Curable condensation compounds based on alkoxyl-functional polysiloxanes

Abstract

The present invention relates to curable condensation compounds based on alkoxyl-functional polysiloxanes, which are obtainable by the reaction of an acetoxy-bearing siloxane with at least one alkoxyl-functional polysiloxane in the presence of a catalyst, which is end-stopped.

Description

Technical Field

[0001] This invention relates to curable condensation compounds based on alkoxy-functionalized polysiloxanes, their preparation methods, and their use in coating systems that, among other properties, have a tendency to repel dirt. Background Technology

[0002] Coatings are applied to surfaces for decorative, functional, or protective purposes. The need for surface protection is increasing in various industries such as aerospace, automotive, rail vehicles, shipbuilding, and wind energy.

[0003] Various techniques are used for the functionalization of surfaces and coatings. Methods for surface functionalization by micro- and nano-structuring coatings derived from shark scale structures are known in the literature. Such surfaces are used in rotor blades of ships, aircraft, wind power equipment, or as components of pipes to reduce flow resistance. Self-healing coatings have also been developed, in which encapsulated functional active ingredients are released in the event of mechanical damage to the system and subsequently exhibit their healing activity. These self-healing surfaces are of interest for corrosion prevention.

[0004] Another known problem is soiling caused by vandalism, such as graffiti on walls or objects. This problem not only troubles local authorities but also particularly affects transportation companies. This is because cleaning such surfaces is very inconvenient and costly.

[0005] Significant efforts have been made in developing cleaning technologies for removing graffiti. Conventional techniques involve removing the surface with paint removers such as dichloromethane, benzene, or toluene. Depending on the substrate, temperature, colorant, and specific exposure time, colorants may be removed, for example, by using a high-pressure cleaner. This process can / must be repeated multiple times. Any graffiti residue can then be removed by sandblasting, which may require refinishing the surface to restore its previous appearance. Another technique is the expensive and inconvenient repainting or recoating of the surface, which is also time-consuming and incurs considerable costs.

[0006] Antifouling coatings / fouling stripping coatings are also known to prevent, or at least significantly inhibit, the overgrowth of algae and bivalves on surfaces in constant contact with water. Especially in the case of structures in permanent contact with water, such as hulls, buoys, fishing nets, suction and drainage pipes for cooling, offshore drilling facilities, or tanks exposed to seawater and / or freshwater, the adhesion and overgrowth of organisms (biofouling) can cause considerable economic losses. In the case of ships, these conditions, for example, lead to increased friction and associated increased fuel consumption. In the case of static structures, surfaces also suffer mechanical damage due to increased resistance to waves or flow, which results in shorter maintenance cycles and thus a shorter service life.

[0007] Foul-release coatings are typically based on polysiloxanes or silicone elastomers. Their mechanism of action is to form an anti-stick surface, on which aquatic organisms cannot adhere or have such low adhesion that they will detach from the water due to movement.

[0008] Therefore, it is known to add polysiloxanes to coatings to obtain specific properties. For example, by chemically modifying the polydimethylsiloxane chain, the most important organosilicon properties, such as compatibility, sliding resistance, or scratch resistance, can be controlled. The use of polysiloxanes is extensive and highly complex.

[0009] Since the early days of the organosilicon industry, condensable crosslinkable hydroxyl and / or especially alkoxy-terminated and acetoxy-functionalized polydiorganosiloxanes have been significant as typical representatives of organosilicon resin precursors. For example, the teachings of EP 0157 318 B1 are intended for the preparation of general formula R 2 a Si(OR 1 ) b O (4-a-b) / 2 A method for obtaining organosilicon resin precursors, which is obtained by alcoholysis / hydrolysis and partial condensation of organochlorosilanes with alcohol / water.

[0010] CN105131293 B relates to acetoxy-functionalized MQ resins and their preparation. In a hydrolysis medium composed of dilute hydrochloric acid and ethanol, hexamethyldisiloxane and tetraethoxysilane are first converted into ethoxy-functionalized organosilicon resin prepolymers, which are then modified in a second step by reacting with organoacetoxysilanes to obtain self-crosslinked acetoxy-MQ resins.

[0011] Clarke's (US 3 032 529) teachings take a similar approach, describing stabilized organopolysiloxane resins. To prepare storage-stable organosilicon coating systems that cure at room temperature for 24 hours on wood, plastic, metal, and ceramic surfaces, this literature teaches the acylation of pure and / or mixed incompletely condensed ≡Si-OH-terminated diorganosiloxanes with an acylating agent, preferably a triacyloxysilane, to remove all Si-bonded hydroxyl groups.

[0012] US 4,585,705 (Broderick et al.) does not emphasize the use of acetoxysiloxanes, but rather relates to release coatings based on organopolysiloxanes that can be cured on substrates, including hydroxy-functionalized methyl, phenyl and mixed methyl / phenyl resins and methyltrimethoxysilanes (derives), as well as small proportions of trimethylsilyl-terminated diorganosiloxanes and titanates.

[0013] It is also known that linking terminal hydroxyl-functionalized siloxanes (PDM siloxanes) with polyfunctional acetoxysilanes as crosslinking agents can produce hydrolytically unstable siloxane prepolymers that provide acetoxy groups (HFMark, Concise Encyclopedia of Polymer Science and Technology, 3rd ed., p. 1112, Wiley-Verlag, (2013) and Ashoffman et al., Biomaterials Science: An Introduction to Material in Medicine, 2nd ed., pp. 83-84, Elsevier Acad. Press, San Diego, (2004)).

[0014] In US 2009 / 0226609, Boisvert et al. claimed protection for a Q-titanium-based silicone resin prepared by reacting a system consisting of bis(tert-butoxy)diacetoxysilane, tetrahydrofuran, water, and tetra(tert-butoxy)titanium.

[0015] According to C. Robeyns et al. (Progress in Organic Coatings 125, 287-315, (2018), the process begins with the hydrolysis of di(tert-butoxy)diacetoxysilane to form ortho-silica Si(OH)4, which is then condensed with tetra(tert-butoxy)titanium to release 4 equivalents of tert-butanol to obtain a mixed titanium-organosilicon resin.

[0016] However, the use of titanates presents a problem regarding their tendency to decompose in the presence of water, as this leads to the formation and precipitation of insoluble tetravalent titanium hydroxide, which causes turbidity, particularly in coating systems. This is especially true for systems where hydrolysis occurs in the presence of titanates. To overcome this problem, particularly in the production of anti-abrasion coating systems of transparent polycarbonate, Leclaire (US 5,357,024) proposed a dilution reaction of alkoxysilane hydrolysates with condensable ≡SiOH groups with acyl titanate compounds, followed by the addition of water, resulting in a siloxane prepolymer with titanium incorporated therein, based on solids in the range of 20 wt% to 30 wt% TiO2. Leclaire obtains the acyl titanate compounds by reacting tetraalkyl titanates or tetraalkoxytitanium compounds with carboxylic acids in a non-aqueous solvent (e.g., in alcohols).

[0017] When using these hydrolyzable titanium compounds, Leclaire did not observe the formation of precipitates in the coating matrix, even when silane hydrolysis was performed under harsh conditions. Leclaire explained this observation by hypothesizing that the acyl groups bound within the titanium compounds reduced their reactivity.

[0018] US 5,357,024 further teaches that these acyl titanates are obtained from tetraalkyl titanates in which the alkoxy functional groups are replaced by acyloxy functional groups. This preparation is carried out in the absence of water by reacting a tetraalkoxytitanium of formula Ti(OR')4 (where the R' groups may be the same or different) with a carboxylic acid RCOOH, wherein the amount of acid used in the reaction is selected to be 1-4 equivalents of acid to 1 equivalent of tetraalkoxytitanium, depending on the number of substituted alkoxy functional groups. The reaction is preferably carried out in the presence of a suitable non-aqueous solvent, such as an alcohol like isopropanol.

[0019] To obtain the silane AB3 precursor for the formation of hyperbranched polyethoxysiloxanes, Jaumann et al. described a reaction of tetraethoxysilane with acetic anhydride at 137 °C for at least 36 hours (even 89 hours in a paper by M. Jaumann, 04.09.2008, RWTH Aachen, page 47), which releases ethyl acetate to form acetoxytriethoxysilane as the AB3 precursor, with a yield of only about 39%. To improve the unsatisfactory reaction kinetics, Jaumann also used both low and high doses of tetraethyl orthotitanate as catalysts. Adding 0.155 mol% tetraethyl orthotitanate reduced the reaction time required to reach approximately 94% conversion to 14.5 hours. Adding 0.95 mol% of tetraethyl orthotitanate reduces the reaction time to 1.5 hours to achieve a conversion of approximately 88%, but significantly decreases product purity. In the resulting polyethoxysiloxane, approximately 6 mol% of all silicon atoms originate from the tetraethoxysilane used (M. Jaumann's paper, 04.09.2008, RWTHAachen, pp. 47-50).

[0020] Also reflecting Jaumann's work, WO 2014 / 187972 claims protection under the provisions of 29 The complex calculation formula for Si NMR spectra shows that highly branched, fluorine-free polyalkoxysiloxanes with a branching level (VG) greater than 0.4 are used in the production of antifouling surface coatings. These highly branched polyalkoxysiloxanes are prepared using tetraethoxysilane, acetic anhydride, and tetrakis(trimethylsiloxy)titanium, or... 40. Preparation or use of acetic anhydride and titanium isopropoxide (IV) 40. Preparation of acetic anhydride and α-n-butyl-ω-(trimethoxysilyl)ethyl polydimethylsiloxane.

[0021] The purpose of the teachings of WO 2019 / 200579, which does not emphasize polyalkoxysiloxanes, is to produce polysiloxane compositions for the production of non-corrosive elastomers that crosslink at room temperature, said polysiloxane compositions containing hydroxyl-terminated polyorganosiloxanes, diacetoxysilanes, polyfunctional alkoxysilanes, as well as fillers and catalysts.

[0022] WO 2012 / 040305 discloses a method containing a weight-average molecular weight M w Curable compositions of organosiloxane block copolymers exceeding 20,000 g / mol, wherein these organosiloxane block copolymers are generated by reacting an organosiloxane resin with silanol groups (component b) with a linearly geminal diacetoxy-substituted organosiloxane (component a). "Geminal diacetoxy-substituted" here means that the organosiloxane has two adjacent acetoxy groups [-Si-(OAc)2] at the terminal positions of the silicon atoms. These geminal diacetoxy-substituted organosiloxanes are prepared by reacting silanol-terminated polydiorganosiloxanes with alkyltriacetoxysilanes. Therefore, this process results in multiple crosslinks around the center of the acetoxysilane used. During this process, the acetic acid formed must be removed from the system. Removing the released acetic acid is difficult because it forms hydrogen bonds that hinder its thermal decomposition. Ensuring that the linear organosiloxane block copolymers are acid-free (and water-free) is essential, as they would otherwise be unusable on acid-sensitive substrates. A solvent is also required for preparation because the reactants or sesquioxanes used are solids. Summary of the Invention

[0023] Therefore, one object of the present invention is to provide compounds suitable for producing coating systems, wherein these compounds have improved anti-adhesion properties without significantly impairing other properties and without the disadvantages mentioned in the prior art.

[0024] To achieve this objective, condensation compounds of the type specified at the beginning are proposed, which can be obtained by reacting an acetoxy-terminated siloxane of formula (I) and / or formula (II) with at least one alkoxy-functionalized polysiloxane of formula (III) in the presence of a catalyst.

[0025]

[0026] Wherein R = alkyl and / or phenyl having 1 to 4 carbon atoms, preferably R = methyl, and 1 ≤ x ≤ 500, preferably 3 ≤ x ≤ 100, more preferably 5 ≤ x ≤ 40.

[0027] or

[0028]

[0029] Where 0 ≤ a ≤ 100 and 1 ≤ b ≤ 10, preferably 2 ≤ a ≤ 30 and 1 ≤ b ≤ 6, more preferably 3 ≤ a ≤ 10 and 2 ≤ b ≤ 5.

[0030] R 1 c Si(OR 2 ) d O (4-c-d) / 2 Equation (III)

[0031] Where c is not less than 0 and not greater than 2, and d is not less than 0 and not greater than 4, and the sum of c and d is less than 4.

[0032] R 1 The same or different and independently formed straight-chain or branched, saturated or monounsaturated or polyunsaturated or aromatic hydrocarbon groups, and

[0033] R 2 It is an alkyl group consisting of 1 to 8 carbon atoms, preferably methyl or ethyl.

[0034] It has been discovered that the curable condensation compounds according to the present invention can be used to produce coating systems with anti-adhesion properties, especially anti-graffiti effects. Furthermore, coatings produced therefrom unexpectedly exhibit better surface slip than conventional coatings.

[0035] Tests have shown that coatings prepared with the curable condensation compound according to the invention prevent or reduce the adhesion of any type of dirt and do not show any impairment to other properties.

[0036] The various segments of the siloxane chain indicated in equations (I) to (III) can be statistically distributed. Statistically distributed chains can have a block-like structure containing any number and any order or follow a random distribution; they can also have alternating structures or form gradients along the chain; in particular, they can also form any mixed form.

[0037] The coefficients described herein and the range of values ​​indicated for the coefficients can be considered as the average of the possible statistical distributions of actual structures and / or mixtures thereof.

[0038] In the context of this invention, the term "polymer" not only covers compounds having at least three repeating units of one or more monomers in their molecules, but also, in particular, covers compositions of compounds having a certain molecular weight distribution and an average molecular weight of at least 200 g / mol. This definition takes into account the fact that such compounds are customarily referred to as polymers in the relevant industrial sectors, even if they do not appear to meet the definition of a polymer according to the OECD or REACH guidelines.

[0039] Unless otherwise stated, all percentages are expressed as weight percentages.

[0040] Unless otherwise stated, measurements recorded below were performed under standard conditions (25°C and 1013 mbar).

[0041] When averages are recorded below, unless otherwise stated, the values ​​discussed are weight averages.

[0042] Particularly suitable terminally balanced acetoxy-containing siloxanes of formula (I) and / or formula (II) and their preparation are known in the prior art. Thus, for example, linear or branched polysiloxanes with terminal acetoxy groups can be obtained by reacting a linear polysiloxane equilibrate (= pre-equilibrate) with a reaction medium consisting of acetic anhydride, trifluoromethanesulfonic acid and acetic acid as the sole reactant.

[0043] Numerous synthetic methods are known to those skilled in the art. Only a few are listed here, and they are also intended to be part of this invention: it is conceivable to use trifluoromethanesulfonic acid, or a balanced acetoxysiloxane of linear or branched structure type of formula (I) or (II) (the preparation of which can be inferred from the teachings of European patent application EP3611215A1), according to which a mixture of cyclic siloxanes, particularly including D4 and / or D5, and / or D / T type cyclic-branched siloxanes, is reacted with acetic anhydride in the presence of acetic acid using trifluoromethanesulfonic acid as a catalyst.

[0044] European patent applications with application numbers EP 18189072.4, EP 18189075.7 and EP 18189074.0 relate to methods for preparing acetoxy-modified siloxanes, wherein DT siloxane cyclics or simple siloxane cyclics containing only D units are used as reactants, respectively.

[0045] To obtain unbranched but linear SiOC-linked organosilicon polyether structures, European patent applications EP18189072.4 and EP 18189074.0 describe the preparation of equilibrium α,ω-diacetoxy polydimethylsiloxanes by reacting siloxane cyclic compounds (D4 / D5) with acetic anhydride in the presence of trifluoromethanesulfonic anhydride. The method involves contacting the reactants with trifluoromethanesulfonic acid in an amount of 0.1 to 0.3% by mass based on the total mass of the reaction mixture while thoroughly mixing the reactants, and then heating to a temperature of 140 to 160°C for 4 to 8 hours. During this process, the initially slightly turbid reaction mixture becomes a clear, equilibrium trifluoromethanesulfonic acid-catalyzed α,ω-diacetoxy polydimethylsiloxane, containing, in addition to the trifluoromethanesulfonic acid used, 0.125 mol of free acetic anhydride, based on the equivalent amount of acetic anhydride chemically bonded within the α,ω-diacetoxy polydimethylsiloxane.

[0046] European patent application EP18210035.4 describes (i) a reaction system for preparing siloxanes with acetoxy functional groups, comprising a) silanes and / or siloxanes with alkoxy groups and / or b) silanes and / or siloxanes with acetoxy groups, c) silanes and / or siloxanes with hydroxyl groups, d) optional simple siloxane cyclic bodies and / or DT cyclic bodies, e) a reaction medium, including acetic anhydride, perfluoroalkyl sulfonic acid and preferably acetic acid, and (ii) a method for preparing linear or branched siloxanes with acetoxy functional groups.

[0047] The branched siloxane with terminal acetoxy groups to be used according to the present invention can be obtained, for example, by the method described in unpublished patent applications EP19176875.3 and EP19176874.6, and begins with a D / T type cyclic-branched siloxane, in a first step reacting the D / T type cyclic-branched siloxane with acetic anhydride under acid catalysis, optionally in a blend with a simple siloxane cyclic and / or a hydroxyl-containing siloxane and / or a silane with acetoxy and / or alkoxy groups, to obtain an acetoxy-containing branched siloxane, and then in a second step, the acetoxy-containing branched siloxane is reacted with an acid, preferably a superacid, especially acetic acid. The oxoalkane balance, wherein the D / T type cyclic-branched siloxane is a mixture of D / T type cyclic-branched siloxanes and siloxanes having D and T units, may also include siloxanes having Q units, provided that, in these mixtures, based on the total amount of all silicon atoms, the proportion of silicon atoms from Q units is ≤10% by mass to ≥0% by mass, preferably ≤5% by mass to ≥0% by mass, wherein application document 19176875.3 further includes the following condition: if the D / T type cyclic-branched siloxane used is a mixture of D / T type cyclic-branched siloxanes that do not contain siloxanes having Q units, then the acid used in steps 1 and / or 2 is not only trifluoromethanesulfonic acid or not only trifluoromethanesulfonic acid and acetic acid.

[0048] Preferably, the terminally balanced acetoxysiloxane of formula (I) has only D units.

[0049] Preferably, a linear polydimethylsiloxane with terminally balanced α,ω-acetoxy groups is used in the reaction.

[0050] Preferably, the terminally balanced acetoxylated siloxanes of formula (I) and / or formula (II) are neutralized.

[0051] The neutralization of acetoxysiloxanes in Brønsted acid solutions, particularly trifluoromethanesulfonic acid solutions, is described in patent application EP 19176868.8. For this purpose, the acetoxysiloxane to be neutralized is mixed with a certain amount of solid and / or liquid and / or gaseous base suitable for neutralizing the Brønsted acid, particularly trifluoromethanesulfonic acid, present therein, and the neutralized acetoxysiloxane is separated from the formed salt. To ensure neutralization, it is preferable to use an excess of the base for neutralization in stoichiometric proportions based on the equivalent of the acid to be neutralized.

[0052] Acetoxysiloxanes and siloxanes with acetoxy groups are used as synonyms in this article.

[0053] Suitable alkoxy-functionalized polysiloxanes of formula (III) are also commonly referred to as silicone resins. This formula relates to the smallest unit of the average structural formula of the silicone polymer. The number of repeating units can be determined by the number-average M determined by GPC. n establish.

[0054] The production of these types of silicone resins is well known in the literature (see, for example, W. Noll–Chemieund Technologie der Silicone [Chemistry and Technology of the Silicones], Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 1960) and is also described in German patent application DE 34 12648.

[0055] R 1 The group is preferably independently a saturated, branched, or unbranched alkyl group having 1 to 17 carbon atoms and / or a monounsaturated or polyunsaturated, branched, or unbranched alkenyl group having 2 to 17 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Alkyl and alkenyl groups are more preferably having up to 12, more preferably up to 8 carbon atoms. All R groups are also more preferably... 1 The functional group is methyl and / or phenyl.

[0056] R 2 The group is preferably a saturated, branched, or unbranched alkyl group having 1 to 8 carbon atoms independently. 2 Preferably selected from methyl or ethyl. The latter is particularly suitable for phenyl polysiloxanes or phenylalkyl polysiloxanes specified as HAPS-free (free of harmful air pollutants), which do not contain solvents such as toluene, xylene or benzene and release only ethanol, not methanol, during catalytic hydrolysis-condensation crosslinking at room temperature.

[0057] Preferred compounds of general formula (III) have methyl and / or ethyl groups as R. 2 The group, wherein the alkoxy functionality is 3% to 50% by weight, preferably 5% to 40% by weight, and more preferably 7% to 30% by weight, based on the total mass of the compound.

[0058] The weight-average molecular weight M of compounds of general formula (III) w Preferably, the concentration is 200 to 20000 g / mol, more preferably 200 to 10000 g / mol, even more preferably 300 to 3000 g / mol, or especially preferably 400 to 2000 g / mol.

[0059] For the reaction according to the present invention, the alkoxy functionalization of the polysiloxane of general formula (III) plays a major role.

[0060] In the context of this invention, alkoxy functionality refers to the presence of an alkyl group bonded to silicon via oxygen in the polysiloxane. Preferably, alkoxy functionality refers to the presence of a Si-OR group. Alkoxy functionality represents the mass ratio of alkoxy groups based on the polysiloxane.

[0061] It should be noted here that the use of alkoxy-functionalized polysiloxanes of formula (III) has been found to be superior to the use of silanols detailed in the prior art. Siloxanes with ≡SiOH groups exhibit very limited storage stability, especially under the influence of trace amounts of acid and alkali that are always present. Furthermore, silanol-functionalized polysiloxanes, which are typically used in coating systems, are usually solids and always require solvents for processing in order to further functionalize or apply them. Once applied to a substrate, polysiloxanes with silanol groups are less reactive than systems with alkoxy groups and require high temperatures to crosslink. Therefore, it is not possible to use silanol-functionalized polysiloxanes on heat-sensitive substrates. Consequently, silanol-functionalized polysiloxanes are not suitable for external applications on non-heatable substrates, such as for anti-graffiti coatings.

[0062] R is preferred. 1 Polysiloxanes of general formula (III) of methyl (referred to as methyl silicone resins) having an alkoxy functionality of 7% to 35% by weight and a weight-average molar mass of 300 to 2000 g / mol based on the total mass of the polysiloxane.

[0063] R is also preferred. 1 These are polysiloxanes of the general formula (III) of phenyl (referred to as phenyl resins). Based on the polysiloxanes, they preferably have an alkoxy group in a proportion of 1% to 40% by weight, more preferably 3% to 35% by weight, and most preferably 5% to 30% by weight.

[0064] More preferably, the weight-average molecular weight M of the phenyl resin w The concentration is 200 to 10000 g / mol, preferably 200 to 3000 g / mol, and more preferably 300 to 2000 g / mol.

[0065] The weight-average molecular weight M of phenyl resin w More preferably, it is 700 to 2000 g / mol.

[0066] In another embodiment, R is preferably referred to as a methyl-phenyl resin. 1 Polysiloxanes of general formula (III), including phenyl and methyl.

[0067] Particularly preferred methyl-phenyl resins have methoxy and / or ethoxy groups as alkoxy groups. Based on polysiloxanes, the proportion of alkoxy groups, more particularly the proportion of methoxy and / or ethoxy groups, is at least 1% by weight, preferably 2% to 40% by weight, more preferably 3% to 35% by weight, and most preferably 5% to 30% by weight.

[0068] Based on the number of moles in the resin, the ratio of phenyl to methyl groups is preferably in the range of 1:0.1 to 0.1:1, more preferably in the range of 0.5:1 to 1:0.5.

[0069] In the case of using chemical (empirical) formulas in this invention, the specified coefficients can be not only absolute values ​​but also average values.

[0070] For polymeric compounds, the coefficients are preferably expressed as average values.

[0071] Unless otherwise stated, all percentages are expressed as weight percentages.

[0072] Unless otherwise stated, measurements reported below were performed under standard conditions (25°C and 1013 mbar).

[0073] When averages are reported below, unless otherwise stated, the values ​​discussed are weight averages.

[0074] The condensation compounds according to the present invention are preferably prepared using catalysts selected from the following: tin diacetate, tin dioctanoate, dibutyltin diacetylacetone, dibutyltin dilaurate, tin tetraacetate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dioleate, dioctyltin dilaurate, dioctyltin dinedecanoate, dimethoxydibutyltin, dimethyltin, dibutyltin benzylmaleate, bis(triethoxysilyloxy)dibutyltin, diphenyltin diacetate, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetoacetate)titanium (diisopropoxybis(e thylacetoacetato)titanium), dipropoxybis(acetylacetone)titanium, diisopropoxybis(acetylacetone)titanium, dibutoxybis(acetylacetone)titanium, triisopropoxyallyl titanium acetate, isopropoxyoctanediol-titanium oxide or bis(acetylacetone)titanium oxide, lead diacetate, lead di-2-ethylhexanoate, lead dineodecanate, lead tetraacetate, lead tetrapropionate, zinc acetylacetone, zinc 2-ethylhexanoate, zinc diacetate, bis(2-ethylhexanoyl)zinc, zinc dineodecanate, zinc diundecenoate, zinc dimethacrylate, zirconium tetra(2-ethylhexanoyl)dichloride, zirconium tetra(methacryloyl)dichloride, cobalt diacetate, bismuth carboxylate, and bismuth trifluoromethanesulfonate. Other catalysts that can be used are iron(II) and iron(III) compounds, such as iron(III) acetylacetonate or iron(II) acetate; aluminum compounds, such as aluminum acetylacetonate; calcium compounds, such as calcium ethylenediaminetetraacetate; or magnesium compounds, such as magnesium ethylenediaminetetraacetate.

[0075] Another option is to use perfluoroalkyl sulfonic acids, such as trifluoromethanesulfonic acid or perfluorobutanesulfonic acid, as catalysts.

[0076] The catalyst according to the invention, which is described and illustrated in detail below, is preferred.

[0077] The reaction preferably includes at least one crosslinking agent of formula (IV).

[0078] R 3 e Si(OR 4 ) f Formula (IV)

[0079] Where e is not less than 0 and not greater than 2, f is not less than 2 and not greater than 4, and the sum of e and f is 4.

[0080] R 3 = A saturated or unsaturated alkyl group consisting of 1 to 8 carbon atoms, or an organic moiety consisting of 1 to 8 carbon atoms and 1 to 2 nitrogen atoms, or an aromatic moiety having 6 to 20 carbon atoms, and

[0081] R 4= An alkyl or acyl group consisting of 1 to 8 carbon atoms.

[0082] The alkyl group is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl. The aromatic moiety is preferably a phenyl moiety. Preferred substituents R 3 It is methyl or phenyl, or a mixture of methyl and phenyl. For R 4 The preferred alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0083] The crosslinking agent is preferably selected from methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxyphenylmethylsilane, and diethoxyphenylmethylsilane.

[0084] Therefore, advantageously, the branching level of the condensation compound can be increased by adding the following substances to the reaction matrix using the method according to the invention:

[0085] a) branched acetoxysiloxanes and / or

[0086] b) Branching crosslinking agent.

[0087] Furthermore, according to the present invention, since the branched condensation compound reacts with additional acetoxysiloxane, there is a possibility of subsequent crosslinking and an increase in molar mass.

[0088] The terms “siloxane” and “polysiloxane”, whether as part of a word or as separate words, shall be understood as synonyms in this invention.

[0089] Based on the total mass of the curable condensation compound, the curable condensation compound according to the present invention preferably contains a crosslinking agent in an amount of 0% to 20% by weight, more preferably 0% to 10% by weight, and even more preferably 0% to 5% by weight.

[0090] Furthermore, it is desirable to provide a method by which curable condensation compounds based on alkoxy-functionalized polysiloxanes can be readily prepared without the disadvantages known in the prior art.

[0091] It has now been surprisingly discovered that, without the use of the organochlorosilanes mentioned at the beginning or the difficult-to-control alcoholysis / hydrolysis operations, it is possible to obtain curable condensation compounds based on alkoxy-functionalized polysiloxanes without ≡Si-OH groups by reacting terminally balanced acetoxy-containing siloxanes of formula (I) and / or formula (II) with at least one alkoxy-functionalized polysiloxane of formula (III) in the presence of a catalyst in a simple and explicit manner.

[0092] Based on the entire organosilicon matrix, the weight ratio of the acetoxy-containing siloxane of formula (I) and / or formula (II) to the alkoxy-functionalized polysiloxane of formula (III) is preferably 1:99 to 99:1, more preferably 3:97 to 50:50, and particularly preferably 5:95 to 30:70.

[0093] Any conventional catalyst can be used. Preferred catalysts have been described above.

[0094] Furthermore, it has been unexpectedly discovered that the method according to the invention is most preferably carried out in the presence of a catalyst compatible with the organosilicon matrix, which is obtained, for example, by reacting titanyl oxide with acetic anhydride or by reacting titanyl oxide with acetoxysiloxane before the condensation reaction to be catalyzed begins.

[0095] The terms "reaction matrix" and "organosilicon matrix" are used synonymously in this document, and they are mainly composed of compounds of formula (I) or (II) and compounds of formula (III).

[0096] More particularly, the catalyst produced by the reaction of titanyl alkyl oxide and acetoxysiloxane according to the present invention can also preferably be prepared in situ.

[0097] Therefore, the preparation of this novel catalyst constitutes another part of the subject matter of this invention. The catalyst according to the invention can preferably be prepared from titanyl oxide and acetic anhydride or from titanyl oxide and acetoxysiloxane. More preferably, the catalyst according to the invention can be prepared in situ from titanyl oxide and acetoxysiloxane (i.e., during the reaction of a compound of formula (I) or (II) with a compound of formula (III)).

[0098] The catalyst produced by the reaction of titanyl alkyl oxide and acetoxysiloxane has excellent compatibility with the reaction matrix and allows both the timely and rapid reaction of alkoxy polysiloxane and acetoxysiloxane and the curing of the curable condensation compound produced therefrom under normal atmosphere.

[0099] In a preferred configuration variant, according to the invention, acetoxysiloxane and alkoxyfunctional polysiloxane can be premixed first, and then contacted with titanane oxide and / or more preferably with a condensation catalyst generated by the reaction of acetoxysiloxane with titanane oxide.

[0100] Alternatively, and preferably, according to the present invention, a condensation catalyst compatible with an organosilicon matrix can be prepared by mixing and pre-reacting an acetoxysiloxane with a titanane oxide. An alkoxy-functionalized polysiloxane is then added to form a condensation-reactive matrix.

[0101] In the context of this invention, the compatibility of the condensation catalyst is determined by whether turbidity occurs after it is introduced into the reaction matrix or after it is formed in situ therein. For this purpose, if an equal volume fraction of a sample taken from the reaction matrix is ​​introduced into a 10 mm thick glass cuvette, and the text immediately following it (printed in black on white paper in Arial font, size 12) can be read under sunlight and / or artificial light without distortion, then the reaction matrix is ​​considered to be turbid, and the condensation catalyst is considered to be compatible according to the invention.

[0102] In another preferred configuration of the invention, acetoxysiloxane, alkoxypolysiloxane, and titanyl oxide react under vigorous mixing.

[0103] According to the present invention, based on a reaction matrix composed of alkoxy polysiloxane and acetoxy siloxane, all the catalysts mentioned can be used in amounts from 0.01 wt% to 10.0 wt%, preferably from 0.05 wt% to 7.5 wt%, more preferably from 0.1 wt% to 5.0 wt%.

[0104] The alkoxy-functional polysiloxanes of formula (III) and terminally balanced acetoxy-containing siloxanes of formula (I) and / or formula (II) for use in the method according to the invention have been described in detail above, including preferred embodiments thereof.

[0105] According to the present invention, the condensation reaction can preferably be carried out by removing R during the reaction. 2 The process is accomplished by forming an acetate from a group and an acetoxy group. The acetate released from the reaction matrix can be removed under standard pressure or, more preferably, under reduced pressure (i.e., by applying an auxiliary vacuum). Other options are known to those skilled in the art.

[0106] According to the present invention, the condensation reaction of alkoxy-functionalized polysiloxanes with acetoxysiloxanes can preferably be carried out in pure form, i.e., without solvent, or in solution. Examples of suitable solvents include aromatic compounds, alkyl aromatic compounds, and aliphatic hydrocarbons.

[0107] It is preferable to use substances with a boiling point higher than that released from the condensation reaction by R. 2 The solvent for the boiling point of acetate esters formed by the group and acetoxy group.

[0108] Condensation reaction and reaction are used as synonyms here.

[0109] Crosslinking agents of formula (IV) are preferred. Preferred crosslinking agent compounds have been described above.

[0110] It is conceivable to use a mixture of at least two crosslinking agents as the crosslinking agent. For example, for the purposes of this invention, a mixture of phenyltrimethoxysilane and methylphenyldimethoxysilane can be used as a monomer blend.

[0111] supplemented by GPC 29 Si NMR spectra (measured on a Bruker Avance III 400 spectrometer with a Bruker PA BBO 400Si BB-HD-10z sample head at a frequency of 79.495 MHz, with a measurement time of 2.569 seconds per scan and 512 scans per spectrum) can be used to observe the reaction. 29 Si NMR spectroscopy, in particular, can monitor conversion rates by observing the characteristic signals of the Si-acetoxy moiety.

[0112] Acetoxysiloxanes typically at -9 ppm 29 The disappearance of the Si NMR signal is a reliable indicator of complete conversion. For example, the reaction mixture according to the invention, as detailed in the examples, achieves quantitative conversion after 1 to 3 hours.

[0113] The curable condensation compounds obtained according to the present invention have a significant advantage in that they are completely free of any siloxane moiety containing ≡Si-OH groups. For example, the disadvantages arising from the presence of increased ≡Si-OH groups in alkoxy-functional polysiloxanes have been well discussed, particularly in WO2014 / 187972, regarding the lack of storage stability of hyperbranched polyalkoxysiloxane additives (page 8), and in patent application EP0771835B1 regarding their lack of storage stability (page 4, lines 29-30), and in EP 0964020B1 regarding insufficient resistance to stain formation during the treatment of alkoxy-functional polysiloxanes in coating compositions (page 3, paragraph

[0026] ).

[0114] The curable condensation compound according to the invention is preferably a clear to slightly turbid liquid with a significantly increased molar mass relative to the starting materials used (formulas (I), (II) and (III)), which can be easily understood by means of GPC analysis.

[0115] It has also been found that the curable condensation compounds according to the invention possess certain self-curing properties (“1K properties”) due to the residual catalyst components in the system.

[0116] If faster partial and complete drying times are required, it is recommended to add a curing catalyst. Common curing catalysts are known to those skilled in the art. Some examples are listed here: 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, tetratetra(isopropyl) titanate, tetratetra(n-butyl) titanate, 1,1,3,3-tetramethylguanidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and dioctyltin dilaurate.

[0117] Another object of the present invention is to provide a coating composition with anti-graffiti effect that does not adversely alter the properties of the substrate. For example, because the coating according to the invention has an anti-graffiti effect, the paint or varnish used to produce graffiti no longer adheres to the substrate or only very weakly adheres to the substrate, and the sprayed substrate should be easy to clean, such that water, cloth, surfactant, pressure cleaner, and mild solvent are sufficient. The complex cleaning processes known in the prior art can be avoided as much as possible.

[0118] It has been quite surprisingly discovered that the coating according to the invention can withstand multiple cleaning cycles without losing its anti-graffiti effect. Therefore, the coating according to the invention is far superior to those of the prior art in terms of its technical lifespan. For example, users do not need to apply a new protective layer after each cleaning process, which translates to economic benefits.

[0119] Surprisingly, coated products having a coating containing the curable condensation compound of the present invention have anti-adhesion properties, anti-graffiti properties, anti-friction properties, and / or anti-fouling properties.

[0120] The use of the curable condensation compound according to the invention in the production of coatings having anti-adhesion, anti-graffiti, anti-friction, and / or anti-fouling properties also constitutes part of the subject matter of this invention.

[0121] Coatings, varnishes, paints, inks, coverings, sealants, and adhesives that can be obtained by using the curable condensation compounds according to the invention also constitute another part of the subject matter of the invention.

[0122] Those skilled in the art will know that coatings may also contain adhesion promoters, such as aminosilanes, UV stabilizers, fillers, pigments, thixotropic agents (e.g., fumed silica), reactive diluents or crosslinking agents (e.g., silanes), solvents (e.g., xylene), leveling agents, defoamers, or accelerators.

[0123] The present invention will be described in detail below through working examples. Detailed Implementation

[0124] method

[0125] Nuclear magnetic resonance (NMR)

[0126] NMR spectroscopy was performed using a Bruker Avance III 400 spectrometer. Measurements were taken at 79.495 MHz using a Bruker PA BBO 400SiBB-HD-10z sample head. 29 Si NMR spectroscopy. The measurement time was 2.569 seconds per scan, with 512 scans per spectrum.

[0127] Gel permeation chromatography (GPC)

[0128] Molar mass and molar mass distribution were determined according to DIN 55672-1. The described method is not absolute. Instead, calibration is required using commercially available polystyrene standards with linear structures and characterized by independent absolute methods. Instrument: Agilent 1100 from Agilent Technologies, column assembly: SDV 1000 / The length was 65.00 cm, the temperature was 30℃, tetrahydrofuran was used as the mobile phase, the flow rate was 1 ml / min, the sample concentration was 10 g / L, the RI detector was used, and the molar mass ratio was 162-2520000 g.mol. -1 The polystyrene standard was evaluated.

[0129] Anti-graffiti effect

[0130] a) Anti-graffiti effect was determined according to ASTM D7089-06. The condensation compound according to the invention was applied to an aluminum Q-Panel using a 100 μm spiral applicator. The coated panel was dried for 24 hours.

[0131] Then, using a nozzle, half of each panel is coated with commercially available blue nitrocellulose lacquer (FLT Handel & Service GmbH) and allowed to dry for 24 hours. Subsequently, the blue-lacquered panels are subjected to a water jet at 5 bar pressure until the lacquer is completely removed. This typically takes no more than 5 minutes. A small amount of paint residue at the panel edges is ignored here.

[0132] This checks whether the coating exhibits anti-graffiti properties.

[0133] b) Dry the panel that has undergone this first cycle again and apply paint with the nozzle again, then dry it. Repeat the test accordingly with a water jet until the blue paint layer can no longer be removed.

[0134] The number of cycles indicates how often the coating withstands a cleaning process before it loses all its anti-graffiti properties.

[0135] The longer the cleaning cycle of the coating, the greater its economic viability.

[0136] Sliding resistance value G(cN)

[0137] A useful method for measuring anti-slip properties has been found to be a test method that measures friction. This method is performed using a Bluehill instrument from Instron.

[0138] Here, a 500g weight with a specified felt pad is uniformly stretched across the coating surface using a tensile testing machine. The force required for this purpose is measured using an electronic force sensor. The test is performed at a constant speed of 12 mm / s and is repeatable with high accuracy. For testing, the coating composition according to the invention, containing the condensation compound according to the invention, is applied to an aluminum Q-Panel with the aid of a 100 μm spiral applicator and dried for 24 hours.

[0139] The lower the sliding resistance value G(cN), the higher the surface sliding property of the coating.

[0140] Compatibility of the catalyst according to the present invention

[0141] According to the present invention, the compatibility of the condensation catalyst is determined by the presence or absence of turbidity after the introduction of the condensation catalyst or after the condensation catalyst is formed in situ in the reaction matrix.

[0142] For this purpose, if an aliquot of a sample taken from the reaction matrix is ​​introduced into a 10 mm thick glass cuvette, and the text (font: Arial; font weight: standard; font color: black on white paper) immediately following it can be read under sunlight and / or artificial light without distortion, then the reaction matrix is ​​considered to be turbid, and the catalyst is considered to be compatible according to the present invention.

[0143] Other conditions

[0144] In the context of this invention, when values ​​are recorded as a percentage (%), unless otherwise stated, these values ​​are weight percent values. In the case of compositions, percentages are based on the entire composition unless otherwise defined. When average values ​​are mentioned in the following examples, they are numerical averages unless otherwise stated. When measurements are mentioned below, unless otherwise stated, they were determined at a pressure of 101325 Pa, a temperature of 23°C, and an ambient relative humidity of approximately 40%.

[0145] Materials and equipment

[0146] • Decamethylcyclopentasiloxane, from Dow

[0147] Acetic anhydride, from Merck

[0148] Acetic acid, 100%, from JTBaker

[0149] • Trifluoromethanesulfonic acid, from Alfa Aesar

[0150] Potassium acetate, from Sigma-Aldrich

[0151] • Polydimethylsiloxane diol, from Wacker

[0152] Tetrabutyl titanate, from ABCR

[0153] Tetraisopropyl titanate, from ABCR

[0154] Toluene, from Reininghaus Chemie

[0155] ·Silikophen AC1000 (poly(methyltrimethoxysilane)) from Evonik Industries

[0156] V5000 (poly(phenyltriethoxysilane)), from Evonik Industries

[0157] • Dowsil 3074 intermediate (methoxy-functionalized phenyl (methyl) silicone resin), from Dow

[0158] ·Dynasylan AMEO (3-aminopropyltriethoxysilane), from Evonik Industries

[0159] Rotavapor R-300 rotary evaporator, from Büchi

[0160] Rotavapor B-300Base oil bath, from Büchi

[0161] • Standard glass strip, from

[0162] • BK3 drying recorder, from The Mickle Laboratory Engineering

[0163] • Aluminum Q-Panel, 6 inches x 3 inches, from Q-Lab

[0164] • Colored spray paint, silky matte blue, FLT Handel & Service GmbH

[0165] Example

[0166] 1. Preparation of the curable condensation compound according to the present invention

[0167] 1.1 Preparation of terminally balanced acetoxy-containing siloxanes

[0168] First, terminally balanced α,ω-diacetoxy polydimethylsiloxanes were prepared, referred to hereinafter as α,ω-diacetoxysiloxanes for better readability. These α,ω-diacetoxysiloxanes are prepared by reacting siloxane cyclic compounds (D4 and / or D5) with acetic anhydride in the presence of trifluoromethanesulfonic acid and acetic acid, as disclosed in European applications EP18172882.5 and EP18172876.7. Therefore, following the teachings of these documents, three α,ω-diacetoxysiloxanes A, B, and C with average siloxane chain lengths of about 10, 15, and 35 monomer units were prepared. The acid present in the α,ω-diacetoxysiloxanes was then neutralized with potassium acetate, and the precipitated salt was filtered off. To remove volatile components, the α,ω-diacetoxysiloxanes were distilled at 130°C under an auxiliary vacuum of 5 mbar for one hour.

[0169] Table 1:

[0170] α,ω-diacetoxysiloxane A 10 α,ω-diacetoxysiloxane B 15 α,ω-diacetoxysiloxane C 35

[0171] 1,2-alkoxy-functionalized polysiloxanes

[0172] Use the alkoxy polysiloxanes listed in Table 2.

[0173] Table 2:

[0174]

[0175] Example 1 (Invention)

[0176] In a rotary evaporator (Rotavapor R-300) with a heated bath, 100.0 g of Silikophen AC1000, 10.0 g of α,ω-diacetoxysiloxane B, and 0.5 g of tetraisopropyl titanate were first placed into a 500 ml single-necked round-bottom flask. The mixture was then first stirred at 100 rpm for 1 hour at a heated bath temperature of 130 °C and ambient pressure. An auxiliary vacuum of 600 mbar was first applied for 2 hours, followed by an auxiliary vacuum of 100 mbar for another 2 hours. The methyl acetate formed during the reaction was collected in a collecting flask. The final product retained in the original flask... 29 Si NMR spectroscopy indicated that the terminal acetoxy group of α,ω-diacetoxysiloxane B had been completely converted due to the disappearance of the signal at -9 ppm. GPC analysis of the clear, colorless product showed a number-average molecular weight M. n It is 894 g / mol, and the weight-average molecular weight M wThe concentration is 4627 g / mol, thus proving that: compared with the starting material of Silikophen AC 1000 (M n 586 and M w Compared to 859 g / mol, the molecular weight is significantly increased.

[0177] Example 2 (Invention)

[0178] Similar to Example 1, 400.0 g of Silikophen AC1000, 80.0 g of α,ω-diacetoxysiloxane B, and 2.5 g of tetrabutyl titanate were weighed into a 2000 ml single-necked round-bottom flask and reacted on a rotary evaporator. The final product... 29 Si NMR spectroscopy indicated that the terminal acetoxy group derived from α,ω-diacetoxysiloxane B had been completely converted due to the disappearance of the signal at -9 ppm. GPC showed that the number-average molecular weight M n It is 884 g / mol, and the weight-average molecular weight M w The concentration is 7767 g / mol, thus proving that: compared with the starting material of Silikophen AC 1000 (M n 586 and M w Compared to 859 g / mol, the molecular weight is significantly increased.

[0179] Example 3 (Invention)

[0180] 100.0 g of Dowsil 3074 intermediate, 7.5 g of α,ω-diacetoxysiloxane A, and 0.4 g of tetraisopropyl titanate were weighed into a 500 ml single-necked round-bottom flask. The conversion of this reaction mixture was carried out similarly to that in Example 1. The result was a nearly colorless, slightly turbid liquid. Due to the… 29 The signal superposition in the Si NMR correlation shift region makes it impossible to show the terminal acetoxy conversion of α,ω-diacetoxysiloxane A via this method. However, GPC measurements indicate that the number-average molecular weight M n It is 1492 g / mol, and the weight-average molecular weight M w The concentration is 2681 g / mol, thus demonstrating that it is compatible with the Dowsil 3074 intermediate starting material (M). n =899g / mol and M w Compared to (1345 g / mol), the molecular weight is significantly increased.

[0181] Example 4 (Invention)

[0182] 100.0 g of Dowsil 3074 intermediate, 10.0 g of α,ω-diacetoxysiloxane B, and 0.4 g of tetraisopropyl titanate were weighed into a 500 ml single-necked round-bottom flask. The conversion of this reaction mixture was carried out similarly to that in Example 1. The separated product was an almost colorless, slightly turbid liquid. Due to the... 29 The signal superposition in the Si NMR correlation shift region makes it impossible to show the terminal acetoxy conversion of α,ω-diacetoxysiloxane B by this method. However, GPC measurements indicate that the number-average molecular weight M n It is 1449 g / mol, and the weight-average molecular weight M w The concentration is 2801 g / mol, thus demonstrating that it is compatible with the Dowsil 3074 intermediate starting material (M). n =899g / mol and M w Compared to (1345 g / mol), the molecular weight is significantly increased.

[0183] Example 5 (Invention)

[0184] 100.0 g V5000, 10.0 g α,ω-diacetoxysiloxane B, and 0.5 g tetraisopropyl titanate were weighed into a 500 ml single-necked round-bottom flask. The conversion of this reaction mixture was carried out similarly to that in Example 1. The separated product was a pale yellow liquid with minimal turbidity. The final product... 29 Si NMR spectroscopy indicated that α,ω-diacetoxysiloxane B was completely converted due to the disappearance of the signal at -9 ppm (a characteristic signal of the terminal acetoxy group). Supplemental GPC analysis of the final product showed a number-average molecular weight M. n It is 1070 g / mol, and the weight-average molecular weight M w The value is 1457 g / mol, therefore it is consistent with the V5000 starting material (M) used. n =806 g / mol and M w Compared to (976 g / mol), the molecular weight is significantly increased.

[0185] 2. Preparation of the catalyst solution according to the present invention and its use in the preparation of the curable condensation compound according to the present invention.

[0186] Example 6 (Invention)

[0187] A catalyst solution consisting of 1.00 g tetraisopropyl titanate, 0.37 g acetic anhydride, and 2.00 g toluene was prepared. After the exothermic reaction was reduced, the resulting clear catalyst solution was ready for direct use.

[0188] Similar to Example 1, 100.0 g of Silikophen AC1000, 10.0 g of α,ω-diacetoxysiloxane C, and 1.0 g of catalyst solution were weighed into a 500 ml single-necked round-bottom flask. An aliquot of the homogeneous reaction matrix was introduced into a 10 mm thick glass cuvette. If the text following the aliquot (font: Arial; font weight: standard; font color: black on white paper) could be read under artificial light without distortion, the reaction matrix was considered to be turbid and the catalyst was considered compatible according to the present invention. After reintroducing the sample into the reaction mixture, it was heated to 130 °C on a rotary evaporator and the reaction was carried out. The final product... 29 Si NMR spectroscopy indicated that the terminal acetoxy group derived from the α,ω-diacetoxysiloxane C had been completely converted due to the signal disappearance at -9 ppm. GPC showed that the number-average molecular weight M n It is 831 g / mol, and the weight-average molecular weight M w The concentration is 2893 g / mol, therefore it is similar to the starting material of Silikophen AC1000 (M). n 586 and M w Compared to 859 g / mol, the molecular weight is significantly increased.

[0189] Example 7 (Invention)

[0190] Initially, 6.0 g (0.0211 mol) of titanium isopropoxide (IV) in 50 g of toluene was added to a 250 mL multi-necked flask at 23 °C with stirring. Then, a solution consisting of 94.0 g of α,ω-diacetoxysiloxane B and 50 g of toluene was added metered over 10 minutes via a dropping funnel. The clarified reaction mixture was then heated to 80 °C for one hour, followed by removal of volatiles on a rotary evaporator at 70 °C under an assisted vacuum of less than 5 mbar. The liquid residue was pale yellow and transparent.

[0191] 50g of Silikophen AC1000 (poly(methyltrimethoxysilane)) was added to a 250ml four-necked flask at 23°C with stirring. Then, 5g of terminally balanced α,ω-diacetoxysiloxane B (neutralized with potassium acetate, filtered, and distilled at 130°C under an auxiliary vacuum of less than 5 mbar, free of volatiles, chain length N = 13.6, M...) was added. w =1112.9 g / mol, through 29(Si NMR spectroscopy determination). 4.6 g of the prepared titanium catalyst was added while stirring. An aliquot of the homogeneous reaction matrix was introduced into a 10 mm thick glass cuvette. If the text immediately following the aliquot (font: Arial; font weight: standard; font color: black on white paper) could be read under artificial light without distortion, the reaction matrix was considered to be turbid and the catalyst to be compatible according to the present invention. After reintroducing the sample into the reaction mixture, it was heated to 130 °C. After a 1-hour reaction time, volatile components were removed by applying an auxiliary vacuum ranging from 600 mbar to 100 mbar for an additional 4 hours.

[0192] The residue separated after cooling was a clear, pale yellow product, and its corresponding... 29 Si NMR spectroscopy showed that the acetoxysiloxane used was completely converted.

[0193] 2. Performance Testing

[0194] 2.1 Anti-graffiti effect

[0195] Anti-graffiti properties were determined using panels coated and cured with the curable condensation compounds according to the invention (Examples 1 to 6). Examples 1, 2, and 6 were cured without the addition of a curing catalyst. In Examples 3, 4, and 5, 5.0% by weight of Dynasylan AMEO based on the total mass of the resin was added as a curing catalyst; see Table 3.

[0196] As a comparative example CE1, Silikophen AC1000 was applied to a panel and cured with 1.5 wt% (based on total resin) of tetrabutyl titanate (TnBT). As a comparative example CE2, Dowsil 3074 intermediate was applied to a panel and cured with 5.0 wt% (based on total resin) of Dynasylan AMEO.

[0197] The results are listed in Table 3. Comparative examples CE1 and CE2 were found to exhibit no anti-graffiti effect because the sprayed paint layer was not removable. The coatings according to the invention, containing curable condensation compounds 1-6, exhibit anti-graffiti effect. Some coatings according to the invention even withstood up to five cleaning cycles.

[0198] Table 3: Anti-graffiti effect

[0199] 1 have 2 2 have 2 3 AMEO 5.0 have 5 4 AMEO 5.0 have 3 5 AMEO 5.0 have 1 6 - have 2 CE1 TnBT 1.5 none 0 CE2 AMEO 5.0 none 0

[0200] 2.3 Surface smoothness

[0201] As a comparative example CE3, Silikophen AC1000 was applied to a panel and cured with the aid of 1.5 wt% (based on total resin) of tetrabutyl titanate. The results are summarized in Table 4. It was found that the slip values ​​of the coatings according to the invention in Examples 1 and 6 were significantly lower than those in the comparative example (CE3). Therefore, the surface slip properties of the coatings according to the invention are better than those of the comparative examples.

[0202] Table 4: Smoothness Value

[0203] 1 129 6 66 CE3 229

Claims

1. A curable condensation compound that can be obtained by reacting a terminally balanced acetoxy-containing siloxane of formula (I) and / or formula (II) with at least one alkoxy-functionalized polysiloxane of formula (III) in the presence of titanium alkoxide. Formula (I), Where R = alkyl and / or phenyl with 1 to 4 carbon atoms, and 1 ≤ x ≤ 500, or Equation (II), Where 0 ≤ a ≤ 100 and 1 ≤ b ≤ 10, R 1 c Si(OR 2 ) d O (4-c-d) / 2 Formula (III) Where c is not less than 0 and not greater than 2, and d is not less than 0 and not greater than 4, and the sum of c and d is less than 4. R 1 The same or different and independently formed straight-chain or branched, saturated or monounsaturated or polyunsaturated or aromatic hydrocarbon groups, and R 2 Alkyl groups consisting of 1 to 8 carbon atoms Its features are, The curable condensation compound does not contain ≡Si-OH groups.

2. The condensation compound according to claim 1, characterized in that... R = methyl.

3. The condensation compound according to claim 1, characterized in that... 3≤x≤100。 4. The condensation compound according to claim 1, characterized in that... 5≤x≤40。 5. The condensation compound according to claim 1, characterized in that... 2≤a≤30 and 1≤b≤6.

6. The condensation compound according to claim 1, characterized in that... 3≤a≤10 and 2≤b≤5.

7. The condensation compound according to claim 1, characterized in that... R 2 It can be methyl or ethyl.

8. The condensation compound according to any one of claims 1-7, characterized in that... The reaction includes at least one crosslinking agent of formula (IV). R 3 e Si(OR 4 ) f Formula (IV) Where e is not less than 0 and not greater than 2, f is not less than 2 and not greater than 4, and the sum of e and f is 4. R 3 =A saturated or unsaturated alkyl group consisting of 1 to 8 carbon atoms or an aromatic moiety having 6 to 20 carbon atoms, and R 4 =Alkyl or acyl groups consisting of 1 to 8 carbon atoms.

9. The condensation compound according to any one of claims 1-7, characterized in that... The terminally balanced acetoxysiloxanes of formula (I) or (II) have been neutralized.

10. The condensation compound according to any one of claims 1-7, characterized in that... A linear polydimethylsiloxane with α,ω-acetoxy groups was used in the reaction.

11. The condensation compound according to any one of claims 1-7, characterized in that... The alkoxy-functionalized polysiloxane has an R group that is methyl and / or phenyl. 1 Group.

12. The condensation compound according to any one of claims 1-7, characterized in that... The weight-average molecular weight of the alkoxy-functionalized polysiloxane is 200 to 20,000 g / mol.

13. The condensation compound according to claim 12, characterized in that... The weight-average molecular weight of the alkoxy-functionalized polysiloxane is 200 to 10,000 g / mol.

14. The condensation compound according to claim 12, characterized in that... The weight-average molecular weight of the alkoxy-functionalized polysiloxane is 300 to 3000 g / mol.

15. The condensation compound according to claim 12, characterized in that... The weight-average molecular weight of the alkoxy-functionalized polysiloxane is 400 to 2000 g / mol.

16. The condensation compound according to any one of claims 1-7, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy group of the alkoxy functional polysiloxane has a mass ratio of 3% to 50% by weight.

17. The condensation compound according to claim 16, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy functional polysiloxane has an alkoxy mass ratio of 5% to 40% by weight.

18. The condensation compound according to claim 16, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy functional polysiloxane has an alkoxy mass ratio of 7% to 30% by weight.

19. The condensation compound according to any one of claims 1-7, characterized in that... The titanium alkyl oxide is selected from tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, dipropoxybis(acetylacetone) titanium, diisopropoxybis(acetylacetone) titanium, dibutoxybis(acetylacetone) titanium, triisopropoxyallyl titanium acetate, and isopropoxyoctanediol-titanium oxide.

20. The condensation compound according to claim 8, characterized in that... The crosslinking agent is selected from methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxyphenylmethylsilane, and diethoxyphenylmethylsilane.

21. A method for preparing the condensation compound according to any one of claims 1-20, characterized in that... An acetoxy-terminated siloxane of formula (I) and / or formula (II) is reacted with at least one alkoxy-functionalized polysiloxane of formula (III) in the presence of a titanyl oxide.

22. The method according to claim 21, characterized in that, Based on the entire organosilicon matrix, the weight ratio of the acetoxy-containing siloxane of formula (I) and / or formula (II) to the alkoxy-functionalized polysiloxane of formula (III) is 1:99 to 99:

1.

23. The method according to claim 22, characterized in that, Based on the entire organosilicon matrix, the weight ratio of the acetoxy-containing siloxane of formula (I) and / or formula (II) to the alkoxy-functionalized polysiloxane of formula (III) is 3:97 to 50:

50.

24. The method according to claim 22, characterized in that, Based on the entire organosilicon matrix, the weight ratio of the acetoxy-containing siloxane of formula (I) and / or formula (II) to the alkoxy-functionalized polysiloxane of formula (III) is from 5:95 to 30:

70.

25. The method according to any one of claims 21-24, characterized in that... The terminally balanced acetoxysiloxane of formula (I) or formula (II) has been neutralized and optionally distilled.

26. The method according to any one of claims 21-24, characterized in that... The siloxane with acetoxy groups has D units.

27. The method according to any one of claims 21-24, characterized in that... Linear polydimethylsiloxanes with α,ω-acetoxy groups were used.

28. The method according to any one of claims 21-24, characterized in that... Using R 1 Alkoxy-functionalized polysiloxanes with methyl and / or phenyl groups.

29. The method according to any one of claims 21-24, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy group of the alkoxy functional polysiloxane has a mass ratio of 3% to 50% by weight.

30. The method according to claim 29, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy functional polysiloxane has an alkoxy mass ratio of 5% to 40% by weight.

31. The method according to claim 29, characterized in that, Based on the total mass of the compound of formula (III), the alkoxy functional polysiloxane has an alkoxy mass ratio of 7% to 30% by weight.

32. The method according to any one of claims 21-24, characterized in that... The titanium alkyl oxide is selected from tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetoacetate) titanium, dipropoxybis(acetylacetone) titanium, diisopropoxybis(acetylacetone) titanium, dibutoxybis(acetylacetone) titanium, triisopropoxyallyl titanium acetate, and isopropoxyoctanediol-titanium oxide.

33. The method according to any one of claims 21-24, characterized in that... Using at least one crosslinking agent of formula (IV) R 3 e Si(OR 4 ) f Formula (IV) Where e is not less than 0 and not greater than 2, f is not less than 2 and not greater than 4, and the sum of e and f is 4. R 3 =A saturated or unsaturated alkyl group consisting of 1 to 8 carbon atoms or an aromatic moiety having 6 to 20 carbon atoms, and R 4 =Alkyl or acyl groups consisting of 1 to 8 carbon atoms.

34. The method according to claim 33, characterized in that... The crosslinking agent is selected from methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxyphenylmethylsilane, and diethoxyphenylmethylsilane.

35. The method according to any one of claims 21-24, characterized in that... Removal of R during the reaction 2 Acetates formed by groups and acetoxy groups.

36. The method according to claim 35, characterized in that... The resulting acetate is removed from the reaction by distillation and / or optionally by applying an auxiliary vacuum.

37. The method according to any one of claims 21-24, characterized in that... The reaction is complete for the acetoxysiloxane / silane used.

38. Use of the curable condensation compound according to any one of claims 1-20 in the production of coatings having anti-adhesion, anti-graffiti and / or anti-fouling properties.

39. A coating product having a coating comprising a curable condensation compound according to any one of claims 1-20.

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