POLYMERIZATION OF A SILANE-MODIFIED POLYMER FORMED BY RADICAL CHAIN ​​POLYMERIZATION IN A POLYOL OR IN A PREPOLYMER WITH TERMINAL ISOCYANATE GROUPS AND ITS USE IN POLYURETHANE FORMULATIONS

Description

[0001] The present invention relates to a process for producing a polymer composition in which a silane-modified polymer is polymerized by radical chain polymerization with ethylene-unsaturated monomers in a polyol or in a prepolymer with terminal isocyanate groups, and to a polymer composition produced by this process. The invention further relates to a process for producing a moisture-curing polyurethane hot melt adhesive composition and a one-component polyurethane adhesive, based on the polymer composition according to the invention, together with the moisture-curing polyurethane hot melt adhesive composition and the one-component polyurethane adhesive produced therein. Background of the invention

[0002] Depending on the application, adhesives require, for example, a long open time, as joining is often done manually. At the same time, rapid strength development after joining is needed, as the joined parts should be processed further as quickly as possible. This conflicting property profile is resolved in polyurethane adhesives, for example, by incorporating an acrylate polymer in powder form into a polyether-based polyurethane. The latter enables a long open time, while the acrylate polymer ensures a high initial stack. Incorporating the acrylates is often problematic because they introduce a lot of air and are difficult to dissolve. This can be overcome by polymerizing the acrylate polymers directly in a polyol, which is then converted to polyurethane. This process also allows the use of acrylate polymers whose glass transition temperature is below room temperature.Furthermore, these can be modified as desired with co-monomers. However, the properties of the adhesives are limited because the acrylate polymer is a thermoplastic that softens at higher temperatures or exhibits lower resistance to certain chemicals.

[0003] In summary, the resistance of reactive adhesives to temperature and certain chemicals is impaired by the use of thermoplastic materials, such as acrylate polymers. Furthermore, bonding inorganic materials with polyurethane adhesives without surface treatment leads to adhesion problems.

[0004] US Patent 5,018,337 discloses the folding and gluing of cardboard packaging using a class of low-viscosity reactive urethane hot melt adhesives. The adhesive formulations used therein enable rapid curing and a temperature-resistant bond that is resistant to aromatic oils, solvents, or petrochemical vapors.

[0005] US 5,021,507 A concerns acrylic-modified reactive urethanes and teaches in column 2, lines 58 to 68 that for ethylene-unsaturated monomers with moisture-reactive functional groups, it is necessary that the monomers are added only after the formation of the prepolymer and then polymerize by means of radical polymerization.

[0006] Further information on the state of the art can be found in WO 2016 / 123418 A1 or WO 01 / 81495 A2.

[0007] The present invention is based on the objective of improving the state of the art or offering an alternative. Summary of the invention

[0008] According to a first aspect of the present invention, the stated problem is solved by a method for producing a polymer composition according to claim 1. Further embodiments are the subject of the further independent and dependent claims.

[0009] In a first aspect, the invention relates to a method for producing a polymer composition, wherein the method comprises the following steps: a) Combining: (i) a polyol or a prepolymer with terminal isocyanate (NCO) groups with (ii) an ethylene-unsaturated monomer containing no active hydrogen and lacking moisture-reactive functional groups (monomer type A), and (iii) an ethylene-unsaturated monomer containing no active hydrogen and lacking a moisture-reactive functional group (monomer type B); b) polymerizing the mixture from step a) using a radical polymerization process with a chain transfer agent to obtain a low-molecular-weight polymer; c) optionally heating the mixture from step b) to a temperature of 100°C to 160°C for 10 to 60 minutes to partially crosslink the polyol or prepolymer with terminal NCO groups with the low-molecular-weight polymer.

[0010] The following terminology should be explained: The ethylene-unsaturated group allows the radical polymerization of the monomers to form a polymer. The absence of active hydrogen in the monomers ensures that they do not participate in the subsequent addition reaction to form the polyurethane. Monomer type A contributes to the construction of the polymer chain, while monomer type B, due to its moisture-reactive group, allows a reaction with the polyol or isocyanate groups of the prepolymer, with the moisture-reactive groups of the polymer, or in applications such as with inorganic substrates to improve adhesion to these substrates.

[0011] The polymer produced according to the invention using monomers with ethylene unsaturated groups, which is preferably an acrylate polymer, is hereinafter also referred to as an ethylene-based polymer.

[0012] By modifying the ethylene-based polymer, preferably an acrylate polymer, with silanes, it can react with moisture after application, thereby crosslinking. This leads to increased resistance to heat and certain chemicals. Additionally, silanes react with inorganic materials, such as glass or metal, thereby increasing the bond strength to these materials. This also expands the range of applications for these adhesives. Under the influence of additional heat, crosslinking can be accelerated, resulting in the formation of a permanently tacky polymer film. Furthermore, it is possible to produce reactive adhesives that do not contain monomeric isocyanates and are therefore label-free. This allows for safe handling of the adhesives and eliminates the need for complex precautions during use.

[0013] The polymers can be used for adhesives, sealants and coatings, reactive hot melt adhesives, textile adhesives, adhesives for the wood and furniture sector, automotive adhesives, adhesives in the construction sector, liquid 1-component adhesives, sealants, primers and coatings.

[0014] The basic technical concept of the invention is based on the modification of ethylene-based polymers, and in particular acrylate polymers, with silanes to improve their property profile. Possible improvements include the following: Increased temperature resistance through crosslinking of the silanes. A reaction of the silanes with inorganic substrates to improve adhesion to them. Possible production of products with isocyanate monomer concentrations below 0.1%, which are therefore label-free.

[0015] The invention offers several advantages over the prior art. Thermoplastic acrylate polymers are converted into reactive polymers that react with moisture to form thermosets, thereby exhibiting higher resistance to heat and specific chemicals. Since the silane groups are statistically distributed throughout the polymer and not only at the ends, as is the case with polyaddition products or subsequent silanization, the crosslinking density and thus the material's durability are increased. Silanes also offer the possibility of reacting with inorganic materials such as glass or metals, thereby increasing the bond strength to these materials. This expands the adhesion spectrum or enables the bonding of inorganic materials with organic materials such as plastics. Furthermore, three synthesis routes are available, which also allow the production of materials without isocyanate monomers.This means these products do not require labeling and are not subject to any restrictions.

[0016] The present polymer composition can be used as a novel intermediate for the production of various polyurethanes. In particular, the following possibilities arise: Production of a silane-modified ethylene-based polymer (preferably an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, followed by the reaction of the polyol or the prepolymer with terminal NCO groups to form a thermoplastic polyurethane. Production of a silane-modified ethylene-based polymer (preferably an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, followed by the reaction of the polyol or the prepolymer with terminal NCO groups to form a reactive polyurethane. Production of a silane-modified ethylene-based polymer (preferably an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, followed by the reaction of the polyol or the prepolymer with terminal NCO groups to form a reactive polyurethane, which is then reacted with aminosilanes or mercaptosilanes to form a silane-terminated polyurethane. The invention in detail

[0017] The polymerization of monomer type A with monomer type B according to the invention is generally carried out by placing all monomers together in the reaction vessel and allowing them to react randomly according to their relative concentrations and relative reactivity, so that statistical polymers are formed. However, to increase or decrease the heterogeneity of the polymers, one or more of the ethylene unsaturated monomers can also be added during the polymerization.

[0018] It is conceivable that the monomers, according to monomer type A and monomer type B, are added stepwise, so that the radical polymerization is initiated after the addition of a defined mixture of monomer type A and monomer type B, and only after polymer formation, which is accompanied by almost complete consumption of the monomers, is another defined mixture of monomer type A and monomer type B added to the reaction mixture. This stepwise addition prevents overheating of the reaction mixture due to the exothermic nature of the polymerization reaction.

[0019] The radical polymerization process is preferably carried out at a temperature of less than 100°C, more preferably at a temperature of 40 to 95°C and particularly preferably at a temperature of 80 to 90°C.

[0020] It is preferred if the weight ratio of monomer type A and monomer type B defined in the first step is also maintained during the second addition.

[0021] It is also conceivable that the amount of monomer type A in the second step is greater than the amount of monomer type A in the first addition. Preferably, the ratio of monomer type A in the first addition to monomer type A in the second addition is between 1:1 and 1:10, more preferably between 1:2 and 1:8, and particularly between 1:3 and 1:7.

[0022] Accordingly, it is conceivable that the amount of monomer type B in the second step is greater than the amount of monomer type B in the first addition. Preferably, the ratio of monomer type B in the first addition to monomer type B in the second addition is between 1:1 and 1:10, more preferably between 1:2 and 1:8, and particularly between 1:35 and 1:7.

[0023] In the optional step (c) of the process, the mixture from step b), containing the low-molecular-weight polymer as a result of radical polymerization, is heated to such an extent that partial cross-linking of the polyol or the prepolymer with terminal NCO groups occurs with the low-molecular-weight polymer. Due to its moisture-reactive groups, the low-molecular-weight polymer can react with the hydroxyl groups of the polyol or the isocyanate groups of the prepolymer. This reaction leads to a polymer composition with increased temperature resistance.

[0024] In the optional step (c), the silane groups can alternatively or additionally react with each other. This reaction also leads to a polymer composition with increased temperature resistance.

[0025] According to the invention, a polyol or a prepolymer with terminal NCO groups is used in the process for producing the polymer composition.

[0026] Regarding the polyol, this should be understood to mean that at least one polyol can be used here, meaning two, three, four, or even more polyols. Preferably, exactly one polyol is used in the process.

[0027] Advantageously, the polyol used in the process according to the invention has a water content of a maximum of 0.1 wt.% and preferably a maximum of 0.05 wt.%.

[0028] Suitable polyols are selected from the group consisting of polyesters, hydroxyl-containing polycaprolactones, polyoxyalkylene polyols (synonymous with the term "polyglycol"), monosubstituted glycol esters, polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyhydrocarbon polyols, polyacrylate polyols, polymethacrylate polyols, polyalcohols, bisphenols, polycarbonate polyols, polyhydroxy functional fats and oils, and mixtures thereof.

[0029] Diols, polyethylene oxides or polypropylene oxides are particularly suitable.

[0030] Suitable polyols include, on the one hand, the aforementioned high-molecular-weight polyoxyalkylene polyols, preferably polyethylene oxides or polyoxypropylene diols with a degree of unsaturation lower than 0.02 mEq / g and with a molecular weight in the range of 400 to 18,000 g / mol, particularly those with a molecular weight in the range of 1,000 to 4,000 g / mol. PPG 2000 or PPG 4000 are particularly suitable.

[0031] To achieve a higher cross-linking density, higher-level alcohols such as triols and tetraols can also be used. Examples include glycerol, trimethylolpropane, and pentaerythritol.

[0032] Polyoxyalkylene polyols, also called polyether polyols, polyglycols or oligoetherols, are also suitable. These are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran, or mixtures thereof, possibly polymerized with the aid of a starter molecule with two or more active hydrogen atoms such as water, ammonia, or compounds with one or more OH or NH groups such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane. 1,1,1-Trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds.

[0033] Polyester polyols are particularly suitable those produced from dihydric to trihydric, especially dihydric, alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,12-hydroxystearyl alcohol, 1,4-cyclohexanedimethanol, dimer fatty acid diol (dimerdiol), hydroxypivalic acid neopentyl glycol esters, glycerol, 1,1,1-trimethylolpropane, or mixtures of the aforementioned alcohols, with organic di- or tricarboxylic acids, especially dicarboxylic acids, or their anhydrides or esters, such as succinic acid, glutaric acid, etc. Adipic acid, trimethyladipic acid, cortic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acidTrimellitic acid and trimellitic anhydride, or mixtures of the aforementioned acids, as well as polyester polyols made from lactones such as ε-caprolactone and starters such as the aforementioned di- or trihydric alcohols.

[0034] It is also conceivable to use polycarbonate polyols, such as those that can be obtained by reacting, for example, the alcohols mentioned above – used to build polyester polyols – with dialkyl carbonates, diaryl carbonates or phosgene.

[0035] Also suitable are polyhydroxy functional fats and oils, for example natural fats and oils, especially castor oil; or polyols obtained by chemical modification of natural fats and oils – so-called oleochemical polyols – for example epoxy polyesters or epoxy polyethers obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, of the degradation products or derivatives thereof.Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols as well as fatty acid esters, especially the methyl esters (FAME), which can be derivatized to hydroxy fatty acid esters, for example by hydroformylation and hydrogenation.

[0036] It is also conceivable to use polyhydrocarbon polyols. These are also called oligohydrocarbonols and include, for example, polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene, or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; and polyhydroxy-functional polymers of dienes, especially 1,3-butadiene, which can also be produced by anionic polymerization. polyhydroxy functional copolymers of dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example polyhydroxy functional acrylonitrile / butadiene copolymers such as those made from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers, as well as hydrogenated polyhydroxy functional polymers or copolymers of dienes.

[0037] In addition to the polyols mentioned above, small amounts of low-molecular-weight dihydric or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher-molecular-weight alcohols, and low-molecular-weight alkoxylation products of the aforementioned dihydric and polyhydric alcohols may also be present. as well as mixtures of the aforementioned alcohols being used in the production of the polyurethane polymer containing isocyanate groups.

[0038] It is also conceivable that, in addition to these polyols, small amounts of low molecular weight di- or polyhydric amines such as ethylenediamine, toluenediamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene-polyphenylenamine; or amino alcohols such as ethanolamine and diethanolamine, as well as mixtures of the aforementioned amines and amino alcohols, can be used in the production of the polyurethane polymer containing isocyanate groups.

[0039] The process for producing the polymer composition can also include the use of a prepolymer with terminal NCO groups. This means that at least one such prepolymer can be used, and therefore two, three, four, or even more prepolymers are possible. Preferably, exactly one prepolymer with terminal NCO groups is used in the process.

[0040] According to one advantage, it can be provided that the prepolymer with terminal NCO groups has a molar ratio of NCO to OH groups of between 1.5 to 1 and 2.0 to 1.

[0041] In one embodiment, the prepolymer with terminal NCO groups is produced by reacting a diol with diisocyanate.

[0042] Suitable polyols are selected from the group consisting of polyesters, hydroxyl-containing polycaprolactones, polyglycols, monosubstituted glycol esters, polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyhydrocarbon polyols, polyacrylate polyols, polymethacrylate polyols, polyalcohols, bisphenols, polycarbonate polyols, polyhydroxy functional fats and oils, and mixtures thereof.

[0043] Diols, polyethylene oxides or polypropylene oxides are particularly suitable.

[0044] Suitable polyols include the aforementioned high-molecular-weight polyglycols, preferably polyethylene oxides or polyoxypropylene diols with a degree of unsaturation lower than 0.02 mEq / g and a molecular weight in the range of 400 to 18,000 g / mol, particularly those with a molecular weight in the range of 1,000 to 4,000 g / mol. PPG 2000 or PPG 4000 are especially suitable.

[0045] A mixture of polyols can also be used. Advantageously, this is a mixture of two or more polyethylene oxides or a mixture of two or more polyoxypropylene diols. A mixture of PPG1000 and PPG400 is particularly advantageous.

[0046] For the production of the prepolymer with terminal isocyanate groups, the diisocyanates known to those skilled in the art for the production of polyurethane polymers can be used.

[0047] It is also possible that the diisocyanate for this prepolymer synthesis is selected from the group consisting of ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene 1,3-diisocyanate, cyclohexylene 1,4-diisocyanate, cyclohexylene 1,2-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,2-diphenylpropane 4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, and diphenyl 4,4'-diisocyanate. Azobenzene 4,4'-diisocyanate, diphenylsulfone 4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene 2,4-diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, block diisocyanates and carbodiimide-modified diisocyanates,as well as any mixtures of the aforementioned diisocyanates. Diphenylmethane diisocyanates are preferably used, and 4,4'-diphenylmethane diisocyanate (4,4'-MDI) is particularly preferred.

[0048] In the radical polymerization process, an initiator can be used that is either a peroxide initiator or an azo initiator. Preferred initiators are dilauroyl peroxide, dibenzoyl peroxide, and azobis(isobutyronitrile). The use of dilauroyl peroxide is particularly preferred.

[0049] It is also conceivable that an auxiliary substance and / or an additive is added to the reaction mixture in the process according to the invention. Examples include surfactants, fillers, further flame retardants, nucleating agents, oxidation stabilizers, sliding and demolding aids, dyes and pigments, optionally stabilizers (e.g., against hydrolysis, light, heat, or discoloration), inorganic and / or organic fillers, reinforcing agents, and plasticizers. Suitable auxiliary and additive substances can be found, for example, in the Plastics Handbook, Volume 7 "Polyurethanes," by Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag, Munich, Vienna, 1993.

[0050] To adjust the viscosity, a solvent can be added to the reaction mixture at any point during the process according to the invention. Examples of solvents are triethyl phosphate (TEP), pentamethyldiethylenetriamine (PMDETA), triethylenediamine (TEDA), monoethylene glycol, polyethylene glycol, and propylene carbonate (PC); and mixtures of two or more of the aforementioned solvents. If the solvent is a polyol, addition after completion of the radical polymerization is advantageous.

[0051] To accelerate the reaction, a catalyst can be added to the reaction mixture in the process according to the invention.

[0052] Beispielsweise sind geeignete Katalysatoren N,N-Dimethylethanolamin (DMEA), N,N-Dimethylcyclohexylamin (DMCHA), Bis(N,N-dimethylaminoethyl)ether (BDMAFE), N,N,N',N',N"-Pentamethyldiethylenetriamin (PDMAFE), 1,4-Diazadicyclo[2,2,2]octan (DABCO), 2-(2-Dimethylaminoethoxy)-ethanol (DMAFE), 2-((2-Dimethylaminoethoxy)-ethylmethyl-amino)ethanol, 1-(bis(3-Dimethylamino)-propyl)amino-2-propanol, N,N',N"-tris(3-Dimethylamino-propyl)hexahydrotriazin, Dimorpholinodiethylether (DMDEE), N.N-Dimethylbenzylamin, N,N,N',N",N"-Pentaamethyldipropylenetriamin, N,N'-Diethylpiperazin.Particularly suitable are sterically hindered primary, secondary or tertiary amines, such as dicyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-α-phenethyl)amine, tris-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di-t-butylamine, cyclohexyl-t-butylamine, de-sec-butylamine, dicyclopentylamine, di-α-trifluoromethyl)amine, di-(α-phenylethyl)amine, triphenylmethylamine, and 1,1-diethyln-propylamine.Other sterically hindered amines include morpholines, imidazoles, ether compounds such as dimorpholine diethyl ether or dimorpholine dimethyl ether; N-ethylmorpholine, N-methylmorpholine, bis(dimethylaminoethyl) ether, imidazoles, nomethylimidazoles, 1,2-dimethylimidazoles, N,N,N',N',N",N"-pentamethyldiethylenetriamine, N,N,N',N',N',N",N"-pentaethyldiethylenetriamine, N,N,N',N',N',N",N"-pentamethyldipropylenetriamine, bis(diethylaminoethyl) ether and bis(dimethylaminopropyl) ether.

[0053] According to the invention, monomer type A is an ethylene unsaturated monomer containing no active hydrogen and lacking moisture-reactive functional groups.

[0054] According to the invention, a monomer of monomer type A is used in the process for producing the polymer composition. This is to be understood as meaning that at least one monomer of this type can be used, i.e., two, three, four or even more monomers of type A. Preferably, two monomers of monomer type A are used in the process.

[0055] Examples of monomer type A are selected from the group consisting of C1 to C12 esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate or n-butyl methacrylate, vinyl esters such as vinyl acetate or vinyl propionate, vinyl ethers, fumarates, maleates, styrenes, acrylonitriles, ethylene, or mixtures thereof.

[0056] Particularly suitable as monomer type A is n-butyl methacrylate or methyl methacrylate or a mixture thereof.

[0057] According to the invention, monomer type B is an ethylene unsaturated monomer containing no active hydrogen and possessing a moisture-reactive functional group.

[0058] According to the invention, a monomer of monomer type B is used in the process for producing the polymer composition. This is to be understood as meaning that at least one monomer of this type can be used, i.e., two, three, four or even more monomers of type B. Preferably, exactly one monomer of monomer type B is used in the process.

[0059] Furthermore, it is advantageous if, within the scope of the invention, the monomer type B is selected from the group consisting of vinyl compounds, acrylates, methacrylates, fumarates, maleates, styrenes, acrylonitriles, ethylenes, or mixtures thereof, wherein these have a moisture-reactive functional group.

[0060] A suitable moisture-reactive group is the isocyanate group or the silane group. Preferably, monomer type B has a silane group as the moisture-reactive group.

[0061] Advantageously, the invention may provide that monomer type B is selected from the group consisting of vinyltrichlorosilane, methylvinyldichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiacetoxysilane, vinyltriisopropoxysilane, vinyltriisopropenoxysilane, vinyltris(methylethylketoximino)silane, divinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane. 3-Methyacryloxy-propylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy-propyl-tris(2-methoxyethoxy)silane, 4-(3-trimethoxysilylpropyl)benzylstyrene sulfonate, allyl-triethoxysilane,Allyltrimethoxysilane and oligomers of these silanes.

[0062] Methacryloxypropyltrimethoxysilane is particularly suitable as monomer type B.

[0063] According to the invention, a chain transfer agent is used in the radical polymerization process to reduce the average degree of polymerization of the finished polymer and to obtain a low-molecular-weight polymer. Chain transfer agents for radical polymerizations are known to those skilled in the art.

[0064] It may be advantageous if, within the scope of the invention, the chain transfer agent is a halogenated organic compound, an unsaturated aromatic compound or a thiol, preferably selected from the group consisting of tetrachloromethane, 2,4-diphenyl-4-methyl-1-pentene, dodecyl mercaptan, thioglycolic acid, octylthioglycolate and thioglycerol.

[0065] The preferred chain transfer agent is dodecyl mercaptan.

[0066] Furthermore, it is conceivable that in the process for producing the polymer composition, the polyol is present in an amount of 20% to 90% by weight, preferably 40% to 80% by weight and particularly preferably 50% to 60% by weight, based on the total weight of the components polyol, monomer type A and monomer type B.

[0067] Accordingly, it is conceivable that in the process for producing the polymer composition, the prepolymer with the terminal NCO groups is present in an amount of 20% to 90% by weight, preferably 40% to 80% by weight and particularly preferably 50% to 60% by weight, based on the total weight of the components prepolymer, monomer type A and monomer type B.

[0068] In another possibility, it can be provided that in the process for producing the polymer composition, monomer type A is present in an amount of 30% to 95% by weight, preferably 50% to 90% by weight and particularly preferably 70% to 85% by weight, based on the total weight of monomer type A and monomer type B.

[0069] It may also be possible that in the process for producing the polymer composition, monomer type B is present in an amount of 5% to 70% by weight, preferably 10% to 50% by weight and particularly preferably 15% to 30% by weight, based on the total weight of monomer type A and monomer type B.

[0070] According to a further advantage, the low molecular weight polymer can be provided to have a number-average molar mass of 3,000 to 200,000 g / mol, preferably of 5,000 to 100,000 g / mol and particularly preferably of 10,000 to 60,000 g / mol.

[0071] In a second aspect, the invention relates to a polymer composition that can be produced or is produced by the process according to the invention.

[0072] The synthesis of the silane-modified ethylene-based polymer in a polyol according to the invention yields a polymer composition with improved properties compared to a silane-modified ethylene-based polymer synthesized in the PU prepolymer. Structurally, the formation of an interpenetrating network in the polymer composition according to the invention is advantageous for its physicochemical properties. It exhibits increased temperature resistance and improved barrier properties against oil.

[0073] If the optional step (c) is carried out in the process according to the invention, this polymer composition is characterized in that the polyol or the prepolymer is partially cross-linked with the low molecular weight polymer produced by radical polymerization.

[0074] Preferably, the polymer composition may have a glass transition temperature of between -50 and 100 °C, preferably between -30 and 70 °C and particularly preferably between 0 and 60 °C.

[0075] A further advantage can be achieved within the scope of the invention if it has a viscosity of 5,000 to 25,000 mPa.s, and preferably of 7,000 to 21,000 mPa.s measured at 90°C.

[0076] It can be advantageous if the polymer composition within the scope of the invention is solvent-free. Further reaction with a polyisocyanate to form a polyurethane thus yields a solvent-free PU polymer.

[0077] The invention also relates to the use of the polymer composition according to at least one of the preceding claims as an adhesive, sealant, or coating agent. In particular, it is provided that the polymer composition, as a one-component composition, cures with moisture and upon raising the temperature to more than 100°C.

[0078] The invention also relates to a method for producing a moisture-curing polyurethane hot melt adhesive composition, wherein the method comprises the following steps: a) Providing a polymer composition according to the invention; b) Adding sufficient polyisocyanate to achieve the desired isocyanate content and isocyanate index, and polymerizing using an addition polymerization process; c) Optionally adding an aminosilane or a mercaptosilane and converting to a silane-terminated polyurethane.

[0079] The synthesis of the silane-modified ethylene-based polymer in a polyol according to the invention yields a polyurethane hot melt adhesive composition with improved properties compared to a silane-modified ethylene-based polymer synthesized in the PU prepolymer. Specifically, the PU hot melt according to the invention exhibits higher temperature resistance, increased chemical resistance, and improved adhesion to inorganic materials. Furthermore, the polymer composition obtained demonstrated improved barrier properties against oil.

[0080] Commercially available polyisocyanates, especially diisocyanates, can be used as polyisocyanates for the production of the polyurethane polymer.

[0081] It is also possible that the polyisocyanate is selected from the group consisting of ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, and diphenyl-4,4'-diisocyanate. Azobenzene 4,4'-diisocyanate, diphenylsulfone 4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanato-triphenylmethane, 1,3,5-triisocyanato-benzene, 2,4,6-triisocyanato-toluene and 4,4'-dimethyldiphenylmethane-2,2',5,5-tetraisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, block diisocyanates and carbodiimide-modified polyisocyanates, as well as any mixtures of the aforementioned isocyanates.

[0082] Advantageously, the invention may provide that in the process for producing a moisture-curing polyurethane hot melt adhesive composition the free isocyanate content is between 0 and 20%, preferably between 0 and 15% and particularly preferably between 0 and 10%.

[0083] In another possibility, it can be provided that in this process the isocyanate index is between 0.5 and 10, preferably between 1 and 3 and particularly preferably between 1.5 and 2.5.

[0084] According to optional step c), the moisture-curing polyurethane hot melt adhesive composition obtained in step b) can be converted to a silane-terminated polyurethane by adding an aminosilane or a mercaptosilane.

[0085] According to the invention, an aminosilane or a mercaptosilane is used in step c). This is to be understood as meaning that at least one aminosilane or a mercaptosilane can be used here, i.e., two, three, four or even more aminosilanes or mercaptosilanes. Preferably, exactly one aminosilane or exactly one mercaptosilane is used in the process.

[0086] Preferably the aminosilane is an aminosilane AS of formula (I),

[0087] The R1< group represents a linear or branched, monovalent hydrocarbon residue with 1 to 12 carbon atoms, which may optionally contain one or more C-C multiple bonds and / or optionally cycloaliphatic and / or aromatic components. In particular, R1< represents a methyl, ethyl, or isopropyl group.

[0088] The R2< group represents an acyl group or a linear or branched, monovalent hydrocarbon group with 1 to 12 carbon atoms, which optionally has one or more C-C multiple bonds and / or optionally cycloaliphatic and / or aromatic components. Preferably, the R2< group represents an acyl or alkyl group with 1 to 5 carbon atoms, in particular a methyl, ethyl, or isopropyl group.

[0089] The term R3< represents a linear or branched, divalent hydrocarbon residue with 1 to 12 carbon atoms, optionally containing cyclic and / or aromatic components, and optionally one or more heteroatoms. Preferably, the term R3< represents an alkylene residue with 1 to 3 carbon atoms, particularly with 3 carbon atoms.

[0090] Furthermore, the index a represents a value of 0, 1 or 2, in particular 0 or 1.

[0091] The residue R 4< represents a hydrogen atom or a linear or branched hydrocarbon residue with 1 to 20 C atoms, which may have cyclic features, or a residue of formula (II).

[0092] The residues R 6< and R 7< stand independently for a hydrogen atom or for a residue from the group comprising -R 9< , -CN and -COOR 9< .

[0093] The residue R 8< stands for a hydrogen atom or for a residue from the group comprising -CH 2 -COOR 9< , -COOR 9< , -CONHR 9< , -CON(R 9< ) 2 , -CN, -NO 2 , -PO(OR 9< ) 2 , -SO 2 R 9< and - SO 2 OR 9< .

[0094] The residue R 9< stands for a hydrocarbon residue with 1 to 20 C atoms, possibly containing at least one heteroatom.

[0095] Examples of suitable aminosilanes AS of formula (I) are primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes such as N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; the products of the Michael-type addition of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic and methacrylic acid esters, acrylic or methacrylic acid amides, maleic and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, for example N-(3-trimethoxysilyl-propyl)-aminosuccinic acid dimethyl ester and diethyl ester; as well as analogues of the aforementioned aminosilanes with ethoxy or isopropoxy groups instead of the methoxy groups on the silicon. Secondary aminosilanes are particularly suitable as aminosilane AS, especially aminosilane AS where R4 in formula (I) is different from H.Michael-type adducts are preferred, especially N-(3-trimethoxysilyl-propyl)-amino-succinic acid diethyl ester.

[0096] In this document, the term "Michael acceptor" refers to compounds which, due to the double bonds they contain that are activated by electron acceptor residues, are capable of undergoing nucleophilic addition reactions with primary amino groups (NH2 groups) in a manner analogous to Michael addition (hetero-Michael addition).

[0097] In another aspect, the invention relates to a moisture-curing polyurethane hot melt adhesive composition that can be produced or is produced by the previously disclosed method.

[0098] A further advantage can be achieved within the scope of the invention if the polyurethane hot melt adhesive composition has a viscosity of 10 mPas to 150,000 mPas at 120°C. The viscosity is preferably between 1,000 and 100,000 mPas, particularly preferably between 3,000 and 75,000 mPas, and especially between 2,000 and 50,000 mPas.

[0099] The invention also relates to the use of the moisture-curing polyurethane hot melt adhesive composition according to the invention as an adhesive, sealant, or coating material. In particular, it is intended that it be used as an adhesive.

[0100] The invention also relates to a method for producing a 1K polyurethane adhesive comprising the following steps: a) Providing the polymer composition according to the invention, wherein, in the production of which, instead of the temperature increase in optional step c), the polymer is cooled to a temperature of 80 to 20°C; b) Adding a polyisocyanate according to the invention to achieve a desired free isocyanate content and desired isocyanate index; c) Optionally cooling to a temperature of 80 to 20°C for a period of 0.5 to 5 hours.

[0101] Commercially available polyisocyanates, especially diisocyanates, can be used as polyisocyanates for the production of the polyurethane polymer.

[0102] It is also possible that the polyisocyanate is selected from the group consisting of ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, and diphenyl-4,4'-diisocyanate. Azobenzene 4,4'-diisocyanate, diphenylsulfone 4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanato-triphenylmethane, 1,3,5-triisocyanato-benzene, 2,4,6-triisocyanato-toluene and 4,4'-dimethyldiphenylmethane-2,2',5,5-tetraisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, block diisocyanates and carbodiimide-modified polyisocyanates, polymeric diphenylmethane diisocyanate (PMDI), and any mixtures of the aforementioned isocyanates.

[0103] In a preferred embodiment, a diphenylmethane isocyanate (MDI) or polymeric diphenylmethane diisocyanate (PMDI) is used as the polyisocyanate.

[0104] MDI can be a mixture of two or three of its isomers, namely 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate. However, only one isomer can also be used, which is then preferably 4,4'-diphenylmethane diisocyanate.

[0105] Polymeric diphenylmethane diisocyanate (PMDI), also known as technical grade MDI, is a mixture of methylenediphenyl isocyanates and homologous aromatic polyisocyanates. However, the term "polymeric diphenylmethane diisocyanate" is technically incorrect, as it is not a polymer but a mixture of compounds with several (typically up to six) phenylene groups, each bearing an isocyanate group. Polymethylene polyphenyl isocyanate is also a common trade name.

[0106] According to an advantageous embodiment of the invention, it can be provided that the free isocyanate content set in step b) of the process is between 2 and 40%, preferably between 5 and 30% and particularly preferably between 10 and 20%.

[0107] Furthermore, within the scope of the invention, it is conceivable that the isocyanate index set in step b) of the process is between 1.5 and 20, preferably between 2 and 15 and particularly preferably between 4 and 10.

[0108] In another aspect, the invention relates to a 1K polyurethane adhesive which can be produced or is produced by the previously disclosed method.

[0109] In another possibility, the 1K polyurethane adhesive may have a viscosity of 5,000 to 25,000 mPa.s, and preferably of 6,000 to 21,000 mPa.s, measured at 20 °C.

[0110] The invention also relates to the use of the 1K polyurethane adhesive according to the invention as an adhesive, coating compound or sealant, in particular as a multi-purpose adhesive, assembly adhesive, construction adhesive, paper and packaging adhesive, film laminating adhesive, adhesive for ceramic and metallic materials, wood, glass, sandwich systems, textiles, reinforcing fabrics, materials in the field of aircraft, military or shipbuilding.

[0111] In a further aspect, the invention relates to a polyurethane composition comprising a) 5 to 90 wt.% of a urethane polymer or urethane prepolymer produced by addition polymerization of a polyisocyanate and a polyol; b) 10 to 95 wt.% of a low molecular weight polymer of ethylene unsaturated monomers not containing active hydrogen, wherein at least one of the monomers is an ethylene unsaturated monomer with a siloxane group.

[0112] In one embodiment of the invention, the polyurethane composition is characterized in that the low molecular weight polymer consists of more than 50%, preferably more than 75% and further preferably 100% of an ethylene unsaturated monomer with a siloxane group.

[0113] In a preferred embodiment of the invention, the polyurethane composition is characterized in that the ethylene unsaturated monomer with a siloxane group is a silane-modified acrylate.

[0114] In a second aspect, the invention relates to the use of an ethylene unsaturated monomer with a siloxane group for copolymerization with ethylene unsaturated monomers that do not contain active hydrogen in a polyol or in a prepolymer with the terminal NCO groups as a solvent.

[0115] In one embodiment of the invention, the use is characterized in that the ethylene unsaturated monomer with a siloxane group is a silane-modified acrylate.

[0116] In an additional aspect, the invention relates to an acrylate copolymer comprising: a) 5 to 95 wt.% of one or more acrylate monomers not containing active hydrogen, preferably selected from the group consisting of butyl methacrylate and methyl methacrylate; b) 5 to 95 wt.% of one or more acrylate monomers with a siloxane side group, preferably a 3-methacryloxypropyltrimethoxysilane. Definitions

[0117] In this document, substance names beginning with "Poly", such as polyol or polyisocyanate, refer to substances that formally contain two or more of the functional groups appearing in their name per molecule.

[0118] In this document, the term "polymer" encompasses, on the one hand, a group of chemically uniform macromolecules that differ in degree of polymerization, molar mass, and chain length, and which are produced by a polymerization reaction (polymerization, polyaddition, polycondensation). On the other hand, the term also includes derivatives of such a group of macromolecules from polymerization reactions; that is, compounds obtained by changes, such as additions or substitutions, of functional groups on given macromolecules, and which may be chemically uniform or chemically heterogeneous. Furthermore, the term includes copolymers and so-called prepolymers, that is, reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.

[0119] In this document, the term "copolymer" refers to a polymer composed of two or more different types of monomer units. This distinguishes a copolymer from a homopolymer, which consists of only one (real or imagined) type of monomer and therefore has only one repeating unit. Copolymers can be divided into five classes, namely: 1.) Statistical copolymers, in which the distribution of the two monomers in the chain follows a statistical distribution; 2.) Gradient copolymers, which are similar in principle to statistical copolymers, but in which the proportion of one monomer increases and that of the other decreases along the chain; 3.) Alternating copolymers, in which the two monomers alternate; 4.) Block copolymers and segment copolymers, which consist of longer sequences or blocks of each monomer; and 5.) Graft copolymers, in which blocks of one monomer are grafted onto the backbone of another monomer.

[0120] In this document, the term "low molecular weight polymer" refers to a polymer with a number-average molar mass of 200,000 g / mol or less.

[0121] The term "polyurethane polymer" encompasses all polymers produced using the so-called diisocyanate polyaddition process. This also includes polymers that are almost or entirely free of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates, and polycarbodiimides.

[0122] In this document, "active hydrogen" refers to hydrogen bonded to N, O, or S (also known as "Zerewitinoff active hydrogen") that yields methane upon reaction with methylmagnesium iodide according to a process discovered by Zerewitinoff. Typical examples of compounds containing active hydrogen are those containing carboxyl, hydroxyl, amino, imino, or thiol groups as functional groups.

[0123] Accordingly, the monomer that does not contain active hydrogen (monomer type B) is a monomer that does not have any carboxyl, hydroxyl, amino, imino or thiol groups.

[0124] According to the present application, a "functional group" is a group of atoms in an organic compound that significantly determines the material properties and reactivity of the compound. Chemical compounds that contain the same functional groups are grouped into classes of substances due to their often similar properties.

[0125] In this document, a "moisture-reactive functional group" is defined as a functional group that reacts with water. This reaction can lead to the cross-linking of two or more such groups, thereby curing the corresponding polymer. Moisture-reactive (curable) groups are known to those skilled in the art in the field of polymers. Examples include the silane group and the isocyanate group.

[0126] In this document, the terms "silane" and "organosilane" refer to compounds which, on the one hand, have at least one, usually two or three, alkoxy or acyloxy groups directly bonded to the silicon atom via Si-O bonds, and, on the other hand, have at least one organic residue directly bonded to the silicon atom via a Si-C bond. Such silanes are also known to those skilled in the art as organoalkoxysilanes and organoacyloxysilanes, respectively.

[0127] Accordingly, the term "silane group" refers to the silicon-containing group bonded to the organic residue of the silane via the Si-C bond. Silanes, or rather their silane groups, have the property of hydrolyzing upon contact with moisture and are therefore classified as moisture-reactive groups.

[0128] Organosilanes whose organic residue contains an amino group or a mercapto group are called "aminosilanes" or "mercaptosilanes," respectively. "Primary aminosilanes" are those that have a primary amino group, i.e., an NH₂ group bonded to an organic residue. "Secondary aminosilanes" are those that have a secondary amino group, i.e., an NH₂ group bonded to two organic residues.

[0129] In this document, "molecular weight" refers to the molar mass (in grams per mole or in Daltons) of a molecule. "Mean molecular weight" in this document always refers to the number mean of the molecular weight distribution Mn (number mean). The term "number mean molar mass" is also used synonymously with "mean molecular weight."

[0130] The term "polymeric diphenylmethane diisocyanate" (PMDI) refers to a mixture of methylenediphenyl isocyanates and homologous aromatic polyisocyanates. The term "polymeric diphenylmethane diisocyanate" is chemically incorrect, as it is not a polymer but a mixture of compounds with several (typically up to six) phenylene groups, each bearing an isocyanate group. Polymethylene polyphenyl isocyanate is also a common trade name.

[0131] Within the scope of the present application, a "chain transfer agent" is defined as an organic molecule capable of carrying out chain transfer. A chain transfer reaction is a reaction during chain polymerization in which the activity of a growing polymer chain is transferred to another molecule. Chain transfer reactions decrease the average degree of polymerization of the finished polymer. Chain transfer agents for radical polymerizations are known to those skilled in the art.

[0132] In this document, the term "solvent" refers to compounds as listed as organic solvents in CD Römpp Chemie Lexikon, 9th edition, version 1.0, Georg Thieme Verlag, Stuttgart 1995. The polyols or prepolymers with terminal NCO groups used according to the invention are not covered by this definition, although they function as solvents for the monomers and also for the low-molecular-weight polymer produced by radical polymerization.

[0133] In this document, "solid" refers to substances that do not change their shape without external influence or are difficult to deform; in particular, they are not flowable. "Liquid" refers to substances that are deformable and flowable, including highly viscous and pasty substances.

[0134] In this document, a composition is referred to as "one-component" (abbreviated as "1K") if all its components are mixed and stored in the same container and are moisture-curable. A composition is referred to as "two-component" if its components are stored in two separate containers. The two components are mixed together shortly before or during application, after which the mixture cures. This curing process is initiated or completed by exposure to moisture.

[0135] It should be expressly noted that, within the context of this patent application, indefinite articles and indefinite numerical expressions such as "one...", "two...", etc., are generally to be understood as minimum values, i.e., "at least one...", "at least two...", etc., unless the context or the specific text of a particular passage indicates that only "exactly one...", "exactly two...", etc., is meant. Furthermore, all numerical values, as well as information on process parameters and / or device parameters, are to be understood in a technical sense, i.e., as being subject to the usual tolerances. Even the explicit inclusion of the limitation "at least" or "at least" or similar should not be interpreted as meaning "exactly one" when simply using "one," i.e., without the inclusion of "at least" or similar.

[0136] Unless otherwise stated, the percentages in this document refer to weight percentages.

[0137] The embodiments shown here are merely examples of the present invention and should therefore not be interpreted as limiting. Alternative embodiments considered by a person skilled in the art are likewise covered by the scope of protection of the present invention. Examples of implementation 1. Production of a polymer composition according to the invention

[0138] Based on the polymerization of acrylate polymers in polyols, a basic formulation according to Table 1 was modified by the use of acrylate silanes. Specifically, an organofunctional 3-methacryloxypropyltrimethoxysilane was used at concentrations of 5%, 10%, and 12.5%.

[0139] To produce a silane-modified acrylate polymer, the feedstock is heated to 90 °C in a glass reactor under a nitrogen atmosphere. After 30 minutes, the monomers are added over 2 hours at 90 °C, and the initiator is then added. The post-reaction then takes place over 2 hours with the additional addition of the initiator. Table 1: Basic formulation & modifications of IC406-23 Raw materials Portion [%] Reference (without silane) 1: Reference with 5% silane 2: Reference with 10% silane 3: Reference with 12.5% ​​silane Template PPG 2000 57,7 57,7 57,7 57,7 N-BMA 8,6 7,6 6,6 6 MMA 3,2 2,8 2,4 2,2 Silane 0 1,4 2,8 3,6 Dodecyl mercaptan 0,2 0,2 0,2 0,2 Dilauroyl peroxide 0,2 0,2 0,2 0,2 dosage Dilauroyl peroxide 0,1 0,1 0,1 0,1 N-BMA 21,8 19,3 16,7 15,2 MMA 8,1 7,1 6,1 5,6 Silane 0 3,5 7,1 9,1 Dilauroyl peroxide 0,1 0,1 0,1 0,1 (PPG-2000 = polypropylene glycol MW = 2000; N-BMA = butyl methacrylate; MMA = methyl methacrylate; silane = 3-methacryloxypropyltrimethoxysilane)

[0140] Rheological analyses showed that a 5% addition of silane hardly altered the basic properties of the acrylate (see Table 2). Increasing the silane content to 12.5% ​​significantly reduced the system's viscosity, making it flowable even at room temperature. Table 2: Rheological properties of silane-modified acrylate polymers in polyol Try viscosity Internal Cohesion G' 20°C tan Delta = 1 @ 120 °C (mPas) @ 140 °C (mPas) Reference: Acrylate* without silane 5.359 3.265 0,01 34 °C 1: Acrylate* with 5% silane 5.332 3.265 0,01 27 °C 2: Acrylate* with 10% silane 3.626 2.487 0,01 21 °C 3: Acrylate* with 12.5% ​​silane 1.749 1.100 0,00 11 °C * Acrylate = IC406-23

[0141] IC406-23 was modified with varying concentrations of 3-methacryloxypropyltrimethoxysilane to subsequently produce moisture-curing polyurethane adhesives. Surprisingly, it was found that increased silane content in the acrylate fraction also resulted in a viscosity-reducing effect when used to produce polyurethane hot melts, thus eliminating the need for plasticizers. Example 1 liquid PUR adhesive:

[0142] IC406-23 was calculated for a glass transition temperature of 40°C, modified with 12.5% ​​3-methacryloxypropyltrimethoxysilane, and polymerized in PPG 4000 (PCC Rokita Rokopol DE4020) (IC1760-5 with PPG 4000). This was then converted to the polyurethane adhesive IC1701-45 (Table 2). Table 2: Formulation of IC1701-45 Raw materials Portion [%] IC1760-5 47,6 PPG 4000 7 DMDEE 0,4 pMDI 45

[0143] Table 3 below compares the properties of IC1701-45 with those of a commercially available 1-component PUR adhesive, IC1701-22. This comparison clearly demonstrates the significantly improved performance of the silaneacrylate-modified system when bonding wood. Table 3: Properties of IC1701-22 & IC1701-45 Designation Viscosity @ 20 °C * [mPas] NCO content [%] D1** [N / mm²< ] D4** [N / mm²<] WATT91*** [N / mm²< ] open time**** [min] IC 1701-22 6000 11 11,1 4,52 5,8 25-30 IC 1701-45 7600 13,3 17 7,11 8,21 10 * Brookfield DVII, Sp. 6, 20 rpm; ** DIN EN 204; *** DIN EN 14257 **** Internal method: A 300 µm polymer film is applied to a strip of kraft paper (60 x 8 cm), and paper strips (9 x 2 cm) are pressed onto it with finger pressure at defined time intervals (e.g., 1, 2, etc. minutes). After cross-linking, the paper strips are removed and evaluated. The time during which at least 70% of the paper remains adhered to the adhesive film is recorded. Example 2 PUR hot melt adhesive (textile):

[0144] IC406-23 was calculated for a glass transition temperature of -6 °C, modified with 12.5% ​​3-methacryloxypropyltrimethoxysilane, and polymerized in PPG 1000 (PCC Rokita Rokopol D1002) (IC1760-6). This was subsequently converted to the polyurethane adhesive IC768-3 (Table 4).

[0145] To produce a polyurethane adhesive, further polyols and additives are added to the silane-modified acrylate IC1760-6 at 90 °C and homogenized for 45 minutes at approximately 10 mbar. The 4,4'-MDI is then added and the mixture is stirred for 60 minutes. Before filling the containers, the polyurethane adhesive is degassed again at approximately 10 mbar. Table 4: Formulation of IC768-3 Raw materials Portion [%] IC1760-6 51,73 PPG Triol 11,75 PPG 400 13,98 Additive 0,51 4.4'-MDI 22,04

[0146] The following table compares the properties of IC768-3 with a PUR hot melt adhesive (textile). A significant increase in the internal strength (cohesion) of the silaneacrylate-modified variant is evident. Table 5: Properties of IC764-42 & IC768-3 Try w(NCO) [%] viscosity Internal Cohesion G' 20°C tan Delta = 1 @ 90°C [mPas] @ 120°C [mPas] @ 140°C [mPas] IC764-42 2,3 21.200 5.912 3.300 0,02 2°C IC768-3 1,6 53.000 15.000 7.600 0,06 9°C Measurement method for determining internal cohesion G' and tan Delta:

[0147] Using the Modular Compact Rheometer 301 (Anton Paar), an oscillation measurement was performed as a function of temperature (160 to -20 °C). G' and G" and their ratio (tan Δ) to each other were recorded at each temperature. G' describes the solid fraction and G" the liquid fraction of a material. The "internal cohesion G'" at 20 °C thus describes the solid fraction of the material, or rather, its cohesion. When G' and G" are equal, tan Δ = 1. This is achieved at a specific temperature, which is then recorded. At this temperature, a state is described in which the material is neither a liquid nor a solid. If the temperature is lowered further, ideally a "solid" state is present. Example 3: Production of a PUR hot melt adhesive (textile):

[0148] To prepare a prepolymer with terminal isocyanate (NCO) groups IC768-15 (see Table 6), a polyol mixture is heated to 120 °C and homogenized for 45 minutes at approximately 10 mbar. The 4,4'-MDI is then added and the mixture is stirred for 60 minutes under a nitrogen atmosphere. Table 6: Formulation of the prepolymer IC768-15 Raw materials Portion [%] PPG 1000 59,0 PPG 400 7,9 4.4'-MDI 33,1 [NCO] / [OH] 1,7:1 (PPG 1000 = Polypropylene glycol Mn = 1000; PPG 400 = Polypropylene glycol Mn = 400; 4,4'-MDI = 4,4'-Diphenylmethane diisocyanate; [NCO] / [OH] = Molar ratio of NCO to OH groups in the obtained prepolymer).

[0149] To subsequently synthesize a silane-modified acrylate polymer IC768-17 (see Table 7) from the prepolymer IC768-15, the IC768-15 is cooled to 70 °C. After adding a portion of the monomers, the initiator, and the chain transfer agent, the mixture is heated to 90 °C. After 30 minutes, the monomers are added over 2 hours at 90 °C, and more initiator is added. The post-reaction then takes place over 2 hours with an additional addition of initiator. The PUR hot melt adhesive can then be filled at 90 °C.

[0150] To investigate potential undesired side reactions during polymerization with the prepolymer IC768-15 (see Table 7) in more detail, a reference synthesis is necessary. For this purpose, PPG 1000 (see Table 6) was chosen as the template instead of the prepolymer IC768-15, thus representing IC1760-9 (see Table 7). After polymerization, it is reacted with PPG 400 and 4,4'-MDI to form a polyurethane adhesive IC768-7 (see Table 8), as already described in Example 2. Table 7: Formulation of IC768-17 & IC1760-9 Test number IC768-17 IC1760-9 Raw materials Portion [%] Template: PPG 1000 - 57,7 IC768-15 69,9 - BA 3,1 4,4 MMA 2,8 3,9 Silane 2,5 3,5 Dodecyl mercaptan 0,13 0,2 Dilauroyl peroxide 0,13 0,2 dosage Dilauroyl peroxide 0,07 0,1 BA 7,9 11,1 MMA 7,0 9,8 Silane 6,4 9,0 Dilauroyl peroxide 0,07 0,1 (BA=butyl acrylate; MMA=methyl methacrylate; silane = 3-methacryloxypropyltrimethoxysilane) Table 8: Formulation of IC768-7 Raw materials Portion [%] IC1760-9 71,3 PPG 400 5,5 4.4'-MDI 23,2 [NCO] / [OH] 1,7

[0151] The product analysis (see Table 9) indicates that the polymerization of silane-modified acrylate polymer proceeds independently in the presence of reactive isocyanate groups: The measurement results are within the tolerance limits of the product specification. Table 9: Properties of IC768-17 vs. IC768-7 Try w(NCO) [%] viscosity Internal Cohesion G' 20°C tan Delta = 1 @ 120°C [mPas] @ 140°C [mPas] IC768-7 3,4 4.100 2.900 0,01 - IC768-17 3,2 5.900 4.700 0,01 -

Claims

1. A process for producing a polymer composition comprising the following steps: a) Combination of: (i) a polyol or a prepolymer with terminal isocyanate (NCO) groups (ii) an ethylenically unsaturated monomer containing no active hydrogen and having no moisture-reactive functional groups (monomer type A), and (iii) an ethylenically unsaturated monomer containing no active hydrogen and having a moisture-reactive functional group (type B monomer); b) polymerization of the mixture from step (a) using a radical polymerization process with a chain transfer agent to obtain a low-molecular-weight polymer; c) optional heating of the mixture from step (b) to a temperature of 100 C to 160 °C for 10 to 60 minutes to partially crosslink the polyol or the prepolymer with the terminal NCO groups with the low-molecular-weight polymer.

2. A process according to Claim 1, characterized in that the polyol is selected from the group consisting of polyester, hydroxyl group-containing polycaprolactone, polyoxyalkene polyol, monosubstituted glycol ester, polythioether, polyamide, polyesteramide, polycarbonate, polyacetal, polyhydrocarbon polyol, polyacrylate polyol, polymethacrylate polyol, polyalcohol, bisphenol, polycarbonate polyol, polyhydroxy functional fats and oils, and mixtures thereof, wherein the polyol is preferentially a diol, a polyethylene oxide, or a polypropylene oxide.

3. A process according to at least one of Claims 1 and 2, characterized in that monomer type A is selected from the group consisting of C1 to C12 esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate or n-butyl methacrylate, vinyl esters such as vinyl acetate or vinyl propionate, vinyl ethers, fumarates, maleates, styrenes, acrylonitriles, ethylenes, or mixtures thereof, wherein monomer type A is preferentially n-butyl methacrylate (n-BMA) or methyl methacrylate (MMA) or a mixture thereof.

4. A process according to at least one of the preceding claims, characterized in that monomer type B is selected from the group consisting of vinyl compounds, acrylates, methacrylates, fumarates, maleates, styrenes, acrylonitriles, ethylenes, or mixtures thereof, having a moisture-reactive functional group, which is preferentially a silane group.

5. A process according to Claim 4, characterized in that monomer type B is selected from the group consisting of vinyltrichlorosilane, methylvinyldichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiacetoxysilane, vinyltriisopropoxysilane, vinyltriisopropenoxysilane, vinyltris(methylethylketoximino)silane, divinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methyacryloxypropylmethyldiethoxysilane, 3-methyacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltris(2-methoxyethoxy)silane, 4-(3-trimethoxysilylpropyl)benzylstyrenesulfonate, allyltriethoxysilane, allyltrimethoxysilane and oligomers of these silanes, monomer type A being preferentially methacryloxypropyltrimethoxysilane.

6. A process according to at least one of the preceding claims, characterized in that the initiator used in the radical polymerization process is a peroxide initiator or an azo initiator, which is preferentially selected from the group consisting of dilauroyl peroxide, dibenzoyl peroxide, and azobis (isobutyronitrile).

7. A process according to at least one of the preceding claims, characterized in that the chain transfer agent is an organohalogen compound, an unsaturated aromatic compound or a thiol, which is preferentially selected from the group consisting of tetrachloromethane, 2,4-diphenyl-4-methyl-1- pentene, dodecyl mercaptan (DDM), thioglycolic acid, octylthioglycolate, and thioglycerol, and particularly preferentially dodecyl mercaptan.

8. A process according to at least one of the preceding claims, characterized in that the polyol or the prepolymer with terminal NCO groups is obtained in an amount of 20 percent by weight to 90 percent by weight, preferentially from 40 percent by weight to 80 percent by weight and particularly preferentially from 50 percent by weight to 60 percent by weight on the total weight of the components polyol or prepolymer, monomer type A and monomer type B.

9. A process according to at least one of the preceding claims, characterized in that monomer type A in an amount of 30 percent by weight to 95 percent by weight, preferentially from 50 percent by weight to 90 percent by weight and particularly preferentially from 70 percent by weight to 85 percent by weight, based on the total weight of monomer type A and monomer type B is present.

10. A process according to at least one of the preceding claims, characterized in that monomer type B in an amount of 5 percent by weight to 70 percent by weight, preferentially from 10 percent by weight to 50 percent by weight and particularly preferentially from 15 percent by weight to 30 percent by weight, based on the total weight of monomer type A and monomer type B is present.

11. A process according to at least one of the preceding claims, characterized in that the low-molecular-weight polymer has a number-average molecular weight of 3,000 to 200,000 g / mol, preferentially of 5,000 to 100,000 g / mol and particularly preferentially of 10,000 to 60,000 g / mol.

12. A polymer composition prepared by a process according to at least one of the preceding claims.

13. A polymer composition according to Claim 12, characterized in that the polymer composition has a glass transition temperature of between -50 °C and 100 °C, preferentially between -30 °C and 70 °C, and particularly preferentially between 0 °C and 60 °C.

14. A polymer composition according to Claim 12 or 13, characterized in that the polymer composition has a viscosity of 5,000 to 25,000 mPa.s, and preferentially from 7,000 to 21,000 mPa.s, measured at 90 °C.

15. A polymer composition according to at least one of Claims 12 to 14, characterized in that it is free of solvents.

16. Use of the polymer composition according to at least one of Claims 12 to 15 as an adhesive, sealant, or coating agent, wherein the polymer composition cures as a one-component composition with moisture and by increasing the temperature to more than 100 °C.

17. A process for producing a moisture-hardening polyurethane hot melt adhesive composition comprising the following steps: a) Provision of a polymer composition according to at least one of Claims 12 to 15; b) Addition of sufficient polyisocyanate to achieve the desired isocyanate content and isocyanate index and polymerization through the use of an additive polymerization process; c) Optional addition of an aminosilane or a mercaptosilane and conversion to a silane-terminated polyurethane.

18. A process according to Claim 17, characterized in that the polyisocyanate in step b) is selected from the group consisting of ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl 4,4' diisocyanate, azobenzene 4,4' diisocyanate, diphenyl sulfone 4,4' diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanato-triphenylmethane, 1,3,5-triisocyanato-benzene, 2,4,6-triisocyanato-toluene and 4,4'-dimethyldiphenylmethane-2,2',5,5-tetraisocyanate, 3-isocyanate-methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, polymeric diphenylmethane diisocyanate (PMDI), block diisocyanates and carbodiimide-modified polyisocyanates, and mixtures thereof.

19. A process according to Claim 17 or 18, characterized in that the free isocyanate content is between 0 and 20%, preferentially between 0 and 15%, and particularly preferentially between 0 and 10%.

20. A process according to at least one of Claims 17 to 19, characterized in that the isocyanate index is between 0.5 and 10, preferentially between 1 and 3, and particularly preferentially between 1.5 and 2.5.

21. A moisture-hardening polyurethane hot-melt adhesive composition prepared by a process according to at least one of Claims 17 to 20.

22. A moisture-hardening polyurethane hot-melt adhesive composition according to Claim 21, characterized in that the composition has a viscosity of 10 mPas to 150,000 mPas at 120 °C.

23. Use of the moisture-hardening polyurethane hot-melt adhesive composition according to Claim 21 or 22 as an adhesive, sealant, or coating agent.

24. The process for producing a 1K polyurethane adhesive includes the following steps: a) Provision of a polymer composition according to at least one of Claims 12 to 15, wherein instead of increasing the temperature in optional step (b), the polymerizate is cooled to a temperature of 80 °C to 20 °C; b) Addition of a polyisocyanate to achieve a desired free isocyanate content and isocyanate index; c) Optional cooling to a temperature of 80 °C to 20 °C for a period of 0.5 to 5 hours.

25. Process according to Claim 24, characterized in that in step (b) a polyisocyanate according to Claim 18 is used, the polyisocyanate preferentially being a diisocyanate.

26. A process according to Claim 24 or 25, characterized in that the free isocyanate content is between 2 and 40%, preferentially between 5 and 30%, and particularly preferentially between 10 and 20%.

27. A process according to at least one of Claims 24 to 26, characterized in that the isocyanate index is between 1.5 and 20, preferentially between 2 and 15, and particularly preferentially between 4 and 10.

28. 1K polyurethane adhesive produced by a process according to at least one of Claims 24 to 27.

29. 1K polyurethane adhesive according to Claim 28, characterized in that the 1K polyurethane adhesive has a viscosity of 5,000 to 25,000 mPa.s, and preferentially from 6,000 to 21,000 mPa.s, measured at 90 °C.

30. Use of a 1K polyurethane adhesive according to Claim 28 or 29 as an adhesive, coating compound, or sealant, in particular as a multi-purpose adhesive (household adhesive), assembly adhesive, construction adhesive, paper and packaging adhesive, film laminating adhesive, adhesive for ceramic and metallic materials, wood, glass, sandwich systems, textiles, reinforcement fabrics, materials in the areas of aircraft, military, or shipbuilding.