Organic group oxy silyl terminated polymers based on 1,3-dioxolane co-polymer structural units

Abstract

This invention relates to organohydroxysilyl-terminated polymers (P) having end groups of formula (I): -(CR 1 2) b -SiR a (OR 2 ) 3‑a They contain 1,3-dioxolane copolymer structural units (DP) of general formula (II) in their main chain, wherein R, R 1 R 2 a, b, R 3 R 4 x1+x2 and y1+y2 have the meanings defined in claim 1, provided that in each unit [O-CH2-O-CHR] 3 -CHR 4 -] y1 and [O-CHR] 3 -CHR 4 O-CH2-] y2 In, at least one group R 3 Or R 4 Indicates C1 to C 18 Alkyl groups. The invention also relates to methods for preparing them; and compositions of polymers (P) containing organohydroxysilyl-terminated groups. -[(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).

Description

Technical Field

[0001] This invention relates to crosslinkable silane-terminated polymers comprising 1,3-dioxolane copolymer units in their backbone, methods for their preparation, and compositions comprising the polymer (P). These polymers exhibit high hydrophilicity and thus particularly good curability. Background Technology

[0002] Water-crosslinkable formulations are generally known. They are widely used as adhesives and sealants and also for coatings. Important moisture-reactive adhesives for such products are silyl-functionalized polymers. Among these, linear or monobranched polypropylene glycols and / or polyurethanes based on these polypropylene glycols are preferred, having terminal alkoxysilyl groups at the ends of the respective polymer chains. Therefore, this product combines several advantages:

[0003] • Polymers with polypropylene glycol-based backbones are still liquid before they crosslink, and may even have very long chain lengths required for this application.

[0004] • The alcohols released as pyrolysis products during the cross-linking process are non-corrosive and toxicologically harmless at low concentrations.

[0005] Cured polymer formulations are characterized by very good mechanical properties.

[0006] The corresponding alkoxysilane-terminated polymers have long been known in the prior art and are commercially available, for example under trade names. STP-E (Wacker Chemie AG), MS-polymer (Kaneka) (Bayer AG) or (Momentive).

[0007] However, a drawback of many systems according to the prior art is the low reactivity of the corresponding polymers to moisture, which makes corrosive catalysis necessary. Therefore, the corresponding mixtures typically contain significant amounts of toxicologically harmful tin catalysts.

[0008] Here, it is advantageous to use so-called α-silane-terminated prepolymers having an alkoxysilyl group linked to an adjacent urethane unit via a methylene spacer. These compounds are highly reactive and require neither tin catalysts nor strong acids or bases to achieve high curing rates upon air contact. Corresponding products are described herein under trade names. STP-E is commercially available from Wacker-Chemie AG.

[0009] However, even these systems, which cure particularly rapidly upon contact with atmospheric moisture, still present problems when bonding large areas of non-porous substrates (such as glass, metal, or plastic). For example, the curing rate of deep bond joints is limited not only by the reactivity of the crosslinkable polymer but also by the limited availability of water traces within the joint necessary for curing. Furthermore, when bonding or even sealing non-porous substrates, the latter depends primarily on the rate at which water molecules can diffuse from the surface of the adhesive or sealing joint through the adhesive matrix into deeper joint layers.

[0010] In principle, this problem can be solved by using a so-called two-component system, where the first component consists of a moisture-curing polymer and the second component contains water. If the two components are mixed directly together before application, water is no longer needed to diffuse from atmospheric moisture into the joint, and the adhesive or sealant cures evenly in deeper layers. However, such two-component systems are very unfriendly and even difficult to apply to specialized users. Therefore, they are only used when no single-component alternative exists for the relevant application.

[0011] Therefore, in order to improve the curing of even deep adhesive or sealant joints without using a two-component system, an adhesive matrix that allows for faster water diffusion would be highly desirable.

[0012] Another drawback of all commercially available silane crosslinking polymers to date is their polypropylene glycol-based backbone. For example, polypropylene glycol has so far been produced from feedstocks specifically derived from fossil carbon sources. Therefore, it is desirable that this option also utilize other, more ecologically advantageous polymer units as the basis for the production of silane crosslinkable polymers.

[0013] One way to achieve this is to use CO2 to produce these polymer units, and thus integrate CO2 into the value chain, not as waste, but as a starting material.

[0014] In this regard, polyacetals can be a clearly attractive polymeric unit for the development of novel silane crosslinked polymers. For example, these can be produced via an intermediate stage of cyclic acetals, particularly through CO2 fixation catalytically using green hydrogen.

[0015] However, the problem lies in conventional polyacetals, also known as polyoxymethylene (POM), which, as can be obtained through the polymerization of formaldehyde, trioxane (POM-H), or through the ring-opening polymerization of 1,3-dioxolane (POM-C), are solid at room temperature. Therefore, they are unsuitable for producing adhesives for use in liquid or paste-like adhesives, sealants, or coatings that are applied solvent-free at room temperature and cure only during or after their application. Summary of the Invention

[0016] Therefore, the object of the present invention is to develop silane-terminated polymers based on polymer units that can be produced wholly or partially from non-fossil carbon sources and should also enable better diffusion of water molecules through the polymer matrix.

[0017] This invention relates to organyloxysilyl-terminated polymers (P) having end groups of formula (I):

[0018] -(CR 1 2) b -SiR a (OR 2 ) 3-a (I),

[0019] in

[0020] R can be the same or different and is a monovalent, unsubstituted or substituted SiC-bonded hydrocarbon group.

[0021] R 1 They can be the same or different and are hydrogen atoms or monovalent, unsubstituted or substituted hydrocarbon groups, R 2 They can be the same or different and are hydrogen atoms or monovalent, unsubstituted or substituted hydrocarbon groups; 'a' can be the same or different and is 0, 1 or 2, preferably 0 or 1; and

[0022] b can be the same or different and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3.

[0023] The polymer contains 1,3-dioxolane copolymer units (DP) of general formula (II) in its main chain:

[0024] -[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2

[0025] (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2)] y2 -O-(II),

[0026] in

[0027] R 3 They can be the same or different and are hydrogen or monovalent, unsubstituted or substituted C1 to C2. 18 alkyl groups,

[0028] R 4 They can be the same or different and are hydrogen or monovalent, unsubstituted or substituted C1 to C2. 18 alkyl groups,

[0029] x1+x2 has values ​​ranging from 10 to 2000.

[0030] y1+y2 has values ​​ranging from 3*(x1+x2+y1+y2) / 100 to 90*(x1+x2+y1+y2) / 100.

[0031] The condition is [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 It is C1 to C 18 Alkyl groups.

[0032] The 1,3-dioxolane copolymer unit (DP) of formula (II) comprises randomly distributed or block-distributed units [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 .

[0033] Examples of unsubstituted groups R are alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl groups; hexyl groups, such as n-hexyl groups; heptyl groups, such as n-heptyl groups; octyl groups, such as n-octyl, isooctyl, and 2,2,4-trimethylpentyl; nonyl groups, such as n-nonyl groups; decyl groups, such as n-decyl groups; dodecyl groups, such as n-dodecyl groups; octadecyl groups, such as n-octadecyl groups; cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl groups; alkenyl groups, such as vinyl, 1-propenyl, and 2-propenyl groups; aryl groups, such as phenyl, naphthyl, anthracene, and phenanthrene groups; alkylaryl groups, such as o-, m-, and p-tolyl groups; xylyl groups and ethylphenyl groups; and aralkyl groups, such as benzyl groups, α- and β-phenylethyl groups.

[0034] Examples of substituted groups R are haloalkyl groups and haloaryl groups, such as ortho-, meta-, and p-chlorophenyl groups.

[0035] Preferably, group R is an unsubstituted or halogenated monovalent hydrocarbon group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 or 2 carbon atoms, especially methyl.

[0036] Group R 1 Examples are hydrogen atoms, groups specified for R, and unsubstituted or substituted hydrocarbon groups bonded to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups.

[0037] Group R 1 Preferably, it contains hydrogen atoms and unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, especially hydrogen atoms.

[0038] Group R 2 An instance is a hydrogen atom or an instance specified for an R group.

[0039] Group R 2 Preferably, it is an unsubstituted or halogenated alkyl group having hydrogen atoms or 1 to 10 carbon atoms, particularly preferably an unsubstituted or halogenated alkyl group having 1 to 4 carbon atoms, especially methyl and ethyl.

[0040] Alkyl R 3 and R 4 Examples include hydrogen atoms, straight-chain and branched alkyl groups such as methyl, ethyl, isooctyl, n-octyl, and cycloalkyl groups such as cyclohexyl. Preferably, R 3 and R 4 It is a hydrogen atom or a C1 to C6 alkyl group, with hydrogen atom, methyl, ethyl, n-propyl or isopropyl group being particularly preferred.

[0041] Preferably, in each case, [O-CH2-O-CHR] 3 -CHR 4 -] y1 and [O-CHR] 3 -CHR 4 O-CH2-] y2 The unit contains only one group R 3 Or R 4 It is C1 to C 18 The alkyl group, and the other group in each case is a hydrogen atom.

[0042] Preferably, x1+x2 has a value of 20 to 1000, particularly preferably 30 to 500, specifically 50 to 300.

[0043] Preferably, y1+y2 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, specifically, a value of 14*(x1+x2+y1+y2) / 100 to 25*(x1+x2+y1+y2) / 100.

[0044] The 1,3-dioxolane copolymer unit (DP) of formula (II) preferably has a number average molecular weight M between 750 and 300,000 Daltons, particularly preferably between 1,500 and 125,000 Daltons, especially preferably between 4,000 and 24,000 Daltons, and particularly between 6,000 and 20,000 Daltons. n .

[0045] The organohydroxysilyl-terminated polymer (P) can be branched, preferably having 1 to 3 branching sites and correspondingly 3 to 5 chain ends. Here, only some or even all of the chain ends can be silyl-terminated with formula (I). Preferably, at least 90%, particularly preferably at least 95%, of all chain ends are silyl-terminated with formula (I).

[0046] However, in a preferred embodiment, these polymers (P) are unbranched and therefore have two chain ends. One or even both chain ends may be capped with silanes of formula (I). However, preferably, at least 90%, particularly preferably at least 95%, of all chain ends are capped with silanes of formula (I).

[0047] The organo-based oxysilyl-terminated polymer (P) is preferably produced by reacting a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) of general formula (III):

[0048] H-[(O-CH2-O-CH2-CH2-) x1 (O-CH2-CH2-O-CH2-) x2

[0049] (O-CH2-O-CHR 3 -CHR 4 -) y1 (O-CHR 3 -CHR 4 O-CH2)] y2 -OH(III),

[0050] All variables have the definitions specified for equation (II) and therefore satisfy all the requirements specified for that equation.

[0051] These hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) preferably have a number average molecular weight M between 750 and 300,000 Daltons, particularly preferably between 1,500 and 125,000 Daltons, especially preferably between 4,000 and 24,000 Daltons, and particularly between 6,000 and 20,000 Daltons. n Compared to the polymer unit (DP) of formula (II) produced using 1,3-dioxolane copolymer (DP-OH), the average molar mass is significantly increased by the weight of the two terminal hydrogen atoms.

[0052] In the context of this invention, the number-average molar mass M n Preferably, the polystyrene standard was determined by size exclusion chromatography (SEC) in THF at 60°C at a flow rate of 1.2 ml / min, and by RI (refractive index detector) on a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp., USA, with an injection volume of 100 μl.

[0053] The hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) preferably has a dynamic viscosity between 50 mPas and 500 Pas at 25°C, particularly preferably between 500 mPas and 200 Pas, and especially between 1 Pas and 100 Pas.

[0054] In the context of this invention, the viscosity of the non-paste liquid is preferably measured according to ISO 2555 after heating to 23°C using a DV 3P rotational viscometer from A. Paar (Brookfield Systems) with rotor 6 at 5 Hz.

[0055] Many methods are known for preparing organohydroxyl-terminated silyl-terminated polymers from hydroxyl-functionalized prepolymers (e.g., polypropylene glycol). All these methods can be readily interchanged to convert hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) into the polymer (P) according to the invention. All process parameters such as temperature, reaction time, catalysis, etc., can remain unchanged. The only difference is the use of hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH) as reactants, i.e., as hydroxyl-functionalized polymers.

[0056] In the conventional method (P1), the hydroxyl-containing polymer (DP-OH) is first reacted with a compound having a group and double bond that are reactive to hydroxyl groups, preferably allyl chloride, to obtain the corresponding vinyl-terminated polymer, which is then silanized by hydrosilylation of formula (IV).

[0057] H-SiRa (OR 2 ) 3-a (IV),

[0058] All variables have the definitions specified for equation (I). Suitable methods for carrying out this reaction are known and are described in particular in EP 1 566412A1 (paragraph

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

[0059] In a second, equally common method (P2), the hydroxyl-containing polymer (DP-OH) reacts with at least one isocyanate functional compound. These are preferably di- or polyisocyanates. Examples of conventional diisocyanates are diisocyanate diphenylmethane (MDI), both in the form of crude or industrial grade MDI and in the form of pure 4,4' or 2,4' isomers or mixtures thereof, toluene diisocyanate (TDI), in the form of its various regioisomers, diisocyanate naphthalene (NDI), isophorone diisocyanate (IPDI), or hexamethylene diisocyanate (HDI). Examples of polyisocyanates are polymeric MDI (P-MDI) of the above diisocyanates, triphenylmethane triisocyanate, or tripolyesters (biuret or isocyanurate).

[0060] The isocyanate can be used in either stoichiometric (variant (V2-1)) or in excess (variant (V2-2)) relative to the ratio of isocyanate groups to hydroxyl groups in the hydroxyl-containing polymer (DP-OH). In variant (V2-1), a polyurethane polymer with hydroxyl-terminated chains is obtained, and in variant (V2-2), a polymer with isocyanate groups at the chain ends is obtained.

[0061] The hydroxyl-functionalized polyurethane polymers obtained in variant (V2-1) are preferably reacted with isocyanate-functionalized silanes of formula (V):

[0062] OCN-(CR 1 2) b -SiR a (OR 2 ) 3-a (V),

[0063] These 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 800A (paragraphs

[0011] -

[0022] and Examples 1-5).

[0064] On the other hand, the isocyanate-functionalized polymer obtained in variant (V2-2) is preferably reacted with the isocyanate-reactive silane of formula (VI):

[0065] Z-(CR 1 2) b -SiR a (OR 2 ) 3-a (VI),

[0066] in

[0067] Z is the isocyanate reactive group and all other groups and indices have the definitions specified for formula (I).

[0068] The isocyanate reactive group Z is preferably hydroxyl or amino, particularly preferably an amino group of the formula NHR', wherein R' has one of the definitions specified for the R group or a -CH(COOR")-CH2-COOR" group, wherein R" can be the same or different and has the definition specified for R.

[0069] Examples of group R' are various stereoisomers of cyclohexyl, cyclopentyl, n- and isopropyl, n-, iso- and tert-butyl, pentyl, hexyl or heptyl groups, and phenyl groups.

[0070] 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 straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms or an optionally halogenated aryl group having 6 to 20 carbon atoms.

[0071] The group R is preferably an alkyl group having 1 to 10 carbon atoms, and is particularly preferably a methyl, ethyl or propyl group.

[0072] Suitable methods for carrying out method variants (V2-2) are known and, among others, described in EP 1 093482B1 (paragraphs

[0014] -

[0023] ,

[0039] -

[0055] , and also Example 1 and Comparative Example 1) or EP 1 641854B1 (paragraphs

[0014] -

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

[0073] In a particularly preferred method (P3), the polymer (P) according to the invention is obtained by the direct reaction of a hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) with an isocyanate-functionalized silane of formula (V). Suitable methods for carrying out this reaction are known and, among others, described in EP 1 535 940B1 (paragraphs

[0005] -

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

[0008] -

[0047] ), which will be included in the disclosure of this application.

[0074] The polymer of formula (VII) can be obtained by a preferred method (P3):

[0075] (RO 5 ) 3-a R 4 a Si-(CR 3 2) b -NH-CO-[(O-CH2-O-CH2-CH2-) x1

[0076] (O-CH2-CH2-O-CH2-) x2 (O-CH2-O-CHR 3 -CHR 4 -) y1

[0077] (O-CHR 3 -CHR 4 O-CH2-) y2 ]-O-CO-NH-(CR 3 2) b -SiR 4 a (OR 5 ) 3-a (VII),

[0078] A particularly preferred embodiment of the invention is one in which all variables have the definitions specified in equations (I) and (II) and thus satisfy all the requirements specified for these equations.

[0079] The hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) of general formula (III) above can be produced in a simple manner with a short reaction time.

[0080] This production is preferably carried out via copolymerization of 1,3-dioxolane with one or more alkyl-substituted 1,3-dioxolane of general formula (VII).

[0081]

[0082] In the presence of Lewis or Brønsted acids, where these alkyl groups R 3 and R 4 It has the definition specified for equation (II).

[0083] This method involves the ring-opening polymerization of dioxolane monomers catalyzed by cationic induction. The catalyst is a Lewis acid or a Brønsted acid.

[0084] In this method, the total amount of 1,3-dioxolane and alkyl-substituted 1,3-dioxolane of general formula II is preferably at least 10 mol%, particularly preferably at least 20 mol%, and especially at least 30 mol% of alkyl-substituted 1,3-dioxolane of general formula II.

[0085] The amount of alkyl-substituted 1,3-dioxolane used herein is crucial for the (y1+y2) / (x1+x2+y1+y2) ratio in the hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH) obtained during the copolymerization process. However, it should be noted that this method generally requires the use of slightly more alkyl-substituted 1,3-dioxolane of general formula (VII) than is purely arithmetically necessary, as this is less reactive and correspondingly less frequently incorporated into the polymer chain than unsubstituted 1,3-dioxolane.

[0086] Examples of acids are Lewis acids, such as BF3, AlCl3, TiCl3, SnCl4, SO3, PCl5, POCl3, FeCl3 and their hydrates, and ZnCl2; Brønsted acids, such as boric acid, tetrafluoroboric acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, hypophosphoric acid, sulfuric acid, sulfurous acid, peroxysulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, perchloric acid, hexafluorophosphoric acid, aluminum chloride, zinc chloride, benzenesulfonic acid, p-toluenesulfonic 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 clay; and acid-activated carbon black.

[0087] Boron trifluoride ether and trifluoromethanesulfonic acid are particularly preferred.

[0088] An initiator can be used in this process. Bifunctional alcohols are preferred as initiators, with ethylene glycol being particularly preferred.

[0089] This method can be carried out with or without an aprotic solvent. If an aprotic solvent is used, it is preferably a solvent or solvent mixture having a boiling point or boiling range of up to 120°C at 0.1 MPa. Examples of such solvents are ethers, such as dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, diisopropyl ether, and diethylene glycol dimethyl ether; chlorinated hydrocarbons, such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, and trichloroethylene; hydrocarbons, such as pentane, n-hexane, mixtures of hexane isomers, heptane, octane, gasoline, petroleum ether, benzene, toluene, and xylene; and siloxanes, particularly linear dimethyl polysiloxanes having a trimethylsilyl terminal group, preferably 0 to 6 dimethylsiloxane units, or cyclic dimethyl polysiloxanes, preferably 4 to 7 dimethylsiloxane units, such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentansiloxane.

[0090] Ketones, such as acetone, methyl ethyl ketone, diisopropyl ketone, methyl isobutyl ketone (MIBK); esters, such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, ethyl isobutyrate; carbon disulfide and nitrobenzene, or mixtures of these solvents.

[0091] The term "solvent" does not mean that all reactant components must be dissolved therein. The reaction can also be carried out in a suspension or emulsion of one or more reactants. The reaction can also be carried out in a solvent mixture with miscibility gaps, in which at least one reactant is soluble in each mixed phase in each case.

[0092] Particularly preferably, a solution of trifluoromethanesulfonic acid and an initiator is used, with dichloromethane as the preferred solvent.

[0093] The amount of catalyst and initiator used determines the achievable molecular weight of the 1,3-dioxolane copolymer (DP-OH) of general formula (IV).

[0094] The method is preferably carried out at a temperature between 10°C and 60°C, particularly preferably between 15°C and 40°C, and especially between 21°C and 30°C. A reaction temperature of 23°C is very particularly preferred.

[0095] The reaction is preferably post-treated by deactivating the catalyst with a suitable base, washing with a hydrocarbon such as heptane, and then removing the catalyst by vacuum distillation. Suitable bases include pyridine, triethylamine, or an aqueous solution of sodium hydroxide.

[0096] This invention is based on several surprising discoveries:

[0097] First, hydroxyl-terminated 1,3-dioxolane copolymers (DP-OH), consisting of 1,3-dioxolane and 1,3-dioxolane substituted at the 4- and / or 5-positions, are liquids over a wide temperature range, including room temperature. This also applies when they have an average molar mass >>10,000 Daltons. And given this unexpected property, they are well-suited as polymer units (DP) for constructing the polymer (P) according to the invention via one of the methods P1 to P3 of the invention, and are therefore well-suited for further processing.

[0098] Polymers (P) based on 1,3-dioxolane copolymer units (DP) are highly polar and therefore hydrophilic. Consequently, they are ideal adhesives for use in adhesives and sealants, allowing water molecules to rapidly diffuse into deeper layers of the adhesive or sealing joint, and thus enabling particularly good, rapid, and uniform curing of the corresponding adhesives and sealants.

[0099] Polymer (P) is a suitable binder for adhesives and sealants that, after curing, exhibit superior properties widely comparable to those of conventional silane-terminated polypropylene glycol-based polymers. Therefore, this entirely novel product group (whose raw material basis is obtained via a cyclic acetal intermediate stage through CO2 fixation catalytically using green hydrogen) is an alternative that can completely or at least partially replace existing products (which are uniquely available from fossil carbon sources).

[0100] The organohydroxysilyl-terminated polymers (P) produced according to the present invention can be used wherever organohydroxysilyl-terminated polymers have been used to date. They are particularly suitable as components of crosslinkable compositions, i.e., as binders for adhesives, sealants, and / or coatings. Due to their improved through-curing properties, they are particularly suitable for deep adhesives or sealing joints and are also suitable for large-area adhesion to non-porous substrates.

[0101] Therefore, the present invention also relates to compositions comprising an organo-oxysilyl-terminated polymer (P), and, depending on the specific application or corresponding required distribution, at least one additional component selected from the following: (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.

[0102] The composition according to the invention preferably comprises the following crosslinkable composition:

[0103] (P) Organic-based oxysilyl-terminated polymers (P),

[0104] Optionally (A) a nitrogen-containing organosilicon compound,

[0105] Optionally (B) silicone resin.

[0106] Optionally, (C) catalyst,

[0107] Optionally (D) adhesion promoter,

[0108] Optional (E) water cleaner,

[0109] Optional (F) packing,

[0110] Optional (G) additives and

[0111] Optional (H) aggregate.

[0112] Components (A) to (H) and their preferred amounts are described repeatedly herein, for example, WO-A2015024773 on page 12, line 24 to page 23, line 21, which is included in the disclosure of this application.

[0113] The compositions according to the invention are particularly preferably crosslinkable compositions comprising the following:

[0114] (P) Organic-based oxysilyl-terminated polymers

[0115] (A) Nitrogen-containing organosilicon compounds, optionally (B) silicone resins.

[0116] Optionally, (C) catalyst,

[0117] Optionally (D) an adhesion promoter, and optionally (E) a water remover.

[0118] Optional (F) packing,

[0119] Optional (G) additives and

[0120] Optional (H) aggregate.

[0121] The compositions according to the invention are particularly preferably crosslinkable compositions comprising: (P) organo-oxysilyl-terminated polymers,

[0122] (D) Nitrogen-containing organosilicon compounds, optionally (B) silicone resins.

[0123] Optionally, (C) catalyst,

[0124] Optionally (D) an adhesion promoter, and optionally (E) a water remover.

[0125] Optional (F) packing,

[0126] Optional (G) additives and

[0127] Optional (H) aggregate.

[0128] The components used according to the present invention may each be a type of such component or a mixture of at least two types of the corresponding components.

[0129] The adhesives, sealants, or coatings according to the invention can be produced in any manner known per se, such as by methods and mixing processes commonly used in the preparation of moisture-curing compositions. The order in which the various components are mixed can be varied here as needed.

[0130] The mixing can be carried out at room temperature and ambient atmospheric pressure, i.e., about 900 to 1100 hPa. However, if desired, this mixing can also be carried out at higher temperatures, for example, in the range of 30°C to 130°C. Furthermore, it is possible to mix temporarily or constantly under reduced pressure (e.g., at an absolute pressure of 30 to 500 hPa) to remove volatile compounds and / or air. The mixing according to the invention is preferably carried out under conditions where moisture is excluded.

[0131] The polymers (P) according to the invention have the advantage that they can be produced as quickly and easily as conventional silane crosslinked polymers based on polypropylene glycol.

[0132] The polymers (P) according to the invention have the advantages that they are highly fluid and have relatively low viscosity, which makes them excellent for blending to provide the final adhesives and sealants.

[0133] The polymers (P) according to the invention have the advantage that, although they represent entirely novel product groups, they can be further processed into adhesives and sealants in the same manner as conventional silane crosslinked polymers based on polypropylene glycol. No new or modified plants or new or modified working techniques are necessary for further processing.

[0134] The polymers (P) according to the present invention have the following advantages: they can be used to produce adhesives and sealants with excellent mechanical properties.

[0135] The polymers (P) according to the invention have the advantage that they can be used to produce adhesives and sealants that cure particularly quickly and uniformly.

[0136] The polymer (P) according to the invention has the following advantages: adhesives and sealants produced therefrom have excellent adhesion characteristic curves to a wide variety of substrates, including plastics such as PVC, metals, concrete, wood, mineral substrates, glass, ceramics and painted surfaces, and are therefore suitable for bonding and / or sealing all these materials.

[0137] The polymers (P) according to the invention have the advantages that they are transparent, colorless and color-stable, and are therefore also suitable for producing transparent and crystalline transparent adhesives and sealants.

[0138] The polymers (P) according to the invention have the following advantages: they can be produced by fixing CO2, thus they are particularly climate-friendly.

[0139] Compositions that can be produced from the polymer (P) according to the invention can be used for all intended purposes and can be used in compositions that are stored in the absence of water and crosslinked to form an elastomer when exposed to water at room temperature.

[0140] Compositions that can be produced from the polymer (P) according to the invention are therefore excellently suited for sealing and flexible bonding of, for example, metallic components. Thus, they can be used as mounting adhesives for automotive structures and for the production of buses, trucks, and rail vehicles. Furthermore, they are suitable for window construction, particularly skylight construction, structural glass bonding, or for the production of optoelectronic components, display housings, and for, for example, the production of protective coatings or moldings and for insulation of electrical or electronic devices.

[0141] In the embodiments described below, all viscosity data are based on a temperature of 25°C. Unless otherwise stated, the following embodiments are carried out at ambient atmospheric pressure, i.e., at about 1000 hPa, and at room temperature, i.e., at about 23°C, or at the temperature generated when reactants are combined at room temperature without supplemental heating or cooling, and at a relative humidity of about 50%. Furthermore, unless otherwise stated, all reported parts and percentages refer to weight. Detailed Implementation

[0142] Example

[0143] Production Example 1: Production of hydroxyl-terminated 1,3-dioxolane copolymer (DP-OH)

[0144] Preparation of catalyst solution: In a Schlenk flask 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.

[0145] The 154 ml catalyst solution prepared above was transferred to a laboratory reactor equipped with a KPG stirrer, thermometer, nitrogen inlet, and diaphragm, and the temperature was controlled at 23 °C. 1.15 kg of 4-ethyl-1,3-dioxolane (10.9 mol) and 770 ml of 1,3-dioxolane (10.9 mol) were added to this solution, and the mixture was stirred at 23 °C. During the reaction time, the reaction mixture became more viscous and turned pink. After 5 hours, approximately 20 ml of pyridine and 100 ml of dichloromethane were added until the reaction solution was decolorized. The product mixture was washed first with heptane and then with water until a pH of 7 was reached.

[0146] Finally, all volatile components are removed under vacuum (1 mbar) to obtain a viscous oil.

[0147] Production Example 2: Production of the polymer (P) according to the present invention

[0148] In a 1L three-necked flask equipped with a dropping funnel, a KPG stirrer and a thermometer, 475g of the 1,3-dioxolane copolymer from Example 1 was initially added, heated to 80°C and dried at a pressure of 10 mbar (vacuum) for 2 hours.

[0149] The vacuum was released using nitrogen, and 18.5 g of α-isocyanatomethyl methyldimethoxysilane was added dropwise over 15 minutes with stirring. XL 42 (commercially available from Wacker Chemie AG, D-Munich). The temperature was maintained at 80°C. Then, 0.07 g of a bismuth-containing catalyst (commercially available from OMG-Borchers, D-Langenfeld under the name "Borchi-Kat 315") was added. A slight heating of the reaction mixture was observed (<5°C). The mixture was then stirred at 80°C for 2 hours. Small isocyanate peaks, corresponding to 2% to 5% of the amount of isocyanate groups initially used, were still observed in the IR spectrum of the reaction mixture.

[0150] The mixture was allowed to cool to 50°C, and at this temperature, 1.3 g of methanol was added to eliminate any remaining isocyanate. After 0.5 hours, the reaction mixture was cooled to room temperature. Subsequent IR spectra confirmed the absence of isocyanate.

[0151] Example 1: Adhesive-sealant formulation based on the polymer (P) according to the present invention

[0152] At approximately 25°C, in a laboratory planetary mixer of a PC-Laborsystem equipped with two cross-arm mixers, 168.0 g of the polymer from Production Example 2 was mixed with 8.0 g of vinyltrimethoxysilane (as...). XL10 (commercially available from Wacker Chemie AG, D-Munich) was homogenized at 200 rpm for 2 minutes.

[0153] Then, 220.0 g of ground calcium carbonate (commercially available from Omya, D-Cologne under the name Omyabond 302) coated with stearic acid and having an average particle size (D50%) of approximately 0.4 μm was added and impregnated for 1 minute with stirring at 600 rpm. Finally, 4.0 g of N-[2-aminoethyl]-3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich) was added. Mix GF91 at 200 rpm for 1 minute, then homogenize at 200 rpm for 1 minute under partial vacuum (approximately 100 mbar), stirring until no bubbles remain.

[0154] The resulting composition was filled into two 310 ml PE cartridges (approximately 200 g each) and stored at 20°C for 24 hours prior to the study.

[0155] Comparative example C1:

[0156] The procedure is the same as in Example 1, but instead of the polymer of Production Example 2 according to the present invention, the same amount of polymer with average molar mass (M) is used. n The product is 12000 g / mol of silane-terminated polypropylene glycol and end groups of the formula -OC(=O)-NH-CH2-SiCH3(OCH3)2 (commercially available from Wacker Chemie AG, D-Munich). STP-E10).

[0157] Example 2: Adhesive-sealant formulations based on the polymer (P) according to the present invention

[0158] At approximately 25°C, 116.0 g of the polymer from Production Example 2 was mixed with 80 g of butyl-terminated polymer with a number-average molar mass (M) of 300 g / mol in a laboratory planetary mixer of a PC-Laborsystem equipped with two cross-arm mixers. n Polyethylene glycol (from Clariant, D-Gendorf) commercially available under the name Polyglycol BB 300 and 8.0 g of vinyltrimethoxysilane were homogenized at 200 rpm for 2 minutes.

[0159] Then, add 192.0g of Omyabond 302 and marinate for one minute with stirring at 600rpm. Finally, add 4.0g of 3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG, D-Munich). Mix GF 96 at 200 rpm for 1 minute, then homogenize at 200 rpm for 1 minute under partial vacuum (approximately 100 mbar), stirring until no bubbles remain.

[0160] The resulting composition was filled into two 310 ml PE cartridges (approximately 200 g each) and stored at 20°C for 24 hours prior to the study.

[0161] Comparative example C2:

[0162] The procedure is the same as in Example 3, but instead of the polymer from Production Example 2 according to the present invention, the same amount is used. STP-E10.

[0163] Example 3: Measurement of the property curves of the resulting adhesive-sealant

[0164] The adhesives-sealants obtained in Examples 1 and 2, as well as Comparative Examples C1 and C2, were crosslinked, and their skin formation and mechanical properties were investigated. The results are shown in Table 1.

[0165] Time to Cortical Formation (SFT)

[0166] To determine the skin formation time, the crosslinkable composition obtained in the examples was applied as a 2 mm thick layer onto a PE film and stored under standard conditions (23°C and 50% relative humidity). Skin formation was tested every minute during curing. For this purpose, a dry laboratory spatula was carefully placed on the surface of the sample and pulled upwards. If the sample stuck to a finger, a skin had not yet formed. If no sample remained stuck to a finger, a skin had formed, and the time was recorded.

[0167] Mechanical properties

[0168] Spread these compositions separately on the milled surface The material is applied to a depth of 2mm on the panel and cured for 2 weeks at 23°C and 50% relative humidity.

[0169] Shore A hardness was determined according to DIN 53505.

[0170] Tensile strength was determined according to DIN 53504-S1.

[0171] The elongation at break is determined according to DIN 53504-S1.

[0172] 100% modulus determined according to DIN 53504-S1.

[0173] Table 1:

[0174] SFT[min] 7 7 25 29 Hardness [Shore A] 59 68 21 40 100% Modulus [N / mm] 2.8 3.9 0.6 1.2 Tensile strength [N / mm] 3.4 4.3 1.1 2.4 Elongation at break [%) 133 126 228 190

[0175] *Not of this invention.

Claims

1. An organo-oxymethylsilyl-terminated polymer having an end group of formula (I) -(CR 1 2) b -SiR a (OR 2 ) 3-a (I), in, R is a monovalent, unsubstituted, or substituted hydrocarbon group, which is bonded to the Si atom in formula (I) via a Si-C bond. R 1 They are the same or different and are hydrogen atoms or monovalent, unsubstituted or substituted hydrocarbon groups. R 2 They are the same or different and are hydrogen atoms or monovalent, unsubstituted or substituted hydrocarbon groups. a is the same or different and is 0, 1 or 2, and b is either the same or different and is an integer from 1 to 10. The polymer contains 1,3-dioxolane copolymer units of general formula (II) in its main chain: -[(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, R 3 They are the same or different and are hydrogen or monovalent, unsubstituted or substituted C1 to C2. 18 alkyl groups, R 4 They are the same or different and are hydrogen or monovalent, unsubstituted or substituted C1 to C2. 18 alkyl groups, x1+x2 has values ​​ranging from 10 to 2000. y1+y2 has 3 (x1+x2+y1+y2) / 100 to 90 The value of (x1+x2+y1+y2) / 100, The condition is: in [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 It is C1 to C 18 Alkyl groups.

2. The organo-oxysilyl-terminated polymer according to claim 1, wherein, R is selected from alkyl groups having one or two carbon atoms.

3. The organo-oxysilyl-terminated polymer according to claim 1 or 2, wherein, R 1 It is a hydrogen atom.

4. The organo-oxysilyl-terminated polymer according to claim 1 or 2, wherein, R 2 Selected from methyl groups and ethyl groups.

5. The organo-oxysilyl-terminated polymer according to claim 1 or 2, wherein, R 3 and R 4 Selected from hydrogen atoms and C1 to C6 alkyl groups.

6. The organo-oxymethylsilyl-terminated polymer according to claim 1 or 2, wherein, In each case, in [O-CH2-O-CHR] 3 -CHR 4 -] y1 and [O-CHR] 3 -CHR 4 O-CH2-] y2 The unit contains only one group R 3 or R 4 It is C1 to C 18 The alkyl group, and the other group in each case is a hydrogen atom.

7. The organo-oxymethylsilyl-terminated polymer according to claim 1 or 2, wherein, The 1,3-dioxolane copolymer unit of formula (II) has a number-average molecular weight M of 750 to 300,000 Daltons. n .

8. A method for producing an organo-oxysilyl-terminated polymer according to any one of claims 1 to 7, wherein, Hydroxyl-terminated 1,3-dioxolane copolymers of 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), Reaction with at least one isocyanate-functionalized silane of formula (V) OCN-(CR 1 2) b -SiR a (OR 2 ) 3-a (V), Among them, R, R 1 R 2 R 3 R 4 x1+x2 and y1+y2, a and b have the definitions defined in any one of claims 1 to 7.

9. A composition comprising an organo-oxysilyl-terminated polymer of any one of claims 1 to 7 and at least one additional component selected from (A) nitrogen-containing organosilicon compounds, (B) silicone resins, (C) catalysts, (D) adhesion promoters, (E) water scavengers, (F) fillers, and (G) additives.

10. An adhesive or sealant comprising an organo-oxysilyl-terminated polymer of any one of claims 1 to 7, an organo-oxysilyl-terminated polymer produced by the method of claim 8, or the composition of claim 9.

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