes a slight warming of the reaction mixture (< 5 °C). The mixture is then stirred for 2 hours at 80 °C. A small isocyanate peak is still present in the IR spectrum of the reaction mass, corresponding to 2 to 5% of the originally added amount of isocyanate groups.

[0091] The mixture is cooled to 50 °C, and at this temperature, 1.3 g of methanol is added to destroy any remaining isocyanate. After 0.5 h, the reaction mixture is allowed to cool to room temperature. An IR spectrum recorded subsequently confirms the absence of isocyanate. Example 1: Adhesive sealant formulation based on a polymer according to the invention (P)

[0092] 168.0 g of polymer from production example 2 are homogenized in a PC-Laborsystem laboratory planetary mixer, equipped with two beam mixers, at approx. 25°C with 8.0 g of vinyltrimethoxysilane (commercially available under GENIOSIL ®< XL 10 from Wacker Chemie AG, D-Munich) for 2 minutes at 200 rpm.

[0093] Then, 220.0 g of stearic acid-coated ground calcium carbonate with a mean particle diameter (D50%) of approximately 0.4 µm (commercially available under the name Omyabond 302 from Omya, Cologne, Germany) are added and digested for one minute with stirring at 600 rpm. Finally, 4.0 g of N-[2-Aminoethyl]-3-Aminopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF 91 from Wacker Chemie AG, Munich, Germany) are mixed in for one minute at 200 rpm and homogenized for one minute at 200 rpm under partial vacuum (approximately 100 mbar) with gentle stirring to remove air bubbles.

[0094] The resulting mass is filled into two 310 ml PE cartridges (approx. 200 g per cartridge) and stored for 24 hours at 20°C before the examination. Comparison example V1:

[0095] The procedure is the same as in Example 1, however, instead of the polymer according to the invention from Production Example 2, the identical amount of a silane-terminated polypropylene glycol with a mean molar mass (M n ) of 12000 g / mol and end groups of the formula -OC(=O)-NH-CH 2 -SiCH 3 (OCH 3 ) 2 (commercially available under the name GENIOSIL ®< STP-E10 from Wacker Chemie AG, D-Munich) is used. Example 2: Adhesive sealant formulation based on a polymer according to the invention (P)

[0096] 116.0 g of polymer from production example 2 are homogenized in a laboratory planetary mixer from PC-Laborsystem, equipped with two beam mixers, at approximately 25°C with 80 g of a butyl-terminated polyethylene glycol with a number-average molar mass (M n ) of 300 g / mol (commercially available under the name Polyglycol BB 300 from Clariant, D-Gendorf) and 8.0 g of vinyltrimethoxysilane for 2 minutes at 200 rpm.

[0097] Then, 192.0 g of Omyabond 302 are added and the mixture is digested for one minute at 600 rpm while stirring. Finally, 4.0 g of 3-aminopropyltrimethoxysilane (commercially available under GENIOSIL® GF 96 from Wacker Chemie AG, Munich, Germany) are mixed in for one minute at 200 rpm and homogenized for one minute at 200 rpm under partial vacuum (approx. 100 mbar) while stirring to ensure no bubbles remain.

[0098] The resulting mass is filled into two 310 ml PE cartridges (approx. 200 g per cartridge) and stored for 24 hours at 20°C before the examination. Comparison example V2:

[0099] The procedure is the same as in Example 3, however, instead of the polymer according to the invention from Production Example 2, the identical amount of GENIOSIL ®< STP-E10 is used. Example 3: Determination of property profiles of the manufactured adhesive sealants

[0100] The adhesive sealants obtained in Examples 1 and 2, as well as in the comparative examples V1 and V2, were allowed to crosslink and were examined with regard to their skin formation and mechanical properties. The results are shown in Table 1. Skin formation time (HBZ)

[0101] To determine the skin formation time, the crosslinkable masses obtained in the examples are applied in a 2 mm thick layer to PE film and stored under standard climate conditions (23°C and 50% relative humidity). During curing, skin formation is tested once per minute. A dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to the finger, no skin has yet formed. If no sample sticks to the finger, a skin has formed and the time is recorded. Mechanical properties

[0102] The mixtures are spread onto milled Teflon® plates with a depth of 2 mm and cured for 2 weeks at 23°C and 50% relative humidity.

[0103] The Shore A hardness is determined according to DIN 53505.

[0104] The tensile strength is determined according to DIN 53504-S1. The elongation at break is determined according to DIN 53504-S1.

[0105] The 100% module is determined according to DIN 53504-S1. Table 1: Example 1 V1* 2 V2 * HZB [min] 7 7 25 29 Hardness [Shore A] 59 68 21 40 100% modulus [N / mm] 2, 8 3, 9 0, 6 1,2 Tensile strength [N / mm] 3, 4 4,3 1,1 2,4 Elongation at break [%] 133 126 228 190 * not according to the invention

Claims

1. Organyloxysilyl-terminated polymers (P) having end groups of formula (I)         - (CR12)b-SiRa(OR2)3-a     (I), where R may be identical or different and is a monovalent, unsubstituted or substituted, SiC-bonded hydrocarbon radical, R1 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, R2 may be identical or different and is a hydrogen atom or a monovalent, unsubstituted or substituted hydrocarbon radical, a may be identical or different and is 0, 1 or 2, and b may be identical or different and is an integer from 1 to 10, which comprise 1,3-dioxolane copolymer units (DP) of the general formula (II) in the backbone thereof         -[(O-CH2-O-CH2-CH2-)x1 (O-CH2-CH2-O-CH2-)x2 (O-CH2-O-CHR3-CHR4-)y1 (O-CHR3-CHR4-O-CH2)]y2-O-     (II), where R3 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C1- to C18-alkyl radical, R4 may be identical or different and is hydrogen or a monovalent, unsubstituted or substituted C1- to C18-alkyl radical, x1+x2 has values of 10 to 2000, y1+y2 has values of 3*(x1+x2+y1+y2) / 100 to 90* (x1+x2+y1+y2) / 100, with the proviso that, in the [O-CH2-O-CHR3-CHR4-]y1 and [O-CHR3-CHR4O-CH2-]y2 units, in each case at least one radical R3 or R4 is a C1- to C18-alkyl radical.

2. Organyloxysilyl-terminated polymers (P) according to Claim 1, in which R is selected from alkyl radicals having 1 or 2 carbon atoms.

3. Organyloxysilyl-terminated polymers (P) according to either of the preceding claims, in which R1 is a hydrogen atom.

4. Organyloxysilyl-terminated polymers (P) according to any of the preceding claims, in which R2 is selected from methyl radical and ethyl radical.

5. Organyloxysilyl-terminated polymers (P) according to any of the preceding claims, in which R3 and R4 are selected from hydrogen atoms and C1- to C6-alkyl radicals.

6. Organyloxysilyl-terminated polymers (P) according to any of the preceding claims, in which in each case only one radical R3 or R4 in the [O-CH2-O-CHR3-CHR4-]y1 and [O-CHR3-CHR4O-CH2-]y2 units is a C1- to C18-alkyl radical, whereas the other radical in each case is a hydrogen atom.

7. Organyloxysilyl-terminated polymers (P) according to any of the preceding claims, in which the 1,3-dioxolane copolymer units (DP) of formula (II) have a number-average molecular weight Mn between 750 and 300 000 daltons, measured according to the method as described in the application.

8. Process (P3) for producing the organyloxysilyl-terminated polymers (P) according to any of Claims 1 to 7, in which hydroxyl group-terminated 1,3-dioxolane copolymers (DP-OH) of the general formula (III)         H-[(O-CH2-O-CH2-CH2-)x1 (O-CH2-CH2-O-CH2-)x2 (O-CH2-O-CHR3-CHR4-)y1 (O-CHR3-CHR4-O-CH2)]y2-OH     (III), are reacted with at least one isocyanate-functional silane of formula (V)         OCN-(CR12)b-SiRa(OR2)3-a     (V), where R, R1, R2, R3, R4, x1+x2 and y1+y2, a and b have the definitions given in Claims 1 to 7.

9. Composition comprising the organyloxysilyl-terminated polymers (P) according to any of Claims 1 to 7 and at least one further constituent selected from (A) nitrogen-containing organosilicon compounds, (B) silicone resins, (C) catalysts, (D) adhesion promoters, (E) water scavengers, (F) fillers, (G) additives and (H) aggregates.

10. Adhesive or sealant containing organyloxysilyl-terminated polymers (P) according to any of Claims 1 to 7, organyloxysilyl-terminated polymers (P) produced according to Claim 8 or a composition according to Claim 9.