Polyisocyanate composition

Abstract

The present invention relates to a polyisocyanate composition comprising at least one bridged cis-tetrahydrofuran-2, 3, 4-triazole-2, 3, 4-triazole-2, 3, 4-triazole-2, 3, 4- and at least one isocyanurate, iminooxadiazinedione, allophanate, carbamate, urea, uretdione, oxadiazinetrione, carbodiimide, thiocarbamate, thioallophanate and / or biuret structure and / or a structure comprising at least one bridging trans-tetrahydrofuran-2, 5-diyl-dimethylene unit and at least one bridging trans-tetrahydrofuran-2, 5-dimethylene unit and at least one of isocyanurate, iminooxadiazinedione, allophanate, carbamate, urea, uretdione, oxadiazinetrione, carbodiimide, thiocarbamate, thioallophanate and biuret structure and / or at least one bridging trans-tetrahydrofuran-2, 5-dimethylene unit. The present invention relates to a polymer comprising at least one (2, 5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, carbamate, urea, uretdione, oxadiazinetrione, carbodiimide, thiocarbamate, thioallophanate and / or biuret structure.

Description

[0001] This invention relates to polyisocyanate compositions. The invention further relates to methods for preparing such polyisocyanate compositions, uses of such polyisocyanate compositions, two-component systems comprising said polyisocyanate compositions, and molded articles, coatings, and composite parts that can be obtained therefrom.

[0002] Oligopolymerization or polymerization of isocyanates, especially the formation of mixtures of higher molecular weight oligomers, is well known. The reaction of relatively small amounts of isocyanates with each other is called oligopolymerization. The reaction of relatively large amounts of isocyanates is called polymerization. In the context of this invention, the oligopolymerization or polymerization of the aforementioned isocyanates is collectively referred to as isocyanate modification or isocyanate alteration. All products obtained by such methods are collectively referred to in this document as polyisocyanate compositions or simply polyisocyanates. These polyisocyanates contain free isocyanate groups (NCO groups), which can optionally be temporarily deactivated by a blocking agent; they are extremely high-quality starting materials for the preparation of a variety of polyurethane plastics and coating compositions.

[0003] Polyisocyanates used in coating compositions for high-quality coatings are particularly low-monomer derivatives prepared from hexamethylene 1,6-diisocyanate (HDI). HDI isocyanurate polyisocyanates, or HDI polyisocyanates containing an iminooxadiazine dione and an isocyanurate structure, are particularly suitable for the purpose of creating resilient, highly robust coatings. These are described, for example, in HJ Laas, R. Halpaap, J. Pedain, J. prakt. Chem. 1994, 336, 185-200. These polyisocyanates typically have an isocyanate functionality of 3 or greater (F...). NCO (), where isocyanate functionality refers to the average number of NCO groups per molecule.

[0004] The disadvantages of HDI-based polyisocyanates include a relatively long physical drying time, resulting in low coating process efficiency, and the requirement of a catalyst, at least at lower temperatures. Similar to HDI, pentamethylene 1,5-diisocyanate (PDI) is an established monomer, as described, for example, in W. Siefken, Liebigs Ann. Chem. 1949, 562, page 122, or DE 1493360 B1 and DE 1900514 A1.

[0005] GB936370 describes a general laboratory synthesis of monomeric isocyanates of furan and tetrahydrofuran via liquid-phase phosgenation of dihydrochloride, which is a rather inefficient and complex method on a large scale. No further modification or application testing is described.

[0006] WO2011 / 098272A2 describes mixtures of short-chain and long-chain renewable diisocyanates for the preparation of polyurethanes. In very long lists of short-chain renewable diisocyanates, furan-based diisocyanates are often mentioned, but neither application examples nor preferences are described.

[0007] WO2021 / 180709A1 describes specific open-chain isocyanates containing ether groups for isocyanate modification, with the aim of reducing the catalyst dosage in the isocyanate modification reaction itself, which is entirely different from the catalyst technology used in coating applications. No application examples are described.

[0008] In contrast to the aforementioned monomeric furans and tetrahydrofurans, as well as other open-chain diisocyanates containing ether groups, isophorone diisocyanates (IPDI) have been used in coating applications and are known for their good drying properties (resulting in shorter drying times). However, the disadvantages of IPDI polyisocyanates include insufficient flexibility and reduced solvent resistance in the resulting coatings, as well as their low chemical reactivity.

[0009] WO2020 / 109125A1 describes a mixture of polyisocyanates primarily composed of PDI and IPDI, which exhibits improved properties compared to a mixture of HDI and IPDI. However, these PDI / IPDI polyisocyanate mixtures require further preparation, and even their properties still have room for improvement.

[0010] In conclusion, there is still no solution available to address the shortcomings of existing technologies.

[0011] Therefore, one object of the present invention is to provide a polyisocyanate composition that combines the rapid drying time of a prepared coating composition with the excellent solvent resistance of the resulting coating, without the need to mix polyisocyanates from different monomeric diisocyanates, and which allows curing even at low temperatures without the addition of a catalyst for coating applications.

[0012] This objective has been achieved by a polyisocyanate composition comprising at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbamate and / or biuret structure and / or comprising at least one bridging trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbamate and / or biuret structure.

[0013] The terms "comprising," "containing," etc., preferably refer to "consistent with," and very particularly preferably refer to "consisting with." In this invention, any numerical range described herein is intended to include all subranges contained therein. For example, the range "1 to 10" is intended to include all subranges between the minimum value 1 and the maximum value 10 (and including both the minimum value 1 and the maximum value 10), i.e., a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0014] According to the present invention, the cis and trans stereoisomers of (tetrahydrofuran-2,5-diyl)-dimethylamine are collectively referred to as "TEFUDA", and are also respectively referred to as "cis-TEFUDA" and "trans-TEFUDA". The cis and trans stereoisomers of 2,5-bis(isocyanate methyl)tetrahydrofuran are collectively referred to as "TEFUDI", and are also respectively referred to as "cis-TEFUDI" and "trans-TEFUDI". For clarity, cis-TEFUDA or cis-TEFUDI corresponds to the (2R,5S) and (2S,5R) configurations, and trans-TEFUDA or trans-TEFUDI corresponds to the (2R,5R) and (2S,5S) configurations.

[0015] According to the present invention, the bridging cis- and / or trans-tetrahydrofuran-2,5-dimethyl-dimethylene unit is a structural unit that is connected via an exocyclic CH2 portion to a nitrogen atom of an isocyanate group, a nitrogen atom of an isocyanurate group, a nitrogen atom of an iminooxadiazine dione group, a nitrogen atom of a urethane group, a nitrogen atom of a urethane group, a nitrogen atom of a urethane dione group, a nitrogen atom of an oxadiazine trione group, a nitrogen atom of a carbodiimide group, a nitrogen atom of a thiourethane group, a nitrogen atom of a thiourethane group, or a nitrogen atom of a biuret group, and is connected via another exocyclic CH2 portion to a nitrogen atom of any independently selected of the aforementioned functional groups. Preferably, the bridging cis- and / or trans-tetrahydrofuran-2,5-dimethyl-dimethylene unit is a structural unit that is connected via an exocyclic CH2 portion to a nitrogen atom of an isocyanurate group, a nitrogen atom of an iminooxadiazine dione group, a nitrogen atom of a urethane group, a nitrogen atom of a urethane group, a nitrogen atom of a urethane dione group, a nitrogen atom of an oxadiazine trione group, a nitrogen atom of a carbodiimide group, a nitrogen atom of a thiourethane group, a nitrogen atom of a thiourethane group, or a nitrogen atom of a biuret group, and is connected via another exocyclic CH2 portion to a nitrogen atom of any independently selected of the aforementioned functional groups or to a nitrogen atom of an isocyanate group. The naming of the two exocyclic CH2 portions can also be switched. This bridging unit can be via a standard 1 H- and / or 13 C-NMR measurements are used for detection.

[0016] The isocyanurate structure or isocyanurate group is understood as a structural unit that is randomly linked to each other or randomly linked to a functional group via the above-mentioned cis- and / or trans-tetrahydrofuran-2,5-dimethyl)-dimethylene units according to the oligomer distribution.

[0017] Isocyanurate structure The iminooxadiazine dione structure (also known as the iminooxadiazine dione group) is understood as a structural unit that is randomly linked to each other or randomly linked to a functional group via the above-mentioned cis- and / or trans-tetrahydrofuran-2,5-dimethyl)-dimethylene units according to the oligomer distribution.

[0018] Iminooxadiazine dione structure The urethane ester structure (also known as the urethane ester group) is understood as a unit that is randomly linked to each other or randomly linked to a functional group via the above-mentioned cis- and / or trans-tetrahydrofuran-2,5-dimethyl)-dimethylene units according to the oligomer distribution.

[0019] Urea carbamate structure The presence of the aforementioned isocyanurate, iminooxadiazine dione, and / or urethane structures can be detected by standard 1 H- and / or 13 Determined by C-NMR measurements.

[0020] In a first preferred embodiment, the polyisocyanate composition of the present invention is characterized in that it comprises at least one isocyanurate, iminooxadiazine dione, urethane, urea dione, and / or biuret structure, preferably at least one isocyanurate, iminooxadiazine dione, urethane, and / or urea dione structure, more preferably at least one isocyanurate, iminooxadiazine dione, and / or urea dione structure. This has the advantage that the curing speed of the applied coating can be further improved.

[0021] In other words, the aforementioned first preferred embodiment should be understood as the bridging cis- and / or trans-tetrahydrofuran-2,5-dimethyl-dimethylene unit being a structural unit that is connected via an exocyclic CH2 moiety to a nitrogen atom of an isocyanurate group, a nitrogen atom of an iminooxadiazine dione group, a nitrogen atom of a urethane group, a nitrogen atom of a urea dione group, or a nitrogen atom of a biuret group, and is connected via another exocyclic CH2 moiety to a nitrogen atom of any independently selected of the aforementioned functional groups or to a nitrogen atom of an isocyanate group. The naming of the two exocyclic CH2 moiety can also be switched. This bridging unit can be via standard... 1 H- and / or 13 C-NMR measurements are used for detection.

[0022] In a preferred embodiment, the polyisocyanate composition of the present invention is characterized by having an NCO content of 5.8 to 25.9% by weight, preferably 7.8 to 24.9% by weight, and particularly preferably 9.7 to 23.9% by weight, as determined according to DIN EN ISO 11909:2007-05, based on the total weight of the polyisocyanate composition.

[0023] In a preferred embodiment, the polyisocyanate composition of the present invention is characterized by having a residual monomer content of less than 1 wt%, preferably less than 0.5 wt%, and more preferably less than 0.1 wt%, based on the total weight of the polyisocyanate composition.

[0024] The content of residual monomer 2,5-bis(isocyanate methyl)tetrahydrofuran was determined by gas chromatography using an internal standard according to DIN EN ISO 10283:2007-11.

[0025] In a preferred embodiment, the polyisocyanate composition of the present invention comprises, based on the total solid content of the polyisocyanate composition of the present invention, ≥70% by weight, preferably ≥85% by weight, more preferably ≥95% by weight, and very preferably 100% by weight, a polyisocyanate comprising at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbamate, and / or biuret structure and / or a polyisocyanate comprising at least one bridging trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiourea carbamate, thiourea carbamate, and / or biuret structure.

[0026] Further preferably, the polyisocyanate composition of the present invention contains, based on the total solid content of the polyisocyanate composition of the present invention, ≥70% by weight, preferably ≥85% by weight, more preferably ≥95% by weight, and very preferably ≥100% by weight, a polyisocyanate comprising at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, and / or urea carbamate structure and / or a polyisocyanate comprising at least one bridging trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, and / or urea carbamate structure.

[0027] The present invention further relates to a polyisocyanate composition comprising a) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one structure selected from isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbamate, and biuret, and / or comprising b) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one structure selected from isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbamate, and biuret.

[0028] In a further embodiment, the present invention relates to a polyisocyanate composition comprising a) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one structure selected from isocyanurate, iminooxadiazine dione, urethane, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbodiformate and biuret, and / or comprising b) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one structure selected from isocyanurate, iminooxadiazine dione, urethane, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourea carbodiformate and biuret.

[0029] In a further embodiment, the present invention relates to a polyisocyanate composition comprising a) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one structure selected from isocyanurates, iminooxadiazine diones, urethane, urea diones, and biurets, and / or comprising b) at least one polyisocyanate, wherein the at least one polyisocyanate comprises at least one bridging trans-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one structure selected from isocyanurates, iminooxadiazine diones, urethane, urea diones, and biurets. Unless the context clearly indicates otherwise, the three foregoing embodiments may be combined in any way with other claims, aspects, and embodiments of the invention.

[0030] Optionally, the polyisocyanate compositions of the present invention may comprise other bridging units derived from other monomeric diisocyanates, such as those derived from pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2-methylpentane 1,5-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, 4-isocyanate methyl octane 1,8-diisocyanate, 3(4)-isocyanate methyl-1-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate, etc. Cyanocyanate (IPDI), 1,3- and 1,4-bis(isocyanate methyl)benzene (XDI), 1,3- and 1,4-bis(isocyanate methyl)cyclohexane (H6XDI), toluene 2,4- and 2,6-diisocyanate (TDI), bis(4-isocyanate phenyl)methane (4,4'MDI), 4-isocyanate phenyl-2-isocyanate phenylmethane (2,4'MDI), and polycyclic products obtainable by formaldehyde-aniline polycondensation and subsequent conversion of the resulting (poly)amine into the corresponding (poly)isocyanate (polymer MDI).

[0031] When using or including other monomeric diisocyanates as bridging units, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2-methylpentane 1,5-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, 4-isocyanate methyl octane 1,8-diisocyanate, 3(4)-isocyanate methyl-1-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis(isocyanate methyl)benzene (XDI) and / or 1,3- and 1,4-bis(isocyanate methyl)cyclohexane (H6XDI) are preferred. Pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, 4-isocyanate methyl octane and / or 1,8-diisocyanate are particularly preferred, and pentamethylene diisocyanate (PDI) and / or hexamethylene diisocyanate (HDI) are even more preferred.

[0032] The amount of optional other isocyanates, other than the essential cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran, is guided by the specific application and can vary over a wide range if they are actually used, preferably 0 to 5% by weight, more preferably 0 to 2% by weight, and more preferably 0 to 1% by weight, based on the total amount of monomeric compounds having NCO groups. However, most preferably, only cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran are bridging units in the polyisocyanate compositions of the present invention to maximize the positive technical effects of the essential TEFUDI.

[0033] The method by which the aforementioned isocyanates, including cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran, are produced, whether or not phosgene is used, is irrelevant. Phosgeneization in the liquid or gas phase is preferred in the industrial production of isocyanates, and even more preferably by gas-phase phosgeneization as described, for example, in EP 0764 633 A2. TEFUDI is preferably prepared from the corresponding diamine.

[0034] The present invention further relates to a method for preparing a polyisocyanate or a polyisocyanate composition, the method comprising a conversion step of 2,5-bis(isocyanate methyl)tetrahydrofuran to the polyisocyanate or polyisocyanate composition, and obtaining, or being able to obtain, preferably directly obtaining, the polyisocyanate or polyisocyanate composition according to the method of converting 2,5-bis(isocyanate methyl)tetrahydrofuran to the polyisocyanate or polyisocyanate composition.

[0035] The necessary precursors of cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran can be obtained from various sources, but are preferably obtained from bio-based sources.

[0036] When other monomeric diisocyanates are used or included as bridging units, the total content of monomeric diisocyanates (including 2,5-bis(isocyanate methyl)tetrahydrofuran) is preferably less than 1% by weight, more preferably less than 0.5% by weight, and more preferably less than 0.1% by weight, based on the total weight of the polyisocyanate composition. The residual monomeric diisocyanate content is determined by gas chromatography using an internal standard according to DIN EN ISO 10283:2007-11.

[0037] Dynamic viscosity was determined at 23°C using an MCR 501 rheometer (from Anton Paar) according to DIN EN ISO 3219:1994-10. Measurements at different shear rates ensured that Newtonian flow behavior could be assumed. Therefore, details regarding shear rates can be omitted.

[0038] The present invention further relates to a method for preparing the polyisocyanate compositions of the present invention, said method comprising a reaction in the presence of at least one cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran optionally in the presence of at least one catalyst, optionally in the presence of other co-reactants selected from alcohols, thiols, amines, water, CO2, or other isocyanates having an NCO functionality >1. In this respect, the term "reaction" also includes the modification of the polyisocyanates of the present invention or the polyisocyanate compositions of the present invention by cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran.

[0039] Typically, the methods of this invention use cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran monomers to obtain the polyisocyanate compositions of this invention by forming bridging units between isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourethane carbamate and / or biuret structures. Such modifications to TEFUDI can be based, for example, in J. Prakt. Chem. 336 (1994) 185–200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503, or in EP-A 0 336 205, EP-A 0 339 396, EP-A 0 798 299, EP-A 0 962 454, EP-A 0 962 455, EP-A 2 785 760, EP-A 2 The method described in 883 895, EP-A 3 107922, EP-A 3 107 948 and EP-A 3 337 836 shall be used.

[0040] Besides cis-2,5-bis(isocyanate-methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate-methyl)tetrahydrofuran themselves, the co-reactants optionally used in the methods of the present invention and optionally most likely included in the polyisocyanate compositions of the present invention in reactive form can be conventional bifunctional and higher-functionality co-reactants with Zerevitinoff active hydrogen, as is common in polyurethane chemistry, such as water, alcohols, thiols, and amines. These compounds preferably have an average OH, NH, or SH functionality of at least 1.5. These can be, for example, low molecular weight diols (e.g., ethylene-1,2-diol, propylene-1,3- or -1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), short-chain polyamines, and also polyaspartic esters, polythiols, and / or polyhydroxy compounds, such as polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols, and / or polymethacrylate polyols, and copolymers thereof.

[0041] Other isocyanates having an NCO functionality >1 that may be optionally included in the method of the present invention are preferably selected from the above list. However, TEFUDI is most preferably used as the monomeric diisocyanate having an NCO functionality >1.

[0042] Typical compounds known to be catalytically active for isocyanates are suitable as catalysts for NCO-NCO reactions, for example, for the formation of isocyanurates, iminooxadiazine diones, and / or urethane structures from at least cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran. Besides compounds with ionic structures, these catalysts include, for example, compounds having "onium" cations (ammonium, phosphonium, etc.) and nucleophilic anions such as hydroxyl, alkanoate, carboxylate, heterocycles having at least one negatively charged nitrogen atom in the ring, especially azolate, imidazolate, triazolate, tetrazolate, fluoride, hydrogen difluoride, higher polyfluoride, or mixtures thereof (adducts of more than one equivalent of HF on fluoride-containing compounds), wherein fluoride, hydrogen difluoride, and higher polyfluoride may, under suitable reaction conditions, yield products with a high content of iminooxadiazine dione groups, and neutral bases such as tertiary amines or phosphine. Especially in the latter case, structural variations allow for a wide range of selectivity to be covered; from high ureidone selectivity to high "trimer" selectivity, the latter typically yielding mixtures of isocyanurates and iminooxadiazine diones.

[0043] Optional catalysts can be used alone or in any desired mixture of them. For example, depending on the pK of the base and alcohol used. a In various alcohols, quaternary ammonium hydroxide exists partially or entirely as an ammonium salt with an alkoxide anion in solution. This equilibrium can be completely shifted to the side forming a complete alkoxide formation by removing the reaction water generated by the reaction. Suitable methods for dehydration include all methods known in the literature for this purpose, particularly (azeotropic) distillation, which may be carried out optionally with the aid of a suitable entrainer if the alcohol itself used as a solvent is unsuitable.

[0044] The reaction progress in the method of the present invention can be monitored by titration of the NCO content according to DIN EN ISO 11909:2007-05. When the desired NCO content (“degree of polymerization”) is reached, the reaction is stopped by appropriate means, depending on the modification reaction and / or whether a catalyst is used. Preferably, the catalyst is deactivated by adding a suitable catalyst poison.

[0045] According to a further preferred embodiment, the reaction proceeds to a point where the reaction mixture has an oligomerization degree of 10% to 40%, preferably 15% to 30%.

[0046] "Degree of oligomerization" currently refers to the percentage of isocyanate groups initially present in the starting mixture consumed during the reaction according to the invention. The degree of oligomerization as a percentage can be calculated according to the following formula: Degree of oligomerization = (NCO) 起始 – NCO 结束 ) / NCO 起始 ×100 For example, the reaction can be stopped when the target oligomerization degree is reached. This oligomerization degree is typically reached after a reaction time of 30 minutes to 8 hours, preferably 1 to 6 hours.

[0047] The reaction can be terminated, for example, by cooling the reaction mixture to room temperature. However, it is typically terminated by adding a catalyst poison and optionally followed by briefly heating the reaction mixture to a temperature, for example, above 80°C.

[0048] Examples of suitable catalyst poisons are inorganic acids such as hydrochloric acid, phosphorous acid, or phosphoric acid; acyl chlorides such as acetyl chloride, benzoyl chloride, or isophthaloyl chloride; sulfonic acids and sulfonates such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, dodecylbenzenesulfonic acid, methyl p-toluenesulfonate, and ethyl p-toluenesulfonate; monoalkyl phosphates and dialkyl phosphates such as monotridecyl phosphate, dibutyl phosphate, and dioctyl phosphate; and silylated acids such as trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, tri(trimethylsilyl) phosphate, and diethyl trimethylsilyl phosphate.

[0049] The amount of catalyst poison required to terminate the reaction depends on the amount of catalyst used; typically, an equal amount of catalyst poison is used based on the amount of catalyst initially used. However, considering the potential catalyst loss during the reaction, 20 to 80 equivalent percent of catalyst poison may also be sufficient to terminate the reaction based on the amount of catalyst initially used.

[0050] The catalyst poison can be used as is or dissolved in a suitable solvent. If a solvent is used to dissolve the catalyst poison, TEFUDI is preferred. The dilution can be freely chosen over a very wide range; for example, solutions starting from concentrations of ≥25% by weight, preferably ≥10% by weight, are suitable.

[0051] After the reaction is complete, the reaction mixture is preferably free of volatile components (excess monomeric isocyanate components and any solvents used) by thin-film distillation under reduced pressure (e.g., at pressures below 1.0 mbar, preferably below 0.75 mbar, more preferably below 0.25 mbar) and under extremely mild conditions (e.g., at temperatures of 100 to 200°C, preferably 120 to 180°C).

[0052] In another embodiment of the method of the present invention, the volatile components are removed from the polyisocyanate composition of the present invention by extraction with a suitable solvent that is inert to the isocyanate groups, examples of which are aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane, cyclopentane, or cyclohexane.

[0053] The method of the present invention is preferably carried out in the absence of a solvent. However, if desired, a suitable solvent that is inert to the reactive groups of the starting component may also be used. Suitable solvents are, for example, conventional paint solvents known per se, such as ethyl acetate, butyl acetate, ethylene glycol monomethyl or monoethyl ether acetate, 1-methoxypropyl-2-yl acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, petroleum solvent oils, and more substituted aromatic compounds, such as those commercially available under the names Solventnaphtha, Solvesso®, Isopar®, Nappar®, Varsol® (ExxonMobil Chemical Central Europe, Cologne, Germany) and Shellsol® (Shell Deutschland Oil GmbH, Hamburg, Germany), as well as propylene glycol diacetate. Solvents of diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam, or any desired mixture of such solvents.

[0054] Independent of the solvent optionally used during the modification reaction of TEFUDI to form the bridging unit, the method of the present invention includes the optional step of adding at least one solvent inert to the isocyanate groups to achieve a preferred viscosity of <2000 mPas at 23°C as measured according to DIN EN ISO 3219:1994-10. Such optional solvents are preferably selected from the foregoing list. When carrying out such an optional step, a suitable solvent is preferably added in an amount to achieve a solid content of >50% by weight, more preferably >80% by weight, and most preferably >95% by weight.

[0055] Another aspect of the invention is based on polyisocyanates of cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran, which can be obtained or directly obtained through oligomerization of cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran.

[0056] As an alternative or even more preferred embodiment, a polyisocyanate mixture of the polyisocyanate composition of the present invention with at least one other polyisocyanate is also another aspect of the present invention. Due to the TEFUDI-based polyisocyanate composition of the present invention, such polyisocyanate mixtures of the present invention exhibit the same positive technical effects, with the additional benefit of further improvements depending on the desired application and the specific properties required by that application.

[0057] Suitable at least one other polyisocyanate is generally prepared by modifying simple aliphatic, alicyclic, aryliphatic, and / or aromatic diisocyanates and / or triisocyanates (e.g., those of the types mentioned above) with urea dione, isocyanurate, urethane, biuret, iminooxadiazine dione, and / or oxadiazine trione structures, such as in J. Prakt. Chem. 336 (1994) 185–200, in DE-A 1,670,666, DE-A 1,954,093, DE-A 2,414,413, DE-A 2,452,532, DE-A 2,641,380, DE-A 3,700,209, DE-A 3,900,053, and DE-A 3,928,503, or in EP-A Those used and described in EP-A 0,336,205, EP-A 0,339,396, EP-A 0,798,299, EP-A 0,962,454, EP-A 0,962,455, EP-A 2,785,760, EP-A 2,883,895, EP-A 3,107,922, EP-A 3,107,948, and EP-A 3,337,836. They can also be used in mixtures of two or more of these polyisocyanates.

[0058] In principle, the polyisocyanate mixtures of the present invention can be prepared by mixing at least one TEFUDI-based polyisocyanate composition of the present invention with at least one of the above-described polyisocyanates. If desired, one or more organic solvents inert to isocyanate groups may be added to the polyisocyanate composition of the present invention and / or to at least one other polyisocyanate at any stage during or after the mixing process, or may even have been added as a diluent to the polyisocyanate composition of the present invention and / or to at least one other polyisocyanate. Suitable organic solvents inert to isocyanate groups may be selected from the above list of optional solvents used to prepare the polyisocyanate compositions of the present invention.

[0059] Regarding the residual monomer content, the same limitations are indeed preferred for the polyisocyanate mixtures of the present invention, wherein the total amount of residual monomers, diisocyanate and triisocyanate, is less than 1% by weight, preferably less than 0.5% by weight, and more preferably less than 0.1% by weight, based on the total weight of the polyisocyanate composition. The residual monomer content is determined by gas chromatography using an internal standard according to DIN EN ISO 10283:2007-11.

[0060] The mixing ratio and thus weight ratio of at least one TEFUDI-based polyisocyanate composition of the present invention with at least one of the above-mentioned polyisocyanates can vary widely and are selected based on the desired application. However, it is preferred that the TEFUDI-based polyisocyanate composition is one of the main components, preferably having a solid content of more than 10% by weight, more preferably more than 25% by weight, and most preferably more than 40% by weight in the polyisocyanate mixture of the present invention.

[0061] By selecting the amount of solvent, the solid content of the polyisocyanate composition or mixture according to the invention can vary over a wide range, especially when organic solvents can be used. In this case, it is particularly preferred if the polyisocyanate composition or mixture according to the invention has a solid content of ≥10% and ≤95% by weight, preferably ≥25% and ≤85% by weight.

[0062] The present invention further relates to the use of at least one polyisocyanate composition of the present invention and / or at least one polyisocyanate composition obtained or obtainable according to the method of the present invention, preferably directly obtainable, and / or at least one polyisocyanate of the present invention for reducing the amount of catalyst in curing with at least one NCO reactive compound and / or allowing curing with at least one NCO reactive compound at a temperature below 100°C, preferably below 80°C. In this regard, the term "reducing the amount of catalyst" is preferably understood to be the amount of catalyst required for the reaction of aliphatic NCO groups other than those from TEFUDI with NCO reactive groups.

[0063] The NCO reactive compounds used can be any compounds known to those skilled in the art—including any desired mixtures of each other—having an average OH, NH, or SH functionality of at least 1.5. These can be, for example, low molecular weight diols (e.g., ethylene-1,2-diol, propylene-1,3- or propylene-1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), short-chain polyamines, and also polyaspartic esters, polythiols, and / or polyhydroxy compounds such as polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols, and / or polymethacrylate polyols, and copolymers thereof, hereinafter referred to as polyacrylate polyols.

[0064] According to a further preferred embodiment, the NCO reactive compound is a polyhydroxy compound, preferably a polyether polyol, polyester polyol, polycarbonate polyol, or polyacrylate polyol.

[0065] The present invention further relates to the use of at least one polyisocyanate composition of the present invention and / or at least one polyisocyanate composition obtained or obtainable according to the method of the present invention, preferably directly obtained, and / or at least one polyisocyanate of the present invention in the manufacture of coatings, adhesives, or sealants on substrates, or to the use of at least one polyisocyanate composition of the present invention and / or at least one polyisocyanate composition obtained or obtainable according to the method of the present invention, preferably directly obtained, and / or at least one polyisocyanate of the present invention in coatings, adhesives, or sealants.

[0066] The present invention further relates to a two-component system containing component A) and component B), wherein component A) comprises at least one polyisocyanate composition of the present invention and / or at least one polyisocyanate composition obtained or available by the method of the present invention and / or at least one polyisocyanate of the present invention, and component B) comprises at least one NCO reactive compound.

[0067] The NCO reactive compound of component B) can be any compound known to those skilled in the art—including any desired mixture of each other—having an average OH, NH, or SH functionality of at least 1.5. These can be, for example, low molecular weight diols (e.g., ethylene-1,2-diol, propylene-1,3- or propylene-1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), short-chain polyamines, and also polyaspartic esters, polythiols, and / or polyhydroxy compounds such as polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols, and / or polymethacrylate polyols, and copolymers thereof, hereinafter referred to as polyacrylate polyols.

[0068] In a preferred embodiment of the two-component system of the present invention, the at least one NCO reactive compound is a polyhydroxy compound, preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, and / or a polyacrylate polyol.

[0069] The two-component system of the present invention optionally contains auxiliaries and additives, which may be, for example, cobinders, desiccants, fillers, cosolvents, coloring or effect pigments, thickeners, matting agents, light stabilizers, coating additives such as dispersants, thickeners, defoamers, and other auxiliaries known to those skilled in the art such as adhesives, fungicides, bactericides, stabilizers or inhibitors, and catalysts or emulsifiers.

[0070] The polyisocyanate compositions of the present invention are also suitable for single-component systems in which substantially all free isocyanate groups have been deactivated with one or more capping agents. Deactivated isocyanate groups or capped polyisocyanate compositions can be manufactured, for example, by allowing the polyisocyanate composition to react with a capping agent. Examples of capping agents include oximes, phenols, alcohols, imines, amines, carbamic acids, ureas, imidazoles, imides, thiols, active methylene groups, amides (lactams), and bisulfites.

[0071] Each of the two-component and one-component systems of the present invention can be used as a solvent-borne or water-borne system. In this regard, typical solvents selected from the above examples or water can be used. The present invention further relates to articles comprising at least one cured two-component system of the present invention, or articles at least partially coated with a cured two-component system of the present invention.

[0072] The present invention further relates to molded articles or coatings that can be obtained or produced, preferably directly produced, by optionally curing the two-component system or the one-component system of the present invention under heat and / or in the presence of a catalyst. The present invention further relates to a composite component comprising material at least partially bonded to the molded article or coating of the present invention. The molded article and composite component are also understood as articles.

[0073] The following comparative examples and embodiments are intended to further illustrate the invention, but do not limit the invention.

[0074] Example: Unless otherwise stated, all percentages should be understood as weight percentages.

[0075] All reactions were carried out in a glass apparatus under a nitrogen atmosphere, which had been pre-dried under reduced pressure at 150–200 °C.

[0076] The presence of isocyanurates, iminooxadiazine diones, urethanes, carbamates, ureas, urea, urea diones, oxadiazine triones, carbodiimides, thiocarbamates, thiourea carbamates, and / or biuret structures in polyisocyanates, or simply their presence, is indicated by the molar percentage data or simple presence of these structures. 13 The determination is performed by C NMR spectroscopy and, unless otherwise stated, is always related to the sum of NCO conversion products. Unless otherwise stated, at 100 or 176 MHz ( 13 Approximately 50% of the dried C6D6 sample was measured under C10NMR on a Bruker DPX 400 or DRX 700 instrument. 13 C6D5H, present in the NMR solvent, was used as a reference signal (7.15 ppm, C NMR). 1 H-NMR) or the solvent signal itself (in H-NMR) or the solvent signal itself (in 13 (Average signal of the 1:1:1 triplet at 128.0 ppm in C NMR).

[0077] Dynamic viscosity was determined at 23°C using an MCR 501 rheometer (from Anton Paar) according to DIN EN ISO 3219:1994-10. Measurements at different shear rates ensured that Newtonian flow behavior could be assumed. Therefore, details regarding shear rates can be omitted.

[0078] The NCO content was determined by titration according to DIN EN ISO 10283:2007-11.

[0079] The residual monomer content was determined by gas chromatography using an internal standard according to DIN EN ISO 10283:2007-11.

[0080] Size exclusion chromatography (SEC) using tetrahydrofuran as the eluent, according to DIN 55672-1:2016-03.

[0081] The Hazen color number was measured spectrophotometrically using a LICO400 spectrophotometer from Lange, Germany, according to DIN EN ISO 6271-2:2005-03.

[0082] Starting materials used Setalux DA 870 BA is an acrylic polyol sourced from Allnex GmbH (Deutschland). It has an OH number of 4.2% (based on non-volatile matter) and is supplied in butyl acetate. It has an equivalent weight of 575 g / eq.

[0083] Bayhydrol A 2695, an aqueous hydroxyl-functionalized polyacrylic acid dispersion, from Covestro Deutschland AG. Byk 141 is a silicone defoamer from Byk Additives and Instruments GmbH, Germany. Byk 331 is a silicone surface additive from Byk Additives and Instruments GmbH, Germany. Byk 349 is a silicone surfactant for water-based coatings from Byk Additives and Instruments GmbH, Germany. Addocat 201 Dibutyltin Dilaurate from Lanxess Deutschland GmbH Tinuvin 292 Hindered Amine Light Stabilizer, BASF SE, Germany Tinuvin 1130 Hydroxyphenylbenzotriazole Liquid UV Absorber, BASF SE, Germany MPA 1-methoxypropyl-2-acetic acid ester, anhydrous, obtained from Azelis, St. Augustin Xylene was obtained from Azelis, St. Augustin Butyl acetate was obtained from Azelis, St. Augustin.

[0084] Polyisocyanate 1: 2,5-bis(isocyanate-methyl)tetrahydrofuran (TEFUDI) polyisocyanate containing an isocyanurate structure was prepared by placing 786.40 g (4.32 mol) of freshly degassed TEFUDI into a three-necked round-bottom flask equipped with a nitrogen inlet, thermometer, diaphragm, and magnetic stir bar. The reaction vessel was heated to 60 °C. Subsequently, the TEFUDI was added dropwise in portions with stirring. i A 24% catalyst solution of 5-azaspiro[4.5]dec-5-onium fluoride hydrofluoric acid in PrOH resulted in a slightly exothermic reaction. The reaction mixture was stirred until an NCO content of 38.7% was achieved, and the reaction was stopped by adding an amount equivalent to the catalyst amount of a 40% strong solution of dodecylbenzenesulfonic acid in isopropanol. The mixture was then post-treated by thin-film distillation (0.17 mbar, 160 °C), and the resulting viscous resin was diluted with butyl acetate (BA). The product has the following properties and composition: NCO value: 14.4% Monomer TEFUDI: 0.02% Viscosity (23℃): 530 mPas Solid content: 80% Polyisocyanate 2: 2,5-bis(isocyanate-methyl)tetrahydrofuran (TEFUDI) polyisocyanate containing an isocyanurate structure was prepared by placing 786.40 g (4.32 mol) of freshly degassed TEFUDI into a three-necked round-bottom flask equipped with a nitrogen inlet, thermometer, diaphragm, and magnetic stir bar. The reaction vessel was heated to 60 °C. Subsequently, the TEFUDI was added dropwise in portions with stirring. i A 24% catalyst solution of 5-azaspiro[4.5]dec-5-onium fluoride hydrofluoric acid in PrOH resulted in a slightly exothermic reaction. The reaction mixture was stirred until an NCO content of 38.7% was achieved, and the reaction was stopped by adding an amount equivalent to the amount of catalyst in a 40% strong solution of dodecylbenzenesulfonic acid in isopropanol. The mixture was then post-treated by thin-film distillation (0.17 mbar, 160 °C), and the resulting viscous resin was diluted with methoxypropyl acetate. The product has the following properties and composition: NCO content: 14.4% Monomer TEFUDI: 0.02% Viscosity (23℃): 530 mPas Solid content: 80% Polyisocyanate 3: According to Example 11 of EP-A 330 966, hexamethylene diisocyanate (HDI) polyisocyanate containing an isocyanurate structure was prepared by catalytic trimerization of HDI, wherein the modification was to stop the reaction by adding dibutyl phosphate at an NCO content of 40% in the crude mixture. Unreacted HDI was then separated by thin-film distillation at 130°C and 0.2 mbar. The product has the following characteristics and composition: NCO content: 21.7% Monomer HDI: 0.1% Viscosity (23℃): 3080 mPas Solid content: 100% Polyisocyanate 4: Pentamethylene diisocyanate (PDI) polyisocyanate containing an isocyanurate structure was prepared by the catalytic trimerization of PDI via the method described in WO 2016 / 146579 (for polyisocyanate component A2). The reaction was deactivated by adding an equimolar amount of dibutyl phosphate based on the amount of catalyst used and stirring at 80°C for 30 minutes, resulting in an NCO content of 36.7% in the crude mixture. Unreacted PDI was then separated by thin-film distillation at 140°C and 0.5 mbar. The product has the following characteristics and composition: NCO content: 21.8% Monomer PDI: 0.09% Viscosity (23℃): 9850 mPas Solid content: 100% Polyisocyanate 5: According to Example 2 of EP-A-0 003 765, isophorone diisocyanate (IPDI) polyisocyanate containing an isocyanurate structure was prepared by catalytic trimerization of IPDI. The reaction was deactivated by adding an equimolar amount of dibutyl phosphate based on the amount of catalyst used and stirring at 80°C for 30 minutes, resulting in an NCO content of 30.1% in the crude mixture. Unreacted IPDI was then separated by thin-film distillation at 170°C and 0.3 mbar, and the resulting solid resin was diluted with butyl acetate (BA). The product has the following characteristics and composition: NCO content: 11.9% Individual IPDI: 0.28% Viscosity (23℃): 620 mPas Solid content: 70% Polyisocyanate 6: According to Comparative Example 2a of WO 2018 / 153801, hexamethylene diisocyanate (HDI) containing an iminooxadiazine dione structure was prepared by the trimerization reaction of hexamethylene diisocyanate (HDI) using a 20% solution of 5-azaspiro[4.5]dec-5-onium fluoride hydrofluoric acid in 2-ethylhexanol as a catalyst. The reaction was stopped by adding a 70% strength solution of dodecylbenzenesulfonic acid in isopropanol in an amount equivalent to the catalyst, at an NCO content of 44.8% in the crude mixture, and the unreacted HDI was subsequently separated by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar. The product has the following characteristics and composition: NCO content: 23.5% Monomer HDI: 0.11% Viscosity (23℃): 720 mPas Solid content: 100% Characterization of coating films Drying times T1, T3 and T4 are performed according to DIN EN ISO 9117-5:2010-07.

[0085] The damping of the pendulum rod according to König is determined on a glass plate in accordance with DIN EN ISO 1522:2007-04.

[0086] Solvent resistance was tested according to DIN EN ISO 4628-1:2016-07. Small amounts of each of the solvents xylene, 1-methoxypropyl 2-acetate, ethyl acetate, and acetone were placed in test tubes, with a cotton pad provided at the opening, thus creating a solvent-saturated atmosphere within the test tubes. The test tubes, along with the cotton pads, were then placed on the coating surface, where they were left for 5 minutes. After wiping off the solvent, the damage / softening / adhesion loss of the film was examined and rated (0 = no change, 5 = complete film dissolution). The reported evaluation was presented as four consecutive numbers for each of the four solvents in that order for xylene (X), 1-methoxypropyl 2-acetate (MPA), ethyl acetate (EA), and acetone (A).

[0087] To test the coating's water resistance, a cotton pad was submerged in water and then placed on top of the coating, which was then covered with a small glass vial. The solution remained on the coating for 24 hours. After this time, the water was removed from the coating using fresh water. The panel was then dried with paper and inspected, and recorded as having "bubbles" or "no bubbles".

[0088] Condensation test DIN EN ISO 6270-2 CH:2018-04 Rapid weathering studies of CAM 180 under UV radiation were conducted according to SAE J2527. The test plate was checked every 250 hours.

[0089] Perform UV-A testing on the coating material according to DIN EN ISO 16474-3:2014-03 (Cycle 1). Check the test panel every 250 hours.

[0090] The ΔE value (yellowing, CAM 180) can be calculated using the L, a, and b values ​​determined by a color space laboratory according to DIN EN ISO / CIE 11664-4:2019-04 using "Dr. Lange - Micro Color II".

[0091] formulation Solvent-based coatings Formulation Example 1 Component A: Setalux DA 870 BA (48.11 g) was mixed with 0.25 g Byk 141 (delivery form), 1.50 g Byk 331 (10% solution in butyl acetate (BA), 1.50 g Addocat 201 (1% solution in BA), 1.00 g Tinuvin 292 (50% solution in BA), and 2.00 g Tinuvin 1130 (50% solution in BA). The mixture was diluted with 20.64 g of MPA:xylene:BA 1:1:1 solution.

[0092] Component B: 24.43 g of polyisocyanate 1 was diluted with a solution of 10.00 g of BA and xylene in a 1:1 ratio.

[0093] Pour components A and B into a container at a 1:1 NCO to OH ratio and mix manually for 1 minute. Apply the formulation to a panel using a coating knife, depending on the test to be performed. Allow the panel to dry at room temperature, or at 60°C for 30 minutes, or at 80°C for 30 minutes, or at 140°C for 30 minutes. The cured dry film thickness is approximately 50 μm.

[0094] Formulation Example 1 contains a) a reduced catalyst and b) no catalyst. As described in the preceding examples, coatings were prepared using half the amount of catalyst (Example 1a, 0.75 g Addokat 201) and without catalyst (Example 1b, without Addokat 201).

[0095] Table 1: Overview of the Examples (Examples 2-5 are comparative examples) .

[0096] The formulation was prepared as described above, wherein the amounts of hardener and solvent in component B are as outlined in the table above.

[0097] Water-based coatings Formulation Example 6 (Starting formulation without additives) Component A: Combine Bayhydrol A 2695 (58.51 g) with Byk 349 (0.13 g) and water (9.00 g). Stir the mixture in a Dispermat CV50 dissolver at 2000 U / min for 2 minutes.

[0098] Component B: Polyisocyanate 2 was further dissolved in MPA (3.96 g) and stirred for 2 minutes at 2000 U / min using a Dispermat CV50 dissolver.

[0099] Components A and B were mixed together to obtain an NCO to OH ratio of 1.5:1 and mixed for 2 minutes at 2000 U / min using a Dispermat CV50 dissolver. The formulation was applied to the panel using a coating knife. The wet film thickness was approximately 150 μm. The panel was dried at room temperature for 7 days or at 60°C for 30 minutes.

[0100] Comparative Example 7 Alternative component B: Polyisocyanate 6 (19.14 g) was dissolved in MPA (10.30 g). The formulation was prepared as described above.

[0101] Table 2: Application results of solvent-based coatings .

[0102] Table 3: Results of Continued Application of Solvent-Based Coatings .

[0103] Table 4: Application results of water-based coatings .

[0104] Discussion of Results As shown in Example 1, polyisocyanate 1 produces solvent-based films exhibiting the advantages of the combined effects observed with HDI and IPDI trimers (Comparative Example 5). These coatings dry rapidly (reaching T4 in 8 hours after room temperature curing) and are sufficiently hard (pendulum hardness >140 s) after 7 days of curing, exhibiting considerable solvent resistance. Water resistance tests did not result in the bubble formation seen with HDI and IPDI trimers. After weathering (CAM 180 and UV-A), the new system showed no significant loss in gloss and yellowing, indicating it is weather stable. Furthermore, as shown in Examples 1a and 1b of the invention, this result can also be obtained with lower catalyst loadings or even without any catalyst. Example 6 (polyisocyanate 2) demonstrates that the polyisocyanate compositions of the present invention can also be used in aqueous systems. Compared to the standard system with polyisocyanate 6 (Comparative Example 7), these systems exhibit comparable hardness and improved chemical resistance, and also have the added advantage of faster drying in aqueous systems.

Claims

1. A polyisocyanate composition comprising at least one bridging cis-tetrahydrofuran-2,5-dimethyl-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourethane carbamate, and / or biuret structure. And / or contains at least one bridging trans-tetrahydrofuran-2,5-dimethyl)-dimethylene unit and at least one isocyanurate, iminooxadiazine dione, urethane, carbamate, urea, urea dione, oxadiazine trione, carbodiimide, thiocarbamate, thiourethane, and / or biuret structure.

2. The polyisocyanate composition according to claim 1, characterized in that... It comprises at least one isocyanurate, iminooxadiazine dione, urethane, urea dione and / or biuret structure, preferably at least one isocyanurate, iminooxadiazine dione, urethane and / or urea dione structure, more preferably at least one isocyanurate, iminooxadiazine dione and / or urea dione structure.

3. The polyisocyanate composition according to claim 1 or 2, characterized in that... It has an NCO content of 5.8 to 25.9% by weight, preferably 7.8 to 24.9% by weight, and particularly preferably 9.7 to 23.9% by weight, as determined according to DIN EN ISO 11909:2007-05, based on the total weight of the polyisocyanate composition.

4. The polyisocyanate composition according to any one of claims 1 to 3, characterized in that... It has a residual monomer content of less than 1% by weight, preferably less than 0.5% by weight, and more preferably less than 0.1% by weight, based on the total weight of the polyisocyanate composition.

5. A method for preparing a polyisocyanate composition comprising a reaction of at least one cis-2,5-bis(isocyanate methyl)tetrahydrofuran and / or trans-2,5-bis(isocyanate methyl)tetrahydrofuran optionally in the presence of at least one catalyst, optionally in the presence of other co-reactants selected from alcohols, thiols, amines, water, CO2 or other isocyanates having an NCO functionality > 1.

6. Use of at least one polyisocyanate composition according to any one of claims 1 to 4 and / or at least one polyisocyanate composition obtained or obtainable by the method according to claim 5, preferably directly obtainable, in coatings, adhesives or sealants.

7. A two-component system comprising component A) and component B), wherein component A) comprises at least one polyisocyanate composition according to any one of claims 1 to 4 and / or at least one polyisocyanate composition obtained or available by the method according to claim 5, and component B) comprises at least one NCO reactive compound.

8. The two-component system claimed in claim 7, wherein the at least one NCO reactive compound is a polyhydroxy compound, preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, and / or a polyacrylate polyol.

9. An article comprising at least one cured two-component system as claimed in claim 7 or 8, or an article at least partially coated with a cured two-component system as claimed in claim 7 or 8.