Organyloxysilyl-terminated polymers based on 1,3-dioxolane copolymer units

Abstract

The present invention relates to a compound of formula (I): -(CR 1 2) b -SiR a (OR 2 ) 3-a (I) An organyloxysilyl-terminated polymer (P) having a terminal group of General formula (II): -[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2 (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2)] y2 -O- (II) The main chain contains 1,3-dioxolane copolymer units (DP), In the formula, R, R 1 , R 2 , a, b, R 3 , R 4 , x1+x2 and y1+y2 are defined in claim 1; where [O-CH2-O-CHR 3 -CHR 4 -] y1 and [O-CHR 3 -CHR 4 O-CH2-] y2 In each case there is at least one group R 3 or R 4 C1~C 18 the organyloxysilyl-terminated polymer (P) having the definition that the -alkyl group is an alkyl group; a method for its preparation; and compositions comprising the organyloxysilyl-terminated polymer (P).

Description

[Technical Field]

[0001] The present invention relates to crosslinkable silane-terminated polymers containing 1,3-dioxolane copolymer units in their backbones, methods for their preparation, and compositions containing polymer (P). The polymers of the present invention have high hydrophilicity, which results in particularly good cure. [Background technology]

[0002] Moisture-crosslinkable formulations are generally known. They are widely used as adhesives, sealants and also as coatings. Important moisture-reactive binders for such products are silyl-functionalized polymers. Among these, linear or monobranched polypropylene glycols and / or polyurethanes based on these polypropylene glycols, each carrying a terminal alkoxysilyl group at the end of the polymer chain, are preferred. This product group therefore combines several advantages: Polymers with a polypropylene glycol-based backbone are still liquid before crosslinking, even at the very long chain lengths required for this application; The alcohols released as cleavage products during crosslinking are non-corrosive and toxicologically harmless at the low concentrations released; The cured polymer formulations are characterized by very good mechanical properties.

[0003] Corresponding alkoxysilane-terminated polymers have long been known in the prior art and are commercially available, for example, under the trade names GENIOSIL® STP-E (Wacker Chemie AG), MS-Polymer (Kaneka), DESMOSEAL® (Bayer AG) or SPUR® (Momentive).

[0004] However, a drawback of many prior art systems is the low reactivity of the corresponding polymers towards moisture, which requires active catalysis, and therefore the corresponding mixtures usually contain significant amounts of toxicologically harmful tin catalysts.

[0005] Here, the use of so-called α-silane-terminated prepolymers, which have alkoxysilyl groups linked to adjacent urethane units by methylene spacers, is advantageous. This class of compounds is highly reactive and does not require tin catalysts or strong acids or bases to achieve high curing rates in contact with air. Corresponding products are also commercially available from Wacker-Chemie AG under the trade name GENIOSIL® STP-E.

[0006] However, even these systems, which cure particularly rapidly upon contact with atmospheric moisture, still encounter problems when bonding large areas of non-porous substrates such as glass, metal, and plastic. For example, the cure rate of deep adhesive joints is limited not only by the reactivity of the cross-linkable polymer, but also by the limited water footprint within the joint required for cure. The latter, when bonding or sealing non-porous substrates, depends primarily on the rate at which water molecules diffuse from the surface of the adhesive or seal joint through the adhesive matrix to the deeper bond layer.

[0007] In principle, this problem can be solved by using so-called two-component systems, where the first component contains a moisture-curing polymer and the second component contains water. If both components are mixed immediately before application, the diffusion of water from atmospheric moisture into the interior of the joint is unnecessary, and the adhesive or sealant cures uniformly even in deeper layers. However, such two-component systems are very cumbersome to use and difficult to apply, even for professional users. Therefore, they are only used when no one-component alternative exists for the respective application.

[0008] Therefore, an adhesive matrix that allows for more rapid water diffusion is highly desirable to allow improved cure even in deep adhesive or sealant joints without the use of two-component systems.

[0009] A further drawback of all currently commercially available silane-crosslinked polymers is their polypropylene glycol-based backbone. For example, polypropylene glycol has been produced from raw materials that have been obtained exclusively from fossil carbon sources. Therefore, this option would be desirable in that other, more environmentally friendly polymer units could be used as the basis for the production of silane-crosslinked polymers.

[0010] One way to achieve this goal is to use CO2 to produce these polymer units, incorporating CO2 into the value chain as a starting material rather than as a waste product.

[0011] In this context, polyacetals may be very attractive polymer units for the development of novel silane-crosslinked polymers. For example, they can be produced via the intermediate step of cyclic acetals, especially by catalytic fixation of CO2 with green hydrogen.

[0012] However, classical polyacetals, also known as polyoxymethylenes (POM), which can be obtained, for example, by the polymerization of formaldehyde and trioxane (POM-H) or by the ring-opening polymerization of 1,3-dioxolane (POM-C), have the disadvantage that they are solid at room temperature. Therefore, they are not suitable for the production of binders for liquid or pasty adhesives, sealants, or coatings that are intended to be applied solvent-free at room temperature and to harden only during or after application.

[0013] It is therefore an object of the present invention to develop silane-terminated polymers based on polymer units that can be produced in whole or in part from non-fossil carbon sources and that also allow for better diffusion of water molecules through the polymer matrix.

[0014] The present invention relates to a compound of formula (I): -(CR 1 2) b -SiR a (OR 2 ) 3-a(I) [In the formula, R may be the same or different, The Si atom in the formula is bonded to SiC. Monovalent unsubstituted or substituted Charcoal is a hydrogen hydride group, R 1 may be the same or different and are a hydrogen atom or a monovalent unsubstituted or substituted hydrocarbon group, R 2 may be the same or different and are a hydrogen atom or a monovalent unsubstituted or substituted hydrocarbon group, a may be the same or different and is 0, 1 or 2, preferably 0 or 1; and b may be the same or different and is an integer of 1 to 10, preferably 1, 3, or 4, and particularly preferably 1 or 3.] an organyloxysilyl-terminated polymer (P) having a terminal group of General formula (II): -[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2 (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2)] y2 -O- (II) [In the formula, R 3 may be the same or different, and are hydrogen or monovalent unsubstituted or substituted C1-C 18 is an alkyl group, R 4 may be the same or different, and are hydrogen or monovalent unsubstituted or substituted C1-C 18 is an alkyl group, The value of x1+x2 is 10 to 2000, The value of y1+y2 is 3*(x1+x2+y1+y2) / 100~90*(x1+x2+y1+y2) / 100. The main chain contains 1,3-dioxolane copolymer units (DP) of where [O-CH2-O-CHR 3 -CHR 4 -] y1 and [O-CHR 3 -CHR 4 O-CH2-] y2 In each case, at least one group R 3 or R 4が C1~C 18 -alkyl groups.

[0015] The 1,3-dioxolane copolymer unit (DP) of formula (II) is the unit [O-CH2-O-CH2-CH2-] x1 , [O-CH2-CH2O-CH2-] x2 , [O-CH2-O-CHR 3 -CHR 4 -] y1 , [O-CHR 3 -CHR 4 O-CH2-] y2 are included in random distribution or blocks.

[0016] Examples of unsubstituted R include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl; hexyl groups such as n-hexyl; heptyl groups such as n-heptyl; octyl groups such as n-octyl, isooctyl, and 2,2,4-trimethylpentyl; nonyl groups such as n-nonyl; decyl groups such as n-decyl; and dodecyl groups such as n-dodecyl. octadecyl groups such as n-octadecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; alkenyl groups such as vinyl, 1-propenyl, and 2-propenyl; aryl groups such as phenyl, naphthyl, anthryl, and phenanthryl; alkaryl groups such as o-, m-, and p-tolyl; xylyl and ethylphenyl; and aralkyl groups such as benzyl, as well as α- and β-phenylethyl groups.

[0017] Examples of substituents R are haloalkyl groups and haloaryl groups such as o-, m- and p-chlorophenyl groups.

[0018] The radical R is preferably an unsubstituted or halogen-substituted monovalent hydrocarbon radical having 1 to 6 carbon atoms, particularly preferably an alkyl radical having 1 or 2 carbon atoms, in particular a methyl radical.

[0019] base R 1 Examples of are hydrogen atoms, groups specified for R, and unsubstituted or substituted hydrocarbon groups bonded to a carbon atom through nitrogen, phosphorus, oxygen, sulfur, carbon, or a carbonyl group.

[0020] base R 1 is preferably a hydrogen atom and an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, in particular a hydrogen atom.

[0021] base R 2 Examples of are hydrogen atoms or the examples specified for the R groups.

[0022] base R 2 is preferably a hydrogen atom or an unsubstituted or halogen-substituted alkyl group having 1 to 10 carbon atoms, particularly preferably an unsubstituted or halogen-substituted alkyl group having 1 to 4 carbon atoms, in particular a methyl group and an ethyl group.

[0023] Alkyl group R 3 and R 4 Examples of R are a hydrogen atom, linear and branched alkyl groups such as methyl, ethyl, isooctyl, n-octyl, and the like, and cycloalkyl groups such as cyclohexyl. 3 and R 4 is a hydrogen atom or a C1-C6 alkyl group, and is particularly preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group.

[0024] In each case, preferably [O-CH2-O-CHR 3 -CHR 4 -] y1 and [O-CHR 3 -CHR 4 O-CH2-] y2 Unit base R 3 or group R 4 One of them is C1~C 18 -alkyl group, and the other group is in each case a hydrogen atom.

[0025] x1+x2 preferably has a value of 20 to 1000, particularly preferably 30 to 500, and particularly preferably 50 to 300.

[0026] y1+y2 preferably has a value of 5*(x1+x2+y1+y2) / 100 to 50*(x1+x2+y1+y2) / 100, particularly preferably a value of 10*(x1+x2+y1+y2) / 100 to 30*(x1+x2+y1+y2) / 100, and in particular a value of 14*(x1+x2+y1+y2) / 100 to 25*(x1+x2+y1+y2) / 100.

[0027] The 1,3-dioxolane copolymer units (DP) of formula (II) preferably have a number average molecular weight Mn of 750 to 300,000 daltons, particularly preferably 1,500 to 125,000 daltons, particularly preferably 4,000 to 24,000 daltons, particularly preferably 6,000 to 20,000 daltons.

[0028] The organyloxysilyl-terminated polymer (P) may be branched, preferably having 1 to 3 branching sites and corresponding 3 to 5 chain ends, some or all of which may be terminated with a silane group of formula (I). Preferably, at least 90%, particularly preferably at least 95%, of all chain ends are terminated with a silane group of formula (I).

[0029] However, in a preferred embodiment, the polymer (P) is unbranched and therefore has two chain ends. One or both chain ends may be terminated with a silane group of formula (I). However, preferably, at least 90%, particularly preferably at least 95%, of all chain ends are terminated with a silane group of formula (I).

[0030] The organyloxysilyl terminated polymer (P) preferably has the general formula (III): H-[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2 (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2)] y2 -OH (III) wherein all variables have the definitions specified in formula (II) and therefore all requirements specified in this formula are met. It is prepared by reacting hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) of

[0031] In this context, the hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) preferably have a number average molecular weight M of 750 to 300,000 daltons, particularly preferably 1,500 to 125,000 daltons, particularly preferably 4,000 to 24,000 daltons, in particular 6,000 to 20,000 daltons. n Compared to the polymer unit (DP) of formula (II) obtained by using 1,3-dioxolane copolymer (DP-OH), the average molar mass is clearly increased by the weight of the two terminal hydrogen atoms.

[0032] In the context of the present invention, the number-average molar mass M nis preferably determined by size exclusion chromatography (SEC) against polystyrene standards in THF at 60°C with a flow rate of 1.2 ml / min and an injection volume of 100 μl, and detection by RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA.

[0033] The hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) preferably have a kinematic viscosity at 25° C. of 50 mPas to 500 Pas, particularly preferably 500 mPas to 200 Pas, in particular 1 Pas to 100 Pas.

[0034] In the context of the present invention, the viscosity of non-pasty liquids is measured according to ISO 2555, preferably after heating to 23°C, using a DV 3 P rotational viscometer from A. Paar (Brookfield systems), spindle 6 at 5 Hz.

[0035] Numerous methods are known for preparing organyloxysilyl-terminated polymers from hydroxyl-functional prepolymers, such as polypropylene glycol. All of these methods can be easily transposed to convert hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) into the polymers (P) of the present invention. In this case, all process parameters, such as temperature, reaction time, and catalysis, may be maintained unchanged. The only difference is that hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) are used as reactants, i.e., hydroxyl-functional polymers.

[0036] In the general method (P1), a hydroxyl group-containing polymer (DP-OH) is first reacted with a compound having a group reactive with a hydroxyl group and a double bond, preferably allyl chloride, to obtain the corresponding vinyl-terminated polymer, which is then converted into a compound of formula (IV): H-SiR a (OR 2 ) 3-a (IV) wherein all variables have the definitions specified in formula (I). The reaction is then hydrosilylated with a silane of formula (I). Suitable methods for carrying out this reaction are known and are described in particular in EP 1566412A1 (paragraph

[0144] ff, method (a)). Furthermore, the instructions for carrying out the silylation of the hydroxyl-terminated polypropylene glycol used in the preparation examples specifically described in EP 1566412A1 can be directly applied to the silylation of the hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH).

[0037] A second, equally common method (P2) involves reacting a hydroxyl-containing polymer (DP-OH) with at least one isocyanate-functional compound. These are preferably diisocyanates or polyisocyanates. Examples of common diisocyanates include diisocyanatodiphenylmethane (MDI), both crude and technical grades of MDI, as well as the pure 4,4' or 2,4' isomers or mixtures thereof, toluene diisocyanate (TDI) in various positional isomers, diisocyanatonaphthalene (NDI), isophorone diisocyanate (IPDI), or hexamethylene diisocyanate (HDI). Examples of polyisocyanates are polymeric MDI (P-MDI), triphenylmethane triisocyanate, or the trimerized products (biurets or isocyanurates) of the aforementioned diisocyanates.

[0038] In this context, the isocyanate may be used in a stoichiometric deficiency (variant (V2-1)) or excess (variant (V2-2)) relative to the ratio of isocyanate groups to hydroxyl groups of the hydroxyl-containing polymer (DP-OH). Variant (V2-1) results in a polyurethane polymer whose chain ends are terminated with hydroxyl groups, while variant (V2-1) results in a polymer whose chain ends are composed of isocyanate groups.

[0039] The hydroxyl-functional polyurethane polymer obtained in variant (V2-1) is preferably a polyurethane having the formula (V): OCN-(CR1 2) b -SiR a (OR 2 ) 3-a (V) wherein the groups and indices have one of the definitions specified in formula (I). Suitable methods for carrying out this reaction are known and are described in particular in EP 0 931 800 A (paragraphs

[0011] to

[0022] and Examples 1 to 5).

[0040] On the other hand, the isocyanate-functional polymer obtained in variant (V2-2) is preferably prepared by the addition of a compound represented by formula (VI): Z-(CR 1 2) b -SiR a (OR 2 ) 3-a (VI) wherein Z is an isocyanate-reactive group, and all other groups and indices have the definitions specified in formula (I). isocyanate-reactive silane.

[0041] The isocyanate-reactive group Z is preferably a hydroxyl group or an amino group, particularly preferably an amino group of formula NHR′, where R′ has one of the definitions specified for the R group or is —CH(COOR″)—, where R″ may be the same or different and have the definition specified for R.

[0042] Examples of radicals R' are cyclohexyl, cyclopentyl, n- and isopropyl, n-, iso- and t-butyl, pentyl, the various stereoisomers of hexyl or heptyl, and also the phenyl radical.

[0043] The group R' is preferably a -CH(COOR'')-CH2-COOR'' group or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms and optionally substituted with halogen.

[0044] The radical R'' is preferably an alkyl radical having 1 to 10 carbon atoms, particularly preferably a methyl, ethyl or propyl radical.

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

[0014] to

[0023] ,

[0039] to

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

[0014] to

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

[0046] In a particularly preferred method (P3), the polymer (P) of the present invention is obtained by direct reaction of a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) with an isocyanate-functional silane of formula (V). Suitable methods for carrying out this reaction are known, and are in particular described in EP 1535940 B1 (paragraphs

[0005] to

[0025] and Examples 1 to 3 and Comparative Examples 1 to 4) or EP 1896523 B1 (paragraphs

[0008] to

[0025] ).

[0047] ), which are incorporated herein by reference.

[0047] Polymers of formula (VII) obtainable by the preferred method (P3) (RO 5 ) 3-a R 4 a Si-(CR 3 2) b -NH-CO-[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2 (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2-) y2 ]-O-CO-NH-(CR 3 2) b -SiR 4 a (OR 5 ) 3-a(VII), wherein all variables have the definitions specified in formulas (I) and (II), and therefore it is a particularly preferred embodiment of the invention when all requirements specified for these formulas are met.

[0048] The hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) of the above general formula (III) can be prepared by a simple method in a short reaction time.

[0049] In this specification, the preparation is preferably carried out by reacting 1,3-dioxolane with one or more compounds of general formula (VII) [ka] with an alkyl-substituted 1,3-dioxolane in the presence of a Lewis acid or a Bronsted acid, wherein the alkyl group R 3 and R 4 has the definition specified for formula (II).

[0050] This method involves the ring-opening polymerization of dioxolane monomers using cationic derivative catalysts, either Lewis or Bronsted acids.

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

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

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

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

[0055] In this method, an initiator may be used, preferably a difunctional alcohol, particularly preferably ethylene glycol.

[0056] This process can be carried out in the presence or absence of an aprotic solvent. When an aprotic solvent is used, a solvent or solvent mixture having a boiling point or boiling range of up to 120°C at 0.1 MPa is preferred. Examples of such solvents include ethers such as dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, diisopropyl ether, and diethylene glycol dimethyl ether; chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, and trichloroethylene; hydrocarbons such as pentane, n-hexane, hexane isomer mixtures, heptane, octane, benzine, petroleum ether, benzene, toluene, and xylene; and siloxanes, particularly preferably trimethylsilyl-terminated siloxanes having 0 to 6 dimethylsiloxane units. Examples of suitable solvents include linear dimethylpolysiloxanes having a dimethylsiloxane group, or cyclic dimethylpolysiloxanes preferably having 4 to 7 dimethylsiloxane units, such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, and methyl isobutyl ketone (MIBK); esters such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, and ethyl isobutyrate; carbon disulfide and nitrobenzene, or mixtures of these solvents.

[0057] The term "solvent" does not imply that all reactants must be dissolved therein. Reactions can also be carried out in a suspension or emulsion of one or more reactants. Reactions can also be carried out in solvent mixtures with miscibility gaps, in each case at least one reactant is soluble in each mixed phase.

[0058] Particularly preferably, a solution of trifluoromethanesulfonic acid and initiator is used, with methylene chloride being the preferred solvent.

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

[0060] The process is preferably carried out at temperatures of 10 to 60° C., particularly preferably 15 to 40° C., in particular 21 to 30° C. A reaction temperature of 23° C. is particularly preferred.

[0061] The reaction is preferably worked up by deactivating the catalyst with a suitable base, washing with a hydrocarbon such as heptane, and then removing the catalyst by distillation under reduced pressure. The suitable base is preferably pyridine, triethylamine, or aqueous sodium hydroxide.

[0062] The present invention is based on several surprising discoveries: First, hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) composed of 1,3-dioxolane and 4- and / or 5-substituted 1,3-dioxolanes are liquid over a wide temperature range, including room temperature. This is true even when the average molar mass is >10,000 Daltons. Given this surprising property, they are highly suitable as polymeric units (DP) for constructing the inventive polymers (P) by one of the inventive methods P1 to P3 and are therefore highly suitable for further processing.

[0063] Polymers (P) based on 1,3-dioxolane copolymer units (DP) are highly polar and therefore hydrophilic. They are therefore ideal binders for adhesives and sealants, allowing rapid diffusion of water molecules into the deeper layers of the adhesive or sealing joint and therefore particularly good, rapid and uniform curing of the corresponding adhesives and sealants.

[0064] Polymer (P) is a suitable binder for adhesives and sealants, and after curing it exhibits excellent properties that are almost comparable to those of conventional silane-terminated polypropylene glycol-based polymers. This completely novel product family, whose raw material base is obtained via the intermediate step of cyclic acetals by catalytic fixation of CO2 with green hydrogen, is an alternative, completely or at least partially, to existing products derived exclusively from fossil carbon sources.

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

[0066] The present invention therefore also relates to compositions comprising an organyloxysilyl-terminated polymer (P) and, depending on the specific application or the respective requirement profile, at least one further component selected from (A) a nitrogen-containing organosilicon compound, (B) a silicone resin, (C) a catalyst, (D) an adhesion promoter, (E) a water scavenger, (F) a filler, (G) an additive and (H) an aggregate.

[0067] The composition of the present invention preferably comprises (P) organyloxysilyl-terminated polymer (P), optionally (A) a nitrogen-containing organosilicon compound; optionally (B) a silicone resin; optionally (C) a catalyst; optionally (D) an adhesion promoter; optionally (E) a water scavenger; optionally (F) a filler; optionally (G) additives, and Optionally (H) aggregates A crosslinkable composition comprising:

[0068] Components (A) to (H) and their preferred amounts are frequently described, for example, on page 12, line 24 to page 23, line 21 of WO-A2015024773, which is incorporated herein by reference.

[0069] The composition of the present invention is particularly preferably (P) organyloxysilyl-terminated polymers, (A) nitrogen-containing organosilicon compound, optionally (B) a silicone resin; optionally (C) a catalyst; optionally (D) an adhesion promoter; optionally (E) a water scavenger; optionally (F) a filler; optionally (G) additives, and Optionally (H) aggregates A crosslinkable composition comprising:

[0070] The composition of the present invention is particularly preferably (P) organyloxysilyl-terminated polymers, (D) nitrogen-containing organosilicon compound, optionally (B) a silicone resin; optionally (C) a catalyst; optionally (D) an adhesion promoter; optionally (E) a water scavenger; optionally (F) a filler; optionally (G) additives, and Optionally (H) aggregates The crosslinkable composition comprises:

[0071] Each of the components used in the present invention may be one of such components or may be a mixture of at least two of the respective components.

[0072] The adhesives, sealants or coatings according to the invention can be prepared by any method known per se, such as by methods and mixing processes common to the preparation of moisture-curable compositions, where the order in which the various components are mixed with one another can be varied as required.

[0073] The mixing can be carried out at room temperature and atmospheric pressure, i.e., about 900-1100 hPa. However, if necessary, the mixing can also be carried out at higher temperatures, for example, in the range of 30-130°C. Furthermore, in order to remove volatile compounds and / or air, it is possible to mix temporarily or continuously under reduced pressure, for example, at an absolute pressure of 30-500 hPa. The mixing according to the invention is preferably carried out with the exclusion of moisture.

[0074] The polymer (P) of the present invention has the advantage that it can be prepared quickly and easily, just like conventional silane-crosslinked polymers based on polypropylene glycol.

[0075] The polymers (P) of the present invention have the advantage that they are highly fluid and have relatively low viscosities, allowing them to be easily formulated to give finished adhesives and sealants.

[0076] The polymers (P) of the present invention, although a completely new product family, have the advantage that they can be further processed into adhesives and sealants in the same way as conventional silane-crosslinked polymers based on polypropylene glycol, and no new or modified plants or new or modified operating techniques are required for further processing.

[0077] The polymers (P) of the present invention have the advantage that they can be used to prepare adhesives and sealants having excellent mechanical properties.

[0078] The polymers (P) according to the invention have the advantage that they can be used to produce adhesives and sealants which cure particularly rapidly and uniformly.

[0079] The polymers (P) of the present invention have the advantage that the adhesives and sealants that can be produced therefrom have excellent adhesion properties to a myriad of substrates, such as plastics, including PVC, metals, concrete, wood, mineral substrates, glass, ceramics and painted substrates, and are therefore suitable for bonding and / or sealing all of these materials.

[0080] The polymers (P) of the present invention have the advantage of being transparent, colorless and color stable and are therefore also suitable for the production of transparent and crystal clear adhesives and sealants.

[0081] The polymers (P) of the invention can be produced by fixing CO2 and thus have the advantage of being particularly climate friendly.

[0082] Compositions that can be prepared from the polymer (P) of the present invention can be stored with the exclusion of water and used for any intended purpose, such as compositions that crosslink to form elastomers upon exposure to water at room temperature.

[0083] Therefore, compositions that can be produced from the polymers (P) of the present invention are highly suitable for sealing and flexible bonding of metal parts, for example. They can therefore be used as mounting adhesives for the construction of automobiles and the manufacture of buses, trucks, and rail vehicles. They are also suitable for the construction of windows, especially skylights, and the bonding of structural glass, or for the manufacture of photovoltaic elements, display cases, for example for the manufacture of protective coatings and moldings, and for the insulation of electrical or electronic equipment.

[0084] In the examples described below, all viscosity data is based on a temperature of 25° C. Unless otherwise specified, the following examples are carried out at ambient atmospheric pressure, i.e., about 1000 hPa, and room temperature, i.e., about 23° C., or the temperature that occurs when the reactants are mixed at room temperature and a relative humidity of about 50% without additional heating or cooling. Furthermore, unless otherwise specified, all parts and percentages reported are by weight. [Example]

[0085] Preparation Example 1: Preparation of hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) Preparation of catalyst solution: In a Schlenk flask equipped with a septum, 150 ml of dry dichloromethane, 15 ml of ethylene glycol and 1.14 ml of trifluoromethanesulfonic acid were mixed under a nitrogen atmosphere.

[0086] 154 ml of the catalyst solution prepared above was transferred to a laboratory reactor equipped with a KPG stirrer, thermometer, nitrogen connection, and septum, and temperature-controlled at 23°C. To this solution, 1.15 kg of 4-ethyl-1,3-dioxolane (10.9 mol) and 770 ml (10.9 mol) of 1,3-dioxolane were added, and the mixture was stirred at 23°C. The reaction mixture became viscous during the reaction time and turned pink. After 5 hours, 20 ml of pyridine and 100 ml of dichloromethane were added until the reaction solution was decolorized. The resulting mixture was washed first with heptane and then with water until the pH reached 7.

[0087] Finally, all volatile components were removed under vacuum (1 mbar) to give a viscous oil.

[0088] Production Example 2: Production of Polymer (P) of the Present Invention A 1 L three-neck flask equipped with a dropping funnel, a KPG stirrer and a thermometer was initially charged with 475 g of the 1,3-dioxolane copolymer obtained in Example 1, heated to 80° C. and dried at a pressure of 10 mbar (vacuum) for 2 hours.

[0089] The vacuum was released with nitrogen, and 18.5 g of α-isocyanatomethylmethyldimethoxysilane (GENIOSIL® XL 42, commercially available from Wacker Chemie AG, Munich, Germany) was added dropwise with stirring over 15 minutes. The temperature remained at 80°C. Next, 0.07 g of a bismuth-containing catalyst (commercially available from OMG-Borchers, D-Langenfeld under the name "Borchi-Kat 315") was added. The reaction mixture warmed slightly (<5°C). The mixture was then stirred at 80°C for 2 hours. After this time, a small isocyanate peak was still present in the IR spectrum of the reaction mixture, corresponding to 2-5% of the amount of isocyanate groups initially used.

[0090] The mixture was allowed to cool to 50°C, at which point 1.3 g of methanol was added to scavenge any residual isocyanate. After 0.5 hours, the reaction mixture was allowed to cool to room temperature. An IR spectrum recorded thereafter confirmed the absence of isocyanate.

[0091] Example 1: Adhesive-sealant formulations based on polymer (P) of the invention 168.0 g of the polymer obtained in Preparation Example 2 was homogenized with 8.0 g of vinyltrimethoxysilane (commercially available as GENIOSIL® XL10 from Wacker Chemie AG, Munich, Germany) using a PC-Laborsystem laboratory planetary mixer equipped with two cross-arm mixers at 200 rpm at 25°C for 2 minutes.

[0092] Then, 220.0 g of stearic acid-coated ground calcium carbonate with an average particle size (D50%) of approximately 0.4 μm (available commercially under the name Omyabond 302 from Omya, D-Cologne) was added and macerated for 1 minute while stirring at 600 rpm. Finally, 4.0 g of N-[2-aminoethyl]-3-aminopropyltrimethoxysilane (available commercially under the name GENIOSIL® GF91 from Wacker Chemie AG, Munich, Germany) was mixed for 1 minute at 200 rpm, homogenized under partial vacuum (approximately 100 mbar) at 200 rpm, and stirred until no air bubbles remained.

[0093] The composition thus obtained was filled into two 310 ml PE cartridges (approximately 200 g per cartridge) and stored at 20° C. for 24 hours before being investigated.

[0094] Comparative Example C1: The procedure was the same as in Example 1, but instead of the polymer of Preparation Example 2 of the present invention, the average molar mass (M n A silane-terminated polypropylene glycol (commercially available under the name GENIOSIL® STP-E10 from Wacker Chemie AG, Munich, Germany) having a .DELTA. of 12000 g / mol and end groups of the formula -OC(=O)-NH-CH2-SiCH3(OCH3)2 was used.

[0095] Example 2: Adhesive-sealant formulation based on polymer (P) of the invention 116.0 g of the polymer obtained in Preparation Example 2 were homogenized with 80 g of butyl-terminated polyethylene glycol (commercially available under the name Polyglycol BB300 from Clariant, D-Gendorf) having a number-average molar mass (Mn) of 300 g / mol and 8.0 g of vinyltrimethoxysilane in a laboratory planetary mixer manufactured by PC-Laborsystem, equipped with two cross-arm mixers, at 200 rpm at 25° C. for 2 minutes.

[0096] Then, 192.0 g of Omyabond 302 was added and macerated with stirring at 600 rpm for 1 minute. Finally, 4.0 g of 3-aminopropyltrimethoxysilane (commercially available as GENIOSIL® GF96 from Wacker Chemie AG, Munich, Germany) was mixed at 200 rpm for 1 minute, homogenized under partial vacuum (approximately 100 mbar) at 200 rpm for 1 minute, and stirred until no air bubbles remained.

[0097] The composition thus obtained was filled into two 310 ml PE cartridges (approximately 200 g per cartridge) and stored at 20° C. for 24 hours before being investigated.

[0098] Comparative Example C2: The procedure was the same as in Example 3, except that the polymer of Preparation Example 2 of the present invention was replaced with the same amount of GENIOSIL® STP-E10.

[0099] Example 3: Determination of the property profile of the produced adhesive / sealant The adhesive-sealants obtained in Examples 1 and 2 and Comparative Examples C1 and C2 were crosslinked and investigated with respect to skin formation and their mechanical properties, the results of which are shown in Table 1.

[0100] Skin formation time (SFT) To measure the skin formation time, the crosslinkable compositions obtained in the examples were applied in a 2 mm thick layer to a PE film and stored under standard conditions (23°C, 50% relative humidity). During curing, the formation of a skin was tested once per minute. For this purpose, a dry laboratory spatula was carefully placed on the surface of the sample and pulled upwards. If the sample was still attached to the finger, no skin had yet formed. If the sample was not attached to the finger, a skin had formed and the time was recorded.

[0101] Mechanical properties Each composition was spread to a depth of 2 mm onto a milled Teflon panel and cured for 2 weeks at 23°C and 50% relative humidity.

[0102] Shore A hardness was measured according to DIN 53505.

[0103] The tensile strength was measured according to DIN 53504-S1.

[0104] The elongation at break was determined according to DIN 53504-S1.

[0105] The 100% modulus was determined according to DIN 53504-S1.

[0106] [Table 1]

Claims

1. Formula (I): -(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ (I) [In the formula, R may be the same or different and is a monovalent unsubstituted or substituted hydrocarbon group bonded to the Si atom in the formula by a SiC bond, R １ may be the same or different and are a hydrogen atom or a monovalent unsubstituted or substituted hydrocarbon group, R ２ may be the same or different and are a hydrogen atom or a monovalent unsubstituted or substituted hydrocarbon group, a may be the same or different and is 0, 1 or 2; b may be the same or different and is an integer from 1 to 10. An organyloxysilyl-terminated polymer (P) having a terminal group represented by General formula (II): -[(O-CH ２ -O-CH ２ -CH ２ -) ｘ１ (O-CH ２ -CH ２ -O-CH ２ -) ｘ２ (O-CH ２ -O-CHR ３ -CHR ４ -) ｙ１ (O-CHR ３ -CHR ４ -O-CH ２ )] ｙ２ -O- (II) [In the formula, R ３ may be the same or different, and are hydrogen or monovalent unsubstituted or substituted C １ ~C １８ - is an alkyl group, R ４ may be the same or different, and are hydrogen or monovalent unsubstituted or substituted C １ ~C １８ - is an alkyl group, The value of x1+x2 is 10 to 2000, The value of y1+y2 is 3*(x1+x2+y1+y2) / 100 to 90*(x1+x2+y1+y2) / 100.] The main chain contains 1,3-dioxolane copolymer units (DP) represented by However, [O-CH ２ —O—CHR ３ -CHR ４ -] ｙ１ and [O-CHR ３ -CHR ４ O-CH ２ -] ｙ２ In each case, at least one group R ３ or R ４ is C １ ~C １８ The organyloxysilyl-terminated polymer (P) is an alkyl group.

2. 2. The organyloxysilyl-terminated polymer (P) of claim 1, wherein R is selected from alkyl groups having 1 to 2 carbon atoms.

3. R １ The organyloxysilyl-terminated polymer (P) according to claim 1, wherein is a hydrogen atom.

4. R ２ 2. The organyloxysilyl-terminated polymer (P) of claim 1, wherein is selected from a methyl group and an ethyl group.

5. R ３ and R ４ is a hydrogen atom and C １ ~C ６ 2. The organyloxysilyl-terminated polymer (P) according to claim 1, wherein the alkyl groups are selected from the group consisting of aryl, aryloxysilyl ...

6. In each case, [O—CH ２ —O—CHR ３ -CHR ４ -] ｙ１ and [O-CHR ３ -CHR ４ O-CH ２ -] ｙ２ Unit R ３ group or R ４ One of the groups is C １ ~C １８ 2. The organyloxysilyl-terminated polymer (P) according to claim 1, wherein the first group is an alkyl group, and the other groups are in each case hydrogen atoms.

7. Organyloxysilyl terminated polymer (P) according to claim 1, wherein the 1,3-dioxolane copolymer units (DP) of formula (II) have a number average molecular weight Mn of 750 to 300,000 Daltons.

8. A method (P3) for producing the organyloxysilyl-terminated polymer (P) according to claim 1, comprising: General formula (III): H-[(O-CH ２ -O-CH ２ -CH ２ -) ｘ１ (O-CH ２ -CH ２ -O-CH ２ -) ｘ２ (O-CH ２ -O-CHR ３ -CHR ４ -) ｙ１ (O-CHR ３ -CHR ４ -O-CH ２ )] ｙ２ -OH (III) a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) represented by the formula: At least one compound of formula (V): OCN-(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ (V) [In the formula, R, R １ , R ２ , R ３ , R ４ , x1 + x2 and y1 + y2, a and b have the definitions specified in claim 1. with an isocyanate-functional silane of (P3).

9. 10. A composition comprising the organyloxysilyl-terminated polymer (P) of claim 1 and at least one additional component selected from (A) a nitrogen-containing organosilicon compound, (B) a silicone resin, (C) a catalyst, (D) an adhesion promoter, (E) a moisture scavenger, (F) a filler, (G) an additive, and (H) an aggregate.

10. 10. An adhesive or sealant comprising the organyloxysilyl terminated polymer (P) agent of claim 1, an organyloxysilyl terminated polymer (P) produced by the method of claim 8, or the composition of claim 9.

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