WO2025114504A1

WO2025114504A1 - Curable composition including a silane-modified polymer comprising poly-1,3-propanediol repeating units

Info

Publication number: WO2025114504A1
Application number: PCT/EP2024/084035
Authority: WO
Inventors: Jan-Erik DAMKE; Maximilian Maier; Oleksandr SHYSHOV
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2023-12-01
Filing date: 2024-11-29
Publication date: 2025-06-05
Anticipated expiration: 2026-06-01

Abstract

The invention relates to a curable composition comprising, I. at least one compound of Formula (I) Y-[(CR¹ ₂)_b-SiR_a(OR²)_3-a]_x(I) wherein, in Formula (I), Y denotes an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon, wherein said polymer radical comprises poly-1,3-propanediol repeating units, R is independently selected from a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R¹ is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R² is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10, preferably 1, 2 or 3, especially preferably 1 or 2, a is independently selected from 0, 1 and 2, preferably 0 and 1, and b is independently selected from an integer from 1 to 10, preferably 1, 3 and 4, particularly preferably 1 and 3, in particular 3; II. optionally surface treated silica, III. optionally a catalyst. The invention also relates to an adhesive, sealant, or coating material comprising the curable composition and to the use of the curable composition as an adhesive, sealant, or coating material.

Description

Curable composition including a silane-modified polymer comprising poly-1 ,3-propanediol repeating units

The invention relates to a curable composition including a silane-modified polymer (SMP) comprising poly-1 , 3-propanediol repeating units. In addition, the invention relates to an adhesive, sealant, or coating material comprising the curable composition and to the use of the curable composition as an adhesive, sealant, or coating material.

One-component, moisture-curing adhesives and sealants have for years played an important part in numerous technical applications. As well as the polyurethane adhesives and sealants with free isocyanate groups and the traditional silicone adhesives and sealants based on dimethylpolysiloxanes, there has recently also been increasing use of so-called silane modified adhesives and sealants. These adhesives are distinguished by a broad range of adhesion to a wide variety of substrates without any surface pretreatment such as using primers.

Polymer systems having reactive silyl groups are known in principle. In the presence of atmospheric moisture, polymers having silyl groups with hydrolyzable substituents are capable of condensing with one another at room temperature, splitting off the hydrolyzed residues. Depending on the concentration of silyl groups having hydrolyzable substituents and the structure of these silyl groups, mainly long- chain polymers (thermoplastics), relatively wide-mesh, three-dimensional networks (elastomers) or highly crosslinked systems (thermosets) are formed during this process. The polymers generally comprise an organic backbone which carries, for example, alkoxysilyl or acyloxysilyl groups at the ends. The organic backbone can be, for example, polyurethane, polyester, or polyether.

Polymers with silyl groups at the ends or in a side chain are described for example in WO 2019/094414 A1 , which discloses a moisture curable, silane modified terpolymer comprising: at least one polyether segment; at least one segment selected from polytetrahydrofuran or polycarbonate; and at least one polysiloxane segment, each of the segments covalently bonded to an adjacent segment by a urethane linkage; and at least one terminal silyl hydrolysable group connected to the polymer via isocyanate linkages, wherein each terminal silyl hydrolysable group comprises one to three hydrolysable groups.

However, polytetrahydrofuran-based SMPs are usually highly viscous, affecting processing and formulation. E.g., in production, polytetrahydrofuran 2000-based polyols need to be heated to make them processable. Subsequent formulation space is limited, to keep the formula handling properties acceptable.

For decreasing viscosity, shorter chained polytetra hydrofurans can be used to manufacture SMPs, however, mechanical properties in the application, in particular elastic bonding, are not sufficient. On the other hand, no pure poly-1 ,2-propanediol-based SMPs are commercially available and conventional compositions suffer from low adhesion and a less versatile adhesion spectrum. Subsequent formulation space is limited, to keep the formula handling properties acceptable.

Poly-1 ,2-propanediol-based SMPs are usually highly viscous, affecting processing and formulation. For decreasing viscosity, shorter chained poly-1 ,2-propanediol-based polyols could be used to manufacture SMPs, however, mechanical properties in the application, in particular elastic bonding, would not be sufficient.

Other approaches have been identified to make a silane modified polymer that will provide improved adhesion for a final adhesive composition. One frequent drawback is that these approaches result in silane modified polymers having a high viscosity. The high viscosity of a silane modified polymer necessarily leads to a high viscosity in adhesive compositions comprising that silane modified polymer.

Prior compositions suffer from one or more issues of high viscosity, low adhesion, poor low temperature performance or low tensile strength. Thus, there is a need for improved silane modified polymers for use in adhesives. There is a continuing need to make a silane modified polymer that will not only provide enhanced adhesion to adhesive compositions but also have a lower viscosity so that those adhesive compositions have a viscosity that is practical for commercial application.

Apart from that consumers have start to ask for CO2 reduced products without any compromise in performance. Commercially available solutions for CO2-reduced SMPs are usually only based on mass-balance schemes, which are suboptimal in terms of the chain of custody/directly attributable CO2 reduction. Also available polyols with mass-balance are not solving described performance/viscosity mismatch.

Therefore, it was the object of the present invention to provide curable compositions, which can overcome the above-discussed drawbacks and disadvantages of conventional curable compositions.

The present invention has achieved said objectives by providing a curable composition in accordance with claim 1 . Preferred embodiments of said curable composition are described in the depending claims. In addition, an adhesive, sealant, or coating material comprising the curable composition and the use of the curable composition as an adhesive, sealant, or coating material are protected by further independent claims.

The present invention describes a curable composition comprising,

I. at least one compound of Formula (I)

Y-[(CR¹2)b-SiRa(OR²)3-a]x (I) wherein, in Formula (I),

Y denotes an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon, wherein said polymer radical comprises poly-1 ,3-propanediol repeating units,

R is independently selected from a monovalent, optionally substituted, SiC-bonded hydrocarbon radical,

R¹ is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group,

R² is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10, preferably 1 , 2 or 3, especially preferably 1 or 2, a is independently selected from 0, 1 and 2, preferably 0 and 1 , and b is independently selected from an integer from 1 to 10, preferably 1 , 3 and 4, particularly preferably 1 and 3, in particular 3;

II. optionally surface treated silica,

III. optionally a catalyst.

The solution of the present invention is advantageous in several aspects:

The curable composition of the invention does not suffer from high viscosity, low adhesion, poor low temperature performance or low tensile strength. By contrast, the curable composition of the invention exhibits a combination of favorable properties, especially a comparable low viscosity, an excellent adhesion, an outstand low temperature performance and a high tensile strength.

Compared to conventional curable compositions based on silane-modified polymers comprising polytetra hydrofuran repeating units, the curable composition of the invention is usually moderately viscous, which positively affects processing and formulation.

Even for the manufacture of SMPs with shorter chained poly-1 , 2-propanediol-based repeating units, the mechanical properties in the application, in particular elastic bonding, are still sufficient.

Finally, the curable composition of the invention has a very versatile adhesion spectrum.

Besides, use of bio-based materials, especially bio-based poly-1 ,3-propanediol provides curable compositions with reduced C02-footprint compared to conventional state of the art SMPs, which causes less impact on the environment and are more ecologically beneficial and sustainable.

The present invention also relates to an adhesive, sealant, or coating material comprising the curable composition. In another aspect, the present invention relates to the use of the curable composition as an adhesive, sealant, or coating material.

The term “curable composition” is understood to be a substance or mixture of multiple substances, which is curable by physical or chemical measures. In this regard, these chemical or physical measures can be, for example, the supplying of energy in the form of heat, light, or other electromagnetic radiation, but also simply bringing into contact with atmospheric moisture, water, or a reactive component. The composition thereby changes from an original state to a state that has a higher hardness. In preferred embodiments, the curable composition of the present invention is a moisture curable composition.

As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

The term "at least one," as used herein, means 1 or more, i.e., 1 , 2, 3, 4, 5, 6, 7, 8, 9, or more. With reference to an ingredient, the indication refers to the type of ingredient and not to the absolute number of molecules. "At least one polymer" thus means, for example, at least one type of polymer, i.e., that one type of polymer or a mixture of several different polymers may be used. Together with the weight indication, the indication refers to all compounds of the stated type which are contained in the composition/mixture, i.e., that the composition contains no further compounds of this type besides the stated quantity of the compounds in question.

The terms “comprising”, “comprises” and “comprised of’ as used herein are synonymous with “including”, “includes”, “containing” or “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. If used, the phrase "consisting of’ is closed and excludes all additional elements. Further, the phrase "consisting essentially of excludes additional material elements but allows the inclusion of non-material elements that do not substantially change the nature of the invention.

When amounts, concentrations, dimensions and other parameters are expressed in the form of a range, a preferable range, an upper limit value, a lower limit value or preferable upper and limit values, it should be understood that any ranges obtainable by combining any upper limit or preferable value with any lower limit or preferable value are also specifically disclosed, irrespective of whether the obtained ranges are clearly mentioned in the context.

The term “about”, as used herein in connection with a numerical value, relates to a variance of ±20%, preferably ±10% of the respective value. The words "preferred", "preferably", “desirably” and “particularly”, and synonyms thereof, are used frequently herein to refer to embodiments of the disclosure that may afford particular benefits, under certain circumstances. However, the recitation of one or more preferable, preferred, desirable or particular embodiments does not imply that other embodiments are not useful and is not intended to exclude those other embodiments from the scope of the disclosure.

As used throughout this application, the word “may” is used in a permissive sense - that is meaning to have the potential to - rather than in the mandatory sense.

As used herein, room temperature is 23°C plus or minus 2°C. As used herein, “ambient conditions” means the temperature and pressure of the surroundings in which the composition is located or in which a coating layer or the substrate of said coating layer is located.

The molecular weights given in the present text refer to number average molecular weights (M_n), unless otherwise stipulated. All molecular weight data refers to values obtained by gel permeation chromatography (GPC) carried out using Water 2695 HPLC equipped with 3 Polypore columns and using a Rl detector at 35 °C. Stabilized Tetrahydrofuran (THF) was used as eluent at 1 mL/min flow rate. The calibration of the device was carried out using polystyrene standards.

As used herein, “polydispersity” refers to a measure of the distribution of molecular mass given in a resin sample. The polydispersity is calculated by dividing the weight average molecular weight (M_w) by the number average molecular weight (M_n).

For convenience in the description of the process of this invention, unsaturation provided by CH2=CH- CH2- terminal groups is referred to as “allyl” unsaturation.

As used herein, “Ci-Ca alkyl” group refers to a monovalent group that contains 1 to 8 carbon atoms, that is a radical of an alkane and includes linear and branched organic groups. Examples of alkyl groups include but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n- pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or may be substituted with one or more substituents such as halo, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide and hydroxy. The halogenated derivatives of the exemplary hydrocarbon radicals listed above might, in particular, be mentioned as examples of suitable substituted alkyl groups. In general, however, a preference for unsubstituted alkyl groups containing from 1 to 6 carbon atoms (C1-C6 alkyl) - for example unsubstituted alkyl groups containing from 1 to 4 atoms (C1-C4 alkyl) - should be noted. As used herein, the term “C2-C8 alkenyl” group refers to an aliphatic hydrocarbon group which contains 2 to 8 carbon atoms and at least one carbon-carbon double bond, e.g., ethenyl, propenyl, butenyl, or pentenyl and structural isomers thereof such as 1- or2-propenyl, 1-, 2-, or 3-butenyl, etc. Alkenyl groups can be linear or branched and substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl.

As used herein, the term “C2-C8 alkynyl” group refers to an aliphatic hydrocarbon group which contains 2 to 8 carbon atoms and at least one carbon-carbon triple bond, e.g., ethynyl (acetylene), propynyl, butynyl, or pentynyl and structural isomers thereof as described above. Alkynyl groups can be linear or branched and substituted or unsubstituted.

The term “C3-C10 cycloalkyl” is understood to mean a saturated, mono-, bi- ortricyclic hydrocarbon group having from 3 to 10 carbon atoms. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

As used herein, a ”Ce-Ci8 aryl” group used alone or as part of a larger moiety - as in “aralkyl group” - refers to optionally substituted, monocyclic, bicyclic and tricyclic ring systems in which the monocyclic ring system is aromatic or at least one of the rings in a bicyclic or tricyclic system is aromatic. The bicyclic and tricyclic ring systems include benzofused 2-3 membered carbocyclic rings. Exemplary aryl groups include: phenyl; indenyl; naphthalenyl; tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. And a preference for phenyl groups may be noted.

As used herein, an “aralkyl” group refers to an alkyl group that is substituted with an aryl group. As example of an aralkyl group is benzyl.

The terms “Ci-Ceo alkylene” group and “C1-C20 alkylene” group refer respectively to divalent groups that contain from 1 to 60 of from 1 to 20 carbon atoms, that are radicals of an alkane and include linear, branched, or cyclic groups, which groups may be substituted or unsubstituted and may optionally be interrupted by at least one heteroatom.

As used herein, the term “alkenylene” group refers to a divalent aliphatic hydrocarbon group having at least one carbon-carbon double bond that is a radical of an alkene. An alkenylene group can be linear or branched and substitutes or unsubstituted.

As used herein, the term “alkynylene” group refers to a divalent aliphatic hydrocarbon group having at least one carbon-carbon triple bond, that is a radical of an alkyne. An alkynylene group can also have one or more carbon-carbon double bonds. An alkynylene group can be linear or branched and substituted or unsubstituted. As used herein, the term “arylene” group refers to a divalent group that is a radical of an aryl group. Suitable arylene group includes phenylene, furanylene, piperidylene, and naphthylene.

As used herein, the term “aralkylene” group refers to a divalent group that is a radical of an aralkyl group. An aralkylene can be represented by the formula -R-Ar- where R is an alkylene and Ar is an arylene, i.e., an alkylene is bonded to an arylene. Suitable aralkylene groups includes xylylene and toluenylene.

Where mentioned, the expression “contain at least one heteroatom” means that the main chain or side chain of a residue comprises at least one atom that differs from carbon atom and hydrogen. Preferably the term “heteroatom” refers to nitrogen, oxygen, silicon, sulfur, phosphorus, halogens such as chlorine (Cl), bromine (Br), fluor (F). Oxygen (O) and nitrogen (N) may be mentioned as typical heteroatoms in the context of the present invention.

As used herein, the term “hydrocarbon residue” includes saturated or unsaturated hydrocarbon residues.

As used herein, the term “heterocyclic compound” refers to a saturated or unsaturated, monocyclic, bicyclic, polycyclic or fused compound containing at least one heteroatom, preferably O, S, N, and/or P, in the ring structure.

As used herein, the term “halogen” refers to fluorine, chlorine, bromine or iodine and correspondingly the term “halide” denotes fluoride, chloride, bromide, or iodide anions.

The term “pseudohalogen” refers to inorganic or organic groups which, when in the form of anions exhibit chemical properties similar to those of the halide ions. Pseudohalogen groups include, although are not exclusive to, azido (N3), thiocyano (SCN) and cyano (CN).

(I) silane modified polymer

The curable composition of the invention comprises at least one compound of Formula (I) Y-[(CR¹2)b-SiRa(OR²)3-a]x (I) wherein, in Formula (I),

Y denotes an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon wherein said polymer radical comprises poly-1 ,3-propanediol repeating units,

R¹ is independently selected from hydrogen ora monovalent, optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R² is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10, preferably 1 , 2 or 3, especially preferably 1 or 2, a is independently selected from 0, 1 and 2, preferably 0 and 1 , and b is independently selected from an integer from 1 to 10, preferably 1 , 3 and 4, particularly preferably 1 and 3, in particular s.

Preferred compounds of Formula (I) include a-silane and y-silane type modified polymers comprising poly-1 ,3-propanediol repeating units. The silane modified polymers preferably refer to silane-modified polyethers, silane-modified polyester polyethers, silane modified polyacrylate polyethers, and silane- modified polyurethane polyethers, i.e., polymers featuring hydrolysable silyl groups at the terminal ends of the respective prepolymer main chain.

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2- n-butyl, iso-butyl, tert, pentyl radical; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, iso-octyl radicals and the 2,2,4- trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; alkenyl radicals, such as vinyl, 1 -propenyl and 2-propenyl radicals; aryl radicals, such as the phenyl, 2- propenyl and 2-propenyl radicals; and phenyl-, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the a- and the B-phenylethyl radical.

The R radical is preferably a monovalent hydrocarbon radical having 1 to 6 carbon atoms which is optionally substituted by halogen atoms, particularly preferably an alkyl radical having 1 or 2 carbon atoms, in particular methyl radical.

Examples of radicals R¹ are hydrogen atoms, the radicals indicated for R and optionally substituted hydrocarbon radicals bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl groups.

Preferably, R¹ is hydrogen or hydrocarbon radicals with 1 to 20 carbon atoms, especially hydrogen.

Examples of R² are hydrogen or the examples given for R. Preferably, the R² radicals are hydrogen or alkyl radicals containing 1 to 10 carbon atoms, optionally substituted by halogen atoms, particularly preferably alkyl radicals containing 1 to 4 carbon atoms, in particular the methyl and ethyl radicals.

For the purposes of the present invention, polymers on which the polymer radical Y is based, are all polymers in which preferably at least 50%, more preferably at least 70%, particularly preferably at least 90%, of all bonds in the main chain are carbon-carbon, carbon-nitrogen or carbon-oxygen bonds. Polymer radical Y comprises poly-1 ,3-propanediol repeating units and optionally additional organic polymer repeating units, preferably from polyoxyalkylenes, such as polyoxyethylene, polyoxy-1 , 2- propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers, such as polyisobutylene, polyethylene or polypropylene and copolymers of polyisobutylene with isoprene; polyisoprenes; polyurethanes; polyesters; polyamides; polyacrylates; polymethacrylates; or polycarbonates, wherein Y is preferably bonded to each group -[(CR¹ ₂)b-SiR_a(OR²)_3-a]x via -O-C(=O)-NH- , -NH-C(=O)O-, -NH- C(=O)-NH-, -NR'-C(-O)-NH- , NH-C(=O)-NR'-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -O-C(=O)-, -O- C(=O)-O-, -S-C(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -S-C(=O)-, -S-C(=O)-S-, -C(-O) , -S-, -O- or -NR'- , wherein R' may be the same or different and has a meaning specified for R, or represents a group - CH(COOR")-CH2-COOR", wherein R" can be the same or different and has the meaning specified for R. Examples of radicals R' include cyclohexyl-, cyclopentyl-, n- and iso-propyl-, n-, iso- and t-butyl-, the various sterioisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical. R' is preferably a group - CH(COOR")-CH2-COOR" or an optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which is optionally substituted by halogen atoms; R" is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl, ethyl or propyl radical.

According to a preferred embodiment of the invention, the polymer radical Y in Formula (I) comprises poly-1 ,3-propanediol repeating units and optionally additional organic polymer repeating units from polyoxyalkylenes, in particular polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylenepolyoxybutylene copolymer; hydrocarbon polymers, in particular polyisobutylene, polyethylene or polypropylene or copolymers of polyisobutylene with isoprene; polyisoprenes; polyurethanes; polyesters; polyamides; polyacrylates; or polymethacrylates.

According to a particularly preferred embodiment of the invention, the radical Y in Formula (I) comprises poly-1 ,3-propanediol repeating units and optionally additional organic polymer repeating units from polyoxyalkylenes, in particular polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene- polyoxybutylene copolymer; polyurethanes; polyesters; polyacrylates; or polymethacrylates, more preferably polyoxyalkylenes, in particular polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylenepolyoxybutylene copolymer; polyurethanes; or polyesters.

According to the invention the polymer radical Y comprises poly-1 ,3-propanediol repeating units. Thus, Y preferably denotes an x-valent polymer radical, wherein said polymer is a homopolymer or copolymer of 1 ,3-propanediol. More preferably, Y comprises units having the general formula (VI) -(O-CH₂-CH₂-CH₂)_y- (VI) wherein y is within the range of from 5 to 250, preferably from 8 to 173, more preferably from 17 to 87, most preferably from 32 to 37. In addition, Y preferably denotes an x-valent polymer radical having a molecular weight within the range of from 500 Dalton to 10,000 Dalton, more preferably from 1 ,000 Dalton to 5,000 Dalton, most preferably from 1 ,900 Dalton to 2,100 Dalton.

According to a particularly preferred embodiment of the invention, Y denotes an x-valent polymer radical comprising poly-1 ,3-propanediol repeating units and optionally additional organic polymer repeating units from polyoxyalkylenes, in particular polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene-polyoxybutylene copolymer; polyurethanes; or polyesters, wherein said polymer radical has a hydroxyl number within the range of from 16 mg KOH/g to 350 mg KOH/g, more preferably from 36 mg KOH/g to 175 mg KOH/g, most preferably from 53 mg KOH/g to 60 mg KOH/g, wherein said hydroxyl number can be experimentally determined by means of potentiometric titration, as a measure for the number of free hydroxyl groups in the relevant defined reference amount, for example per gram of the x-valent polymer radical.

According to a particularly preferred embodiment of the invention, the compound of Formula (I) comprises from 10 wt.% to 100 wt.%, preferably from 10 wt.% to 80 wt.%, more preferably from 40 wt.% to 60 wt.% of poly-1 ,3-propanediol moieties, based on the total amount of the compound of Formula (I), wherein Y preferably comprises from 10 wt.% to 100 wt.% of biogenic carbon, more preferably from 50 wt.% to 100 wt.% of biogenic carbon, based on the total amount of carbon in Y. Most preferably, Y is made from 1 ,3-propandiol with 100 wt. % of biogenic carbon and the compound of Formula (I) is also made by use of at least 30 wt.%, more preferably at least 40wt.%, in particular at least 48 wt.%, of biogenic carbon, based on the total amount of carbon in the compound of Formula (I).

Said bio-based or biogenic carbon is differentiated from petroleum-based carbon in accordance with differentiation methodology described in Standard ASTM D6866. It is known in the art that carbon-14 (C-14), which has a half-life of about 5,700 years, is found in biobased or biogenic materials but not in fossil fuels. Thus, "bio-based" or "biogenic" materials refer to organic materials in which the carbon comes from non-fossil biological sources. Examples of biobased or biogenic materials include, but are not limited to, sugars, starches, corns, natural fibers, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and any combination thereof.

As used herein, the term “biobased carbon” refers to organic carbon of renewable origin like agricultural, plant, animal, fungi, microorganisms, marine, or forestry materials living in a natural environment in equilibrium with the atmosphere.

As used herein, the term “biogenic carbon” refers to carbon (organic and inorganic) of renewable origin like agricultural, plant, animal, fungi, microorganisms, macroorganisms, marine, or forestry materials.

The detection of C-14 is indicative of a bio-based or biogenic material. C-14 levels can be determined by measuring its decay process (disintegrations per minute per gram carbon or dpm/gC) through liquid scintillation counting and this technique has been used for decades by archaeologists to date fossils.

In Formula (I), the radical Y preferably denotes poly-1 ,3-propanediol repeating units-containing polyurethane radicals, poly-1 ,3-propanediol repeating units-containing polyoxypropylene radicals, poly-1 ,3-propanediol repeating units-containing polyester radicals or poly-1 ,3-propanediol repeating units-containing polyacrylate radicals. In particular, Y preferably denotes an x-valent polymer radical, wherein said polymer is a homopolymer of 1 ,3-propanediol.

Compounds of Formula (I) can have the groups -[(CR¹2)b-SiR_a(OR²)3-_a]x bound in the manner described at any desired position in the polymer, such as located at the terminal ends or located in between the terminal ends, i.e., as side groups of the polymer main chain, particularly preferably at the terminal ends of the polymer chain.

The end groups of the compounds according to Formula (I) are preferably those of the Formula (II) or Formula (III)

-O-C(=O)-NH-(CR¹ ₂)b-SiR_a(OR²)_3-a (II) and

-NH-C(=O)-NR'-(CR¹ ₂)b-SiR_a(OR²)_3-a (III), wherein the residues and indices are as above defined. Particularly, a compound according to Formula (I) may denote silane-terminated polyethers and silane- terminated polyurethane-polyethers, in particular silane-terminated polypropylene glycols and silane- terminated polyurethane-polyethers each having dimethoxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl or triethoxysilyl end groups bonded via -O-C(=O)-NH-(CR¹2)b- groups or -NH- C(=O)-NR'-(CR¹2)b-groups, wherein R', R¹ and b are as defined above.

The average molecular weights M_n of the compounds according to Formula (I) are preferably at least 400 g/mol, particularly preferably at least 600 g/mol, in particular at least 800 g/mol and preferably at most 30 000 g/mol, particularly preferably at most 19 000 g/mol, in particular at most 13 000 g/mol.

The viscosity of compounds according to Formula (I) is preferably at least 0.2 Pas, preferably at least 1 Pas, particularly preferably at least 5 Pas, and preferably at most 1 ,000 Pas, preferably at most 700 Pas, each measured at 20°C.

According to various preferred embodiments, the compound according to Formula (I) comprises at least one polymer having at least one silane-functional group of the Formula (IV)

-Xo-R³-Si(R⁴)_k(R⁵)₃-k (IV), wherein

X is a divalent linking group containing at least one heteroatom;

R³ is selected from divalent hydrocarbon residues having 1 to 12 carbon atoms; each R⁴ is, independently of one another, selected from a hydrocarbon radical containing 1 to 20 carbon atoms and each R⁵ is, independently of one another, selected from a hydroxyl group or a hydrolysable group, wherein R⁴ and R⁵ are substituents directly bound with the Si atom orthe two of the substituents R⁴ and R⁵ form a ring together with the Si atom to which they are bound; k is 0, 1 , or 2; and o is 0 or 1 .

In this context, the divalent bonding group (linking group) X comprising at least one heteroatom is understood to be a divalent chemical group which links the polymer backbone of the polymer with the residue R³ of the Formula (IV).

In various embodiments, the divalent linking group X in the Formula (IV) is selected from -O-, -S-, - N(R")-, -R”’-O-, a substituted or unsubstituted amide, carbamate, urethane, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group, wherein R” is a hydrogen or a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms; and R’” is a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms. The term “substituted” in relation to these groups means that a hydrogen atom present in these groups may be replaced by a non-hydrogen moiety, such as alkyl or aryl groups, preferably C1-12 alkyl or Ce-14 aryl groups.

In preferred embodiments, the linking group X is urethane or urea group, more preferably urethane group. Urethane group can be formed, for example, either when the polymer backbone comprises terminal hydroxy groups and isocyanatosilanes are used as a further component, or conversely when a polymer having terminal isocyanate groups is reacted with an alkoxysilane comprising terminal hydroxy groups. Similarly, urea group can be obtained if a terminal primary or secondary amino group - either on the silane or on the polymer - is used, which reacts with a terminal isocyanate group that is present in the respective reactant. This means that either an aminosilane is reacted with a polymer having terminal isocyanate groups or a polymer that is terminally substituted with an amino group is reacted with an isocyanatosilane. Urethane and urea groups advantageously increase the strength of the polymer chains and of the overall crosslinked polymer.

In preferred embodiments, the linking group X is selected from the group consisting of -O-C(=O)-N(R”)- , -N(R”)-C(=O)O-, -N(R”)-C(=O)-N(R”)-, -N(R”)-C(=O)-, -C(=O)-N(R”)-, -C(=O)-O-, -O-C(=O)-, -O- C(=O)-O-, -S-C(=O)-N(R”)-, -N(R”)-C(=O)-S- , -C(=O)-S-, -S-C(=O)-, -S-C(=O)-S- , -C(=O)-, -S-, -O-, - NR”-, and -R”’-O-, wherein R” and R’” are as defined above. In more preferred embodiments, the linking group X is selected from -O-C(=O)-N(R”)-, -N(R”)-C(=O)O-, -N(R”)-C(=O)-N(R”)-, -S-, - O-, -N(R”)-, or -R”’-O-, wherein R” and R’” are as defined above. In particularly preferred embodiments, the linking group X is selected from -O-C(=O)-N(R”)-, -N(R”)-C(=O)-N(R”)-, -O-, or - R”’-O-, wherein R” and R’” are as defined above, more preferably -O-C(=O)-NH- or -NH-C(=O)-NH-, most preferably -O-C(=O)- NH-.

The index "0" corresponds to 0 (zero) or 1 , i.e., the linking group X links the polymer backbone with the residue R³ (0 = 1), or the polymer backbone is bound or linked directly with the residue R³ (0 = 0). In preferred embodiments, 0 is 1.

The residue R³ is a divalent hydrocarbon residue having 1 to 12 carbon atoms. The hydrocarbon residue can be a linear, branched or cyclic alkylene residue and can be substituted or unsubstituted. The hydrocarbon residue can be saturated or unsaturated. In preferred embodiments, R³ is a divalent hydrocarbon residue having 1 to 6 carbon atoms. The curing rate of the composition can be influenced by the length of the hydrocarbon residues which form one of the binding links or the binding link between polymer backbone and silyl residue. Particularly preferably, R³ is a methylene, ethylene or n- propylene, in particular a methylene or n-propylene.

Alkoxysilane-functional compounds having a methylene group as binding link to the polymer backbone - so-called “a silanes” - have a particularly high reactivity of the silyl group. In general, a lengthening of the binding hydrocarbon chain leads to reduced reactivity of the polymers. In particular, “y silanes” - which comprise the unbranched propylene residue as binding link - have a balanced ratio between necessary reactivity (acceptable curing times) and delayed curing (open assembly time, possibility of corrections after bonding).

R⁴ and R⁵ are substituents directly bound with the Si atom or the two of the substituents R⁴ and R⁵ can form a ring together with the Si atom to which they are bound. In preferred embodiments, R⁴ and R⁵ are the substituents directly bound with the Si atom.

Each R⁴ in the Formula (IV) is, independently of one another, selected from a hydrocarbon radical containing 1 to 20 carbon atoms, preferably Ci to Ca alkyl groups, more preferably a methyl or an ethyl.

Each R⁵ in the Formula (IV) is, independently of one another, selected from a hydroxyl group or a hydrolysable group, preferably Ci to Ca alkoxy groups, or Ci to Ca acyloxy groups.

In preferred embodiments, each R5 is, independently of one another, selected from Ci to Ca alkoxy groups, in particular methoxy, ethoxy, i-propyloxy or i-butyloxy group. When k is 0 or 1 , combinations of more than one group are also possible. However, acyloxy groups, such as an acetoxy group -O-CO- CHa, can also be used as hydrolyzable groups.

In preferred embodiments, k is 0 or 1 .

In particularly preferable embodiments, the silyl group, i.e., -Si(R⁴)k(R⁵)3-k, is selected from alkyldialkoxysilyl or trialkoxysilyl, preferably selected from methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl, most preferably methyldimethoxysilyl or trimethoxysilyl. Alkoxy groups are advantageous, since no substances which irritate mucous membranes are released during the curing of compositions comprising alkoxy groups. The alcohols formed by hydrolysis of the residues are harmless in the quantities released and evaporate.

In general, polymers comprising di- or trialkoxysilyl groups have highly reactive linking points which permit rapid curing, high degrees of crosslinking and thus good final strengths. The particular advantage of dialkoxysilyl groups lies in the fact that, after curing, the corresponding compositions are more elastic, softer and more flexible than systems comprising trialkoxysilyl groups. They are therefore suitable in particular for use as sealants. In addition, they split off even less alcohol during curing and are therefore of particular interest when the quantity of alcohol released is to be reduced.

With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a harder, stronger material is desired after curing. In addition, trialkoxysilyl groups are more reactive and therefore crosslink more rapidly, thus reducing the quantity of catalyst required, and they have advantages in "cold flow" - the dimensional stability of a corresponding cured material under the influence of feree and possibly temperature.

Methoxy and ethoxy groups as comparatively small hydrolyzable groups with low steric bulk are very reactive and thus permit a rapid cure, even with low use of catalyst. They are therefore of particular interest for systems in which rapid curing is desirable.

Interesting configuration possibilities are also opened up by combinations of the two groups. If, for example, methoxy is selected for one of the R⁵ and ethoxy for the other R^b within the same alkoxysilyl group, the desired reactivity of the silyl groups can be adjusted particularly finely if silyl groups carrying exclusively methoxy groups are deemed too reactive and silyl groups carrying ethoxy groups not reactive enough for the intended use.

In addition to methoxy and ethoxy groups, it is of course also possible to use larger residues as hydrolyzable groups, which by nature exhibit lower reactivity. This is of particular interest if delayed curing is also to be achieved by means of the configuration of the alkoxy groups.

The silane-functional group of Formula (IV) can be a lateral group within the polymer chain of the respective polymer or a terminal group of the respective polymer. In preferred embodiments, the silane- functional group of Formula (IV) is a terminal group of the polymer.

In preferred embodiments, the polymer has at least two silane-functional groups of Formula (IV). In this case, the polymer can have at least one lateral silane-functional group of Formula (IV) and at least one terminal silane-functional group of Formula (IV); or at least two lateral silane-functional groups of Formula (IV); or at least two terminal silane-functional groups of Formula (IV).

In particularly preferred embodiments, the polymer has at least two terminal silane-functional groups of Formula (IV). Then, each polymer chain comprises at least two linking points at which the condensation of the polymers can be completed, splitting off the hydrolyzed residues in the presence of atmospheric moisture. In this way, regular and rapid crosslinkability is achieved so that bonds with good strengths can be obtained. In addition, by means of the quantity and the structure of the hydrolyzable groups - for example by using di- or trialkoxysilyl groups, methoxy groups or longer residues - the configuration of the network that can be achieved as a long-chain system (thermoplastics), relatively wide-mesh three-dimensional network (elastomers) or highly crosslinked system (thermosets) can be controlled, so that inter alia the elasticity, flexibility and heat resistance of the finished crosslinked compositions can be influenced in this way. In preferred embodiments, the polymer backbone of the polymer is selected from polyethers, poly(meth)acrylic acid ester-polyethers, polyester-polyethers, polyurethane-polyethers, poly-a-olefin- polyethers, more preferably polyethers or polyurethane-polyethers, or copolymers of at least two of said polymers such as polyether and poly(meth)acrylic acid ester-polyether-copolymers.

A “polyether”, “polyoxyalkylene”, or “polyalkylene glycol”, as used interchangeably herein, is understood to be a polymer in which the organic repeating units comprise ether functionalities C-O-C in the main chain. Examples for such polymers are polypropylene glycol and polyethylene glycol and copolymers thereof. Polymers having lateral ether groups, such as cellulose ethers, starch ethers and vinyl ether polymers, as well as polyacetals such as polyoxymethylene (POM) are not included in the polyethers.

A “poly(meth)acrylic acid ester” is understood to be a polymer based on (meth)acrylic acid esters, which therefore has as a repeating unit the structural motif -CH2-CR’(COOR”)-, where R’ denotes a hydrogen atom (acrylic acid ester) or a methyl group (methacrylic acid ester) and R” denotes linear alkyl residues, branched alkyl residues, cyclic alkyl residues and/or alkyl residues comprising functional substituents, for example methyl, ethyl, isopropyl, cyclohexyl, 2-ethylhexyl or 2-hydroxyethyl residues.

A “polyurethane" is understood to be a polymer which has at least two urethane groups -NH-CO-O-in the main chain.

In particularly preferred embodiments, the silane-modified polymer has a polyether backbone. Polyethers have a flexible and elastic structure, with which compositions having excellent elastic properties can be produced. Polyethers are not only flexible in their backbone, but at the same time strong. Thus, for example, polyethers are not attacked or decomposed by water and bacteria, in contrast to, e.g., polyesters, for example.

The number average molecular weight M_n of the polyether on which the polymer is based is for preference 500 g/mol to 100,000 g/mol (daltons), more preferably 500 g/mol to 50,000 g/mol, particularly preferably 1 ,000 g/mol to 30,000 g/mol and in particular 2,000 g/mol to 20,000 g/mol, most preferably 8,000 g/mol to 20,000 g/mol. Number average molecular weights of at least 500 g/mol are advantageous for the polyethers of the present invention since the corresponding compositions have a balanced ratio of viscosity (ease of processing), strength and elasticity.

The silane-modified polymers discussed above are can be synthesized using known methods and processes, such as addition reactions, e.g., hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds containing isocyanate-active groups. In this regard, reference may be made to, for instance EP1535940B1 and EP1896523B1. Alternative synthetic routes are further disclosed in WO 2013/026654 A1 .

The amount of one or more compound of Formula (I), i.e., one type of compound of Formula (I) or different kinds of compound of Formula (I), i.e., two or more different kinds of compound of Formula (I), as herein defined above, in the curable composition of the invention is typically in the range of about 10 to about 95 wt.-%, preferably in the range of about 10 to about 90 wt.-%, even more preferably in the range of about 15 to about 85 wt.-%, for instance about 15, 16, 17, 18,19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85 wt.-%, based on the total weight of curable composition.

In the context of the aforementioned curable compositions, it will be readily recognized that, in addition to generally fast curing rates, a prominent advantage of curable compositions of the invention is that neither tin catalysts nor strong acids or bases need be included for curing purposes.

A typical curable composition of the invention further comprises, in addition to the aforementioned component of Formula (I), further ingredients generally known in the art for the purpose of inclusion in curable, particularly moisture curable compositions. A non-exhaustive list of further ingredients to be optionally included comprises further reactive silane or siloxane compounds, fillers, catalysts, adhesion promotors, water scavengers, reactive and non-reactive diluents, solvents, plasticizers, rheology modifiers, preservatives, UV stabilizers, pigments and colorants.

Suitable curable compositions of the invention can be used both in pure form and in the form of a solution or emulsion or suspension.

Suitable solvents may be selected from ethers (e.g. diethyl ether, methyl-t-butyl ether, ether derivatives of glycol, THF), esters (e.g. ethyl acetate, butyl acetate, glycol ester), hydrocarbons (e.g. (e.g. pentane, cyclopentane, hexane, cyclohexane, heptane, octane or also longer-chained branched and unbranched alkanes), ketones (e.g. acetone, methyl ethyl ketone), aromatics (e.g. acetone, methyl ethyl ketone), aromatics (e.g. ethyl acetate, butyl acetate, glycol esters) (e.g. toluene, xylene, ethylbenzene, chlorobenzene) and alcohols (e.g. methanol, ethanol, glycol, propanol, isopropanol, glycerine, butanol, iso-butanol, t-butanol).

However, curable compositions that are free of organic solvents may be preferred due to ecological and/or health concerns. In various embodiments, the curable composition of the invention is thus substantially free of organic solvent. In the context of the present invention, the term “substantially free” refers to compositions comprising less than about 1 wt.-%, preferably less than about 0.5 wt.-%, more preferably less than about 0.1 wt.% of the respective ingredient. For instance, a composition substantially free of organic solvent comprises, in the context of the present invention, less than about 1 wt.-% organic solvent.

(II) surface treated silica

According to preferred embodiments, the curable composition of the invention comprises surface- treated silica.

The silica preferably has a BET surface area of 10 to 250 m²/g. When it is used, it can cause additional increase in the viscosity of the curable composition to achieve a thixotropic formulation and it can contribute to strengthening the cured compostion.

It is likewise conceivable to use silica with a BET surface area, advantageously with 100 to 250 m²/g, particularly 110 to 170 m²/g, as a filler. Because of the higher BET surface area, the same effect, e.g., strengthening ofthe cured composition, can be achieved at a smallerweight proportion of silicic acid. Further substances can thus be used to improve the composition described herein in terms of other requirements.

(III) catalyst

According to preferred embodiments, the curable composition comprises at least one curing catalyst, preferably selected from tin catalysts, titanium catalysts, aluminum catalysts, or zirconium catalysts, more preferably tin catalysts or titanium catalysts, or mixtures thereof.

In various embodiments, the curing catalyst may be a tin compound, preferably an organotin compound or an inorganic tin salt. Tin in these tin compounds is preferably bivalent or tetravalent. The curing catalyst can be added to the composition particularly as a crosslinking catalyst. Suitable inorganic tin salts are, for example, tin(ll) chloride and tin(IV) chloride. Organotin compounds (tin organyles) are used preferably as the tin compounds, however. Suitable organotin compounds are, for example, the 1 ,3-dicarbonyl compounds of bivalent or tetravalent tin, for example, the acetylacetonates such as di(n- butyl)tin(IV) di(acetylacetonate), di(n-octyl)tin(IV) di(acetylacetonate), (n-octyl)(n-butyl)tin(IV) di(acetylacetonate); the dialkyl tin(IV) dicarboxylates, for example, di-n-butyltin dilaurate, di-n-butyltin maleate, di-n-butyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin diacetate, or the corresponding dialkoxylates, for example, di-n-butyltin dimethoxide; oxides of tetravalent tin, for example, dialkyltin oxides, such as, for example, di-n-butyltin oxide and di-n-octyltin oxide; and the tin(ll) carboxylates such as tin(ll) octoate or tin(ll) phenolate. Suitable furthermore are tin compounds of ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, nonadecylic acid, myristic acid, such as, for example, di(n-butyl)tin(IV) di(methyl maleate), di(n-butyl)tin(IV) di(butyl maleate), di(n- octyl)tin(IV) di(methyl maleate), di(n-octyl)tin(IV) di(butyl maleate), di(n-octyl)tin(IV) di(isooctyl maleate); and di(n-butyl)tin(IV) sulfide, (n-butyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2COO), (n- octyl)₂Sn(SCH₂CH₂COO), (n-octyl)₂Sn(SCH2CH2COOCH2CH₂OCOCH2S), (n-butyl)₂-Sn(SCH₂COO-i- CaHi7)2, (n-octyl)2Sn(SCH2COO-i-CaHi7)2, and (n-octyl)2Sn(SCH2COO-n-CaHi7)2.

Preferably, the tin compound is selected from 1 ,3-dicarbonyl compounds of bivalent or tetravalent tin, the dialkyltin(IV) dicarboxylates, the dialkyltin(IV) dialkoxylates, the dialkyltin(IV) oxides, the tin(ll) carboxylates, and mixtures thereof.

Particularly preferably, the tin compound is a dialkyltin(IV) oxide (e. g. di-n-octyltin oxide) or dialkyltin(IV) dicarboxylate, particularly di-n-butyltin dilaurate, di-n-butyltin diacetate, or di-n-octyltin dilaurate.

Additionally, or alternatively, other metal-based condensation catalysts may be used, including, without limitation, compounds of titanium such as organotitanates or chelate complexes, cerium compounds, zirconium compounds, molybdenum compounds, manganese compounds, copper compounds, aluminum compounds, orzinc compounds ortheir salts, alkoxylates, chelate complexes, or catalytically active compounds of the main groups or salts of bismuth, lithium, strontium, or boron.

Further suitable (tin-free) curing catalysts are, for example, organometallic compounds of iron, particularly the 1 ,3-dicarbonyl compounds of iron such as, e.g., iron(lll) acetylacetonate.

Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixtures of boron halides can also be used as curing catalysts. Particularly preferred are boron trifluoride complexes such as, e.g., boron trifluoride diethyl etherate, which as liquids are easier to handle than gaseous boron halides.

Further, amines, nitrogen heterocycles, and guanidine derivatives are suitable in general for catalysis. An especially suitable catalyst from this group is 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Titanium, aluminum, and zirconium compounds, or mixtures of one or more catalysts from one or more of the just mentioned groups may also be used as catalysts.

Suitable as titanium catalysts are compounds that have hydroxy groups and/or substituted or unsubstituted alkoxy groups, therefore titanium alkoxides of the general formula

Ti(OR^z)₄, wherein R^z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, and the 4 alkoxy groups -OR^Z are identical or different. Further, one or more of the -OR^Z groups can be replaced by acyloxy groups -OCOR^Z.

Likewise suitable as titanium catalysts are titanium alkoxides in which one or more alkoxy groups are replaced by a hydroxy group or halogen atoms.

Further, titanium chelate complexes can be used.

Aluminum catalysts can also be used as curing catalysts, e.g., aluminum alkoxides

AI(OR^Z)₃, wherein R^z has the above meaning; i.e., it is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms and the three R^z groups are identical or different. In the case of aluminum alkoxides as well, one or more of the alkoxy groups can be replaced by acyloxy groups - OC(O)R^Z.

Further, aluminum alkoxides can be used in which one or more alkoxy groups are replaced by a hydroxy group or halogen atoms.

Of the described aluminum catalysts, the pure aluminum alcoholates are preferred in regard to their stability to moisture and the curability of the mixtures to which they are added. In addition, aluminum chelate complexes are preferred.

Suitable as zirconium catalysts are, e.g.: tetramethoxyzirconium or tetraethoxyzirconium.

Diisopropoxyzirconium bis(ethyl acetoacetate), triisopropoxyzirconium (ethyl acetoacetate), and isopropoxyzirconium tris(ethyl acetoacetate) are used with very particular preference.

Further, zirconium acylates, halogenated zirconium catalysts, or zirconium chelate complexes can also be used.

In addition, carboxylic acid salts of metals or also a mixture of a number of such salts can be employed as curing catalysts, whereby these are selected from the carboxylates of the following metals: calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt, and/or zirconium.

Of the carboxylates, the calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, and zirconium carboxylates are preferred, because they exhibit a high activity. Calcium, vanadium, iron, zinc, titanium, and zirconium carboxylates are particularly preferred. Won and titanium carboxylates are very particularly preferred.

Further, phosphorous containing organic compounds or mixtures thereof can be used as alternative to metal-based catalysts. Examples are triethylphosphat or 2-ethylhexyl-phosphat.

Alternatively strong Bronstedt acids, especially organic acids such as dodecylbenzenesulfonic acid can be used as catalysts.

(IV) compound containing units of Formula (V)

According to preferred embodiments, the curable composition of the invention comprises at least one compound containing units of Formula (V)

R⁶c(R⁷O)dR⁸eSiO(4-c-d-e)/2 (V) wherein R⁶ is independently selected from hydrogen, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted aliphatic hydrocarbon radical, which bridges two units of the Formula (V), R⁷ is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical, R⁸ is independently selected from a monovalent, SiC-bound, optionally substituted aromatic hydrocarbon residue, c is 0, 1 , 2 or 3, d is 0, 1 , 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1 , and e is 0, 1 or 2, preferably 0 or 1 , with the proviso that the sum of c+d+e is less than or equal to 3, wherein in at least 40% of the units of Formula (V) the sum c+e is preferably equal to 0 or 1 .

In preferred embodiments, a compound containing units of Formula (V) contains units of Formula (V) in amounts of about 80 wt.-%, preferably about 85, more preferably at least about 90 wt.-%. Even more preferably, a compound containing units of Formula (V) consists of units of Formula (V).

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2- n-butyl, iso-butyl, tert.-pentyl radical; hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical, iso-octyl radicals and the 2,2, - trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; alkenyl radicals, such as vinyl, 1 -propenyl and 2-propenyl radicals; aryl radicals, such as the phenyl, 2- propenyl and 2-propenyl radicals; and phenyl-, naphthyl, anthryl and phenanthryl radicals; alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the a- and the B-phenylethyl radical.

Examples of residues R⁶ are the aliphatic examples given above for R. However, R⁶ can also be a divalent aliphatic radical, which links two silyl groups of Formula (V), such as alkylene radicals having 1 to 10 carbon atoms, such as methylene, ethylene, propylene or butylene radicals. A particularly common example of a divalent aliphatic radical is the ethylene radical. However, the radical R⁶ is preferably a monovalent SiC-bonded aliphatic hydrocarbon radical with 1 to 18 carbon atoms, which may be substituted with halogen atoms, particularly preferably aliphatic hydrocarbon radicals with 1 to 6 carbon atoms, especially the ethyl radical.

Examples for residue R⁷ are hydrogen atom or the examples given for residue R. Preferably, the R⁷ radical is a hydrogen atom or an alkyl radical with 1 to 10 carbon atoms that is optionally substituted with halogen atoms, particularly preferably an alkyl radical with 1 to 4 carbon atoms, especially the methyl and ethyl radical.

Examples of radicals R⁸ are the aromatic radicals indicated above for R. Particularly, the R⁸ radicals are SiC-bonded aromatic hydrocarbon radicals with 1 to 18 carbon atoms, optionally substituted with halogen atoms, such as ethylphenyl, tolyl, xylyl, chlorophenyl, naphthyl or styryl radicals, particularly preferably the phenyl radical.

Preferred are curable compositions in which at least 90% of all R⁶ radicals are methyl radicals, at least 90% of all R⁷ radicals are methyl, ethyl, propyl or isopropyl radicals and at least 90% of all R⁸ radicals are phenyl radicals.

Particularly, curable compositions of the invention may be used, which have at least 20%, particularly preferably at least 40%, of units of the Formula (V) in which c is equal to 0, in each case based on the total number of units of Formula (V).

Further, curable compositions may be used, which, in each case based on the total number of units of Formula (V), have at least 10%, particularly preferably at least 20%, and at most 80%, particularly preferably at most 60%, of units of Formula (V) in which c is 2. Curable compositions are preferably used which, in each case based on the total number of units of Formula (V), contain at least 80%, particularly preferably at least 95%, of units of Formula (V) in which d is 1 or 0.

Further preferred curable compositions are those, which, in each case based on the total number of units of Formula (V), contain at least 60%, particularly preferably at least 70%, preferably at most 99%, particularly preferably at most 97%, of units of Formula (V), in which d is 0.

Further preferred examples of curable compositions are those, which, in each case based on the total number of units of Formula (V), have at least 1 %, preferably at least 10%, in particular at least 20%, of units of Formula (V), in which e is not equal to 0. Furthermore, curable compositions may be used, which exclusively contain units of Formula (V), in which e is not equal to 0, but particularly preferably at least 10%, particularly preferably at least 20%, preferably at most 80%, particularly preferably at most 60%, of the units of Formula (V) have e equal 0.

Further examples of the above defined curable compositions are those, which, in each case based on the total number of units of Formula (V), have at least 20%, particularly preferably at least 40%, of units of Formula (V), in which e is 1 . Curable compositions may be used, which exclusively comprise units of Formula (V), in which e equals 1 , but particularly preferably at least 10%, particularly preferably at least 20%, preferably at most 80%, particularly preferably at most 60%, of the units of Formula (V) have e equal 0.

Further examples of the curable compositions are those, which, based on the total number of units of Formula (V), have at least 50% of units of Formula (V), in which the sum of c+e is 0 or 1 .

Further examples of the curable compositions are those, which, in each case based on the total number of units of the Formula (V), have at least 20%, particularly preferably at least 40%, of units of Formula (V), in which e is 1 and c is 0. Preferably, at most 70%, particularly preferably at most 40% of all units of Formula (V) have d not equal 0.

Furthermore, those curable compositions may be advantageously used, which, in each case based on the total number of units of Formula (V), have at least 20%, particularly preferably at least 40%, of units of Formula (V), in which e denotes and c equals 0, and which additionally have at least 1 %, preferably at least 10%, of units of Formula (V), wherein c denotes 1 or2, preferably 2, and e equals 0. Particularly at most 70%, more particularly preferably at most 40% of all units of Formula (V) have d not equal 0 and at least 1 % of all units of Formula (V) have d equal 0. According to a particularly preferred embodiment of the invention, the curable composition comprises at least one organosilicon compound selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1 ,2-bis(triethoxysilyl)ethane and their partial hydrolysates, yet more preferably tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane and/or their partial hydrolysates.

(V) aminosilane and/or aminosilane oligomer

According to preferred embodiments, the curable composition of the invention comprises at least one aminosilane and/or aminosilane oligomer, preferably as adhesion promoters.

Said aminosilanes may be selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-amino- ethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylamino-methyl- trimethoxy-silane, (N-2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N- phenylamino)propyl-trimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N- dimethylaminopropyl)aminopropylmethyldimethoxysilane, tri[(3-triethoxysilyl)propyl]amine, tri[(3- trimethoxysilyl)propyl]amine, and the oligomers thereof, 3-(N,N- dimethylamino)propyltrimethoxysilane, 3-(N,N-dimethylamino)propyltriethoxysilane, (N,N- dimethylamino)methyltri methoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N- diethylamino)propyltri methoxysilane, 3-(N,N-diethylamino)-propyltriethoxysilane, (N,N- diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3- trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyltrimethoxy silane, 4-amino-3,3-dimetylbutyltriethoxy silane, N-(n-butyl)-3-aminopropyltrimethoxysilane, and mixtures thereof, particularly preferably of 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-(N,N- dimethylamino)propyl-tri methoxysilane, 3-(N,N-dimethylamino)propyltriethoxysilane, (N,N- dimethylamino)methyl-trimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N- diethylamino)propyltri methoxysilane, 3-(N,N-diethylamino)-propyltriethoxysilane, (N,N- diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyl-triethoxysilane, bis(3- trimethoxysilyl)propylamine, and bis(3-triethoxysilyl)propylamine, 4-amino-3,3- dimethylbutyltrimethoxy silane, 4-amino-3,3-dimetylbutyltriethoxy silane, or N-(n-butyl)-3- aminopropyltrimethoxysilane, or oligomers obtained from the condensation of at least one of the above-mentioned aminosilanes, or mixtures thereof. The above-mentioned monomeric aminosilanes or oligomers can be oligomerized together with alkyl-, alkenyl- or aryl-alkoxysilanes, preferably methyltri(m)ethoxysilane, ethyltri(m)ethoxysilane, propyltri(m)ethoxysilane, vinyltri(m)ethoxysilane, n-butyltri(m)ethoxysilane, isobutyltri(m)ethoxysilane, phenyltri(m)ethoxysilane, and/or octyltri(m)ethoxysilane.

In various embodiments, the curable composition further comprise at least one aminosilane as described above, in particular one of the tertiary aminosilanes. “Tertiary aminosilane”, as used herein, refers to an aminosilane wherein the nitrogen atom of the amino group is covalently linked to three non-hydrogen residues.

(VI) surface-treated calcium carbonate

According to preferred embodiments, the curable composition of the invention optionally comprises surface-treated calcium carbonate.

Preferred surface treated calcium carbonate particles comprise a treatment layer on the surface of the calcium carbonate particles comprising i. at least one aliphatic aldehyde and/or salty reaction products thereof, and/or ii. at least one mono-substituted succinic anhydride consisting of succinic anhydride monosubstituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or salty reaction products thereof, and/or

Hi. at least one polydialkylsiloxane, and/or iv. at least one alkylsilane, and/or v. mixtures of the materials according to i. to iv.

Particularly preferred surface treated calcium carbonate particles comprise a hydrophobic coating and are preferably coated with alkylsilane with comprising 4 to 22 carbon atoms e.g., hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane and others or aliphatic carboxylic acid or a salt thereof. Saturated or unsaturated carboxylic acids comprising 4 to 22 carbon atoms, preferably comprising 6 to 16 carbon atoms, more preferably comprising 10 to 12 carbon atoms are also particularly preferred for said coating, wherein saturated carboxylic acids are most preferred. In that context, use of lauric acid and of stearic acid, especially of stearic acid is particularly favored.

(VII) one further silane-modified polymer

According to preferred embodiments, the curable composition of the invention optionally comprises at least one further silane-modified polymer, preferably a compound of Formula (I’)

Y’-[(CR¹ ₂)b-SiRa(OR²)3-a]x (I’) wherein, in Formula (I’),

Y denotes an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon, R is independently selected from a monovalent, optionally substituted, SiC-bonded hydrocarbon radical,

Examples of R² are hydrogen or the examples given for R.

Preferably, the R² radicals are hydrogen or alkyl radicals containing 1 to 10 carbon atoms, optionally substituted by halogen atoms, particularly preferably alkyl radicals containing 1 to 4 carbon atoms, in particular the methyl and ethyl radicals. For the purposes of the present invention, polymers on which the polymer radical Y’ is based, are all polymers in which at least 50%, preferably at least 70%, of all bonds in the main chain are carboncarbon, carbon-nitrogen or carbon-oxygen bonds. Polymer residues Y are preferably organic polymer residues which are polyoxyalkylenes, such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylenepolyoxybutylene copolymer as polymer chain; hydrocarbon polymers, such as polyisobutylene, polyethylene or polypropylene and copolymers of polyisobutylene with isoprene; polyisoprenes; polyurethanes; polyesters; polyamides; polyacrylates; polymethacrylates; and polycarbonates and which preferably are bonded to each group -[(CR¹2)b-SiR_a(OR²)3-_a]x via -O-C(=O)-NH- , -NH-C(=O)O-, -NH-C(=O)-NH-, -NR'-C(-O)-NH- , NH-C(=O)-NR'-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -O-C(=O)-, - O-C(=O)-O-, -S-C(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -S-C(=O)-, -S-C(=O)-S-, -C(-O) , -S-, -O- or - NR'-, wherein R' may be the same or different and has a meaning specified for R, or represents a group -CH(COOR")-CH2-COOR", wherein R" can be the same or different and has the meaning specified for R. Examples of radicals R' include cyclohexyl-, cyclopentyl-, n- and iso-propyl-, n-, iso- and t-butyl-, the various sterioisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical. R' is preferably a group - CH(COOR")-CH2-COOR" or an optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which is optionally substituted by halogen atoms; R" is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl, ethyl or propyl radical.

In Formula (I’), the radical Y’ preferably denotes polyoxyalkylene radicals, especially polyoxypropylene- containing polyurethane radicals or polyoxypropylene radicals.

Compounds of Formula (I’) can have the groups -[(CR¹2)b-SiR_a(OR²)3-_a]x bound in the manner described at any desired position in the polymer, such as located at the terminal ends or located in between the terminal ends, i.e. as side groups of the polymer main chain, particularly preferably at the terminal ends of the polymer chain.

The end groups of the compounds according to Formula (I’) are preferably those of the Formula (IT) or Formula (III’)

-O-C(=O)-NH-(CR¹ ₂)b-SiR_a(OR²)_3-a (II’) and

-NH-C(=O)-NR'-(CR¹2)b-SiR_a(OR²)_3.a (III’), wherein the residues and indices are as above defined.

Particularly, a compound according to Formula (I) may denote silane-terminated polyethers and silane- terminated polyurethanes, in particular silane-terminated polypropylene glycols and silane-terminated polyurethanes each having dimethoxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl or triethoxysilyl end groups bonded via -O-C(=O)-NH-(CR¹2)b- groups or -NH-C(=0)-NR'-(CR¹2)b-groups, wherein R', R¹ and b are as defined above.

The average molecular weights M_n of the compounds according to Formula (I’) are preferably at least 400 g/mol, particularly preferably at least 600 g/mol, in particular at least 800 g/mol and preferably at most 30 000 g/mol, particularly preferably at most 19 000 g/mol, in particular at most 13 000 g/mol.

The viscosity of compounds according to Formula (I’) is preferably at least 0.2 Pas, preferably at least 1 Pas, particularly preferably at least 5 Pas, and preferably at most 1 ,000 Pas, preferably at most 700 Pas, each measured at 20°C. polymer (VII)

According to various preferred embodiments, the silane-modified polymer (VII) comprises at least one polymer having at least one silane-functional group of the Formula (IV’)

-X₀-R³-Si(R⁴)k(R⁵ k (IV’), wherein

X is a divalent linking group containing at least one heteroatom;

In this context, the divalent bonding group (linking group) X comprising at least one heteroatom is understood to be a divalent chemical group which links the polymer backbone of the polymer with the residue R³ of the Formula (IV’).

In various embodiments, the divalent linking group X in the Formula (IV’) is selected from -O-, -S-, - N(R")-, -R’”-O-, a substituted or unsubstituted amide, carbamate, urethane, urea, imino, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group, wherein R” is a hydrogen or a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms; and R’” is a linear or branched and substituted or unsubstituted hydrocarbon residue having 1 to 12 carbon atoms. The term “substituted” in relation to these groups means that a hydrogen atom present in these groups may be replaced by a non-hydrogen moiety, such as alkyl or aryl groups, preferably C1-12 alkyl or Ce-14 aryl groups. In preferred embodiments, the linking group X is urethane or urea group, more preferably urethane group. Urethane group can be formed, for example, either when the polymer backbone comprises terminal hydroxy groups and isocyanatosilanes are used as a further component, or conversely when a polymer having terminal isocyanate groups is reacted with an alkoxysilane comprising terminal hydroxy groups. Similarly, urea group can be obtained if a terminal primary or secondary amino group

- either on the silane or on the polymer - is used, which reacts with a terminal isocyanate group that is present in the respective reactant. This means that either an aminosilane is reacted with a polymer having terminal isocyanate groups or a polymer that is terminally substituted with an amino group is reacted with an isocyanatosilane. Urethane and urea groups advantageously increase the strength of the polymer chains and of the overall crosslinked polymer.

The index "o" corresponds to 0 (zero) or 1 , i.e., the linking group X links the polymer backbone with the residue R³ (o = 1) or the polymer backbone is bound or linked directly with the residue R³ (o = 0). In preferred embodiments, o is 1.

Alkoxysilane-functional compounds having a methylene group as binding link to the polymer backbone

- so-called “a silanes” - have a particularly high reactivity of the silyl group.

In general, a lengthening of the binding hydrocarbon chain leads to reduced reactivity of the polymers. In particular, “y silanes” - which comprise the unbranched propylene residue as binding link - have a balanced ratio between necessary reactivity (acceptable curing times) and delayed curing (open assembly time, possibility of corrections after bonding).

Each R⁴ in the Formula (IV’) is, independently of one another, selected from a hydrocarbon radical containing 1 to 20 carbon atoms, preferably Ci to Ca alkyl groups, more preferably a methyl or an ethyl.

Each R⁵ in the Formula (IV’) is, independently of one another, selected from a hydroxyl group or a hydrolysable group, preferably Ci to Ca alkoxy groups, or Ci to Ca acyloxy groups.

In preferred embodiments, each R⁵ is, independently of one another, selected from Ci to Ca alkoxy groups, in particular methoxy, ethoxy, i-propyloxy or i-butyloxy group. When k is 0 or 1 , combinations of more than one group are also possible. However, acyloxy groups, such as an acetoxy group -O-CO- CHa, can also be used as hydrolyzable groups.

In preferred embodiments, k is 0 or 1 .

In particularly preferable embodiments, the silyl group, i.e., -Si(R⁴)k(R⁵)a-k, is selected from alkyldialkoxysilyl or trialkoxysilyl, preferably selected from methyldimethoxysilyl, ethyldiethoxysilyl, trimethoxysilyl, or triethoxysilyl, most preferably methyldimethoxysilyl or trimethoxysilyl. Alkoxy groups are advantageous, since no substances which irritate mucous membranes are released during the curing of compositions comprising alkoxy groups. The alcohols formed by hydrolysis of the residues are harmless in the quantities released and evaporate.

With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a harder, stronger material is desired after curing. In addition, trialkoxysilyl groups are more reactive and therefore crosslink more rapidly, thus reducing the quantity of catalyst required, and they have advantages in "cold flow" - the dimensional stability of a corresponding foam under the influence of feree and possibly temperature.

The silane-functional group of Formula (IV’) can be a lateral group within the polymer chain of the respective polymer or a terminal group of the respective polymer. In preferred embodiments, the silane- functional group of Formula (IV’) is a terminal group of the polymer.

In preferred embodiments, the polymer has at least two silane-functional groups of Formula (IV’). In this case, the polymer can have at least one lateral silane-functional group of Formula (IV’) and at least one terminal silane-functional group of Formula (IV’); or at least two lateral silane-functional groups of Formula (IV’); or at least two terminal silane-functional groups of Formula (IV’).

In particularly preferred embodiments, the polymer has at least two terminal silane-functional groups of Formula (IV’). Then, each polymer chain comprises at least two linking points at which the condensation of the polymers can be completed, splitting off the hydrolyzed residues in the presence of atmospheric moisture. In this way, regular and rapid crosslinkability is achieved so that bonds with good strengths can be obtained. In addition, by means of the quantity and the structure of the hydrolyzable groups - for example by using di- or trialkoxysilyl groups, methoxy groups or longer residues - the configuration of the network that can be achieved as a long-chain system (thermoplastics), relatively wide-mesh three-dimensional network (elastomers) or highly crosslinked system (thermosets) can be controlled, so that inter alia the elasticity, flexibility and heat resistance of the finished crosslinked compositions can be influenced in this way. In preferred embodiments, the polymer backbone of the polymer is selected from polyethers or copolymers thereof.

The number average molecular weight M_n of the polyether on which the polymer is based is for preference 500 to 100,000 g/mol (daltons), more preferably 500 to 50,000, particularly preferably 1 ,000 to 30,000 and in particular 2,000 to 20,000 g/mol, most preferably 8,000 to 20,000 g/mol. Number average molecular weights of at least 500 g/mol are advantageous for the polyethers of the present invention since the corresponding compositions have a balanced ratio of viscosity (ease of processing), strength and elasticity.

The silane-modified polymers discussed above are commercially available products or can be synthesized using known methods and processes, such as addition reactions, e.g., hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds containing isocyanate-active groups. In this regard, reference may be made to, for instance EP1535940B1 and EP1896523B1. Alternative synthetic routes are further disclosed in WO 2013/026654 A1.

Silane modified polymers suitable for employment in the context of the present invention include, without limitation, polymers and prepolymers commercially available under the brand name GENIOSIL®, specific examples suitable for employment according to the present invention are the a- silane polyether type prepolymers GENIOSIL® STPE-E10 and -E30; the y-silane polyether type prepolymers GENIOSIL® STPE-E15 and -E35, the a-silane polyether-polyurethane type prepolymers of the GENIOSIL® XB series, an example of which is GENIOSIL® XB 502; GENIOSIL® XT; GENIOSIL® XM; and GENIOSIL® WP. Moreover, examples of curable polypropylene oxide resins include various known reactive polypropylene oxide resins, such as Kaneka MS polymer available from Kaneka Corporation.

The amount of one or more silane modified prepolymers, i.e. one type of silane modified prepolymer or different kinds of silane modified prepolymers, i.e. two or more different kinds of silane modified prepolymers, as herein defined above, in silane-modified polyether (IV’) is typically in the range of about 10 to about 95 wt.-%, preferably in the range of about 10 to about 90 wt.-%, even more preferably in the range of about 15 to about 85 wt.-%, for instance about 15, 16, 17, 18,19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85 wt.-%, based on the total weight of silane-modified polyether (IV’).

In the context of the curable compositions of the claimed invention, it will be readily recognized that, in addition to generally fast curing rates, a prominent advantage of a-silane type curable resin compositions is that neither tin catalysts nor strong acids or bases need be included for curing purposes. Thus, according to various documents, silane-modified polyether (IV) is an a-silane type curable resin composition, i.e. is a curable resin composition comprising at least one a-silane type prepolymer, as herein defined above, preferably in amounts of about 10 to about 95 wt.-%, more preferably about 10 to about 90 wt.-%, such as about 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90 wt.-%, based on the total weight of silane-modified polyether (IV’).

In preferred embodiments, the curable composition according to the invention comprises the following components in the stated proportions by weight:

(1) from 10 wt.-% to 90 wt.-%, preferably 20 wt.-% to 40 wt.-%, of at least one compound of Formula (I), based on the total weight of the composition; and/or

(2) 0 wt.-% to 30 wt.-%, preferably 0.5 wt.-% to 20 wt.-%, of surface treated silica (II), based on the total weight of the curable composition; and/or

(3) 0 wt.% to 3 wt.-%, preferably less than 0.25 wt.-%, of catalyst (III), based on the total weight of the curable composition; and/or

(4) 0 wt.% to 7 wt.-%, preferably 0.2 wt.-% to 3 wt.-%, of compound of Formula (V), based on the total weight of the composition; and/or

(5) 0 wt.-% to 15 wt.-%, preferably 0.2 wt.-% to 7wt.-%, of aminosilane and/or aminosilane oligomer, based on the total weight of the curable composition; and/or

(6) 0 wt.% to 80 wt.%, preferably 20 wt.% to 50 wt.%, of surface treated calcium carbonate, based on the total weight of the curable composition; and/or

(7) 0 wt.% to 70 wt.%, preferably 15 wt.% to 50 wt.-%, of at least one further silane-modified polymer, based on the total weight of the composition, wherein the proportions by weight preferably add up to 100 wt.-%. With regard to the preferred representatives of the individual components and the preferably used quantities thereof, the statements made above in the description of the respective components apply.

The preparation of the curable composition according to the invention can take place by simple mixing of the at least one component of general Formal (I) and optionally the other ingredients described herein. This can take place in suitable dispersing units, e.g., a high-speed mixer.

In this case, preferably, care is taken that the curable composition of the invention does not come into contact with moisture as far as possible, which could lead to an undesirable premature curing. Suitable measures are sufficiently known and comprise, for example, working in an inert atmosphere, possibly under a protective gas, and drying/heating of individual components before they are added.

The invention also relates to an adhesive, sealant, or coating material comprising the curable composition according to the invention.

The invention further relates to the use of the curable composition according to the invention as an adhesive, sealant, or coating material. A further field of application for the compositions is the use as a plugging compound, hole filler, or crack filler. The use as an adhesive and/or sealant is preferred. The compositions are suitable, inter alia, for bonding plastics such as PVC (polyvinyl chloride), ABS (acrylonitrile-butadiene-styrene copolymer), polycarbonate, acrylic materials, in particular PMMA (poly(methyl methacrylate)), metals, glass, ceramic, tile, wood, wood-based materials, paper, paperbased materials, rubber, and textiles, for gluing floors, and for sealing building elements, windows, wall and floor coverings, and joints in general. In this case, the materials can be bonded to themselves or as desired to one another.

Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Moreover, although the foregoing descriptions describe some example embodiments in the context of certain example combinations of elements and/or functions, it should be appreciated that different combinations of elements and/or functions may be provided by alternative embodiments without departing from the scope of the appended claims. In this regard, for example, different combinations of elements and/or functions than those explicitly described above are also contemplated as may be set forth in some of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. The following examples serve to illustrate the invention, but the invention is not limited thereto.

Examples

Unless otherwise stated, the examples which follow are carried out at a pressure of the surrounding atmosphere, in other words approximately at 1 ,000 hPa, and at room temperature, in other words at approximately 23°C., and/or at a temperature which comes about when the components are combined at room temperature without additional heating or cooling, and also at a relative atmospheric humidity of approximately 50%. Furthermore, all figures for parts of percentages, unless otherwise stated, are by weight.

The preparation of silane-modified polymer SMP 1 to SMP 6 were described in the text below.

The formulations were prepared as described in the Tables by a Vaccumspeedmixing mashine (type: DAC 600.2 Vac-P) below and subjected to curing performance tests as follows:

Tensile strength: The tensile strength and elongation at break were determined in accordance with DIN 53504. The samples were cured in a mold at room temperature over seven days. The specimen type S2 (Dog bone) was used and the speed of the pull head in the dynamometer was 200mm/min.

Tensile lap-shear strength (LSS) was measured according to ISO 4587.

Example 1 : preparation of silane-modified polymer SMP 1 [153]

A silane-modified polymer comprising poly-1 ,3-propanediol repeating units was prepared as follows 146,07 g (36,5 mmol) polypropylene glycol having a molecular weight (M) of 4000 g/mol was made ready with 22,13 g (97,5 mmol) IPDI as a diisocyanate, and converted by tin catalysis (TIB KAT® 216) to the NCO-terminated prepolymer at 80°C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached (titrimetrically), 191 ,34 g of the OH-terminated poly-1 ,3-propanediol (96 mmol) Velvetol 2000 was metered in, stirring continued for 1 hour. To check the reaction, the corresponding NCO value was determined; at the end, it was zero and 27,7 g (32 mmol) isocyanatopropyltrimethoxysilane (% NCO= 18.4) was then added to it. After one hour of stirring at 80° C., the resulting polymer was cooled and had 8 g vinyltrimethoxysilane added to it. The viscosity was 87,400 mPas.

Example 2: preparation of silane-modified polymer SMP 2

A silane-modified polymer comprising poly-1 ,3-propanediol repeating units was prepared as follows. 177,00 g (10 mmol) polypropylene glycol having a molecular weight (M) of 8000 g/mol was made ready with 16,05 g (24 mmol) TMXDI as a diisocyanate, and converted by tin catalysis (TIB KAT® 216) to the NCO-terminated prepolymer at 80°C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached (titrimetrically), 145,14 g of the OH-terminated poly-1 ,3-propanediol (14 mmol) Velvetol 2000 was metered in, stirring continued for 1 hour. To check the reaction, the corresponding NCO value was determined; at the end, it was zero and 16,04 g (32 mmol) isocyanatopropyltrimethoxysilane (% NCO= 18.4) was then added to it. After one hour of stirring at 80° C., the resulting polymer was cooled and had 8 g vinyltrimethoxysilane added to it. The viscosity was 127,000 mPas.

Example 3: preparation of silane-modified polymer S MP 3

A silane-modified polymer comprising poly-1 ,3-propanediol repeating units was prepared as follows. 146,07 g (10 mmol) polypropylene glycol having a molecular weight (M) of 4000 g/mol was made ready with 22,13 g (24 mmol) IPDI as a diisocyanate, and converted by tin catalysis (TIB KAT® 216) to the NCO-terminated prepolymer at 80°C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached (titrimetrically), 191 ,34 g of the OH-terminated poly-1 ,3-propanediol (xx mmol) Velvetol 2000 was metered in, stirring continued for 1 hour. To check the reaction, the corresponding NCO value was determined; at the end, it was zero and 27,7 g (32 mmol) isocyanatopropyltrimethoxysilane (% NCO= 18.4) was then added to it. After one hour of stirring at 80° C., the resulting polymer was cooled and had 8 g vinyltrimethoxysilane added to it. The viscosity was 81 ,300 mPas.

Comparative Example 1 : preparation of silane-modified polymer SMP 4

322 g (10 mmol) polypropylene glycol having a molecular weight (M) of 8000 g/mol was made ready with 16.7 g (24 mmol) TMXDI as a diisocyanate, and converted by tin catalysis (TIB KAT® 216) to the NCO-terminated prepolymer at 80°C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached (titrimetrically), 27.8g of the OH-terminated (14 mmol) pTHF 2000 was metered in, stirring continued for 1 hour. To check the reaction, the corresponding NCO value was determined; at the end, it was zero and 6.9 g (32 mmol) isocyanatopropyltrimethoxysilane (% NCO= 18.4) was then added to it. After one hour of stirring at 80° C., the resulting polymer was cooled and had 7,6 g vinyltrimethoxysilane added to it. The viscosity was 125,100 mPas.

Comparative Example 2: preparation of silane-modified polymer SMP 5

280 g (15 mmol) polypropylene glycol 18000 (Acclaim 18200, hydroxyl value = 6.0) was dried under vacuum at 100° C. in a 500 ml three-neck flask. 0.1 g DBTL was added under a nitrogen atmosphere at 80°C., and 68 g (32 mmol) isocyanatopropyltrimethoxysilane (% NCO= 18.4) was then added to it. After one hour of stirring at 80° C., the resulting polymer was cooled and had 6 g vinyltrimethoxysilane added to it. The viscosity was 31 ,300 mPas. Comparative Example 3: preparation of silane-modified polymer SMP 6

384.0 g (32 mmol) of polypropylene ether polyol (Acclaim 12200, hydroxyl value = 9.90) were dried in a 500 ml three-necked flask at 80-90°C under vacuum. Under a nitrogen atmosphere, 0.28 g of bismuth neodecanoate (Borchi Kat 315) were added with stirring. Then, 2.5 g (4.52 mmol) of triisocyanate (Tolonate HDT-LV) were added (NCO/OH ratio = 0.2) with stirring. The mixture was left for one hour at 80-95°C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached titrimetrically (%NCO = 0), 12.9 g (62.69 mmol) of 3- isocyanatopropyltrimethoxysilane (Geniosil GF 40) were added with stirring and the mixture was left for a further hour at 80-95°C (%NCO = 0.00 to 0.09). The resulting polymer was cooled and had 8 g vinyltrimethoxysilane added to it. The viscosity was 29,200 mPas.

Table 1

¹ Geniosil XB502 available from Wacker Chemie AG, Germany

² Aerosil OX 50 available from Evonik Industries AG, Germany ³: HDK N 20 available from Wacker Chemie AG, Germany

⁴: Geniosil GF 96 available from Wacker Chemie AG (Germany)

⁵: Geniosil GF 91 available from Wacker Chemie AG (Germany); adhesion promoter

⁶: Geniosil XL 10 available from Wacker Chemie AG (Germany); water scavenger Table 2: Mechanical data

Table 4: Lap shear strength 7 days

ABS: Acrylonitrile butadiene styrene copolymers are thermoplastic terpolymers, BSP: “Brettsperrholz”: cross laminated timber

Claims

Claims:

1 . A curable composition comprising,

I. at least one compound of Formula (I)

Y-[(CR¹2)b-SiRa(OR²)3-a]x (I) wherein, in Formula (I),

Y denotes an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon, wherein said polymer radical comprises poly-1 ,3-propanediol repeating units, R is independently selected from a monovalent, optionally substituted, SiC-bonded hydrocarbon radical,

II. optionally surface treated silica,

III. optionally a catalyst.

2. The curable composition according to Claim 1 , wherein Y denotes an x-valent polymer radical, wherein said polymer is a homopolymer or copolymer of 1 ,3-propanediol.

3. The curable composition according to Claim 1 or 2, wherein Y comprises units having the general formula (VI)

-(O-CH₂-CH2-CH₂)y- (VI) wherein y is within the range of from 5 to 250, preferably from 8 to 173, more preferably from 17 to 87, most preferably from 32 to 37.

4. The curable composition according to any one of Claims 1 to 3, wherein Y denotes an x- valent polymer radical, wherein said polymer radical has a molecular weight within the range of from 500 g/mol to 10,000 g/mol, more preferably from 1 ,000 g/mol to 5,000 g/mol, most preferably from 1 ,900 g/mol to 2,100 g/mol.

5. The curable composition according to any one of Claims 1 to 4, wherein the polymer radical Y in Formula (I) comprises poly-1 ,3-propanediol repeating units and additional organic polymer repeating units from polyoxyalkylenes, preferably polyoxyethylene, polyoxy-1 ,2- propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers, preferably polyisobutylene, polyethylene or polypropylene or copolymers of polyisobutylene with isoprene; polyisoprenes; polyurethanes; polyesters; polyamides; polyacrylates; or polymethacrylates, preferably from polyoxyalkylenes, preferably polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene-polyoxybutylene copolymer; polyurethanes; polyesters; polyacrylates; or polymethacrylates, more preferably from polyoxyalkylenes, preferably polyoxyethylene, polyoxy-1 ,2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene-polyoxybutylene copolymer; polyurethanes; or polyesters.

6. The curable composition according to any one of Claims 1 to 5, wherein Y denotes an x- valent polymer radical comprising poly-1 ,3-propanediol repeating units and additional organic polymer repeating units from polyoxyalkylenes, preferably polyoxyethylene, polyoxy-

1.2-propylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or polyoxypropylene-polyoxybutylene copolymer; polyurethanes; or polyesters, wherein said polymer radical has a hydroxyl number within the range of from 16 mg KOH/g to 350 mg KOH/g, more preferably from 36 mg KOH/g to 175 mg KOH/g, most preferably from 53 mg KOH/g to 60 mg KOH/g.

7. The curable composition according to any one of Claims 1 to 6, wherein the compound of Formula (I) comprises from 10 wt.% to 80 wt.%, preferably from 40 wt.% to 60 wt.% of poly-

1 .3-propanediol moieties, based on the total amount of the compound of Formula (I).

8. The curable composition according to any one of Claims 1 to 7, wherein Y preferably comprises from 10 wt.% to 100 wt.%, more preferably from 50 wt.% to 100 wt.% of biogenic carbon, based on the total amount of carbon in Y.

9. The curable composition according to any one of Claims 1 to 8, wherein the composition comprises at least one compound containing units of Formula (V)

R⁶c(R⁷O)dR⁸eSiO(4-c-d-e)/2 (V) wherein R⁶ is independently selected from hydrogen, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted aliphatic hydrocarbon radical, which bridges two units of the Formula (V),

R⁷ is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon radical,

R⁸ is independently selected from a monovalent, SiC-bound, optionally substituted aromatic hydrocarbon residue, c is 0, 1 , 2 or 3, d is 0, 1 , 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1 , and e is 0, 1 or 2, preferably 0 or 1 , with the proviso that the sum of c+d+e is less than or equal to 3, wherein in at least 40% of the units of Formula (V) the sum c+e is preferably equal to 0 or 1 .

10. The curable composition according to Claim 9, wherein the composition comprises at least one organosilicon compound selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1 ,2-bis(triethoxysilyl)ethane and their partial hydrolysates, preferably tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane and/or their partial hydrolysates.

1 1 . The curable composition according to any one of Claims 1 to 10, wherein the composition comprises at least one aminosilane and/or aminosilane oligomer.

12. The curable composition according to any one of Claims 1 to 11 comprising a catalyst selected from the group consisting of amines, nitrogen heterocycles, and guanidine derivatives, especially 1 ,8-diazabicyclo[5.4.0]undec-7-ene.

13. The curable composition according to any one of claims 1 to 12, wherein

(4) 0 wt.% to 7 wt.-%, preferably 0.2 wt.-% to 3 wt.-%, of compound of Formula (V), based on the total weight of the composition; and/or (5) 0 wt.-% to 15 wt.-%, preferably 0.2 wt.-% to 7wt.-%, of aminosilane and/or aminosilane oligomer, based on the total weight of the curable composition; and/or

(7) 0 wt.% to 70 wt.%, preferably 15 wt.% to 50 wt.-%, of at least one further silane- modified polymer, based on the total weight of the composition.

14. An adhesive, sealant, or coating material comprising the curable composition according to any one of claims 1 to 13.

15. Use of a curable composition according to any one of claims 1 to 13 as an adhesive, sealant, or coating material.