Free-radical polymerisation of uv-crosslinking silane acrylates in an isocyanate-containing polyurethane matrix

Abstract

The present invention relates to: a method for preparing a polymer composition, in which method a silane-modified monomer is polymerised, within a polyol or within a prepolymer having terminal isocyanate groups, by means of free-radical chain polymerisation with an ethylenically unsaturated monomer and an additional ethylenically unsaturated monomer which has a free-radical photoinitiator group; and a polymer composition prepared by means of said method. The invention also relates to a method for preparing a moisture-curing polyurethane hot melt adhesive composition, a one-component polyurethane adhesive, and a two-component polyurethane adhesive based on the polymer composition according to the invention. The invention also relates to the moisture-curing polyurethane hot melt adhesive composition, the one-component polyurethane adhesive, and the two-component polyurethane adhesive produced using said methods.

Description

[0001] Radical polymerization of UV-curing silane acrylates in an isocyanate-containing polyurethane matrix

[0002] 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 an ethylenically unsaturated monomer and another ethylenically unsaturated polymer containing a radical photoinitiator group 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 hotmelt adhesive composition, a 1-component polyurethane adhesive, and a 2-component polyurethane adhesive based on the polymer composition according to the invention, together with the moisture-curing polyurethane hotmelt adhesive composition produced therewith, the 1-component polyurethane adhesive, and the 2-component polyurethane adhesive.

[0003] Background of the invention

[0004] Depending on the application, adhesives may require a long open time, as joining is often done manually. At the same time, rapid strength build-up after joining is required, as the parts to be joined must be processed further as quickly as possible. This contradictory property profile is resolved in polyurethane adhesives, for example, by using an acrylate polymer in powder form in a polyether-based polyurethane. The latter enables a long open time, while the acrylate polymer ensures a high initial tack. Incorporating acrylates is often problematic because they incorporate a lot of air and are difficult to dissolve. This can be solved by polymerizing the acrylate polymers directly in a polyol, which is then converted to the polyurethane. This process also enables the use of acrylate polymers whose glass transition temperature is below room temperature.Furthermore, they can be modified with comonomers as desired. However, the properties of the adhesives are limited because the acrylate polymer is a thermoplastic that softens at higher temperatures or sometimes exhibits lower resistance to certain chemicals.

[0005] 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 without surface treatment with polyurethane adhesives leads to adhesion problems.

[0006] US 5,021,507 A relates to acrylic-modified reactive urethanes and teaches in column 2, lines 58 to 68 that in the case of ethylenically unsaturated monomers with moisture-reactive functional groups (“moisture reactive functional groups”) it is necessary that the monomers are added only after the formation of the prepolymer and only then polymerize by means of radical polymerization.

[0007] Further prior art can be found in US 5,018,337, WO 2016 / 123418 A1 or WO 01 / 81495 A2.

[0008] The present invention is based on PCT / EP2022 / 060648 of the applicant, which relates to the polymerization of a silane-modified polymer formed by radical chain polymerization in a polyol or in a prepolymer with terminal isocyanate groups, which is then used in polyurethane formulations. The use of polysilane acrylates in the polyurethane adhesive reduces the viscosity, depending on the silane content, and thus also the initial strength. However, the system achieves the opposite effect in the final strength. Moisture crosslinking in a polyurethane adhesive occurs primarily via the reaction of the isocyanate groups and secondarily via the silane groups, thus leading to longer bond pressing times, which can be disadvantageous depending on the application.

[0009] The present invention is based on the object of improving the state of the art or of offering an alternative.

[0010] Summary of the invention

[0011] According to a first aspect of the present invention, the stated object is achieved by a process for producing a polymer composition according to claim 1. Further embodiments are the subject of the further independent and dependent claims.

[0012] In a first aspect, the invention relates to a process for producing a polymer composition, the process comprising the following steps: a) combining:

[0013] (i) a polyol or a prepolymer having terminal isocyanate (NCO) groups with (ii) an ethylenically unsaturated, non-active hydrogen-containing monomer which has no moisture-reactive functional groups (monomer type A), and

[0014] (iii) an ethylenically unsaturated monomer containing no active hydrogen and having a moisture-reactive functional group (monomer type B);

[0015] (iv) an ethylenically unsaturated, non-active hydrogen-containing monomer having a radical photoinitiator group (monomer type C); 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 NCO-terminated prepolymer with the low molecular weight polymer.

[0016] The following terminology is used to explain this:

[0017] The ethylenically unsaturated group allows the radical polymerization of the monomers to form a polymer. The absence of active hydrogen in the monomers ensures that the monomers 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, through the moisture-reactive group, allows reaction with the polyol or the isocyanate groups of the prepolymer, with the moisture-reactive groups of the polymer, or in the application, such as with inorganic substrates to improve adhesion to these substrates.

[0018] Monomer type C introduces a photoreactive group into the polymer, enabling curing via UV radiation. The present invention thus combines moisture crosslinking via silane or isocyanate groups with rapid UV crosslinking via radical polymerization. This represents a so-called "UV moisture dual-cure" system. Strictly speaking, it is even a "triple-cure" system, as three crosslinking mechanisms are used: primary via UV crosslinking, secondary via the reaction of the isocyanate groups, and tertiary via the silane groups.

[0019] The "UV-moisture dual-cure" systems of the present invention primarily offer the advantage of UV curing of UV-active groups and, secondarily, of moisture-curing groups. This makes it possible to generate particularly rapid initial strength using UV light with low-viscosity adhesives, for example, significantly shortening process times in surface lamination. For transparent materials such as transparent films, subsequent crosslinking using UV light is also possible after surface lamination.

[0020] The polymer according to the invention produced by means of monomers having ethylenically unsaturated groups, which is preferably an acrylate polymer, is also referred to below as ethylene-based polymer.

[0021] By modifying the ethylene-based polymer, which is preferably an acrylate polymer, with silanes, the polymer can react with moisture after application and become crosslinked. This increases resistance to heat and certain chemicals. In addition, silanes react with inorganic materials, such as glass or metal, and thereby increase the bond strength. This also expands the field of application of these adhesives. Under the influence of additional heat, crosslinking can be accelerated and a permanently tacky adhesive polymer film is formed. In addition, the production of reactive adhesives is also possible that do not contain monomeric isocyanates and are therefore exempt from hazardous substances. This enables safe handling of the adhesives and does not require any complex measures during use.

[0022] The polymers can be used for adhesives, sealants and coatings, reactive hot melt pressure sensitive 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.

[0023] The technical concept of the invention is based on the modification of ethylene-based polymers, especially acrylate polymers, with silanes to improve their property profile. Possible improvements include the following:

[0024] • Increase in temperature resistance through cross-linking of the silanes.

[0025] • A reaction of the silanes with inorganic substrates to improve adhesion to them.

[0026] Possible production of products with isocyanate monomer concentrations below 0.1%, which are therefore exempt from labeling. Particularly fast initial strength, controllable by UV light.

[0027] The invention offers several advantages over the prior art. Thermoplastic acrylate polymers are converted into reactive polymers that react with moisture to form thermosets, thus offering greater resistance to heat and specific chemicals. Since the silane groups are randomly distributed throughout the polymer and not just terminally, as is the case with polyaddition products or subsequent silanization, the crosslinking density and thus the durability of the material is increased. Silanes also offer the possibility of reacting with inorganic materials such as glass or metals to increase the bond strength to these materials, which broadens the adhesion spectrum or enables the bonding of inorganic materials with organic materials such as plastics. Furthermore, three synthesis routes are available, which also enable the production of materials without isocyanate monomers.This means that these products are exempt from labeling and are not subject to any restrictions.

[0028] The present polymer composition can be used as a novel intermediate for the production of various polyurethanes. In particular, the following possibilities arise:

[0029] • Preparation of a silane-modified ethylene-based polymer (preferably as an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, with subsequent conversion of the polyol or the prepolymer with terminal NCO groups to a thermoplastic polyurethane.

[0030] • Preparation of a silane-modified ethylene-based polymer (preferably as an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, with subsequent conversion of the polyol or the prepolymer with terminal NCO groups to a reactive polyurethane.

[0031] • Production of a silane-modified ethylene-based polymer (preferably as an acrylate polymer) in a polyol or in a prepolymer with terminal NCO groups, with subsequent conversion of the polyol or the prepolymer with terminal NCO groups to a reactive polyurethane, which is then converted with aminosilanes or mercaptosilanes to a silane-terminated polyurethane.

[0032] The Invention in Detail The inventive polymerization of monomer type A with monomer types B and C is generally carried out by bringing all monomers together into the reaction vessel and allowing them to react randomly according to their relative concentrations and relative reactivity, so that random polymers are formed. However, to increase or decrease the non-uniformity of the polymers, one or more of the ethylenically unsaturated monomers can also be added during the polymerization.

[0033] It is conceivable that the monomers according to monomer type A to monomer type C are added in stages, so that the radical polymerization is initiated after the addition of a defined mixture of monomer type A to monomer type C. Only after polymer formation, which is accompanied by almost complete consumption of the monomers, is a defined mixture of monomer type A to monomer type C added to the reaction mixture. This stepwise addition prevents overheating of the reaction mixture due to the exothermic polymerization reaction.

[0034] 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.

[0035] It is preferred if the weight ratio of monomer type A to monomer type C defined in the first step is also maintained in the second addition.

[0036] 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 in particular between 1:3 and 1:7.

[0037] 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 in particular between 1:35 and 1:7.

[0038] Accordingly, it is conceivable that the amount of monomer type C in the second step is greater than the amount of monomer type C in the first addition. The quantitative ratio of monomer type C in the first addition to monomer type C in the second addition is preferably between 1:1 and 1:10, more preferably between 1:2 and 1:8 and in particular between 1:35 and 1:7. In optional step (c) of the process, the mixture from step b), which contains the low molecular weight polymer as a result of the radical polymerization, is heated such that partial crosslinking of the polyol or the prepolymer with terminal NCO groups with the low molecular weight polymer occurs. 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.

[0039] In the optional step (c), the silane groups can alternatively or additionally react with each other. This reaction also results in a polymer composition with increased temperature resistance.

[0040] According to the invention, a polyol or a prepolymer with terminal NCO groups is used in the process for producing the polymer composition.

[0041] With regard to the polyol, this should be understood to mean that at least one polyol can be used, i.e., two, three, four, or even more polyols. Preferably, exactly one polyol is used in the process.

[0042] Advantageously, the polyol used in the process according to the invention has a water content of not more than 0.1% by weight and preferably not more than 0.05% by weight.

[0043] Suitable polyols are selected from the group consisting of polyester, polyether polyols such as polyethylene oxide or polypropylene oxide, hydroxyl-containing polycaprolactone, polyoxyalkylene polyol (synonymous with the term “polyglycol”), 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.

[0044] Polyether polyols such as diols with a molecular weight of 400 to 4000 g / mol, or polypropylene glycol are particularly suitable.

[0045] Suitable polyols include the high-molecular-weight polyoxyalkylene polyols mentioned above, preferably polyethylene oxides or polyoxypropylene diols with an unsaturation level of less than 0.02 mEq / g and a molecular weight in the range of 400 to 18,000 g / mol, especially those with a molecular weight in the range of 1,000 to 4,000 g / mol. PPG 2000 or PPG 4000 are particularly suitable. To achieve a higher crosslinking density, higher-functional alcohols such as triols and tetraols can also be used. Examples include glycerol, trimethylolpropane, and pentaerythritol.

[0046] 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 an initiator molecule having two or more active hydrogen atoms such as, for example, water, ammonia or compounds having one or more OH or NH groups such as, for example, 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.

[0047] Particularly suitable polyester polyols are those which are prepared from di- to trihydric, in particular 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 ester, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, with organic di- or tricarboxylic acids, in particular dicarboxylic acids, or their anhydrides or Esters such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic 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 acid,Trimellitic acid and trimellitic anhydride, or mixtures of the aforementioned acids, as well as polyester polyols made from lactones such as e-caprolactone and starters such as the aforementioned di- or trihydric alcohols.

[0048] It is also conceivable to use polycarbonate polyols, such as those obtainable by reacting, for example, the above-mentioned alcohols used to construct the polyester polyols with dialkyl carbonates, diaryl carbonates or phosgene.

[0049] Also suitable are polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil; or polyols obtained by chemical modification of natural fats and oils - so-called oleochemical polyols, for example the 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 linking, for example by transesterification or dimerization, of the degradation products thus obtained 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, in particular the methyl esters (FAME), which can be derivatized to hydroxy fatty acid esters, for example, by hydroformylation and hydrogenation.

[0050] It is also conceivable to use polyhydrocarbon polyols. These are also called oligohydrocarbonols and include, for example, polyhydroxy-functional polyolefins, polyisobutylenes, and polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene, or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 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.

[0051] In addition to these polyols, small amounts of low molecular weight di- 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-value alcohols, low molecular weight alkoxylation products of The aforementioned di- and polyhydric alcohols, as well as mixtures of the aforementioned alcohols, are used in the production of the polyurethane polymer containing isocyanate groups.

[0052] 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 polyphenyleneamine; 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.

[0053] In the process for producing the polymer composition, a prepolymer with terminal NCO groups can also be used. This means that at least one corresponding prepolymer can be used, i.e., two, three, four, or even more prepolymers. Preferably, exactly one prepolymer with terminal NCO groups is used in the process.

[0054] According to one advantage, the prepolymer with terminal NCO groups can have a molar ratio of NCO to OH groups of between 1.5 to 1 and 2.0 to 1.

[0055] In one embodiment, the NCO-terminated prepolymer is prepared by reacting a diol with diisocyanate.

[0056] Suitable polyols are selected from the group consisting of polyester, hydroxyl-containing polycaprolactone, polyglycols, monosubstituted glycol esters, polythioethers, polyamide, polyesteramide, polycarbonate, polyacetal, polyhydrocarbon polyol, polyacrylate polyol, polymethacrylate polyol, polyalcohol, bisphenol, polycarbonate polyol, polyhydroxy-functional fats and oils and mixtures thereof.

[0057] Diols, polyethylene oxides or polypropylene oxides are particularly suitable.

[0058] Suitable polyols include the high-molecular-weight polyglycols mentioned above, preferably polyethylene oxides or polyoxypropylenediols with a degree of unsaturation below 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 particularly suitable.

[0059] A mixture of polyols can also be used. This is advantageously a mixture of two or more polyethylene oxides or a mixture of two or more polyoxypropylene diols. A mixture of PPG 1000 and PPG 400 is particularly advantageous. Diisocyanates familiar to those skilled in the art for the production of polyurethane polymers can be used to produce the prepolymer with terminal isocyanate groups.

[0060] It may further be 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,

[0061] Hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene-1,3-diisocyanate,

[0062] 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, 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 preferred, and 4,4'-diphenylmethane diisocyanate (4,4'-MDI) is particularly preferred.

[0063] In the radical polymerization process, an initiator that is a peroxide initiator or an azo initiator can be used. Preferred initiators are dilauroyl peroxide, dibenzoyl peroxide, dimethyl 2,2'-azobisisobutyrate, di-(4-tert-butylcyclohexyl) peroxydicarbonate, and azobis(isobutyronitrile). The use of dilauroyl peroxide is preferred.

[0064] During the photoreaction, monomer type A can serve as a co-initiator for UV curing through radical formation due to hydrogen radical abstraction. Tertiary amines or mercapto compounds can serve as additional co-initiators.

[0065] It is also conceivable that an auxiliary substance and / or additive is added to the reaction mixture in the process according to the invention. Examples include surfactants, fillers, other flame retardants, nucleating agents, oxidation stabilizers, lubricants and demolding aids, dyes and pigments, optionally stabilizers, e.g., to protect against hydrolysis, light, heat, or discoloration, inorganic and / or organic fillers, reinforcing agents, and plasticizers. Suitable auxiliary substances and additives can be found, for example, in the Kunststoffhandbuch, Volume 7 "Polyurethane," Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag, Munich, Vienna, 1993.

[0066] To adjust the viscosity, a solvent can also be added to the reaction mixture at any time 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. In the case of a polyol, addition after the end of the radical polymerization is advantageous.

[0067] To accelerate the reaction, a catalyst can be added to the reaction mixture in the process according to the invention.

[0068] 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 here are sterically hindered primary, secondary or tertiary amines, such as, for example, dicyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-a-phenylethylamine, tris-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di-t-butylamine, cyclohexyl-t-butylamine, de-sec-butylamine, dicyclopentylamine, di-a-trifluoromethylethylamine, di-(a-phenylethyl)amine, triphenylmethylamine, and 1,1,-diethyl-n-propylamine.Other sterically hindered amines include morpholines, imidazoles, ether compounds such as dimorpholinodiethyl ether or dimorpholinodimethyl ether; N-ethylmorpholine, N-methylmorpholine, bis(dimethylaminoethyl) ether, imidizoles, N-methylimidazoles, 1,2-dimethylimidazoles, N,N,N',N',N",N"-pentamethyldiethylenetriamine, N,N,N',N',N",N"-pentaethyldiethylenetriamine, N,N,N',N',N",N"-pentamethyldipropylenetriamine, bis(diethylaminoethyl) ether and bis(dimethylaminopropyl) ether.

[0069] According to the invention, monomer type A is an ethylenically unsaturated monomer containing no active hydrogen and having no moisture-reactive functional groups. According to the invention, a monomer of monomer type A is used in the process for preparing the polymer composition. This is to be understood as meaning that at least one monomer of this type can be used here, i.e., two, three, four, or even more monomers of type A. Preferably, two monomers of monomer type A are used in the process.

[0070] Examples of monomer type A are selected from the group consisting of C1 to C12 esters of acrylic acid or methacrylic acid such as glycidyl acrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, diethylhexyl 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.

[0071] Particularly suitable as monomer type A is n-butyl methacrylate or diethylhexyl acrylate or a mixture thereof.

[0072] Monomer type A preferentially acts as a co-initiator in the photoreaction. Through hydrogen abstraction, it is converted into a radical, and reaction with the radical of monomer type C preferentially forms a covalent bond between these monomers.

[0073] According to the invention, monomer type B is an ethylenically unsaturated monomer containing no active hydrogen which has a moisture-reactive functional group.

[0074] 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 here, i.e. also two, three, four, or even more monomers of type B. Preferably, exactly one monomer of monomer type B is used in the process.

[0075] It is furthermore 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, which have a moisture-reactive functional group.

[0076] A suitable moisture-reactive group is the isocyanate group or the silane group. Monomer type B preferably has a silane group as the moisture-reactive group. Advantageously, the invention can provide that the 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 methyacryloxypropylmethyldimethoxysilane, 3 methacryloxy-propyl-tris(2 methoxyethoxy)silane, 4-(3 trimethoxysilylpropyl)benzylstyrene sulfonate, allyltriethoxysilane, allyltrimethoxysilane and oligomers of these silanes.,

[0077] Methacryloxypropyltrimethoxysilane is particularly suitable as monomer type B.

[0078] According to the invention, monomer type c is an ethylenically unsaturated monomer containing no active hydrogen and having a radical photoinitiator group. A radical photoinitiator group is defined in the context of the present invention as a functional group that decomposes in a photolysis reaction after absorbing UV light, thus forming a radical as a reactive species that can start (initiate) a polymerization reaction.

[0079] According to the present invention, the term "UV light" is defined as light with a wavelength of less than 400 nm. Thus, subranges of the UV light claimed here are UVA radiation with a wavelength of between 315 and 400 nm, UVB radiation with a wavelength of between 280 and 315 nm, and UVC radiation with a wavelength of between 100 and 280 nm. Preferably, UVA and / or UVB radiation is used for UV-induced photolysis and thus for UV-induced curing.

[0080] According to the invention, a monomer of monomer type C 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 here, i.e. also two, three, four or even more monomers of type C. Preferably, exactly one monomer of monomer type C is used in the process.

[0081] In a preferred embodiment, the radical photoinitiator group of monomer type C is a radical photoinitiator group of type II. Type II photoinitiators abstract a hydrogen atom from a neighboring molecule.

[0082] This then triggers chain polymerization.

[0083] The radical photoinitiator group of type II is preferably a benzophenone group or an isopropylthioxanthone group.

[0084] Advantageously, the invention can provide that the monomer type C is selected from the group consisting of 4-methacryloyloxybenzophenone, 4-methacryloyloxyethoxybenzophenone, 4-methacryloyloxy-4'-methoxybenzophenone, 4-methacryloyloxyethoxy-4'-methoxybenzophenone, 4-methacryloyloxy-4'-bromobenzophenone, 4-acryloyloxyethoxy-4'-bromobenzophenone, 4-acryloyloxybenzophenone (ABP), 4-(2-acryloyloxyethoxy)benzophenone (AEBP), 4-(2-acryloyloxybutoxy)benzophenone (ABBP), 4-(2-acryloyloxyhexoxy)benzophenone (AHBP).

[0085] ABP or 4-methacryloyloxybenzophenone are particularly suitable as monomer type C.

[0086] According to the invention, a chain transfer agent is used in the radical polymerization process to reduce the average degree of polymerization of the final polymer and obtain a low-molecular-weight polymer. Chain transfer agents for radical polymerizations are known to those skilled in the art.

[0087] It may be advantageous if, within the scope of the invention, the chain transfer agent is a halogen-organic compound, an unsaturated aromatic compound or a thiol, which is preferably selected from the group consisting of tetrachloromethane, 2,4-diphenyl-4-methyl-1-pentene, dodecyl mercaptan, lauryl mercaptan, thioglycolic acid, octyl thioglycolate and thioglycerol.

[0088] The preferred chain transfer agent is dodecyl mercaptan.

[0089] Furthermore, it is conceivable that in the process for producing the polymer composition, the polyol is present in an amount of 20% by weight to 90% by weight, preferably 40% by weight to 80% by weight and particularly preferably 50% by weight to 60% by weight, based on the total weight of the polyol components, monomer types A to C.

[0090] 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% by weight to 90% by weight, preferably from 40% by weight to 80% by weight and particularly preferably from 50% by weight to 60% by weight, based on the total weight of the components prepolymer, monomer type A, monomer type B and monomer type C.

[0091] In a further possibility, it can be provided that in the process for producing the polymer composition, the monomer type A is present in an amount of 30% by weight to 95% by weight, preferably 50% by weight to 90% by weight and particularly preferably 70% by weight to 85% by weight, based on the total weight of the monomer types A to C.

[0092] It may further be possible for the monomer type B to be present in the process for preparing the polymer composition in an amount of from 5% by weight to 70% by weight, preferably from 10% by weight to 50% by weight, and particularly preferably from 15% by weight to 30% by weight, based on the total weight of the monomer types A to C.

[0093] In a further possibility, it can be provided that in the process for producing the polymer composition, the monomer type C is present in an amount of 0.1% by weight to 5.0% by weight, preferably from 0.2% by weight to 4.0% by weight and particularly preferably from 0.3% by weight to 3.0% by weight, based on the total weight of the monomer types A, B and C.

[0094] According to a further advantage, it can be provided that the low molecular weight polymer has a number-average molecular weight 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.

[0095] In a second aspect, the invention relates to a polymer composition which can be produced or is produced by the process according to the invention.

[0096] The inventive synthesis of the silane-modified ethylene-based polymer in a polyol results in 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 inventive polymer composition is advantageous for the physicochemical properties. Thus, it exhibits increased temperature resistance and also improved oil barrier properties. If the optional step (c) is carried out in the inventive process, this polymer composition is characterized in that the polyol or the prepolymer is partially crosslinked with the low-molecular-weight polymer formed by radical polymerization.

[0097] Preferably, the polymer composition may have a glass transition temperature of between -50 and 100 °C, preferably between -40 and 70 °C and particularly preferably between -30 and 60 °C.

[0098] A further advantage can be achieved within the scope of the invention if it has a viscosity of 500 to 25,000 mPa.s, and preferably of 1,000 to 21,000 mPa.s measured at 90°C.

[0099] It can be advantageous if the polymer composition in the context of the invention is free of solvents. Further reaction with a polyisocyanate to form a polyurethane produces a solvent-free PU polymer.

[0100] The invention also provides for the use of the polymer composition according to at least one of the preceding claims as an adhesive, sealant, or coating agent. In particular, the polymer composition, as a one-component composition, cures with moisture and by increasing the temperature to more than 100°C.

[0101] The invention also provides a process for producing a UV- and moisture-curing polyurethane hot melt adhesive composition, the process comprising 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, and d) irradiating with UV light to further crosslink the polymer.

[0102] Through the inventive synthesis of the silane-modified ethylene-based polymer in a polyol, a polyurethane hotmelt adhesive composition with improved properties is obtained through the use of the inventive polymer composition compared to a silane-modified ethylene-based polymer synthesized in the PU prepolymer. Thus, the inventive PU hotmelt exhibits higher temperature resistance, increased chemical resistance, and improved adhesion to inorganic materials. Furthermore, the resulting polymer composition exhibited improved barrier properties for oil. The use of monomer type C also makes the polymer UV-curable, enabling rapid curing.

[0103] Commercially available polyisocyanates, especially diisocyanates, can be used as polyisocyanates for the production of the polyurethane polymer.

[0104] It may further be possible that the polyisocyanate is selected from the group consisting of ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 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, diphenylsulfone 4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanato-triphenylmethane, 1,3,5-T riisocyanato-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 and precondensates of the aforementioned isocyanates.

[0105] Examples of precondensates include HDI biuret and HDI cyanurate.

[0106] The polyisocyanate is preferably an aliphatic isocyanate.

[0107] Advantageously, within the scope of the invention, it can be provided 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%.

[0108] According to a further possibility, the isocyanate index in this process can be between 0.5 and 10, preferably between 1 and 3, and particularly preferably between 1.5 and 2.5. According to the optional step c), the UV- and moisture-curing polyurethane hot-melt adhesive composition obtained in step b) can be converted into a silane-terminated polyurethane by adding an aminosilane or a mercaptosilane.

[0109] According to the invention, an aminosilane or a mercaptosilane is used in step c). This means that at least one aminosilane or one mercaptosilane can be used here, i.e., two, three, four, or even more aminosilanes or mercaptosilanes can be used. Preferably, exactly one aminosilane or exactly one mercaptosilane is used in the process.

[0110] Preferably, the aminosilane is an aminosilane AS of formula (I),

[0111] The rest R 1represents a linear or branched, monovalent hydrocarbon radical having 1 to 12 C atoms, which optionally contains one or more CC multiple bonds and / or optionally cycloaliphatic and / or aromatic moieties. In particular, R 1 for a methyl, ethyl or isopropyl group.

[0112] The rest R 2 represents an acyl radical or a linear or branched, monovalent hydrocarbon radical having 1 to 12 C atoms, which optionally contains one or more CC multiple bonds and / or optionally cycloaliphatic and / or aromatic moieties. Preferably, the radical R 2 for an acyl or alkyl group having 1 to 5 C atoms, in particular for a methyl or for an ethyl or for an isopropyl group.

[0113] The rest R 3represents a linear or branched, divalent hydrocarbon radical having 1 to 12 C atoms, which optionally contains cyclic and / or aromatic moieties, and optionally one or more heteroatoms. Preferably, the radical R 3 for an alkylene radical having 1 to 3 C atoms, in particular having 3 C atoms.

[0114] Furthermore, the index a stands for a value of 0, 1 or 2, in particular for 0 or 1 .

[0115] The rest R 4 represents a hydrogen atom or a linear or branched hydrocarbon radical having 1 to 20 C atoms, which may or may not contain cyclic moieties, or represents a radical of the formula (II).

[0116] The residues R 6 and R 7 independently of one another represent a hydrogen atom or a radical from the group comprising -R 9 , -CN and -COOR 9 .

[0117] The rest R 8stands for a hydrogen atom or for a radical from the group comprising -CH2-COOR 9 , -COOR 9 , -CONHR 9 , -CON(R 9 )2, -CN, -NO2, -PO(OR 9 )2, -SO2R 9 and - SO2OR 9 .

[0118] The rest R 9 represents a hydrocarbon radical having 1 to 20 C atoms, optionally containing at least one heteroatom.

[0119] Examples of suitable aminosilanes AS of the 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 from 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)-amino-succinic acid dimethyl ester and diethyl ester; and analogues of the aminosilanes mentioned with ethoxy or isopropoxy groups instead of the methoxy groups on the silicon. Particularly suitable as aminosilanes AS are secondary aminosilanes, in particular aminosilanes AS in which R4 in formula (I) is other than H.Preferred are the Michael-like adducts, in particular N-(3-trimethoxysilyl-propyl)-amino-succinic acid diethyl ester.

[0120] In this document, the term "Michael acceptor" refers to compounds which, due to the double bonds they contain, activated by electron acceptor residues, are capable of entering into nucleophilic addition reactions with primary amino groups (NH2 groups) in a manner analogous to the Michael addition (hetero-Michael addition). In a further aspect, the invention relates to a UV- and moisture-curing polyurethane hot-melt adhesive composition that can be produced or is produced by the process disclosed above.

[0121] 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 in particular between 2,000 and 50,000 mPas.

[0122] The invention also provides for the use of the UV- and moisture-curing polyurethane hotmelt adhesive composition according to the invention as an adhesive, sealant, or coating agent. In particular, it is intended that it be used as an adhesive.

[0123] The invention also provides a process for producing a 1-component polyurethane adhesive, comprising the following steps: a) providing the polymer composition according to the invention, wherein, during its production, instead of increasing the temperature in optional step c), the polymer is cooled to a temperature of 80 to 20°C; b) adding a polyisocyanate according to the invention in order 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.

[0124] Commercially available polyisocyanates, preferably diisocyanates and especially aliphatic diisocyanates, can be used as polyisocyanates for the production of the polyurethane polymer.

[0125] It may further be 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, 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-T riisocyanato-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), as well as any mixtures of the aforementioned isocyanates.

[0126] In a preferred embodiment, a diphenylmethane isocyanate (MDI) or polymeric diphenylmethane diisocyanate (PMDI) is used as the polyisocyanate.

[0127] 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 be used, which is then preferably 4,4'-diphenylmethane diisocyanate.

[0128] Polymeric diphenylmethane diisocyanate (PMDI), also known as technical MDI, is a mixture of methylene diphenyl isocyanates and homologous aromatic polyisocyanates. However, the term "polymeric diphenylmethane diisocyanate" is technically incorrect, as it is not a polymer, but rather a mixture of compounds containing several (typically up to six) phenylene groups, each carrying an isocyanate group. A common trade name is also polymethylene polyphenyl isocyanate.

[0129] According to an advantageous development of the invention, it can be provided that the free isocyanate content adjusted in step b) of the process is between 2 and 40%, preferably between 5 and 30% and particularly preferably between 10 and 20%.

[0130] Furthermore, it is conceivable within the scope of the invention 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.

[0131] In a further aspect, the invention relates to a 1-component polyurethane adhesive which can be produced or is produced by the method disclosed above.

[0132] According to a further possibility, the 1-component polyurethane adhesive can 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. The invention also relates to the use of the 1-component 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 aircraft, military or shipbuilding sectors.

[0133] In a further aspect, the invention relates to a polyurethane composition comprising a) 5 to 90 wt.% of a urethane polymer or urethane prepolymer prepared by addition polymerization of a polyisocyanate and a polyol; b) 10 to 95 wt.% of a low molecular weight polymer of ethylenically unsaturated monomers containing no active hydrogen, wherein at least one of the monomers is an ethylenically unsaturated monomer having a siloxane group.

[0134] 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 ethylenically unsaturated monomer having a siloxane group.

[0135] In a preferred embodiment of the invention, the polyurethane composition is characterized in that the ethylenically unsaturated monomer having a siloxane group is a silane-modified acrylate.

[0136] In a second aspect, the invention relates to the use of an ethylenically unsaturated monomer having a siloxane group for copolymerization with ethylenically unsaturated monomers which do not contain active hydrogen in a polyol or in a prepolymer having the terminal NCO groups as solvent.

[0137] In one embodiment of the invention, the use is characterized in that the ethylenically unsaturated monomer having a siloxane group is a silane-modified acrylate.

[0138] In an additional aspect, the invention relates to an acrylate copolymer comprising: a) 5 to 95 wt.% of one or more acrylate monomers containing no 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 having a siloxane side group, preferably a 3-methacryloxypropyltrimethoxysilane.

[0139] In a further aspect, the invention relates to a process for producing a 2K polyurethane adhesive, the process comprising the following steps: a. Providing the polymer composition according to the invention, wherein instead of increasing the temperature in optional step b. of the process, the polymer is cooled to a temperature of 80 to 20°C and the polymer composition has epoxy groups, either introduced via one of the monomers A to C, which additionally have an epoxy group as a functional group or introduced via a further ethylenically unsaturated monomer which does not contain active hydrogen and has an epoxy group as a functional group (monomer type D); b. Addition of a polyisocyanate in order to achieve a desired free isocyanate content and desired isocyanate index; c. Optional cooling to a temperature of 80 to 20°C for a period of 0.5 to 5 hours.

[0140] Through these process steps a. to c, the first component of the 2K polyurethane adhesive is produced, which can then be reacted with an epoxy-reactive monomer or prepolymer as the second component of the 2K polyurethane adhesive.

[0141] In the claimed process for producing a 2-component polyurethane adhesive, the second epoxy-reactive component is preferably an amine compound. The skilled person can use known amine compounds suitable for reaction with the epoxy, such as diamines, polyamines, aliphatic amines, aromatic amines, primary amines, or secondary amines. Furthermore, a prepolymer with terminal reactive groups such as an amine group, hydroxyl group, and thiol group can be used, with prepolymers having terminal isocyanate groups being used.

[0142] In a further aspect, the invention relates to a 2K polyurethane adhesive produced by the method described above.

[0143] The invention also relates to the use of the 2-component 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 aircraft, military or shipbuilding sectors.

[0144] Definitions

[0145] 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.

[0146] The term "polymer" in this document encompasses, on the one hand, a collective of chemically uniform macromolecules that differ in terms of degree of polymerization, molecular weight, and chain length, which were produced by a polyreaction (polymerization, polyaddition, polycondensation). On the other hand, the term also encompasses derivatives of such a collective of macromolecules from polyreactions, i.e., compounds that were obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which may be chemically uniform or chemically heterogeneous. The term also encompasses copolymers and so-called prepolymers, i.e., reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.

[0147] The term "copolymer" in this document refers to a polymer composed of two or more different monomer units. This distinguishes a copolymer from a homopolymer, which is composed of only one (real or imaginary) monomer type and, accordingly, has only one repeating unit. Copolymers can be divided into five classes:

[0148] 1 .) statistical copolymers, in which the distribution of the two monomers in the chain follows a statistical distribution,

[0149] 2.) Gradient copolymers, which are in principle similar to statistical copolymers, but in which the proportion of one monomer increases and the other decreases along the chain,

[0150] 3.) Alternating copolymers, in which the two monomers alternate,

[0151] 4.) Block copolymers and segment copolymers consisting of longer sequences or

[0152] blocks of each monomer, and

[0153] 5.) Graft copolymers, in which blocks of one monomer are grafted onto the backbone of another monomer.

[0154] The term "polyurethane polymer" encompasses all polymers produced by the so-called diisocyanate polyaddition process. This also includes polymers that are almost or completely free of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates, and polycarbodiimides.

[0155] In this document, an "active hydrogen" is understood to mean a hydrogen bonded to N, O, or S (synonymously also referred to as "Zerewitinoff-active hydrogen") if it yields methane by reaction with methylmagnesium iodide according to a process discovered by Zerewitinoff. Typical examples of compounds with active hydrogen are compounds containing carboxyl, hydroxyl, amino, imino, or thiol groups as functional groups.

[0156] Accordingly, the monomer that does not contain active hydrogen (monomer type B) is a monomer that does not contain any carboxyl, hydroxyl, amino, imino or thiol groups.

[0157] 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 containing it. Chemical compounds that carry the same functional groups are grouped into substance classes due to their often similar properties.

[0158] In this document, a "moisture-reactive functional group" is understood to mean a functional group that reacts with water. This reaction can lead to the crosslinking of two or more such groups and thus to the curing of the corresponding polymer. Those skilled in the art are familiar with moisture-reactive (curable) groups in the field of polymers. Examples include the silane group and the isocyanate group.

[0159] In this document, a "UV-curing composition" is understood to mean a polymer composition (preferably a polyurethane adhesive) which cures at least partially upon irradiation with UV light due to the presence of radical photoinitiator groups in the polymer.

[0160] A "radical photoinitiator group" is defined in the context of the present invention as a functional group that decomposes in a photolysis reaction after absorbing UV light, thus forming radicals as reactive species that can start (initiate) a polymerization reaction. The term "UV light" is defined according to the present invention as light with a wavelength of less than 400 nm. Thus, subranges of the UV light claimed here are UVA radiation with a wavelength of between 315 and 400 nm, UVB radiation with a wavelength of between 280 and 315 nm, and UVC radiation with a wavelength of between 100 and 280 nm. UVA and / or UVB radiation are preferably used for UV-induced photolysis and thus for UV-induced curing.

[0161] 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 groups or acyloxy groups directly bonded to the silicon atom via Si-O bonds, and, on the other hand, have at least one organic radical directly bonded to the silicon atom via a Si-C bond. Such silanes are also known to the person skilled in the art as organoalkoxysilanes and organoacyloxysilanes, respectively.

[0162] Accordingly, the term "silane group" refers to the silicon-containing group bound 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 considered moisture-reactive groups.

[0163] Organosilanes whose organic residue contains an amino group or a mercapto group are called "aminosilanes" or "mercaptosilanes." Aminosilanes that contain a primary amino group, i.e., an NH2 group bonded to an organic residue, are called "primary aminosilanes." Aminosilanes that contain a secondary amino group, i.e., an NH group bonded to two organic residues, are called "secondary aminosilanes."

[0164] In this document, "molecular weight" refers to the molar mass (in grams per mole or in Daltons) of a molecule. "Mean molecular weight" refers to the number average of the molecular weight distribution M. n (Number average). The term "number average molar mass" is also used as a synonym for "average molecular weight."

[0165] In this document, a “low molecular weight polymer” is understood to mean a polymer with an average molecular weight M n of less than 200,000 g / mol. The average molecular weight M n is preferably less than 100,000 g / mol, particularly preferably less than 80,000 g / mol, furthermore particularly preferably less than 60,000 g / mol and in particular less than 20,000 g / mol. The low molecular weight polymer can, for example, have an average molecular weight M n of 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000 and 100,000 g / mol.

[0166] The term "polymeric diphenylmethane diisocyanate" (PMDI) refers to a mixture of methylene diphenyl isocyanates and homologous aromatic polyisocyanates. From a chemical point of view, the term "polymeric diphenylmethane diisocyanate" is a misnomer, as it is not a polymer, but rather a mixture of compounds with several (typically up to six) phenylene groups, each carrying an isocyanate group. A common trade name is also polymethylene polyphenyl isocyanate.

[0167] For the purposes of this application, a "chain transfer agent" is defined as an organic molecule capable of chain transfer. A chain transfer reaction is a reaction during a chain polymerization in which the activity of a growing polymer chain is transferred to another molecule. Chain transfer reactions reduce the average degree of polymerization of the final polymer. Chain transfer agents for free-radical polymerizations are known to those skilled in the art.

[0168] The term "solvent" in this document 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 in the invention are not covered by this definition, although they act as solvents for the monomers and also the low-molecular polymer formed by radical polymerization.

[0169] In this document, "solid" refers to substances that do not change their shape without external influence or are difficult to deform, but in particular, they are not flowable. "Liquid" refers to substances that can be deformed and are flowable, including highly viscous and pasty substances.

[0170] In this document, "one-component" (abbreviated as "1 K") refers to a composition in which all components of the composition are mixed and stored in the same container and which is curable with moisture. In this document, "two-component" refers to a composition in which the components of the composition are present in two different components, which are stored in separate containers. The two components are only mixed together shortly before or during application of the composition, after which the mixed composition cures. Curing only occurs or is completed upon exposure to moisture.

[0171] It should be expressly pointed out that, in the context of this patent application, indefinite articles and indefinite numerical expressions such as "one...", "two...", etc. are generally to be understood as "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. are intended. Furthermore, all numerical expressions and information on process parameters and / or device parameters are to be understood in the technical sense, i.e., subject to the usual tolerances. Even the explicit specification of the restriction "at least" or "at least" or similar does not imply that the simple use of "one", i.e., without specifying "at least" or similar, means "exactly one."

[0172] Unless otherwise stated, the percentages in this document are by weight.

[0173] The embodiments shown here are merely examples of the present invention and should therefore not be considered limiting. Alternative embodiments contemplated by those skilled in the art are equally encompassed within the scope of the present invention.

[0174] Examples of implementation

[0175] 1. Production of a UV-curing polyacrylate as a base formulation

[0176] Based on the formulation of a polyacrylate IC2068 (see Table 1), the copolymerizable photoinitiator 4-methacryloxybenzophenone was varied in proportions of 1-5% in these experiments, thus producing the polyacrylate batches IC2068-7 to IC2068-11. The ratio of diethylhexyl acrylate to 4-methacryloxybenzophenone varied from 12:1 to 2.4:5.

[0177] To produce a radiation-curing polyacrylate (and alternatively a polysilane acrylate), the solvent polyether polyol is heated to 90 °C in a glass reactor under a nitrogen atmosphere. During heating, the monomers and initiator are added over 30 minutes. Once the temperature reaches 90 °C, stirring is continued for 30 minutes. The monomers and initiator are then added over 2 hours at 90 °C. The post-reaction then takes place over 2 hours with further addition of the initiator.

[0178] Table 1 : Polyacrylate batches IC2068-07 to -11

[0179] (PPG 1000 = polypropylene glycol MW = 1000)

[0180] Viscosity differs little within the test series (see Table 2). Tack measurements using an oscillation and rotation rheometer also confirm the assumption that the amount of 4-methacryloxybenzophenone used initially has little influence on the technical parameters.

[0181] 2. Rheological characterization of UV-curing polyacrylates

[0182] The polyacrylates IC2068-7 to IC2068-11, prepared according to Table 1, were subjected to rheological testing. First, the viscosity was determined at a temperature of 90°C in a Brookfield CAP2000+ viscometer (AMETEK GmbH, Meerbusch, Germany). In addition, the tack was determined at a polymer temperature of 90°C in an MCR 302 oscillation and rotation rheometer (Anton Paar, Graz, Austria) under the following conditions: PP2 plate, gap: 0.1 mm, pre-shear rate: 1000 1 / s. The results are presented in Table 2.

[0183] Table 2: Measurement results for the polyacrylates of the test series IC2068

[0184] As the results listed in Table 2 show, the viscosity hardly differs within the test series. Tack measurements using an oscillation and rotation rheometer also verify the assumption that the amount of 4-methacryloxybenzophenone used initially has little influence on the technical parameters of the polyacrylate polymer. This provides the technological basis for the production of silane-modified polyacrylates.

[0185] 3. Conversion of UV-curing polyacrylates to polyurethane

[0186] To produce a polyurethane adhesive, the polyacrylates IC2068-7 to IC2068-11 prepared according to Table 1 were reacted with 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and additives (UV marker, defoamer, stabilizers) according to Table 3 to form the UV-curable polyurethane prepolymers UV-10 to UV-14. Additional polyols and additives can be added to the polyacrylate / polysilane acrylate at 90 °C. Homogenization takes place for 45 minutes at approximately 10 mbar. The 4,4'-MDI is then added and stirred for 60 minutes. Before filling, the polyurethane adhesive is degassed again at approximately 10 mbar.

[0187] Table 3: Test approaches UV 10 to UV 14

[0188] 4. Rheological characterization of UV-curing polyurethanes

[0189] The polyurethane adhesives UV 10 to UV 14, prepared according to Table 31, were subjected to rheological testing. First, the viscosity was determined at a temperature of 90°C in a Brookfield CAP2000+ viscometer (AMETEK GmbH, Meerbusch, Germany) (spindle 1.5 rpm). In addition, the tack was determined in an MCR302 oscillation and rotation rheometer, also at a polymer temperature of 90°C, under the following conditions: PP12 platen, gap: 0.1 mm, pre-shear rate 1000 1 / s. The results are presented in Table 4.

[0190] Table 4: Measurement results for polyurethane adhesives UV 10 to UV 14 As the measurement results in Table 4 show, the UV-active polyurethane adhesives UV 10 to UV 14 have a low viscosity when applied at 90 °C and are characterized by low inherent tack.

[0191] 5. UV-induced bonding of UV-curing polyurethanes

[0192] The effectiveness of UV activity was investigated in more detail using a 180° peel test and a loop-tack test (based on DIN EN 1713) with the aid of a traction machine within the UV 10 to 14 test series (see Figures 1 and 2). Adhesives were applied to an aluminum foil (foil thickness = 30 μm) at 90 °C in a layer thickness of 50 μm, exposed to UV light (UV belt dryer UN50029, Technigraf, Gräfenwiesbach, Germany, wavelength range = 200 to 400 nm), then bonded directly to a glass plate and rolled with a 2 kg hand roller. After 10 minutes, the tests were carried out on the traction machine. With a UV exposure time of 10 s, an energy quantity of approximately 800 J / cm is generated, whereas with 20 s an energy quantity of approximately 1,600 J / cm is generated.

[0193] The results shown in Figures 1 and 2 can be summarized as follows: The higher the photoinitiator content, the lower the required energy input via UV exposure and the less yellowing of the polyurethane adhesive. UV 10 therefore represents the optimal formulation, particularly with regard to the five-fold increase in surface tack and the increase in bond strength. The successful findings were successfully transferred to the use of UV silane acrylates in the PU system. This was produced in a further test.

[0194] 6. Preparation of a UV-curing silane-modified polyacrylate

[0195] Based on the polymerization of acrylate polymers in polyols, the base formulation IC2068-8 (Table 1) was modified by using a silane-containing methacrylate monomer to obtain the UV- and moisture-curable silane-acrylate IC2068-12. The organofunctional 3-methacryloxypropyltrimethoxysilane was used at 3.0%. The formulation and reaction procedure are shown in Table 5.

[0196] To produce a silane-modified acrylate polymer, the initial mixture is heated to 90 °C in a glass reactor under a nitrogen atmosphere. After 30 minutes, the monomers are added over a period of 2 hours at 90 °C, and the initiator is added. The reaction then continues for 2 hours with the additional addition of the initiator.

[0197] Table 5: Formulation of the UV-curing silane-modified acrylate UV2068-12

[0198] 7. Rheological characterization of the UV-curing silane-modified polyacrylates The UV-curing silane-modified polyacrylate variant IC2068-12 was also rheologically tested using the same method in comparison to the base formulation IC2068-8:

[0199] Table 6: Measurement results for the UV-curing silane-modified polyacrylate IC2068-12 Similar properties can be determined based on rheological studies. 8. Conversion of UV-curing silane-modified polyacrylates to polyurethane

[0200] In order to produce a polyurethane adhesive, the polyacrylate IC2068-12 prepared according to Table 5 was reacted with 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and additives according to Table 7 to form the UV-curable polyurethane prepolymer UV 15. In this case, further polyols and

[0201] Additives are added at 90 °C. Homogenization takes place for 45 minutes at approximately 10 mbar. The 4,4'-MDI is then added and stirred for 60 minutes. Before filling, the polyurethane adhesive is degassed again at approximately 10 mbar.

[0202] Table 7: Test approach UV 15

[0203] 9. Rheological characterization of UV-curing silane-modified polyurethanes

[0204] The polyurethane adhesive UV 15 prepared according to Table 7 was, in comparison to the

[0205] Basic formulation UV 11, also rheologically tested using the same method:

[0206] Table 8: Measurement results for UV-curing silane-modified

[0207] Polyurethane adhesive UV 15

[0208] Rheological investigations reveal slight modifications in the properties.

[0209] 10. UV-induced bonding of UV-curing polyurethanes

[0210] Using a 180° peel test and a loop tack test (based on DIN EN 1713) with a tensile test machine, the bond strength was investigated as a function of UV irradiation time for the UV-curing silane-modified polyurethane adhesive UV 15 compared to the base formulation UV 11 (see Figures 3 and 4). Adhesives were applied to an aluminum foil (foil thickness = 30 pm) at 90 °C in a layer thickness of 50 μm, exposed to UV light (UV belt dryer UN50029, Technigraf, Gräfenwiesbach, Germany, wavelength range = 200 to 400 nm), then bonded directly to a glass plate and rolled with a 2 kg hand roller. After 10 minutes, the tests were carried out on the tensile test machine. With a UV exposure time of 10 s, an energy quantity of approximately 800 J / cm is generated, whereas with 20 s an energy quantity of approximately 1,600 J / cm is generated.

[0211] As Figures 3 and 4 show, the silane-modified polymer UV 15 exhibits improved bond strength compared to the base formulation UV 11 in both test methods. The optimal UV irradiation time was 20 to 30 seconds.

[0212] FIGURES Showing:

[0213] Fig. 1 shows the UV-induced bonding using a 180° peel test for the

[0214] Table 3 shows polyurethane adhesives UV 10 to UV 14. The bond strength is plotted in Newton as a function of the UV irradiation time in seconds.

[0215] Fig. 2 shows the UV-induced bonding using a loop-tack test for polyurethane adhesives UV 10 to UV 14, prepared according to Table 3. The bond strength is plotted in Newtons as a function of the UV irradiation time in seconds. Fig. 3 shows the UV-induced bonding using a loop-tack test for polyurethane adhesives UV 11 and UV 15, prepared according to Table 7. The bond strength is plotted in Newtons as a function of the UV irradiation time in seconds.

[0216] Fig. 4 shows the UV-induced bonding using a 180° peel test for the polyurethane adhesives UV 11 and UV 15 prepared according to the table. The bond strength is plotted in Newton as a function of the UV irradiation time in seconds.

Claims

Patent claims 1 . A process for preparing a polymer composition comprising the following steps: a) combining: (i) a polyol or a prepolymer having terminal isocyanate (NCO) groups with (ii) an ethylenically unsaturated monomer containing no active hydrogen and having no silane groups (monomer type A), and (iii) an ethylenically unsaturated monomer containing no active hydrogen and having a silane group (monomer type B); (iv) an ethylenically unsaturated monomer containing no active hydrogen and having a radical photoinitiator group (monomer type C); b) polymerizing the mixture from step a. using a radical polymerization process with a chain transfer agent to obtain a low molecular weight polymer having an average molecular weight M nof less than 200,000 g / mol; 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 with the low molecular weight polymer having an average molecular weight M n of less than 200,000 g / mol.

2. The method according to claim 1, characterized in that the polyol is selected from the group consisting of polyester, polyether polyols such as polyethylene oxide or a polypropylene oxide, 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 preferably a polyether polyol with a molecular weight between 400 and 40,000 Da, a polyethylene oxide or a polypropylene glycol.

3. Process according to at least one of claims 1 and 2, characterized in that the monomer type A is selected from the group consisting of C1 to C12 esters of acrylic acid or methacrylic acid such as Glycidyl acrylate, glycidyl methacrylate, 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 preferably n-butyl methacrylate (n-BMA) or methyl methacrylate (MMA) or a mixture thereof. The 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, which contain a silane group.Process according to claim 4, characterized in that the monomer type B is selected from the group consisting of vinyltrichlorosilane, methylvinyldichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2methoxyethoxy)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(2methoxyethoxy)silane-, 4-(3-trimethoxysilylpropyl)benzylstyrenesulfonate, allyltriethoxysilane, allyltrimethoxysilane and oligomers of these silanes, wherein the monomer type B is preferably methacryloxypropyltrimethoxysilane. Process according to at least one of the preceding claims, characterized in that the monomer type C is a monomer with a radical photoinitiator group of type II, which is preferably a benzophenone group or an isopropylthioxanthone group and is particularly preferably selected from the group consisting of 4-methacryloyloxybenzophenone, 4-methacryloyloxyethoxybenzophenone, 4-methacryloyloxy-4'-methoxybenzophenone, 4-methacryloyloxyethoxy-4'-methoxybenzophenone, 4-methacryloyloxy-4'-bromobenzophenone, 4-acryloyloxyethoxy-4'-bromobenzophenone, 4- Acryloyloxybenzophenone (ABP), 4-(2-acryloyloxyethoxy)benzophenone (AEBP), 4-(2-acryloyloxybutoxy)benzophenone (ABBP), 4-(2-acryloyloxyhexoxy)benzophenone (AHBP), and particularly preferably ABP or 4-methacryloyloxybenzophenone.

7. Process according to at least one of the preceding claims, characterized in that a peroxide initiator or an azo initiator is used as initiator in the radical polymerization process, which is preferably selected from the group consisting of dilauroyl peroxide, dibenzoyl peroxide, dimethyl 2,2'-azobisisobutyrate, di-(4-tert-butylcyclohexyl) peroxydicarbonate and azobis(isobutyronitrile).

8. The process according to at least one of the preceding claims, characterized in that the chain transfer agent is a halogen-organic compound, an unsaturated aromatic compound or a thiol, which is preferably selected from the group consisting of tetrachloromethane, 2,4-diphenyl-4-methyl-1-pentene, dodecyl mercaptan (DDM), lauryl mercaptan, thioglycolic acid, octyl thioglycolate, and thioglycerol, and particularly preferably dodecyl mercaptan.

9. Process according to at least one of the preceding claims, characterized in that the polyol or the prepolymer with terminal NCO groups is present in an amount of 20% by weight to 90% by weight, preferably from 40% by weight to 80% by weight and particularly preferably from 50% by weight to 60% by weight, based on the total weight of the components polyol or prepolymer, monomer types A to C.

10. Process according to at least one of the preceding claims, characterized in that the monomer type A is present in an amount of 30% by weight to 95% by weight, preferably from 50% by weight to 90% by weight and particularly preferably from 70% by weight to 85% by weight, based on the total weight of the monomer types A, B and C.

11. Process according to at least one of the preceding claims, characterized in that the monomer type B is used in an amount of 5% by weight to 70% by weight, preferably 10% by weight to 50% by weight and particularly preferably from 15% by weight to 30% by weight, based on the total weight of monomer types A, B and C.

12. Process according to at least one of the preceding claims, characterized in that the monomer type C is present in an amount of 0.1% by weight to 5.0% by weight, preferably from 0.2% by weight to 4.0% by weight and particularly preferably from 0.3% by weight to 3.0% by weight, based on the total weight of the monomer types A, B and C.

13. 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, preferably of 5,000 to 100,000 g / mol and particularly preferably of 10,000 to 60,000 g / mol.

14. Polymer composition prepared by a process according to at least one of the preceding claims.

15. Polymer composition according to claim 14, characterized in that the polymer composition has a glass transition temperature of between -50 and 100 °C, preferably between -40 and 70 °C and particularly preferably between -30 and 60 °C.

16. Polymer composition according to claim 14 or 15, characterized in that the polymer composition has a viscosity of 500 to 25,000 mPa.s, and preferably of 1,000 to 21,000 mPa.s, measured at 90°C.

17. Polymer composition according to at least one of claims 14 to 16, characterized in that it is free from solvents.

18. Use of the polymer composition according to at least one of claims 14 to 17 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.

19. A process for producing a UV and moisture-curing polyurethane hot melt adhesive composition comprising the following steps: a) providing a polymer composition according to at least one of claims 14 to 17; b) Addition of sufficient polyisocyanate to achieve the desired isocyanate content and isocyanate index and polymerization using an addition polymerization process; c) Optional addition of an aminosilane or a mercaptosilane and conversion to a silane-terminated polyurethane; d) Irradiation with UV light to further crosslink the polymer. Process according to claim 19, 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 (HDI), 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, 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, polymeric diphenylmethane diisocyanate (PMDI), block diisocyanates and carbodiimide modified polyisocyanates, and mixtures or precondensates thereof, such as HDI biuret or HDI cyanurate, wherein the polyisocyanate is preferably an aliphatic isocyanate. A process according to claim 19 or 20, characterized in that the free isocyanate content is between 0 and 20%.preferably between 0 and 15%, and particularly preferably between 0 and 10%. A process according to at least one of claims 19 to 21, characterized in that the isocyanate index is between 0.5 and 10, preferably between 1 and 3, and particularly preferably between 1.5 and 2.

5. A UV- and moisture-curing polyurethane hot-melt adhesive composition produced by a process according to at least one of claims 19 to 22.

24. UV and moisture-curing polyurethane hot melt adhesive composition according to claim 23, characterized in that the composition has a viscosity of 10 mPas to 150,000 mPas at 120°C.

25. Use of the UV- and moisture-curing polyurethane hot melt adhesive composition according to claim 23 or 24 as an adhesive, sealant or coating agent.

26. A process for producing a 1-component polyurethane adhesive, comprising the following steps: a) providing a polymer composition according to at least one of claims 14 to 17, wherein, instead of increasing the temperature in optional step b, the polymer is cooled to a temperature of 80 to 20°C; b) adding a polyisocyanate 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.

27. The process according to claim 26, characterized in that in step b) a polyisocyanate according to claim 20 is used, wherein the polyisocyanate is preferably an aliphatic diisocyanate.

28. Process according to claim 26 or 27, characterized in that the free isocyanate content is between 2 and 40%, preferably between 5 and 30% and particularly preferably between 10 and 20%.

29. Process according to at least one of claims 26 to 28, characterized in that the isocyanate index is between 1.5 and 20, preferably between 2 and 15 and particularly preferably between 4 and 10.

30. 1K polyurethane adhesive produced by a process according to at least one of claims 26 to 29.

31. 1 K polyurethane adhesive according to claim 30, characterized in that the 1 K polyurethane adhesive has a viscosity of 5,000 to 25,000 mPa.s, and preferably of 6,000 to 21,000 mPa.s, measured at 90°C. Process for producing a 2K polyurethane adhesive comprising the following steps: a) providing a polymer composition according to at least one of claims 14 to 17, wherein instead of increasing the temperature in optional step b.the polymer is cooled to a temperature of 80 to 20°C and the polymer composition has epoxy groups, either introduced via one of the monomers A to C, which additionally have an epoxy group as a functional group or introduced via another ethylenically unsaturated monomer which does not contain active hydrogen and has an epoxy group as a functional group (monomer type D); b) addition of a polyisocyanate in order 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; for the production of the first component of the 2K polyurethane adhesive with an epoxy-reactive monomer or prepolymer as the second component of the 2K polyurethane adhesive.A process according to claim 32, characterized in that the second component is an amine compound or a prepolymer with terminal isocyanate, hydroxyl, thiol, or amine groups. A 2-component polyurethane adhesive produced by a process according to claim 32 or.

33. Use of a 1-component polyurethane adhesive according to claim 30 or 31 or a 2-component polyurethane adhesive according to claim 34 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, reinforcing fabrics, materials in the aircraft, military or shipbuilding sectors.

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