Radical polymerization of UV-crosslinked silane acrylates in polyurethane matrices containing isocyanate groups

Abstract

The invention relates to a method for producing a polymer composition, in which a silane-modified polymer is polymerized by free-radical chain polymerization with an ethylenically unsaturated monomer and a further ethylenically unsaturated polymer having a free-radical photoinitiator group in a polyol or a prepolymer having terminal isocyanate groups, and to a polymer composition produced by this process. The invention also relates to a method for producing moisture-curable polyurethane hot melt adhesive compositions, 1K polyurethane adhesives and 2K polyurethane adhesives on the basis of the polymer composition according to the invention. The invention also relates to moisture curable polyurethane hot melt adhesive compositions, 1K polyurethane adhesives and 2K polyurethane adhesives produced by these methods.

Description

Technical Field

[0001] The present invention relates to a process for producing a polymer composition in which a silane-modified polymer is polymerized by free radical chain polymerization with an ethylenically unsaturated monomer and another ethylenically unsaturated polymer having a free radical photoinitiator group in a polyol or a prepolymer having terminal isocyanate groups, and to a polymer composition produced by this process. The present invention also relates to a process for producing a moisture-curing polyurethane hot melt adhesive composition, a one-component (1K) polyurethane adhesive and a two-component (2K) polyurethane adhesive based on the polymer composition of the present invention, and to the moisture-curing polyurethane hot melt adhesive composition, 1K polyurethane adhesive and 2K polyurethane adhesive produced thereby. Background Art

[0002] Depending on the application, adhesives may require a long exposure time because the joining process is usually carried out manually. At the same time, rapid adhesion is required after joining because the joined parts need to be further processed as soon as possible. In polyurethane adhesives, this problem can be solved, for example, by using a powdery acrylate polymer in a polyether-based polyurethane. The polyether-based polyurethane enables a long exposure time, while the acrylate polymer ensures a high initial adhesion. Adding acrylates usually causes problems because they introduce a large amount of air and are difficult to dissolve. The solution is to polymerize the acrylate polymer directly in a polyol and then convert it into a polyurethane. This process also allows the use of acrylate polymers with a glass transition temperature below room temperature. In addition, these polymers can be modified with comonomers as needed. However, since acrylate polymers are a thermoplastic and soften at higher temperatures or sometimes have low resistance to certain chemicals, the properties of the adhesive are limited.

[0003] In summary, the use of thermoplastic materials such as acrylate polymers weakens the resistance of reactive adhesives to temperature and certain chemicals. In addition, the adhesion of untreated inorganic materials to polyurethane adhesives causes adhesion problems.

[0004] US 5,021,507 A relates to acrylate-modified reactive polyurethanes and teaches in column 2, lines 58 to 68, that for ethylenically unsaturated monomers having moisture-reactive functional groups, the monomers must be added after the prepolymer is formed and then polymerized only by means of free radical polymerization.

[0005] More prior art can be found in US 5,018,337, WO 2016 / 123418 A1 or WO 01 / 81495 A2.

[0006] The present invention is based on the applicant's PCT / EP2022 / 060648, which relates to the polymerization of a silane-modified polymer formed by free radical chain polymerization in a polyol or a prepolymer having terminal isocyanate groups, and then its use in polyurethane formulations. By using polysilane acrylate in a polyurethane adhesive, the viscosity decreases according to the silane content, and thus the initial strength also decreases. However, the system achieves the opposite effect in terms of the final strength. Moisture crosslinking in the polyurethane adhesive mainly occurs through the reaction of isocyanate groups and, secondarily, through silane groups, resulting in a longer pressing time required for adhesion, which can be a disadvantage in certain applications.

[0007] The present invention is based on the purpose of improving the prior art or providing an alternative. Summary of the Invention

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

[0009] In a first aspect, the present invention relates to a method for producing a polymer composition, which comprises the following steps:

[0010] a) Mixing the following components:

[0011] (i) A polyol or a prepolymer having terminal isocyanate (NCO) groups

[0012] (ii) An ethylenically unsaturated monomer (type A monomer) that does not contain active hydrogen and does not have a moisture-reactive functional group, and

[0013] (iii) An ethylenically unsaturated monomer (type B monomer) that does not contain active hydrogen and has a moisture-reactive functional group;

[0014] (iv) An ethylenically unsaturated monomer (type C monomer) that does not contain active hydrogen and has a free radical photoinitiator group;

[0015] b) Polymerizing the mixture from step a) using a free radical polymerization method and a chain transfer agent to obtain a low molecular weight polymer;

[0016] c) Optionally heating the mixture from step b) to a temperature of 100 - 160 °C and maintaining it for 10 - 60 minutes to partially crosslink the polyol or the prepolymer having terminal NCO groups with the low molecular weight polymer.

[0017] For the terms, the following explanations should be made:

[0018] The ethylenically unsaturated groups allow monomers to form polymers by free radical polymerization. The absence of active hydrogen in the monomers ensures that the monomers do not participate in the subsequent addition reactions to form polyurethanes. The type A monomers contribute to the structure of the polymer chains, and the type B monomers allow for reaction with the isocyanate groups of polyols or prepolymers, reaction with the moisture-reactive groups of the polymer, or reaction with inorganic substrates such as in applications to improve adhesion to these substrates through the moisture-reactive groups.

[0019] The type C monomers introduce photo-reactive groups into the polymer, enabling curing by means of UV radiation. In the present invention, moisture crosslinking through silane or isocyanate groups is combined with rapid UV crosslinking by free radical polymerization. Therefore, it is called a "UV moisture dual-curing" system. Strictly speaking, it is even a "triple-curing system" because three crosslinking methods are used: mainly by UV crosslinking, secondly by reaction of isocyanate groups, and finally by reaction of silane groups.

[0020] The "UV moisture dual-curing" system of the present invention mainly provides the advantages of UV curing of UV-active groups, followed by curing through moisture crosslinking groups. This allows the use of UV light to generate particularly rapid initial strength for low-viscosity adhesives, for example, significantly shortening the processing time in surface lamination. For transparent materials (such as transparent films), UV light can also be used for subsequent crosslinking after surface lamination.

[0021] The polymers prepared using monomers having ethylenically unsaturated groups (preferably acrylate polymers) are hereinafter also referred to as vinyl polymers.

[0022] Modifying vinyl polymers (preferably acrylate polymers) with silanes enables them to react with moisture after application, thereby undergoing crosslinking. This can improve heat resistance and resistance to certain chemicals. In addition, silanes can react with inorganic materials (such as glass or metal), thereby improving adhesion to them. This also means that the application range of these adhesives can be expanded. By applying additional heat, crosslinking can be accelerated and a permanently sticky adhesive polymer film can be formed. In addition, reactive adhesives free of any monomeric isocyanates can be produced, and thus are not subject to labeling requirements. This allows for safe handling of the adhesives and does not require any laborious measures during use.

[0023] These polymers can be used in adhesives, sealants and coatings, reactive hot melt adhesives, textile adhesives, adhesives for the wood and furniture industries, automotive adhesives, construction industry adhesives, liquid 1K adhesives, sealants, primers and coatings.

[0024] The basic technical idea of the present invention is based on modifying vinyl polymers (especially acrylate polymers) with silanes to improve their properties. Possible improvements are as follows:

[0025] ·Improving heat resistance through silane crosslinking

[0026] ·Silane reacts with the inorganic substrate to improve the adhesion to the substrate

[0027] ·Products with an isocyanate monomer concentration below 0.1% can be produced, so they are not subject to labeling requirements

[0028] ·Particularly rapid initial strength controllable by UV light

[0029] The present invention has several advantages compared with the prior art. The thermoplastic acrylate polymer is converted into a reactive polymer, which reacts with moisture to form a thermosetting material, so it has higher heat resistance and resistance to special chemicals. Since the silane groups are statistically distributed throughout the polymer, rather than only at the polymer ends as in addition polymerization products or subsequent silanization, the crosslink density and the durability of the material are increased. Silane also provides the possibility of reacting with inorganic materials (such as glass or metal) to increase the adhesion strength to these materials, which expands the adhesion range or enables inorganic materials to adhere to organic materials (such as plastics). In addition, three synthetic routes are available, which also allows the production of materials without isocyanate monomers. This indicates that these products are not subject to labeling requirements or any restrictions.

[0030] This polymer composition can be used as a novel intermediate for the production of various polyurethanes. In particular, the following possibilities emerge:

[0031] ·Prepare a silane-modified vinyl polymer (preferably an acrylate polymer) in a polyol or a prepolymer with terminal NCO groups, and then react it with a polyol or a prepolymer with terminal NCO groups to form a thermoplastic polyurethane

[0032] ·Prepare a silane-modified vinyl polymer (preferably an acrylate polymer) in a polyol or a prepolymer with terminal NCO groups, and then react it with a polyol or a prepolymer with terminal NCO groups to form a reactive polyurethane

[0033] ·Prepare a silane-modified vinyl polymer (preferably an acrylate polymer) in a polyol or a prepolymer with terminal NCO groups, and then react it with a polyol or a prepolymer with terminal NCO groups to form a reactive polyurethane, and then react it with an aminosilane or a mercaptosilane to form a silane-capped polyurethane. Detailed Description of the Invention

[0034] According to the present invention, the polymerization of monomer A with monomers B and C is generally accomplished by combining all the monomers in a reaction vessel and allowing them to react randomly according to their relative concentrations and relative reactivities, thereby forming a statistical polymer. However, in order to increase or decrease the non-uniformity of the polymer, one or more ethylenically unsaturated monomers can also be added during the polymerization process.

[0035] Alternatively, the monomers of monomer A to monomer C can be added stepwise so that free radical polymerization is initiated after adding a specific mixture of monomer A to monomer C, and only after the polymer is formed (accompanied by almost complete consumption of the monomers), is a specific mixture of monomer A to monomer C added to the reaction mixture again. This stepwise addition method can prevent the reaction mixture from overheating due to the exothermic heat of the polymerization reaction.

[0036] The free radical polymerization method is preferably carried out at a temperature below 100 °C, more preferably at a temperature of 40 - 95 °C, and particularly preferably at a temperature of 80 - 90 °C.

[0037] Here, it is also preferred that the weight ratio of monomer A to monomer C defined in the first step remains unchanged in the second addition.

[0038] It is also conceivable that the amount of monomer A in the second step is greater than the amount of monomer A in the first addition. Monomer A 第一次添加 With monomer A 第二次添加 The quantitative ratio is preferably between 1:1 and 1:10, more preferably between 1:2 and 1:8, and particularly preferably between 1:3 and 1:7.

[0039] Correspondingly, it is conceivable that the amount of monomer B in the second step is greater than the amount of monomer B in the first addition. Monomer B 第一次添加 With monomer B 第二次添加 The quantitative ratio is preferably between 1:1 and 1:10, more preferably between 1:2 and 1:8, and particularly preferably between 1:35 and 1:7.

[0040] Correspondingly, it is conceivable that the amount of monomer C in the second step is greater than the amount of monomer C in the first addition. Monomer C 第一次添加 With monomer C 第二次添加 The quantitative ratio is preferably between 1:1 and 1:10, more preferably between 1:2 and 1:8, and particularly preferably between 1:35 and 1:7.

[0041] In an optional step (c) of the present method, the mixture from step (b) (which contains a low molecular weight polymer produced by free radical polymerization) is heated so that the polyol or the prepolymer having terminal NCO groups is partially crosslinked with the low molecular weight polymer. Since the low molecular weight polymer has moisture-reactive groups, it can react with the hydroxyl groups of the polyol or the isocyanate groups of the prepolymer. This reaction results in the polymer composition having higher heat resistance.

[0042] In the optional step (c), the silyl groups can alternatively / additionally react with each other. This reaction also results in the polymer composition having higher heat resistance.

[0043] According to the present invention, a polyol or a prepolymer having terminal NCO groups is used in the method for producing the polymer composition.

[0044] In the case of the polyol, this is to be understood as meaning that at least one polyol can be used here, i.e., two, three, four or more polyols can also be used. Preferably, only one polyol is used in the present method.

[0045] Advantageously, the water content of the polyol used in the method according to the present invention is at most 0.1% by weight, and preferably at most 0.05% by weight.

[0046] Suitable polyols are selected from polyesters, polyether polyols (such as polyethylene oxide or polypropylene oxide), hydroxyl-containing polycaprolactones, polyalkylene oxide polyols (synonymous with the term "polyethylene glycol"), monosubstituted ethylene glycol esters, polysulfides, polyamides, polyester amides, polycarbonates, polyacetals, polyhydrocarbon polyols, polyacrylate polyols, polymethacrylate polyols, polyalcohols, bisphenols, polycarbonate polyols, polyhydroxy-functional fats and oils, and mixtures thereof.

[0047] Particularly suitable are polyether polyols, such as diols or polypropylene glycols having a molecular weight of 400 to 4000 g / mol.

[0048] Suitable polyols are on the one hand the high molecular weight polyalkylene oxide polyols already mentioned, preferably polyethylene oxide or polypropylene oxide diols having an unsaturation of less than 0.02 mEq / g and a molecular weight in the range of 400 to 18,000 g / mol, especially polyethylene oxide or polypropylene oxide diols having a molecular weight in the range of 1,000 to 4,000 g / mol. Particularly suitable are PPG2000 or PPG 4000.

[0049] In order to achieve a higher crosslinking density, higher functionality alcohols such as triols and tetraols can also be used. Examples given here are glycerol, trimethylolpropane or pentaerythritol.

[0050] Also suitable are polyalkylene polyols (also known as polyether polyols, polyethylene glycols or oligoether alcohols). These are polymerization products of ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane or 2,3-epoxybutane, oxetane, tetrahydrofuran or mixtures thereof, which can be polymerized by means of a starting molecule having more than two active hydrogen atoms, the starting molecule being, for example, water, ammonia or a compound having more than one OH or NH group, such as 1,2-ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycol and tripropylene glycol, isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, glycerol, aniline and mixtures of the above compounds.

[0051] Particularly suitable polyester polyols are produced from diols to triols (especially diols) and organic dicarboxylic or tricarboxylic acids (especially dicarboxylic acids) or their anhydrides or esters, the diols and triols being, for example, 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 (dimer diol), neopentyl glycol hydroxypivalate, glycerol, 1,1,1-trimethylol propane or mixtures of the above alcohols; the organic dicarboxylic, tricarboxylic acids or their anhydrides being, for example, 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 above acids, and polyester polyols made from lactones (such as ε-caprolactone) and initiators (such as the above di- or triols).

[0052] The use of polycarbonate polyols can also be considered, for example, obtainable by reacting the above alcohols used for forming polyester polyols with dialkyl carbonates, diaryl carbonates or phosgene.

[0053] Also suitable are polyhydroxy-functional fats and oils, such as natural fats and oils, especially castor oil, or polyols obtained by chemical modification of natural fats and oils (referred to as oleochemical polyols), such as 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 by degradation treatment of natural fats and oils (such as alcoholysis or ozonolysis) and subsequent treatment of the degradation products or their derivatives by chemical bonding (such as by transesterification or dimerization). Suitable degradation products of natural fats and oils are especially fatty acids and fatty alcohols as well as fatty acid esters, especially methyl esters (FAME), which can be derivatized, for example, by hydroformylation and hydrogenation to give hydroxy fatty acid esters.

[0054] The use of polyhydrocarbon polyols is also contemplated. They are also referred to as oligohydrocarbon alcohols and include, for example, polyhydroxy-functional polyolefins, polyisobutene, polyisoprene; polyhydroxy-functional ethylene-propylene, ethylene-butene or ethylene-propylene-diene copolymers, such as copolymers produced by Kraton Polymers, polyhydroxy-functional polymers of dienes (especially polymers of 1,3-butadiene, especially also polymers that can be produced by anionic polymerization), polyhydroxy-functional copolymers of dienes (such as 1,3-butadiene or a mixture of dienes) with vinyl monomers (such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutene and isoprene), such as polyhydroxy-functional acrylonitrile / butadiene copolymers (such as copolymers formed from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers), and hydrogenated polyhydroxy-functional diene polymers or copolymers.

[0055] In the production of polyurethane polymers containing isocyanate groups, in addition to the above polyols, small amounts of low molecular weight diols or polyols are also used, such as 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycol and tripropylene glycol, isomeric butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimerized fatty alcohols, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, glycerol, pentaerythritol, sugar alcohols (such as xylitol, sorbitol or mannitol), sugars (such as sucrose), other higher alcohols, low molecular weight alkoxylated products of the above diols and polyols, and mixtures of the above alcohols.

[0056] It is also possible to consider using, in the production of polyurethane polymers containing isocyanate groups, in addition to the above-mentioned polyols, small amounts of low molecular weight divalent or polyvalent amines, such as ethylenediamine, toluenediamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene-polyaniline or amino alcohols (such as ethanolamine and diethanolamine), as well as mixtures of the above-mentioned amines and amino alcohols.

[0057] In the method for producing a polymer composition, prepolymers having terminal NCO groups can also be used. It should be understood that at least one corresponding prepolymer can be used here, including two, three, four or more prepolymers. Preferably, exactly one prepolymer having terminal NCO groups is used in this method.

[0058] According to an advantageous aspect, prepolymers having terminal NCO groups can be provided, with an NCO to OH group molar ratio of 1.5:1 to 2.0:1.

[0059] In one embodiment, prepolymers having terminal NCO groups are prepared by reacting diols with diisocyanates.

[0060] Suitable polyols are selected from polyesters, hydroxy-containing polycaprolactones, polyethylene glycols, monosubstituted ethylene glycol esters, polythioethers, polyamides, polyester amides, polycarbonates, polyacetals, polyhydrocarbon polyols, polyacrylate polyols, polymethacrylate polyols, polyols, bisphenols, polycarbonate polyols, polyhydroxy-functional fats and oils, and mixtures thereof.

[0061] Diols, polyethylene oxide or polypropylene oxide are particularly suitable.

[0062] Suitable polyols are, on the one hand, the aforementioned high molecular weight polyethylene glycols, preferably polyethylene oxide or polypropylene oxide diols, having an unsaturation of less than 0.02 mEq / g and a molecular weight in the range of 400 - 18,000 g / mol, and in particular, a molecular weight in the range of 1,000 - 4,000 g / mol. Particularly suitable are PPG 2000 or PPG 4000.

[0063] Mixtures of polyols can also be used here. Preferably, this is a mixture of two or more polyethylene oxides or a mixture of two or more polypropylene oxide diols. A mixture of PPG 1000 and PPG 400 is particularly advantageous.

[0064] For the production of prepolymers having terminal isocyanate groups, diisocyanates familiar to experts qualified in the production of polyurethane polymers can be used.

[0065] The diisocyanates used for the synthesis of the prepolymer may also be selected from ethylenediisocyanate, ethylidene diisocyanate, propylenediisocyanate, butylenediisocyanate, pentamethylenediisocyanate, hexamethylenediisocyanate, toluene diisocyanate, cyclopentylidene-1,3-diisocyanate, cyclohexylidene-1,4-diisocyanate, cyclohexylidene-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, xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene 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, blocked diisocyanates and carbodiimide-modified diisocyanates, and any mixtures of the above diisocyanates. Herein, diphenylmethane diisocyanate is preferably used, and 4,4'-diphenylmethane diisocyanate (4,4'-MDI) is particularly preferred.

[0066] In the free radical polymerization method, a peroxide initiator or an azo initiator can be used as the initiator. Preferred initiators are lauroyl peroxide, benzoyl peroxide, dimethyl-2,2'-azobisisobutyrate, di-(4-tert-butyl-cyclohexyl)-peroxydicarbonate, and azobis(isobutyronitrile). Lauroyl peroxide is preferably used.

[0067] During the photoreaction, the A-type monomer can be used as a co-initiator for UV curing by the radicals formed by hydrogen radical abstraction. A tertiary amine or a mercapto compound can be used as an additional co-initiator.

[0068] It is also possible to consider adding auxiliaries and / or additives to the reaction mixture in the process of the present invention. Examples include surface-active substances, fillers, other flame retardants, nucleating agents, oxidation stabilizers, slip agents and release aids, dyes and pigments, optional stabilizers (e.g., stabilizers against hydrolysis, light, heat or discoloration), inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliaries and additives can be found, for example, in "Plastics Handbook", Volume 7, "Polyurethanes", Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag, Munich, Vienna, 1993.

[0069] To adjust the viscosity, a solvent can also be added to the reaction mixture at any time in the process of the present invention. Examples of solvents include triethyl phosphate (TEP), pentamethyldiethylenetriamine (PMDETA), triethylenediamine (TEDA), monoethylene glycol, polyethylene glycol and propylene carbonate (PC), as well as mixtures of two or more of the above solvents. If the solvent is a polyol, it is beneficial to add it after the radical polymerization is completed.

[0070] To accelerate the reaction, a catalyst can be added to the reaction mixture in the process of the present invention.

[0071] For example, suitable catalysts include N,N-dimethylethanolamine (DMEA), N,N-dimethylcyclohexylamine (DMCHA), bis(N,N-dimethylaminoethyl) ether (BDMAFE), N,N,N′,N′,N″-pentamethyldiethylenetriamine (PDMAFE), 1,4-diazabicyclo[2,2,2]octane (DABCO), 2-(2-dimethylaminoethoxy)ethanol (DMAFE), 2-((2-dimethylaminoethoxy)ethylmethylamino)ethanol, 1-(bis(3-dimethylamino)propyl)amino-2-propanol, N,N′,N″-tris(3-dimethylamino-propyl)hexahydrotriazine, dimorpholinediethyl ether (DMDEE), N,N-dimethylbenzylamine, N,N,N′,N″,N″-pentamethyldipropylenetriamine, N,N′-diethylpiperazine. Particularly suitable are sterically hindered primary, secondary or tertiary amines such as dicyclohexylmethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-α-phenylethyl)amine, tri-n-propylamine, dicyclohexylamine, tert-butylisopropylamine, di-tert-butylamine, cyclohexyl-tert-butylamine, di-sec-butylamine, dicyclopentylamine, di-(α-trifluoromethyl-ethyl)amine, di-(α-phenylethyl)amine, triphenylmethylamine and 1,1,-diethyl-n-propylamine. Other sterically hindered amines include morpholines, imidazoles, ether compounds such as dimorpholinediethyl ether or dimorpholinedimethyl ether; N-ethylmorpholine, N-methylmorpholine, bis(dimethylaminoethyl) ether, imidazole, non-methylimidazole, 1,2-dimethylimidazole, 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.

[0072] According to the present invention, the type A monomer is an ethylenically unsaturated monomer that does not contain active hydrogen and does not have a moisture-reactive functional group.

[0073] According to the present invention, the type A monomer is used in the method for producing a polymer composition. This should be understood to mean that at least one monomer of this type can be used here, that is, two, three, four or more type A monomers can also be used. Preferably, two type A monomers are used in the method.

[0074] Examples of the type A monomer are selected from C1 to C12 esters of acrylic acid or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl 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, styrene, acrylonitrile, ethylene or mixtures thereof.

[0075] Particularly suitable type A monomers are n-butyl methacrylate or 2-ethylhexyl acrylate or mixtures thereof.

[0076] The type A monomer is preferably used as a co-initiator in the photochemical reaction. By H abstraction, it is converted into a radical, and then preferably a covalent bond is formed between these monomers by radical reaction with the type C monomer.

[0077] According to the invention, the type B monomer is an ethylenically unsaturated monomer that does not contain active hydrogen and has a moisture-reactive functional group.

[0078] According to the invention, the type B monomer 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. two, three, four or more type B monomers can also be used. Preferably, exactly one type B monomer is used in the process.

[0079] Furthermore, within the scope of the present invention, it is more advantageous if the type B monomer is selected from vinyl compounds, acrylates, methacrylates, fumarates, maleates, styrene, acrylonitrile, ethylene or mixtures thereof, and all have a moisture-reactive functional group.

[0080] Suitable moisture-reactive groups are isocyanate groups or silyl groups. The type B monomer preferably has a silyl group as the moisture-reactive group.

[0081] Advantageously, the present invention can provide B-type monomers selected from vinyltrichlorosilane, methylvinyldichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiacetoxysilane, vinyltriisopropoxysilane, vinyltriisopropenyloxysilane, vinyltris(methylethylketoxime)silane, divinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltris(2-methoxyethoxy)silane, 4-(3-trimethoxysilylpropyl)benzylstyrenesulfonate, allyltriethoxysilane, allyltrimethoxysilane, and oligomers of these silanes.

[0082] A particularly suitable B-type monomer is 3-methacryloxypropyltrimethoxysilane.

[0083] According to the present invention, the C-type monomer is an ethylenically unsaturated monomer that does not contain any active hydrogen and has a free radical photoinitiator group. The free radical photoinitiator group is defined in the context of the present invention as a functional group that decomposes in a photolysis reaction upon absorption of UV light and thus forms free radicals as reactive species, which can initiate (start) a polymerization reaction.

[0084] According to the present invention, the term "UV light" is defined as light having a wavelength less than 400 nm. The sub-ranges of UV light used herein are UVA radiation having a wavelength between 315 nm and 400 nm, UVB radiation having a wavelength between 280 nm and 315 nm, and UVC radiation having a wavelength between 100 nm and 280 nm. Preferably, UVA and / or UVB radiation is used for UV-induced photolysis and thus for UV-induced curing.

[0085] According to the present invention, the C-type monomer is used in the method for preparing the polymer composition. This should be understood to mean that at least one monomer of this type can be used herein, i.e., two, three, four or more C-type monomers can also be used. Preferably, only one C-type monomer is used in the method.

[0086] In a preferred embodiment, the free radical photoinitiator group of the C-type monomer is a type II free radical photoinitiator group. Type II photoinitiators abstract hydrogen atoms from neighboring molecules to initiate chain polymerization.

[0087] Preferably, the type II free radical photoinitiator group is a benzophenone group or an isopropylthioxanthone group.

[0088] Advantageously, the present invention can provide C-type monomers selected from 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-acryloyloxyhexyloxy)benzophenone (AHBP).

[0089] Particularly suitable C-type monomers are ABP or 4-methacryloyloxybenzophenone.

[0090] According to the present invention, a chain transfer agent is used as part of the free radical polymerization method to reduce the average degree of polymerization of the resulting polymer and obtain a low molecular weight polymer. Those skilled in the art are familiar with chain transfer agents for free radical polymerization.

[0091] Within the scope of the present invention, it is beneficial if the chain transfer agent is a halogenated organic compound, an unsaturated aromatic compound or a thiol, and preferably the chain transfer agent is selected from carbon tetrachloride, 2,4-diphenyl-4-methyl-1-pentene, dodecyl mercaptan, lauryl mercaptan, mercaptoacetic acid, octyl mercaptoacetate and thioglycerol.

[0092] Preferably, the chain transfer agent is dodecyl mercaptan.

[0093] Furthermore, it can be envisaged that in the method for preparing the polymer composition, based on the total weight of the polyol and the components of the A-type monomer to the C-type monomer, the amount of the polyol is 20% to 90% by weight, preferably 40% to 80% by weight, particularly preferably 50% to 60% by weight.

[0094] Therefore, it can be envisaged that in the method for preparing the polymer composition, based on the total weight of the prepolymer, the A-type monomer, the B-type monomer and the C-type monomer components, the amount of the prepolymer having terminal NCO groups is 20% to 90% by weight, preferably 40% to 80% by weight, particularly preferably 50% to 60% by weight.

[0095] In another embodiment, in the method for preparing a polymer composition, based on the total weight of monomer A to monomer C, the amount of monomer A is 30% to 95% by weight, preferably 50% to 90% by weight, and particularly preferably 70% to 85% by weight.

[0096] Furthermore, in the method for preparing a polymer composition, based on the total weight of monomer A to monomer C, the amount of monomer B can be 5% to 70% by weight, preferably 10% to 50% by weight, and particularly preferably 15% to 30% by weight.

[0097] In yet another embodiment, in the method for preparing a polymer composition, based on the total weight of monomer A, monomer B and monomer C, the amount of monomer C can be specified as 0.1% to 5.0% by weight, preferably 0.2% to 4.0% by weight, and particularly preferably 0.3% to 3.0% by weight.

[0098] According to another advantageous aspect, the number-average molecular weight of the low molecular weight polymer that can be provided is 3,000 - 200,000 g / mol, preferably 5,000 - 100,000 g / mol, and particularly preferably 10,000 - 60,000 g / mol.

[0099] According to a second aspect, the present invention relates to a polymer composition that can be prepared by the method of the present invention or a polymer composition prepared by the method of the present invention.

[0100] According to the present invention, synthesizing a silane-modified vinyl polymer in a polyol can produce a polymer composition having improved properties compared to a silane-modified vinyl polymer synthesized in a PU prepolymer. Structurally, in the polymer composition according to the present invention, the formation of an interpenetrating network is beneficial to the physicochemical properties. It exhibits higher heat resistance and improved oil seal resistance.

[0101] If the optional step (c) is carried out according to the present invention, the polymer composition is characterized in that the polyol or prepolymer is partially crosslinked with the low molecular weight polymer formed by free radical polymerization.

[0102] Preferably, the glass transition temperature of the polymer composition that can be provided is between -50°C and 100°C, preferably between -40°C and 70°C, and particularly preferably between -30°C and 60°C.

[0103] Within the scope of the present invention, if the viscosity of the polymer composition measured at 90°C is 500 - 25,000 mPa·s, preferably 1,000 - 21,000 mPa·s, further beneficial effects can be achieved.

[0104] If, within the scope of the present invention, the polymer composition is solvent-free, this can be advantageous. A polyurethane is formed by further reaction with a polyisocyanate, thereby producing a solvent-free PU polymer.

[0105] Another object of the present invention is the use of the polymer composition according to at least one of the preceding claims as an adhesive, a sealant or a coating agent. Specifically, the polymer composition cures as a one-component composition in the presence of moisture and when the temperature is raised to above 100 °C.

[0106] The present invention also provides a method for producing a UV- and moisture-curable polyurethane hot melt adhesive composition. The method comprises the following steps:

[0107] a) providing the polymer composition of the present invention

[0108] b) adding a sufficient amount of polyisocyanate to achieve the desired isocyanate content and isocyanate index, and then polymerizing by using an addition polymerization method

[0109] c) optionally adding an aminosilane or a mercaptosilane and converting it into a silane-terminated polyurethane

[0110] d) irradiating with UV light to further crosslink the polymer.

[0111] By synthesizing the silane-modified vinyl polymer of the present invention in a polyol, compared with the silane-modified vinyl polymer synthesized in a PU prepolymer, a polyurethane hot melt adhesive composition with improved properties is obtained by using the polymer composition of the present invention. The PU hot melt adhesive of the present invention has higher heat resistance, higher chemical resistance and better adhesion to inorganic materials. In addition, the resulting polymer composition exhibits better oil-resistant sealing performance. By using a type C monomer, the polymer also becomes UV-curable, enabling rapid curing.

[0112] The polyisocyanate for producing the polyurethane polymer can use commercially available polyisocyanates, especially diisocyanates.

[0113] The polyisocyanate may also be selected from 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, xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl sulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furanediyl diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4''-triisocyanatotriphenylmethane, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 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, blocked diisocyanates, and carbodiimide-modified polyisocyanates, as well as any mixtures and precondensates of the above isocyanates.

[0114] Examples of precondensates include HDI biuret and HDI isocyanurate.

[0115] The polyisocyanate is preferably an aliphatic isocyanate.

[0116] Advantageously, within the scope of the present invention, in the method for producing a moisture-curable polyurethane hot melt adhesive composition, the free isocyanate content is between 0 - 20%, preferably between 0 - 15%, and particularly preferably between 0 - 10%.

[0117] According to a further possibility, in the present method, the isocyanate index is between 0.5 - 10, preferably between 1 - 3, and particularly preferably between 1.5 and 2.5.

[0118] According to optional step (c), the UV and moisture-curable polyurethane hot melt adhesive composition obtained in step (b) can be converted into a silane-terminated polyurethane by adding an aminosilane or a mercaptosilane.

[0119] According to the present invention, an aminosilane or a mercaptosilane is used in step (c). This is to be understood as meaning that at least one aminosilane or one mercaptosilane can be used here, including two, three, four or more aminosilanes or mercaptosilanes. Preferably, exactly one aminosilane or exactly one mercaptosilane is used in the process.

[0120] The aminosilane is preferably an aminosilane AS of formula (I).

[0121]

[0122] The radical R 1 represents a straight-chain or branched monovalent hydrocarbon radical having 1 to 12 carbon atoms, which may optionally have more than one C—C multiple bond and / or may optionally have a cycloaliphatic and / or aromatic moiety. In particular, R 1 represents methyl, ethyl or isopropyl.

[0123] The radical R 2 represents an acyl radical or a straight-chain or branched monovalent hydrocarbon radical having 1 to 12 carbon atoms, which may optionally have more than one C—C multiple bond and / or may optionally have a cycloaliphatic and / or aromatic moiety. The radical R 2 preferably represents an acyl group or an alkyl group having 1 to 5 carbon atoms, especially methyl or ethyl or isopropyl.

[0124] The radical R 3 represents a straight-chain or branched divalent hydrocarbon radical having 1 to 12 carbon atoms, which may optionally have a cyclic and / or aromatic moiety and may optionally have more than one heteroatom. The radical R 3 preferably represents an alkylene group having 1 to 3 carbon atoms, especially having 3 carbon atoms.

[0125] Furthermore, the exponent a represents a value of 0, 1 or 2, especially 0 or 1.

[0126] The radical R 4 represents a hydrogen atom or a straight-chain or branched hydrocarbon radical having 1 to 20 carbon atoms, which may optionally have a cyclic moiety, or represents a group of formula (II).

[0127]

[0128] The radical R 6 and R 7 independently represent a hydrogen atom or a radical selected from —R 9 , —CN and —COOR 9 .

[0129] The radical R 8 is hydrogen or selected from —CH 2 —COOR 9 , —COOR9 、 -CONHR 9 、 -CON(R 9 ) 2 、 -CN, -NO 2 、 -PO(OR 9 ) 2 、 -SO 2 R 9 and -SO 2 OR 9 free radicals.

[0130] The free radical R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, optionally containing at least one heteroatom.

[0131] 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; Michael-type addition products of primary aminosilanes with Michael acceptors, the primary aminosilane being for example 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane, and the Michael acceptor being for example acrylonitrile, acrylic acid and methacrylate esters, acrylic or methacrylamide, diesters of maleic acid and fumaric acid, diesters of citraconic acid and itaconic acid, and the products being for example dimethyl and diethyl N-(3-trimethoxysilyl-propyl)-aminosuccinate, and analogs of the above aminosilanes in which the methoxy groups on silicon are replaced by ethoxy or isopropoxy groups. Particularly suitable aminosilanes AS are secondary aminosilanes, especially those in which R 4 in formula (I) is different from H. Michael-type adducts are preferred, especially preferably diethyl N-(3-trimethoxysilyl-propyl)-aminosuccinate.

[0132] As used herein, the term "Michael acceptor" refers to a compound that, due to the presence of a double bond and activation by an electron acceptor residue, is capable of undergoing a nucleophilic addition reaction with a primary amino group (NH 2 group) in a manner similar to Michael addition (hetero-Michael addition).

[0133] On the other hand, the present invention relates to a UV and moisture-curable polyurethane hot melt adhesive composition obtainable by the above method or a UV and moisture-curable polyurethane hot melt adhesive composition prepared by the above method.

[0134] If the viscosity of the polyurethane hot melt adhesive composition is from 10 mPa·s to 150,000 mPa·s at 120 °C, further beneficial aspects can be achieved within the scope of the present invention. The viscosity is preferably between 1,000 and 100,000 mPa·s, more preferably between 3,000 and 75,000 mPa·s, and particularly preferably between 2,000 and 50,000 mPa·s.

[0135] Another object of the present invention is the use of the UV- and moisture-curing polyurethane hot melt adhesive composition of the present invention as an adhesive, a sealant or a coating agent. In particular, it is used as an adhesive.

[0136] The present invention also includes a method for producing a 1K polyurethane adhesive, comprising the following steps:

[0137] a) providing the polymer composition of the present invention, wherein during production, instead of performing the temperature increase in optional step c), the polymer is cooled to a temperature of 80 °C to 20 °C

[0138] b) adding the polyisocyanate of the present invention to achieve the desired free isocyanate content and isocyanate index

[0139] c) optionally cooling to a temperature of 80 °C to 20 °C for 0.5 - 5 hours.

[0140] The polyisocyanate (preferably diisocyanate) for producing the polyurethane polymer can use commercially available polyisocyanates, in particular aliphatic diisocyanates.

[0141] The polyisocyanate may also be selected from 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, xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl sulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furan diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanatotriphenylmethane, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene 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, blocked diisocyanates and carbodiimide-modified polyisocyanates, polymeric diphenylmethane diisocyanate (PMDI), and any mixture of the above isocyanates.

[0142] In a preferred embodiment, the polyisocyanate may be diphenylmethane diisocyanate (MDI) or polymeric diphenylmethane diisocyanate (PMDI).

[0143] MDI may be a mixture of two or three of its isomers (i.e., 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate). However, when only one isomer can be used, 4,4'-diphenylmethane diisocyanate is preferred.

[0144] Polymeric diphenylmethane diisocyanate (PMDI), also known as industrial MDI, is a mixture of methylene diphenyl isocyanate and homologous aromatic polyisocyanates. However, the term "polymeric diphenylmethane diisocyanate" is actually technically incorrect because it is not a polymer but a mixture of compounds having multiple (usually up to 6) phenyl groups, each of which has an isocyanate group. Common trade names also include polymethylene polyphenyl isocyanate.

[0145] According to a beneficial further improvement of the present invention, it can be stipulated that the free isocyanate content set in step b) of the present method is 2 to 40%, preferably 5 to 30%, and particularly preferably 10 to 20%.

[0146] Furthermore, within the scope of the present invention, it can be envisaged that the isocyanate index set in step b) of the method is 1.5 to 20, preferably 2 to 15, and particularly preferably 4 to 10.

[0147] On the other hand, the present invention relates to a 1K polyurethane adhesive that can be produced by the above method, or a 1K polyurethane adhesive produced by the above method.

[0148] According to a further possibility, it can be stipulated that the viscosity of the 1K polyurethane adhesive measured at 20 °C is 5,000 - 25,000 mPa·s, preferably 6,000 - 21,000 mPa·s.

[0149] Another object of the present invention is the use of the 1K polyurethane adhesive of the present invention as an adhesive, coating compound or sealant, especially as: a multi-functional adhesive, an assembly adhesive, a construction adhesive, a paper and packaging adhesive, a film lamination adhesive, an adhesive for ceramic and metal materials, wood, glass, sandwich systems, textiles, reinforcing fabrics, materials in the aircraft, military or shipbuilding fields.

[0150] On the other hand, the present invention relates to a polyurethane composition, which comprises

[0151] a) 5 - 90% by weight of a polyurethane polymer or polyurethane prepolymer formed by the addition polymerization of a polyisocyanate and a polyol

[0152] b) 10 - 95% by weight of a low molecular weight polymer of ethylenically unsaturated monomers without active hydrogen, wherein at least one monomer is an ethylenically unsaturated monomer having a siloxane group

[0153] In one embodiment of the present 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 ethylenically unsaturated monomers having a siloxane group.

[0154] In a preferred embodiment of the present invention, the polyurethane composition is characterized in that the ethylenically unsaturated monomer having a siloxane group is a silane-modified acrylate.

[0155] In a second aspect, the present invention relates to the use of an ethylenically unsaturated monomer having a siloxane group and an ethylenically unsaturated monomer without active hydrogen for copolymerization in a polyol or a prepolymer having terminal NCO groups as a solvent.

[0156] In one embodiment of the present invention, the use is characterized in that the ethylenically unsaturated monomer having a siloxane group is a silane-modified acrylate.

[0157] On the other hand, the present invention relates to an acrylate copolymer comprising:

[0158] a) 5-95% by weight of one or more acrylate monomers without active hydrogen, preferably selected from butyl methacrylate and methyl methacrylate

[0159] b) 5-95% by weight of one or more acrylate monomers having siloxane side groups, preferably 3-methacryloxypropyltrimethoxysilane

[0160] On the other hand, the present invention relates to a method for producing a 2K polyurethane adhesive, the method comprising the following steps:

[0161] a. Providing the polymer composition of the present invention, without raising the temperature in the optional step b of the present method, but cooling the polymer to a temperature of 80°C to 20°C, the polymer composition having epoxy groups, which are introduced by one of monomers A to C having epoxy groups as functional groups, or by another ethylenically unsaturated monomer (type D monomer) without any active hydrogen and having epoxy groups as functional groups

[0162] b. Adding polyisocyanate to achieve the required free isocyanate content and isocyanate index

[0163] c. Optionally cooling to a temperature of 80°C to 20°C and maintaining for 0.5 - 5 hours.

[0164] Through these method steps a to c, the first component of the 2K polyurethane adhesive is produced, which can then be reacted with an epoxy group-reactive monomer or prepolymer as the second component of the 2K polyurethane adhesive.

[0165] In the required method for producing a 2K polyurethane adhesive, the second epoxy group-reactive component is preferably an amine compound. Those skilled in the art can use known amine compounds suitable for reacting with epoxides, such as diamines, polyamines, aliphatic amines, aromatic amines, primary amines or secondary amines. In addition, prepolymers having terminal reactive groups (such as amine groups, hydroxyl groups and mercapto groups) can be used, so that prepolymers having terminal isocyanate groups can be used.

[0166] On the other hand, the present invention relates to a 2K polyurethane adhesive produced by the above method.

[0167] Another object of the present invention is the use of the 2K polyurethane adhesive of the present invention as an adhesive, coating compound or sealant, especially as: a multi-functional adhesive, an assembly adhesive, a construction adhesive, a paper and packaging adhesive, a film lamination adhesive, an adhesive for ceramic and metal materials, wood, glass, sandwich systems, textiles, reinforcing fabrics, materials in the aircraft, military or shipbuilding fields.

[0168] Definitions

[0169] In this text, substance names starting with "poly" and "multi" (such as polyol or polyisocyanate) refer to substances that formally contain more than two functional groups as shown in the name in each molecular form.

[0170] In this text, the term "polymer" includes not only a collection of macromolecules that are chemically homogeneous but have different degrees of polymerization, molar masses, and chain lengths produced by polymerization reactions (polymerization, addition polymerization, condensation polymerization), but also derivatives of such a collection of macromolecules produced by polymerization reactions, that is, compounds obtained by transforming (such as addition or substitution) the functional groups on a given macromolecule, and these compounds can be chemically homogeneous or chemically heterogeneous. This term also includes copolymers and so-called prepolymers, that is, reactive oligomeric preadducts whose functional groups participate in the formation of macromolecules.

[0171] The term "copolymer" as used in this text refers to a polymer composed of more than two different monomer units. This means that a copolymer is different from a homopolymer, which is composed of only one monomer (actual or assumed) and thus has only one repeating unit. Copolymers can be divided into five categories:

[0172] 1) Statistical copolymers, in which the distribution of the two monomers in the chain follows a statistical distribution

[0173] 2) Gradient copolymers, which are similar in nature to statistical copolymers, but in which the proportion of one monomer increases in the chain while the proportion of the other monomer decreases

[0174] 3) Alternating copolymers, in which the two monomers are arranged alternately

[0175] 4) Block copolymers and segmented copolymers, which consist of longer sequences or blocks of each monomer

[0176] 5) Graft copolymers, in which blocks of one monomer are grafted onto the main chain of another monomer

[0177] The term "polyurethane polymer" includes all polymers produced using the so-called diisocyanate addition polymerization method. This also includes polymers that contain little or almost no urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates, and polycarbodiimides.

[0178] In this text, "active hydrogen" refers to hydrogen bonded to N, O, or S (also known as "Zerewitinoff active hydrogen"), which reacts with methylmagnesium iodide to produce methane according to the method discovered by Zerewitinoff. Typical examples of compounds having active hydrogen are compounds containing carboxyl, hydroxyl, amino, imino, or mercapto groups as functional groups.

[0179] Therefore, a monomer without active hydrogen (type B monomer) is a monomer that does not have any carboxyl, hydroxyl, amino, imino, or mercapto groups.

[0180] According to the present application, a "functional group" is an atomic group in an organic compound that significantly determines the material properties and the reaction behavior of the compound carrying the functional group. Compounds carrying the same functional group are classified into a substance category because of their generally similar properties.

[0181] In this text, a "moisture-reactive functional group" should be understood as a functional group that reacts with water. This reaction can cause crosslinking of two or more such groups, thereby causing curing of the corresponding polymer. In the polymer field, those skilled in the art are familiar with moisture-reactive (curable) groups. Examples include silyl groups and isocyanate groups.

[0182] In this document, a "UV-curable composition" should be understood as a polymer composition (preferably a polyurethane adhesive) that cures at least partially upon irradiation with UV light due to the presence of free radical photoinitiator groups in the polymer.

[0183] In the context of the present invention, a "free radical photoinitiator group" is defined as a functional group that decomposes in a photolysis reaction upon absorption of UV light and forms free radicals as reaction species, which can initiate (start) a polymerization reaction.

[0184] According to the present invention, the term "UV light" is defined as light having a wavelength less than 400 nm. The sub-ranges of UV light used herein are UVA radiation having a wavelength between 315 nm and 400 nm, UVB radiation having a wavelength between 280 nm and 315 nm, and UVC radiation having a wavelength between 100 nm and 280 nm. Preferably, UVA and / or UVB radiation is used for UV light-induced photolysis and thus for UV light-induced curing.

[0185] In this text, the terms "silane" and "organosilane" refer to compounds that have not only at least one (usually two or three) alkoxy or acyloxy groups directly bonded to a silicon atom through an Si-O bond but also at least one organic radical directly bonded to the silicon atom through an Si-C bond. Those skilled in the art also refer to such silanes as organoalkoxysilanes or organoacyloxysilanes.

[0186] Thus, the term "silyl group" refers to a silicon-containing group bonded to an organic residue of a silane via an Si-C bond. Silanes or their silyl groups hydrolyze upon contact with moisture and thus belong to the moisture-reactive groups.

[0187] "Aminosilane" or "mercaptosilane" is an organosilane in which the organic residue has an amino group or a mercapto group. "Primary aminosilane" refers to an aminosilane having a primary amino group (i.e., an NH group bonded to an organic residue). "Secondary aminosilane" refers to an aminosilane having a secondary amino group (i.e., an NH group bonded to two organic residues). 2 group).

[0188] In this document, "molecular weight" refers to the molar mass of a molecule (in g / mol or Dalton). In this document, "average molecular weight" is always understood as the number-average M n (number-average). The term "number-average molecular weight" is also used as a synonym for "average molecular weight".

[0189] In this document, "low molecular weight polymer" is understood to be a polymer with an average molecular weight M n 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, more preferably less than 60,000 g / mol, especially less than 20,000 g / mol. The low molecular weight polymer may have, for example, an average molecular weight M 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 n .

[0190] The term "polymeric diphenylmethane diisocyanate" (PMDI) refers to a substance mixture of methylene diphenyl diisocyanate and homologous aromatic polyisocyanates. The term "polymeric diphenylmethane diisocyanate" is a misnomer from a chemical perspective since it is not a polymer but a mixture of compounds having multiple (usually up to 6) phenyl groups, each of which has an isocyanate group. Common trade names also include polymethylene polyphenyl polyisocyanate.

[0191] For the purposes of this application, a "chain transfer agent" is defined as an organic molecule capable of undergoing chain transfer. A chain transfer reaction is a reaction that occurs during chain polymerization, in which the activity of a growing polymer chain is transferred to another molecule. The chain transfer reaction reduces the average degree of polymerization of the resulting polymer. Those skilled in the art are familiar with chain transfer agents for free radical polymerization.

[0192] As used herein, the term "solvent" shall be understood to mean CD compounds listed as organic solvents in the Chemical Dictionary, 9th Edition, Version 1.0, Georg Thieme Verlag, Stuttgart 1995. Polyols or prepolymers having terminal NCO groups used in the present invention are not within this definition, although they serve as solvents for monomers as well as low molecular weight polymers formed by free radical polymerization.

[0193] As used herein, "solid" refers to a substance that does not change shape or is difficult to deform without external influence, especially a non-flowable substance. Accordingly, "liquid" refers to a substance that can be deformed and flow, which also includes highly viscous and paste-like substances.

[0194] As used herein, "one-component" (abbreviated as "1K") refers to a composition in which all components of the composition are mixed and stored in the same container and the composition can be cured by moisture. As used herein, "two-component" means that the components of the composition are present in two different components and are stored separately in separate containers. Only shortly before or during the application of the composition are the two components mixed together, and the subsequently mixed composition hardens, and the curing occurs or is completed only by the action of moisture.

[0195] It should be clearly stated that in the context of this patent application, indefinite articles and indefinite numbers, such as "a...", "two...", etc., should generally be understood as the minimum information, i.e., "at least one...", "at least two...", etc., unless it can be clearly seen from the context or the specific text of a particular paragraph that it only means "exactly one...", "exactly two...", etc. In addition, all numerical identifications as well as identifications of method parameters and / or equipment parameters should be understood in a technical sense, i.e., with the usual tolerances. In addition, the clear identification of a limitation "at least" or "minimum" or a similar identification should not presume that simply using "one" (i.e., without "at least" or a similar identification) means "exactly one".

[0196] Unless otherwise specified, percentages herein are by weight.

[0197] The embodiments shown herein are only representative examples of the present invention and should not be construed as limiting. Alternative embodiments that can be conceived by those skilled in the art are equally included within the scope of the present invention.

[0198] Examples

[0199] 1. Production of UV-curable polyacrylate as the base formulation

[0200] Based on the formulation of polyacrylate IC2068 (see Table 1), in these experiments, the proportion of the copolymerizable photoinitiator 4-methacryloyloxybenzophenone varied between 1 - 5%, resulting in the production of polyacrylate batches IC2068 - 7 to IC2068 - 11. The ratio of diethylhexyl acrylate to 4-methacryloyloxybenzophenone changed from 12:1 to 2.4:5.

[0201] To produce radiation-curable polyacrylate (or polysilane acrylate), under a nitrogen atmosphere, the solvent polyether polyol was heated to 90 °C in a glass reactor. During heating, the monomers and initiator were added within 30 minutes. Once the temperature reached 90 °C, stirring was continued for another 30 minutes. Then, the monomers and initiator were added at 90 °C within 2 hours. The subsequent reaction was completed within 2 hours, and further initiator was added.

[0202] Table 1: Polyacrylate batches IC2068 - 07 to IC2068 - 11

[0203]

[0204] (PPG 1000 = polypropylene glycol, MW = 1000)

[0205] There were hardly any differences in the viscosities in the test series (see Table 2). Adhesion measurements using an oscillating and rotational rheometer also verified the following hypothesis: The initially used proportion of 4-methacryloyloxybenzophenone had little effect on the technical parameters.

[0206] 2. Rheological properties of UV-cured polyacrylate

[0207] Rheological studies were carried out on polyacrylates IC2068 - 7 to IC2068 - 11 prepared according to Table 1. First, the viscosity was measured at a temperature of 90 °C in a Brookfield-CAP2000+ viscometer (AMETEK GmbH, Melsungen, Germany). In addition, the viscosity (referred to as "adhesion") was also measured at a polymer temperature of 90 °C in an oscillating and rotational rheometer MCR302 (Anton Paar, Graz, Austria) under the following measurement conditions: measuring plate PP2, gap: 0.1 mm, pre-shear: 1000 1 / s. The results are shown in Table 2.

[0208] Table 2: Measurement results of polyacrylates in test series IC2068

[0209]

[0210] As shown in Table 2, the results show that there is little difference in viscosity within the test series. The adhesion measurements carried out using an oscillating and rotational rheometer also verified the following hypothesis: the proportion of 4-methacryloyloxybenzophenone initially used has little effect on the technical parameters of the polyacrylate polymer. This provides a technical basis for the production of silane-modified polyacrylate.

[0211] 3. Conversion of UV-cured polyacrylate to polyurethane

[0212] 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, stabilizer) according to Table 3 to form UV-cured polyurethane prepolymers UV 10 to UV 14. Additional polyol and additives can be added to the polyacrylate / polysilane acrylate at 90 °C. Homogenization was carried out at about 10 mbar for 45 minutes. Then 4,4'-MDI was added and stirred for 60 minutes. Before filling the polyurethane adhesive, degassing was carried out again at about 10 mbar.

[0213] Table 3: Test methods for UV 10 to UV 14

[0214] Raw materials UV 10 UV 11 UV 12 UV 13 UV 14 2068-7 78.8 2068-8 78.8 2068-9 78.8 2068-10 78.8 2068-11 78.8 Additives 0.2 0.2 0.2 0.2 0.2 4,4'-MDI 21.0 21.0 21.0 21.0 21.0

[0215] 4. Rheological characterization of UV-cured polyurethane

[0216] Rheological studies were carried out on the polyurethane adhesives UV 10 to UV 14 prepared according to Table 3. First, the viscosity was measured at 90 °C in a Brookfield-CAP2000+ viscometer (AMETEK GmbH, Melsungen, Germany) (rotor 1.5 rpm). In addition, the viscosity (referred to as "adhesion") was also measured in an oscillating and rotational rheometer MCR302 at a polymer temperature of 90 °C, and the measurement conditions were as follows: measuring plate PP12, gap: 0.1 mm, preshear: 1000 1 / s. The results are listed in Table 4.

[0217] Table 4: Measurement results of polyurethane adhesives UV 10 to UV 14

[0218]

[0219] As shown in the measurement results in Table 4, the UV-active polyurethane adhesives UV 10 to UV 14 have a low viscosity when applied at 90 °C and have the characteristic of low inherent adhesion.

[0220] 5. UV-induced adhesion of UV-cured polyurethane

[0221] The 180° peel test and the loop tack test (based on DIN EN 1713) were carried out using a traction machine, and the effectiveness of UV activity in the UV 10 to UV 14 test series was studied in more detail (see Figure 1 and Figure 2 ). The adhesive was applied to an aluminum foil (foil thickness = 30 μm) at a layer thickness of 50 μm at 90 °C, exposed to UV light (UV belt dryer UN50029, Technigraf, Greifenwiesenbach, Germany, wavelength range = 200 nm to 400 nm), then directly adhered to a glass plate and rolled with a 2 kg manual roller. After 10 minutes, the test was carried out on a traction machine. When the UV exposure time was 10 seconds, an energy of about 800 J / cm was generated, while when the exposure time was 20 seconds, an energy of about 1,600 J / cm was generated.

[0222] Figure 1 and Figure 2 The results shown in

[0223] can be summarized as follows: The higher the proportion of photoinitiator, the lower the energy input required for UV exposure and the lower the degree of yellowing of the polyurethane adhesive. Therefore, UV 10 represents the optimal formulation, especially in terms of a 5-fold increase in surface tack and an increase in bond strength. These successful findings have been successfully transferred to the application of UV silane acrylate in PU systems. This is based on further experiments.

[0223] 6. Preparation of UV-curable silane-modified polyacrylate

[0224] Based on the polymerization of acrylate polymers in polyols, the basic formulation IC2068-8 in Table 1 was modified using a silane-containing methacrylate monomer to obtain a UV- and moisture-curable silane acrylate IC2068-12. The amount of organofunctional 3-methacryloxypropyltrimethoxysilane used was 3.0%. The formulation and reaction control are shown in Table 5.

[0225] To produce the silane-modified acrylate polymer, the sample was heated to 90 °C in a glass reactor under a nitrogen atmosphere. After 30 minutes, the monomers were metered in over 2 hours at 90 °C and an initiator was added. Then the secondary reaction occurred over 2 hours and an additional initiator was added.

[0226] Table 5: Formulation of UV-curable silane-modified acrylate UV2068-12

[0227]

[0228]

[0229] 7. Rheological characterization of UV-curable silane-modified polyacrylate

[0230] The UV-curable silane-modified polyacrylate variant IC2068-12 was also rheologically tested using the same method and compared with the base formulation IC2068-8:

[0231] Table 6: Measurement results of UV-curable silane-modified polyacrylate IC2068-12

[0232]

[0233] Similar properties were found through rheological studies.

[0234] 8. Conversion of UV-curable silane-modified polyacrylate to polyurethane

[0235] To produce the polyurethane adhesive, the polyacrylate IC2068-12 prepared according to Table 5 was reacted with 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and the additives according to Table 7 to form the UV-curable polyurethane prepolymer UV 15. Additional polyols and additives can be added to the polyacrylate / polysilane acrylate at 90 °C. Homogenization was carried out at approximately 10 mbar for 45 minutes. Then 4,4'-MDI was added and stirred for 60 minutes. Before filling the polyurethane adhesive, it was degassed again at approximately 10 mbar.

[0236] Table 7: Test method for UV 15

[0237] Raw materials UV 11 (base) UV 15 2068-8 78.8 2068-12 78.8 Additives 0.2 0.2 4,4'-MDI 21.0 21.0

[0238] 9. Rheological characterization of UV-curable silane-modified polyurethane

[0239] The polyurethane adhesive UV 15 produced according to Table 7 was also rheologically tested using the same method and compared with the base formulation UV 11:

[0240] Table 8: Measurement results of UV-curable silane-modified polyurethane adhesive UV 15

[0241]

[0242] Rheological studies showed a slight change in properties.

[0243] 10. UV-induced adhesion of UV-curable polyurethane

[0244] Using a traction machine, 180° peel tests and loop tack tests (based on DIN EN 1713), the relationship between the adhesion strength of the UV-curable silane-modified polyurethane adhesive UV 15 and the UV irradiation time was studied and compared with the base formulation UV 11 (see Figure 3 and Figure 4)。The adhesive was applied to an aluminum foil (foil thickness = 30 μm) at a layer thickness of 50 μm at 90 °C, exposed to UV light (UV belt dryer UN50029, Technigraf, Greifenwiesenbach, Germany, wavelength range = 200 nm to 400 nm), then directly adhered to a glass plate and rolled with a 2 kg manual roller. After 10 minutes, testing was carried out on a traction machine. When the UV exposure time was 10 seconds, an energy of approximately 800 J / cm was generated, while when the exposure time was 20 seconds, an energy of approximately 1,600 J / cm was generated.

[0245] As Figure 3 and Figure 4 shown, in both test methods, the adhesion strength of the silane-modified polymer UV 15 was higher than that of the base formulation UV 11. The optimal UV light irradiation time was 20 to 30 seconds. Description of the Drawings

[0246] shown as:

[0247] Figure 1 Shows the UV-induced adhesion of the polyurethane adhesives UV 10 to UV 14 prepared according to Table 3 using a 180° peel test. The functional relationship between the adhesion strength (Newton) and the UV irradiation time (seconds) is shown.

[0248] Figure 2 Shows the UV-induced adhesion of the polyurethane adhesives UV 10 to UV 14 prepared according to Table 3 using a loop tack test. The functional relationship between the adhesion strength (Newton) and the UV irradiation time (seconds) is shown.

[0249] Figure 3 Shows the UV-induced adhesion of the polyurethane adhesives UV 11 and UV 15 prepared according to Table 7 using a loop tack test. The functional relationship between the adhesion strength (Newton) and the UV irradiation time (seconds) is shown.

[0250] Figure 4 Shows the UV-induced adhesion of the polyurethane adhesives UV 11 and UV 15 prepared according to the table using a 180° peel test. The functional relationship between the adhesion strength (Newton) and the UV irradiation time (seconds) is shown.

Claims

1. A method for producing a polymer composition, The following steps are involved: a) Mix the following ingredients: (i) Polyol or prepolymer with terminal isocyanate (NCO) groups (ii) an ethylenically unsaturated monomer containing no active hydrogen and having no silane group (A-type monomer), and (iii) Ethylenically unsaturated monomers containing no active hydrogen and having a silane group (B-type monomers) (iv) Ethylenically unsaturated monomers containing no active hydrogen and having a free radical photoinitiator group (C-type monomers) b) polymerizing the mixture from step a) using a free radical polymerization method and a chain transfer agent to obtain a low molecular weight polymer having an average molecular weight Mn of 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 Less than 200,000 g / mol.

2. The method according to claim 1, It is characterized in that The polyol is selected from polyesters, polyether polyols such as polyethylene oxide or polypropylene oxide, hydroxyl-containing polycaprolactones, polyoxyalkylene polyols, monosubstituted glycol esters, polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyhydrocarbon polyols, polyacrylate polyols, polymethacrylate polyols, polyols, bisphenols, polycarbonate polyols, polyhydroxy-functional fats and oils, and mixtures thereof, wherein the polyol is preferably a polyether polyol, polyethylene oxide or polypropylene glycol having a molecular weight between 400 and 40,000 Da.

3. The method according to at least one of claims 1 and 2, It is characterized in that The A-type monomer is selected from 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, styrene, acrylonitrile, ethylene or mixtures thereof, wherein the A-type monomer is preferably n-butyl methacrylate (n-BMA) or methyl methacrylate (MMA) or mixtures thereof.

4. The method according to at least one of the preceding claims, It is characterized in that The B-type monomer is selected from the following substances having a silane group: vinyl compounds, acrylates, methacrylates, fumarates, maleates, styrenes, acrylonitrile, ethylene or mixtures thereof.

5. The method according to claim 4, It is characterized in that The B-type monomer is selected from vinyl trichlorosilane, methyl vinyl dichlorosilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(2-methoxyethoxy)silane, vinyl triacetoxysilane, vinyl methyl diethoxysilane, vinyl dimethylethoxysilane, vinyl methyl dimethoxysilane, vinyl dimethyl methoxysilane, vinyl methyl diacetoxysilane, vinyl triisopropoxysilane, vinyl triisopropenoxysilane, vinyl tri(methyl ethyl ketoxime) silane, divinyl tetramethyl disiloxane, tetravinyl tetramethyl cyclotetrasiloxane, 3-acryloxypropyl dimethylmethoxysilane, 3-acryloxypropyl The present invention relates to methyl methacryloyloxypropyl trimethoxysilane, 3-methyl methacryloyloxypropyl triethoxysilane, 3-methyl methacryloyloxypropyl trimethoxysilane, 3-methyl methacryloyloxypropyl triethoxysilane, 3-methyl methacryloyloxypropyl methyl diethoxysilane, 3-methyl methacryloyloxypropyl methyl dimethoxysilane, 3-methyl methacryloyloxypropyl tri(2-methoxyethoxy) silane, 4-(3-trimethoxysilylpropyl) benzyl styrene sulfonate, allyl triethoxysilane, allyl trimethoxysilane and oligomers of these silanes, wherein the B-type monomer is preferably methacryloyloxypropyl trimethoxysilane.

6. The method according to at least one of the preceding claims, It is characterized in that The C-type monomer is a monomer having a II-type free radical photoinitiator group, and the II-type free radical photoinitiator group is preferably a benzophenone group or an isopropylthioxanthone group. The C-type monomer is particularly preferably selected from 4-methacryloxybenzophenone, 4-methacryloxyethoxybenzophenone, 4-methacryloxy-4'-methoxybenzophenone, 4-methacryloxyethoxy-4'-methoxybenzophenone, 4-methacryloxy-4'-bromobenzophenone, 4-acryloxyethoxy-4'-bromobenzophenone, 4-acryloxybenzophenone (ABP), 4-(2-acryloxyethoxy)benzophenone (AEBP), 4-(2-acryloxybutoxy)benzophenone (ABBP), 4-(2-acryloxyhexyloxy)benzophenone (AHBP), and ABP or 4-methacryloxybenzophenone is particularly preferred.

7. The method according to at least one of the preceding claims, It is characterized in that In the free radical polymerization process, a peroxide initiator or an azo initiator is used as initiator, the initiator preferably being selected from dilauroyl peroxide, dibenzoyl peroxide, dimethyl-2,2'-azobisisobutyrate, di-(4-tert-butyl-cyclohexyl)-peroxydicarbonate and azobis(isobutyronitrile).

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

9. The method according to at least one of the preceding claims, It is characterized in that The amount of the polyol or prepolymer having a terminal NCO group is 20 to 90 wt %, preferably 40 to 80 wt %, particularly preferably 50 to 60 wt %, based on the total weight of the polyol or prepolymer and the A to C monomer components.

10. The method according to at least one of the preceding claims, It is characterized in that Based on the total weight of monomer A, monomer B and monomer C, the amount of monomer A is 30 to 95 wt%, preferably 50 to 90 wt%, and particularly preferably 70 to 85 wt%.

11. The method according to at least one of the preceding claims, It is characterized in that Based on the total weight of the A monomer, the B monomer and the C monomer, the amount of the B monomer is 5 to 70 wt %, preferably 10 to 50 wt %, particularly preferably 15 to 30 wt %.

12. The method according to at least one of the preceding claims, It is characterized in that Based on the total weight of monomer A, monomer B and monomer C, the amount of monomer C is 0.1 to 5.0 wt%, preferably 0.2 to 4.0 wt%, and particularly preferably 0.3 to 3.0 wt%.

13. The method according to at least one of the preceding claims, It is characterized in that The number average molecular weight of the low molecular weight polymer is 3,000-200,000 g / mol, preferably 5,000-100,000 g / mol, and particularly preferably 10,000-60,000 g / mol.

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

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

16. The polymer composition according to claim 14 or 15, It is characterized in that The polymer composition has a viscosity measured at 90° C. of 500-25,000 mPa·s, preferably 1,000-21,000 mPa·s.

17. The polymer composition according to at least one of claims 14 to 16, It is characterized in that The polymer composition contains no solvent.

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 is cured as a one-component composition under moisture by increasing the temperature to above 100°C.

19. A method for producing a UV and moisture curing polyurethane hot melt adhesive composition, The following steps are involved: a) Providing a polymer composition according to at least one of claims 14 to 17 b) adding sufficient polyisocyanate to achieve the desired isocyanate content and isocyanate index, and then polymerizing by using an addition polymerization method c) Optional addition of aminosilane or mercaptosilane and conversion to silane-terminated polyurethane d) Irradiation with UV light to further crosslink the polymer.

20. The method according to claim 19, It is characterized in that The polyisocyanate in step b) is selected from ethylene diisocyanate, ethylene 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, xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate isocyanates, diphenyl sulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, furylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4,4',4"-triisocyanatotriphenylmethane, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and 4,4'-dimethyldiphenylmethane-2,2',5,5-tetraisocyanate, 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, polymeric diphenylmethane diisocyanate (PMDI), blocked diisocyanates and carbodiimide-modified polyisocyanates, as well as mixtures or precondensates of the above isocyanates, such as HDI biuret or HDI cyanurate, wherein the polyisocyanate is preferably an aliphatic isocyanate.

21. The method according to claim 19 or 20, It is characterized in that The free isocyanate content is between 0-20%, preferably between 0-15%, and particularly preferably between 0-10%.

22. The method according to at least one of claims 19 to 21, It is characterized in that The isocyanate index is 0.5-10, preferably 1-3, and particularly preferably 1.5-2.

5.

23. A UV and moisture curing polyurethane hot melt adhesive composition prepared by the method of at least one of claims 19 to 22.

24. The UV and moisture curable polyurethane hot melt adhesive composition according to claim 23, It is characterized in that The composition has a viscosity at 120° C. of 10 to 150,000 mPa·s.

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 method for producing a 1K polyurethane adhesive, The following steps are involved: a) providing a polymer composition as claimed in at least one of claims 14 to 17, wherein the temperature increase in optional step (b) is not carried out, but the polymer is cooled to a temperature of 80° C. to 20° C. b) Adding polyisocyanate to achieve the desired free isocyanate content and the desired isocyanate index c) optionally cooling to a temperature of 80°C to 20°C for 0.5-5 hours.

27. The method according to claim 26, It is characterized in that In step b), the polyisocyanate according to claim 20 is used, preferably an aliphatic diisocyanate.

28. The method according to claim 26 or 27, It is characterized in that The free isocyanate content is 2-40%, preferably 5-30%, particularly preferably 10-20%.

29. The method according to at least one of claims 26 to 28, It is characterized in that The isocyanate index is 1.5-20, preferably 2-15, particularly preferably 4-10. 30 . A 1K polyurethane adhesive prepared according to the method of at least one of claims 26 to 29 .

31. The 1K polyurethane adhesive according to claim 30, It is characterized in that The 1K polyurethane adhesive has a viscosity measured at 90° C. of 5,000-25,000 mPa·s, preferably 6,000-21,000 mPa·s.

32. A method for producing a 2K polyurethane adhesive, the method comprising the following steps for producing a first component of the 2K polyurethane adhesive: a) providing a polymer composition according to at least one of claims 14 to 17, wherein the temperature increase in the optional step b) is not carried out, but the polymer is cooled to a temperature of 80° C. to 20° C., the polymer composition having epoxy groups introduced by one of the monomers A to C which additionally have epoxy groups as functional groups, or by another ethylenically unsaturated monomer (D-type monomer) which does not contain active hydrogen and has epoxy groups as functional groups b) Add polyisocyanate to achieve the desired free isocyanate content and isocyanate index c) optionally cooling to a temperature of 80° C. to 20° C. for 0.5 to 5 hours, In the method, epoxy-reactive monomers or prepolymers are used as the second component of the 2K polyurethane adhesive.

33. The method according to claim 32, It is characterized in that The second component is an amine compound or a prepolymer having a terminal isocyanate group, a hydroxyl group, a mercapto group or an amine group.

34. A 2K polyurethane adhesive, prepared by the method of claim 32 or 33.

35. Use of the 1K polyurethane adhesive according to claim 30 or 31 or the 2K polyurethane adhesive according to claim 34 as an adhesive, coating compound or sealant, in particular as the following: multifunctional adhesive (household adhesive), assembly adhesive, building adhesive, paper and packaging adhesive, film laminating adhesive, adhesive for ceramic and metal materials, wood, glass, sandwich systems, textiles, reinforcing fabrics, materials in the aircraft, military or shipbuilding fields.

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