Polyisocyanate composition

Abstract

The present invention relates to a polyisocyanate composition comprising at least one cross-linked cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure, and / or at least one cross-linked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure.

Description

[Technical Field]

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

[0002] The oligomerization or polymerization of isocyanates, particularly for forming high molecular weight oligomer mixtures, has been known for a long time. The reaction of a relatively small number of isocyanates is called oligomerization. The reaction of a relatively large number of isocyanates is called polymerization. In the context of the present invention, the oligomerization or polymerization of isocyanates described above is collectively referred to as isocyanate modification or isocyanate modification. All products obtained by such methods are collectively referred to herein as polyisocyanate compositions, or simply polyisocyanates. Polyisocyanates contain free isocyanate groups, abbreviated as NCO groups, which may be temporarily deactivated with a blocking agent, and are extremely high-quality starting materials for preparing a wide range of polyurethane plastics and coating compositions.

[0003] Polyisocyanates used in coating compositions for high-quality coatings are, in particular, low monomer derivatives prepared from hexamethylene 1,6-diisocyanate (HDI). Particularly suitable for elastic, highly robust coatings for this purpose are isocyanurate polyisocyanates of HDI, or HDI polyisocyanates containing an iminooxadiazinedione and isocyanurate structure, as described, for example, in HJ Laas, R. Halpaap, J. Pedain, J. Prakt. Chem. 1994, 336, 185-200. These polyisocyanates generally have an isocyanate functional value (F) of 3 or higher. NCO) has the following characteristics, where the isocyanate functional value refers to the average number of NCO groups per molecule.

[0004] The drawbacks of HDI-based polyisocyanates are that the physical drying time is considerably long, the coating process becomes less efficient, and a catalyst is essential, at least at lower temperatures. Similar to HDI, pentamethylene 1,5-diisocyanate (PDI) is an established monomer, as described, for example, by W. Siefken, Liebigs Ann. Chem. 1949, 562, page 122, or in German Patent Application Publication No. 1493360 and German Patent Application Publication No. 1900514.

[0005] British Patent No. 936370 describes a common laboratory synthesis of furan and tetrahydrofuran monomer isocyanates by liquid-phase phosgenation of dihydrochloride salts, which is a considerably inefficient and complex process on a larger scale. Further modification or application tests are not described.

[0006] International Publication No. 2011 / 098272 describes a mixture of short-chain and long-chain renewable diisocyanates for the preparation of polyurethanes. In the extremely long list of short-chain renewable diisocyanates, furan-based diisocyanates are generally mentioned, but neither application examples nor preferred examples are described.

[0007] International Publication No. 2021 / 180709 describes specific chain-type isocyanates containing ether groups for use in isocyanate modification, with the aim of reducing the amount of catalyst added to the isocyanate modification reaction itself. This is entirely different from catalyst technology in coating applications. No application examples are described.

[0008] In contrast to the aforementioned monomers furan and tetrahydrofuran, as well as other chain-type diisocyanates containing ether groups, isophorone diisocyanates (IPDIs) are used in coating applications and are known for their good drying properties, resulting in shorter drying times. However, the drawbacks of IPDI polyisocyanates are the insufficient flexibility and reduced solvent resistance of the resulting coatings, as well as their low chemical reactivity.

[0009] International Publication 2020 / 109125 describes polyisocyanate mixtures, primarily PDI and IPDI, that exhibit improved properties compared to mixtures of HDI and IPDI. However, these PDI / IPDI polyisocyanate mixtures also require more effort to prepare, and there is room for improvement in their properties.

[0010] In summary, no readily available solutions existed to address the shortcomings of conventional technology. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] German Patent Application Publication No. 1493360 Specification [Patent Document 2] German Patent Application Publication No. 1900514 [Patent Document 3] British Patent No. 936370 [Patent Document 4] International Publication No. 2011 / 098272 [Patent Document 5] International Publication No. 2021 / 180709 [Patent Document 6] International Publication No. 2020 / 109125 [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] Therefore, the object of the present invention was to provide a polyisocyanate composition that combines a rapid drying time of the prepared coating composition and excellent solvent resistance of the resulting coating, without the need to mix polyisocyanates from different monomer diisocyanates, and that allows curing for coating applications even at low temperatures without the addition of a catalyst. [Means for solving the problem]

[0013] This objective was achieved by polyisocyanate compositions comprising at least one cross-linked cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure, and / or at least one cross-linked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure.

[0014] References to "include" or "contain" preferably mean "substantially from," and most preferably mean "consisting of." In the present 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 (and both ends of) the stated minimum value of 1 and the stated maximum value of 10, i.e., subranges having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0015] According to the present invention, the cis and trans stereoisomers of (tetrahydrofuran-2-5-diyl)-methaneamine are collectively called "TEFUDA," and are also individually called "cis-TEFUDA" and "trans-TEFUDA," respectively. The cis and trans stereoisomers of 2,5-bis(isocyanatomethyl)tetrahydrofuran are collectively called "TEFUDI," and are also individually called "cis-TEFUDI" and "trans-TEFUDI," respectively. For clarity, cis-TEFUDA or cis-TEFUDI corresponds to the (2R,5S) and (2S,5R) stereoconfigurations, and trans-TEFUDA or trans-TEFUDI corresponds to the (2R,5R) and (2S,5S) stereoconfigurations.

[0016] According to the present invention, a crosslinked cis- and / or trans-tetrahydrofuran-2,5-diyl-methylene unit is a structural unit that is connected via one extraring CH2 moiety to the nitrogen atom of an isocyanate group, an isocyanurate group, an iminooxadiadindione group, an allophanate group, an urethane group, an uretdione group, an oxadiadintrione group, a carbodiimide group, a thiourethane group, a thioallophanate group, or a biuret group, and via the other extraring CH2 moiety to any independently selected nitrogen atom of the aforementioned functional groups. Preferably, the crosslinked cis- and / or trans-tetrahydrofuran-2,5-diyl-methylene unit is a structural unit in which one extraring CH2 moiety is connected to the nitrogen atom of an isocyanurate group, an iminooxadiadindione group, an allophanate group, a urethane group, a uretdione group, an oxadiadintrione group, a carbodiimide group, a thiourethane group, a thioallophanate group, or a biuret group, and the other extraring CH2 moiety is connected to any of the independently selected nitrogen atoms of the aforementioned functional groups or to the nitrogen atom of an isocyanate group. The designation of the two extraring CH2 moieties can also be interchanged. This crosslinked unit is a standard 1H- and / or 13 can be detected by 13 C-NMR measurement.

[0017] The isocyanurate structure or isocyanurate group is understood as a structural unit randomly linked to each other or to a functional group according to an oligomer distribution via the above-mentioned cis- and / or trans-tetrahydrofuran-2,5-diyl)-dimethylene unit.

[0018]

Chemical formula

[0019]

Chemical formula

[0020]

Chemical formula

[0021] In a first preferred embodiment, the polyisocyanate composition of the present invention is characterized by comprising at least one isocyanurate, iminooxadiazinedione, allophanate, uretdione and / or biuret structure, preferably at least one isocyanurate, iminooxadiazinedione, allophanate and / or uretdione structure, and more preferably at least one isocyanurate, iminooxadiazinedione and / or allophanate structure. This has the advantage of being able to further increase the curing rate of the applied coating.

[0022] In other words, the first preferred embodiment described above should be understood as a structural unit in which the crosslinked cis- and / or trans-tetrahydrofuran-2,5-diyl-methylene unit is connected via one extraring CH2 moiety to the nitrogen atom of an isocyanurate group, an iminooxadiadindione group, an allophanate group, an uretdione group, or a biuret group, and via the other extraring CH2 moiety to any of the independently selected nitrogen atoms of the aforementioned functional groups or to the nitrogen atom of an isocyanate group. The designations of the two extraring CH2 moieties can also be interchanged. This crosslinked unit is a standard 1 H- and / or 13 It can be detected by 13C-NMR measurement.

[0023] 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, based on the total weight of the polyisocyanate composition, as determined in accordance with DIN EN ISO 11909:2007-05.

[0024] In a preferred embodiment, the polyisocyanate composition of the present invention is characterized by having a residual monomer 2,5-bis(isocyanatomethyl)tetrahydrofuran 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.

[0025] The residual monomer content of 2,5-bis(isocyanatomethyl)tetrahydrofuran is determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0026] In preferred embodiments, the polyisocyanate composition of the present invention comprises a polyisocyanate comprising 70% by weight or more, preferably 85% by weight or more, more preferably 95% by weight or more, and very preferably 100% by weight, of at least one cross-linked cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure, based on the total solid content of the polyisocyanate composition of the present invention.

[0027] The polyisocyanate composition of the present invention more preferably contains a polyisocyanate comprising 70% or more by weight, preferably 85% or more by weight, more preferably 95% or more by weight, and very preferably 100% or more by weight, of at least one cross-linked cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one isocyanurate, iminooxadiazinedione and / or allophanate structure, and / or at least one cross-linked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazinedione and / or allophanate structure, based on the total solid content of the polyisocyanate composition of the present invention.

[0028] The present invention further comprises a) at least one polyisocyanate, the at least one polyisocyanate comprising at least one cross-linked cis-tetrahydrofuran-2,5-diyl-methylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and biuret, and / or b) The present invention relates to a polyisocyanate composition comprising at least one polyisocyanate, the at least one polyisocyanate comprising at least one crosslinked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate, and biuret.

[0029] In further embodiments, the present invention includes a) at least one polyisocyanate, the at least one polyisocyanate comprising at least one crosslinked cis-tetrahydrofuran-2,5-diyl-methylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and biuret, and / or b) The present invention relates to a polyisocyanate composition comprising at least one polyisocyanate, the at least one polyisocyanate comprising at least one crosslinked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate, and biuret.

[0030] In further embodiments, the present invention relates to a) at least one polyisocyanate comprising at least one polyisocyanate comprising at least one cross-linked cis-tetrahydrofuran-2,5-diyl-dimethylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, uretdione, and biuret, and / or b) at least one polyisocyanate comprising at least one polyisocyanate comprising at least one cross-linked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one structure selected from the group consisting of isocyanurate, iminooxadiazinedione, allophanate, uretdione, and biuret. The three embodiments described above can be optionally combined with other claims, aspects, and embodiments of the present invention unless the context clearly indicates otherwise.

[0031] The polyisocyanate compositions of the present invention include, for example, 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-isocyanatomethyloctane 1,8-diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate (IPDI), and 1,3- and 1,4-bis The product may also contain (isocyanatomethyl)benzene (XDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI), trilene 2,4- and 2,6-diisocyanate (TDI), bis(4-isocyanatophenyl)methane (4,4'MDI), 4-isocyanatophenyl-2-isocyanatophenylmethane (2,4'MDI), and further crosslinking units derived from polycyclic products that can be obtained by formaldehyde-aniline polycondensation and subsequent conversion of the resulting (poly)amine to the corresponding (poly)isocyanate (polymer MDI).

[0032] If other monomer diisocyanates are used or included as crosslinking 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-isocyanatomethyloctane 1,8-diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis(isocyanatomethyl)benzene (XDI), and / or 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI). Pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexane 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, 4-isocyanatomethyloctane and / or 1,8-diisocyanate are particularly preferred, and pentamethylene diisocyanate (PDI) and / or hexamethylene diisocyanate (HDI) are even more preferred.

[0033] The amount of optional additional isocyanates other than the essential cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran is determined by the specific application, and if any additional optional isocyanates are used, they may vary within a wide range, preferably from 0 to 5% by weight, preferably from 0 to 2% by weight, and more preferably from 0 to 1% by weight, based on the total amount of monomer compounds having the NCO group. However, in order to maximize the preferred technical effects of the essential TEFUDI, it is most preferable that only cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran be the crosslinking units in the polyisocyanate composition of the present invention.

[0034] The method by which the isocyanates containing cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran are produced is irrelevant; that is, phosgene may or may not be used. In the industrial production of isocyanates, phosgenation in the liquid or gas phase is preferred, and more preferably, gas-phase phosgenation as described, for example, in European Patent Application Publication No. 0764633. TEFUDI is preferably prepared from the respective diamines.

[0035] The present invention further relates to a method for preparing a polyisocyanate or polyisocyanate composition, comprising a step of converting 2,5-bis(isocyanatomethyl)tetrahydrofuran to a polyisocyanate or polyisocyanate composition, and to a polyisocyanate or polyisocyanate composition that is obtained or can be obtained according to the method of converting 2,5-bis(isocyanatomethyl)tetrahydrofuran to a polyisocyanate or polyisocyanate composition, preferably directly obtained.

[0036] The essential precursors for cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran can be obtained from different sources, but are preferably obtained from bio-based sources.

[0037] If other monomer diisocyanates are used or included as crosslinking units, the total content of monomer diisocyanates, including 2,5-bis(isocyanatomethyl)tetrahydrofuran, is preferably 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 diisocyanate content is determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0038] 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 fluid behavior could be assumed. Therefore, details regarding shear rates can be omitted.

[0039] The present invention further relates to a method for preparing a polyisocyanate composition of the present invention, comprising the reaction of at least one cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran, which may be in the presence of at least one catalyst, and a further co-reactant selected from the group of alcohols, thiols, amines, water, CO2, or further isocyanates having an NCO functional value > 1. In this regard, the term “reaction” also includes the modification of cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran into the polyisocyanate or polyisocyanate composition of the present invention.

[0040] Generally, cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran monomers are used in the method of the present invention to obtain the polyisocyanate composition of the present invention by forming crosslinking units between isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structures. Such variations of TEFUDI are, for example, in J.Prakt.Chem.336(1994)185-200, in German Patent Publication No. 1670666, German Patent Publication No. 1954093, German Patent Publication No. 2414413, German Patent Publication No. 2452532, German Patent Publication No. 2641380, German Patent Publication No. 3700209, German Patent Publication No. 3900053 and German Patent Publication No. 3928503, or in European Patent Publication No. This can be done in accordance with the methods described in European Patent Application Publication No. 0336205, European Patent Application Publication No. 0339396, European Patent Application Publication No. 0798299, European Patent Application Publication No. 0962454, European Patent Application Publication No. 0962455, European Patent Application Publication No. 2785760, European Patent Application Publication No. 2883895, European Patent Application Publication No. 3107922, European Patent Application Publication No. 3107948, and European Patent Application Publication No. 3337836.

[0041] In addition to cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran itself, co-reactants that may be used for the method of the present invention and may be contained in a reacted form in the polyisocyanate composition of the present invention are typically difunctional groups having Zerevitinoff-active hydrogens, which are conventional in polyurethane chemistry, and more highly functional co-reactants, such as water, alcohols, thiols, and amines. These compounds preferably have an average OH, NH, or SH functional value of at least 1.5. These may be, for example, low molecular weight diols (e.g., ethane-1,2-diol, propane-1,3- or -1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), short-chain polyamines, but may also be polyaspartates, 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.

[0042] Further isocyanates having an NCO functional value of >1 that may be included in the method of the present invention are preferably selected from the above list. However, it is most preferable that TEFUDI alone be used as the monomeric diisocyanate having an NCO functional value of >1.

[0043] For example, suitable catalysts for NCO-NCO reactions that may be used to form isocyanurate, iminooxadiazinedione, and / or allophanate structures from at least cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran include typical compounds known to be catalytically active for isocyanates. These catalysts include, for example, ionic compounds with nucleophilic anions such as "onium" cations (ammonium, phosphonium, etc.) and hydroxides, alkanoates, carboxylates, heterocycles having at least one negatively charged nitrogen atom in the ring, particularly azolates, imidazolates, triazolates, tetrazolates, fluorides, hydrogen difluorides, higher polyfluorides, or mixtures thereof (additions of more than one equivalent of HF onto compounds containing fluoride ions) (fluorides, hydrogen difluorides, and higher polyfluorides can yield products with a higher imino-oxadiazinedione group content under appropriate reaction conditions), as well as neutral bases such as tertiary amines or phosphines. In the latter case in particular, structural diversity allows for a wide selectivity range, from high uretdione selectivity to high "trimer" selectivity, which typically results in a mixture of isocyanurates and iminooxadiazinediones.

[0044] Any catalyst can be used individually or in any desired mixture with each other. For example, the pK of the base and alcohol used. a Depending on the value, solutions of quaternary ammonium hydroxides in various alcohols exist partially or completely as ammonium salts with alkoxide anions. This equilibrium can be completely shifted to the side of complete alkoxide formation by removing the reaction water resulting from this reaction. A preferred method for water removal here is all methods known from the literature for this purpose, in particular (azeotropic) distillation, which may be aided by a suitable additive solvent if the alcohol used as the solvent is not suitable on its own.

[0045] The progress of the reaction in the method of the present invention can be monitored by determining the NCO content by titration according to DIN EN ISO 11909:2007-05. Once the desired NCO content ("degree of polymerization") is achieved, the reaction is stopped by appropriate means, depending on whether a denaturation reaction and / or catalyst is used. Preferably, the catalyst is deactivated by the addition of a suitable catalyst poison.

[0046] In a further preferred embodiment, the reaction is carried out to the point where the reaction mixture has a degree of oligomerization of 10% to 40%, preferably 15% to 30%.

[0047] Here, "degree of oligomerization" refers to the percentage of isocyanate groups originally present in the starting mixture that are consumed during the reaction according to the present invention. The degree of oligomerization, expressed as a percentage, can be calculated according to the following formula.

[0048] Oligomerization degree = (NCO start - NCO end) / NCO start × 100.

[0049] The reaction can be stopped, for example, when the target degree of oligomerization is reached. This degree of oligomerization is generally achieved after 30 minutes to 8 hours, preferably 1 to 6 hours, of the reaction time.

[0050] For example, the reaction can be terminated by cooling the reaction mixture to room temperature. However, generally, the reaction is terminated by adding a catalyst poison and then optionally heating the reaction mixture to a temperature above 80°C for a short time.

[0051] Examples of suitable catalyst poisons include inorganic acids such as hydrochloric acid, phosphorous acid, or phosphoric acid; acid chlorides such as acetyl chloride, benzoyl chloride, or isophthaloyl dichloride; sulfonic acids and sulfonic acid esters such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, dodecylbenzenesulfonic acid, methyl and ethyl p-toluenesulfonate; monoalkyl and dialkyl phosphates such as monotridecyl phosphate, dibutyl phosphate, and dioctyl phosphate; and silylated acids such as trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, tris(trimethylsilyl) phosphate, and diethyltrimethylsilyl phosphate.

[0052] The amount of catalyst poison required to terminate the reaction depends on the amount of catalyst used, and generally, an equivalent amount of catalyst poison is used based on the amount of catalyst used at the start. However, considering the potential loss of catalyst during the reaction, 20-80 equivalents of catalyst poison based on the amount of catalyst initially used may also be sufficient to terminate the reaction.

[0053] The catalyst poisons described may be used as is or in solution in a suitable solvent. When a solvent is used to dissolve the catalyst poison, TEFUDI is preferred. The dilution can be freely selected within a very wide range. For example, a solution starting from a concentration of 25% by weight or more, preferably 10% by weight or more, is suitable.

[0054] After the reaction is complete, the reaction mixture is preferably decontaminated by thin-film distillation under very mild conditions, preferably under reduced pressure, for example, less than 1.0 mbar, preferably less than 0.75 mbar, and more preferably less than 0.25 mbar, at a temperature of, for example, 100 to 200°C, preferably 120 to 180°C, to remove volatile components (excess monomer isocyanate components and any additional solvents used).

[0055] In another embodiment of the method of the present invention, the described volatile components are removed from the polyisocyanate composition of the present invention by extraction with a suitable solvent that is inert to the isocyanate group, such as an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, cyclopentane, or cyclohexane.

[0056] The method of the present invention is preferably carried out without a solvent. However, if desired, a suitable solvent that is inert to the reactive groups of the starting components may also be used. Suitable solvents include, for example, ethyl acetate, butyl acetate, ethylene glycol monomethyl or monoethyl ether acetate, 1-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white spirit, and more highly substituted aromatics, such as Solventnaphtha, Solvesso®, Isopar®, Nappar®, Varsol® (ExxonMobil Chemical Central Europe, Cologne, Germany) and Shellsol® (Shell Deutschland Oil). Commonly known paint solvents, such as those marketed under the name GmbH (Hamburg, Germany), as well as solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methyl caprolactam, or any desired mixture of such solvents.

[0057] Regardless of the optional use of solvents in the modification reaction of TEFUDI to form crosslinking units, the method of the present invention includes an optional step of adding at least one solvent inert to isocyanate groups to achieve a preferred viscosity of less than 2000 mPas at 23°C, as measured according to DIN EN ISO 3219:1994-10. Such optional solvents are preferably selected from the list above. If such an optional step is performed, the preferred solvent is added in an amount that preferably achieves a solids content of more than 50% by weight, more preferably more than 80% by weight, and most preferably more than 95% by weight.

[0058] Another aspect of the present invention is a polyisocyanate based on cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran, which can be obtained by oligomerization of cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran or obtained directly.

[0059] As an alternative or more preferred embodiment, a polyisocyanate mixture of the polyisocyanate composition of the present invention and at least one other polyisocyanate is also another aspect of the present invention. Such a polyisocyanate mixture of the present invention exhibits the same preferred technical effects as the TEFUDI-based polyisocyanate composition of the present invention and has additional advantages for further improving specific properties required by and depending on the desired application.

[0060] Suitable at least one other polyisocyanate is generally, for example, in J.Prakt.Chem.336(1994)185-200, German Patent Application Publication No. 1,670,666, German Patent Application Publication No. 1,954,093, German Patent Application Publication No. 2,414,413, German Patent Application Publication No. 2,452,532, German Patent Application Publication No. 2 In Specifications No. 641,380, German Patent Application Publication No. 3,700,209, German Patent Application Publication No. 3,900,053 and German Patent Application Publication No. 3,928,503, or in European Patent Application Publication No. 0,336,205, European Patent Application Publication No. 0,339,396, European Patent Application Publication No. 0,798,299 and European Patent Application Publication No. 0,96 These are all kinds of polyisocyanates prepared by modification of simple aliphatic, alicyclic, araliphatic and / or aromatic diisocyanates and / or triisocyanates, such as those used and described in European Patent Application Publication No. 2,454, European Patent Application Publication No. 0,962,455, European Patent Application Publication No. 2,785,760, European Patent Application Publication No. 2,883,895, European Patent Application Publication No. 3,107,922, European Patent Application Publication No. 3,107,948 and European Patent Application Publication No. 3,337,836, such as those of the above types, into uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures. At least one other polyisocyanate may also be used in mixtures of two or more such polyisocyanates.

[0061] In principle, the polyisocyanate mixtures of the present invention can be produced by mixing at least one TEFUDI-based polyisocyanate composition of the present invention with at least one of the above polyisocyanates. If desired, one or more organic solvents that are inert to isocyanate groups may be added to the polyisocyanate composition of the present invention and / or to at least one of the other polyisocyanates at any stage during or after the mixing process, or even already as a diluent. Suitable organic solvents that are inert to isocyanate groups may be selected from the above-mentioned list of optional solvents for preparing the polyisocyanate composition of the present invention.

[0062] With respect to the residual monomer content, preferably the same limitations apply to the polyisocyanate mixture of the present invention, and 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 in accordance with DIN EN ISO 10283:2007-11.

[0063] The mixing ratio and therefore weight ratio of at least one TEFUDI-based polyisocyanate composition of the present invention to the above-mentioned at least one polyisocyanate can be varied over a wide range and selected based on the desired application. However, it is preferable that the TEFUDI-based polyisocyanate composition is one of the main components of the polyisocyanate mixture of the present invention, preferably exceeding 10% by weight, more preferably exceeding 25% by weight, and most preferably exceeding 40% by weight, of the solid content.

[0064] By selecting the amount of solvent, the solid content of the polyisocyanate composition or polyisocyanate mixture according to the present invention can be varied over a wide range when an organic solvent is used. In this case, it is particularly preferable that the polyisocyanate composition or polyisocyanate mixture according to the present invention has a solid content of 10% by weight or more and 95% by weight or less, preferably 25% by weight or more and 85% by weight or less.

[0065] The present invention further relates to the use of at least one polyisocyanate composition and / or at least one polyisocyanate obtained or obtainable according to the method of the present invention, preferably directly obtained, for reducing the amount of catalyst in curing with at least one NCO-reactive compound, and / or enabling curing with at least one NCO-reactive compound at a temperature of less than 100°C, preferably less than 80°C. In this regard, the term “reducing the amount of catalyst” is preferably understood as the amount of catalyst required for the reaction between an aliphatic NCO group other than TEFUDI and an NCO-reactive group.

[0066] The NCO-reactive compounds used may be any compounds known to those skilled in the art (including any desired mixtures with each other) having an average OH, NH, or SH functional value of at least 1.5. These may be, for example, low molecular weight diols (e.g., ethane-1,2-diol, propane-1,3- or -1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), short-chain polyamines, but may also be polyaspartates, 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).

[0067] In a further preferred embodiment, the NCO-reactive compound is a polyhydroxy compound, preferably a polyether polyol, polyester polyol, polycarbonate polyol, or polyacrylate polyol.

[0068] The present invention further relates to the use of at least one polyisocyanate composition and / or at least one polyisocyanate obtained or obtainable according to the method of the present invention, preferably directly obtained, for producing coatings, adhesives, or sealants on a substrate, or to the use of at least one polyisocyanate composition and / or at least one polyisocyanate obtained or obtainable according to the method of the present invention, preferably directly obtained, in coatings, adhesives, or sealants, or This invention relates to the use of at least one polyisocyanate.

[0069] The present invention further relates to a two-component system comprising component A) a polyisocyanate composition and / or a polyisocyanate of the present invention that can be obtained or obtained according to the method of the present invention, and component B) a polyisocyanate of the present invention that can be obtained according to the method of the present invention, and component B) a polyisocyanate that can be obtained according to the polyisocyanate of the present invention.

[0070] The NCO-reactive compound of component B) used may be any compound known to those skilled in the art (including any desired mixtures with each other) having an average OH, NH, or SH functional value of at least 1.5. These may be, for example, low molecular weight diols (e.g., ethane-1,2-diol, propane-1,3- or -1,2-diol, butane-1,4-diol), triols (e.g., glycerol, trimethylolpropane), and tetraols (e.g., pentaerythritol), or short-chain polyamines, but may also be polyaspartates, 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).

[0071] In a preferred embodiment of the two-component system of the present invention, at least one NCO-reactive compound is a polyhydroxy compound, preferably a polyether polyol, polyester polyol, polycarbonate polyol, and / or polyacrylate polyol.

[0072] The two-component system of the present invention may contain auxiliary agents and additives, which may be, for example, coating additives known to those skilled in the art, such as cobinders, drying agents, fillers, cosolvents, coloring or effect pigments, thickeners, matting agents, light stabilizers, dispersants, and defoamers, as well as other auxiliary agents such as adhesives, fungicides, bactericides, stabilizers or inhibitors, and catalysts or emulsifiers.

[0073] The polyisocyanate compositions of the present invention are also suitable for one-component systems in which essentially all free isocyanate groups are inactivated by one or more blocking agents. Inactivated isocyanate groups or blocked polyisocyanate compositions can be produced, for example, by reacting a polyisocyanate composition with a blocking agent. Examples of blocking agents include oximes, phenols, alcohols, imines, amines, carbamic acids, ureas, imidazoles, imides, mercaptans, activated methylene, acid amides (lactams), and bisulfites.

[0074] Each of the two-component and one-component systems of the present invention can be used as a solvent-based or aqueous system. In this regard, a typical solvent or water selected from the examples described above can be used. The present invention further relates to an article comprising at least one cured two-component system of the present invention, or an article at least partially coated with a cured two-component system of the present invention.

[0075] The present invention further relates to a molded article or coating that can be obtained or produced, preferably directly produced, by curing a two-component system or a one-component system of the present invention, which may be under the action of heat and / or in the presence of a catalyst. The present invention further relates to a composite component comprising at least partially bonded material to at least the molded article or coating of the present invention. The molded article and the composite component are also understood as articles.

[0076] The following comparative examples and examples are intended to further illustrate the present invention, but are not intended to limit it.

[0077] [Examples] All percentages should be understood to mean weight percentages unless otherwise specified.

[0078] All reactions were carried out under reduced pressure in a nitrogen atmosphere in glass apparatus pre-dried at 150-200°C.

[0079] The molar % data or simple presence of isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structures present in the polyisocyanate is 13 determined by 13C NMR spectroscopy and is always related to the total of the NCO conversion products, unless otherwise specified. The measurements are carried out at 100 or 176 MHz ( 13 13C NMR), on a sample of approximately 50% ( 13 13C NMR) in dehydrated C6D6, using a Bruker DPX 400 or DRX 700 instrument. C6D5H present in the NMR solvent is used as the reference signal (7.15 ppm, 1 1H-NMR), or the solvent signal itself ( 13 average signal of a 1:1:1 triplet at 128.0 ppm in 13C NMR).

[0080] The dynamic viscosity was determined at 23 °C using an MCR 501 rheometer (from Anton Paar) in accordance with DIN EN ISO 3219:1994-10. Measurements at different shear rates ensured that Newtonian fluid behavior could be assumed. Therefore, details regarding the shear rate can be omitted.

[0081] The NCO content was determined by titration in accordance with DIN EN ISO 10283:2007-11.

[0082] The residual monomer content was determined by gas chromatography using an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0083] Size exclusion chromatography (SEC) was carried out in accordance with DIN 55672-1:2016-03, using tetrahydrofuran as the eluent.

[0084] The Hazen color number was measured by spectrophotometric method according to DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, Germany.

[0085] Starting materials used Setalux DA 870 BA acrylic polyol was obtained from Allnex GmbH (Germany). It has an OH value of 4.2% (calculated relative to non-volatile substances) and is supplied in butyl acetate. It is available in an equivalent weight of 575 g / eq.

[0086] Bayhydrol A 2695 Aqueous Hydroxyfunctional Polyacrylic Dispersion, Covestro Deutschland AG Byk 141 Byk Additives and Instruments GmbH, silicone defoamer from Germany Byk 331, a silicone surface additive from Byk Additives and Instruments GmbH, Germany. Byk 349 Byk Additives and Instruments GmbH, a silicone surfactant for water-based coatings from Germany. Dibutyltin dilaurate from Addocat 201 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-acetate, anhydrous, was obtained from Azelis, St. Augustine.

[0087] Xylene Azelis, obtained from St. Augustine Butyl acetate (Azelis), obtained from St. Augustine.

[0088] Polyisocyanate 1 2,5-bis(isocyanatomethyl)tetrahydrofuran (TEFUDI) polyisocyanate containing an isocyanurate structure was prepared by adding 786.40 g (4.32 mol) of freshly degassed TEFUDI to a three-necked round-bottom flask equipped with a nitrogen inlet, thermometer, septum, and magnetic stirrer under nitrogen. The reaction vessel was heated to 60°C. Subsequently, a 24% catalyst solution of 5-azaspiro[4.5]decane-5-ium fluoride hydrofluoride in iPrOH was added dropwise under stirring, resulting in a slightly exothermic reaction. The reaction mixture was stirred until an NCO content of 38.7% was reached, and the reaction was stopped by adding an amount equal to the amount of catalyst of a 40% strength 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 had the following characteristics and composition: NCO value: 14.4% Monomer TEFUDI: 0.02% Viscosity (23℃): 530mPas Solids content: 80%

[0089] Polyisocyanate 2 2,5-bis(isocyanatomethyl)tetrahydrofuran (TEFUDI) polyisocyanate containing an isocyanurate structure was prepared by adding 786.40 g (4.32 mol) of freshly degassed TEFUDI to a three-necked round-bottom flask equipped with a nitrogen inlet, thermometer, septum, and magnetic stirrer under nitrogen. The reaction vessel was heated to 60°C. Subsequently, a 24% catalyst solution of 5-azaspiro[4.5]decane-5-ium fluoride hydrofluoride in iPrOH was added dropwise under stirring, resulting in a slightly exothermic reaction. The reaction mixture was stirred until an NCO content of 38.7% was reached, and the reaction was stopped by adding an amount equal to the amount of catalyst of a 40% strength 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 had the following characteristics and composition: NCO content: 14.4% Monomer TEFUDI: 0.02% Viscosity (23℃): 530mPas Solids content: 80%

[0090] Polyisocyanate 3: With the addition of dibutyl phosphate to halt the reaction at a 40% NCO content in the crude mixture, a hexamethylene diisocyanate (HDI) polyisocyanate containing an isocyanurate structure was prepared by catalytic trimerization of HDI according to Example 11 of European Patent Application Publication No. 330966. Unreacted HDI was then separated and removed by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar. The product had the following characteristics and composition: NCO content: 21.7% Monomer HDI: 0.1% Viscosity (23℃) 3080mPas Solids content: 100%

[0091] Polyisocyanate 4: Pentamethylene diisocyanate (PDI) polyisocyanate containing an isocyanurate structure was prepared by catalytic trimerization of PDI (polyisocyanate component A2) according to the method described in International Publication No. 2016 / 146579. Based on the amount of catalyst used, equimolar amounts of dibutyl phosphate were added, and the reaction was inactivated at a crude mixture containing 36.7% NCO by stirring at 80°C for 30 minutes. Unreacted PDI was then separated and removed by thin-film distillation at a temperature of 140°C and a pressure of 0.5 mbar. The product had the following characteristics and composition: NCO content: 21.8% Monomer PDI: 0.09% Viscosity (23°C): 9850 mPas Solids content: 100%

[0092] Polyisocyanate 5: According to Example 2 of European Patent Application Publication No. 0003765, isophorone diisocyanate (IPDI) polyisocyanate containing an isocyanurate structure was prepared via catalytic trimerization of IPDI. Based on the amount of catalyst used, equimolar amounts of dibutyl phosphate were added, and the reaction was inactivated at a crude mixture containing 30.1% NCO by stirring at 80°C for 30 minutes. Unreacted IPDI was then separated and removed by thin-film distillation at a temperature of 170°C and a pressure of 0.3 mbar, and the resulting solid resin was diluted with butyl acetate (BA). The product had the following characteristics and composition: NCO content: 11.9% Monomer IPDI: 0.28% Viscosity (23℃) 620mPas Solids content: 70%

[0093] Polyisocyanate 6: According to Comparative Example 2a of International Publication No. 2018 / 153801, hexamethylene diisocyanate (HDI) containing an iminooxadiadindione structure was prepared by trimerization of hexamethylene diisocyanate (HDI) using a 20% solution of 5-azaspiro[4.5]decane-5-ium fluoride hydrofluoride in 2-ethylhexanol as a catalyst, termination of the reaction at an NCO content of 44.8% crude mixture by adding an amount equal to the amount of catalyst of a 70% strength solution of dodecylbenzenesulfonic acid in isopropanol, and subsequent separation of unreacted HDI by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar. The product had the following characteristics and composition: NCO content: 23.5% Monomer HDI: 0.11% Viscosity (23℃) 720mPas Solids content: 100%

[0094] Characterization of coated films Drying times T1, T3, and T4 were carried out in accordance with DIN EN ISO 9117-5:2010-07.

[0095] On a glass plate, the pendulum damping by König was determined according to DIN EN ISO 1522 DIN EN ISO 1522:2007-04.

[0096] Solvent resistance was tested according to DIN EN ISO 4628-1:2016-07. Small amounts of each solvent—xylene, 1-methoxypropyl-2-acetate, ethyl acetate, and acetone—were placed in test tubes, and cotton pads were packed into the openings to create a solvent-saturated atmosphere inside the test tubes. The test tubes, along with the cotton pads, were then moved onto the surface of the coating and left there for 5 minutes. After wiping off the solvent, the film was examined for fracture / softening / loss of adhesion and assigned a score (0 = no change, 5 = film completely dissolved). The reported evaluations are in the form of four consecutive numbers, with each case being evaluated against four solvents in the order of xylene (X), 1-methoxypropyl-2-acetate (MPA), ethyl acetate (EA), and acetone (A).

[0097] To test the coating's water resistance, a cotton pad was immersed 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 on paper and inspected, and marked as having "bubbles" or "no bubbles".

[0098] Condensation test DIN EN ISO 6270-2 CH:2018-04

[0099] Accelerated weathering tests of CAM 180 were conducted in the presence of UV irradiation, in accordance with SAE J2527. Test plates were inspected every 250 hours.

[0100] UV-A testing of the coating material was performed according to DIN EN ISO 16474-3:2014-03 (Cycle 1). The test plates were checked every 250 hours.

[0101] Using the Delta E (yellowing, CAM 180) "Dr.Lange-Micro Color II," the Delta E value can be calculated from the L, a, and b values ​​determined according to the Lab color space, in accordance with DIN EN ISO / CIE 11664-4:2019-04.

[0102] compound Solvent-based coatings Formulation example 1 Component A: Setalux DA 870 BA (48.11 g) was mixed with 0.25 g Byk 141 (delivered 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.

[0103] Component B: 24.43 g of polyisocyanate 1 was diluted with a 1:1 solution of BA and xylene.

[0104] Components A and B were poured into a container in a 1:1 NCO to OH ratio and mixed by hand for 1 minute. Depending on the test being performed, the mixture was applied to the panel using a coating knife. The panel was dried 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 thickness of the cured dry film was approximately 50 μm.

[0105] a) Formulations containing reduced catalyst and b) Formulations without catalyst Example 1 As described in the previous examples, coatings were prepared with half the amount of catalyst (Example 1a, 0.75 g of Addokat 201) and without the catalyst (Example 1b, without Addokat 201).

[0106] [Table 1]

[0107] The compound was prepared as described above, using the amounts of curing agent and solvent in component B as outlined in the table above.

[0108] Water-based coating Example of formulation 6 (starting formulation without additives) Component A: Bayhydrol A 2695 (58.51 g) was combined with Byk 349 (0.13 g) and water (9.00 g). The mixture was stirred for 2 minutes at 2000 U / min using a Dispermat CV50 disperser.

[0109] 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 disperser.

[0110] Components A and B were mixed together to obtain an NCO to OH ratio of 1.5:1, and the mixture was stirred for 2 minutes at 2000 U / min using a Dispermat CV50 disperser. The mixture was applied to a panel using a coating knife. The thickness of the wet film was approximately 150 μm. The panel was dried at room temperature for 7 days or at 60°C for 30 minutes.

[0111] Comparative Example 7 Alternative ingredient B: Polyisocyanate 6 (19.14 g) was dissolved in MPA (10.30 g). The formulation was prepared as described above.

[0112] [Table 2]

[0113] [Table 3]

[0114] [Table 4]

[0115] Analysis of the results As shown in Example 1, polyisocyanate 1 produces a solvent-resistant film exhibiting the advantages of the combined effect (Comparative Example 5) seen in HDI and IPDI trimmers. These coatings are fast-drying (achieving T4 in 8 hours after curing at room temperature), sufficiently hard after 7 days of curing (pendulum hardness > 140 seconds), and exhibit reasonable solvent resistance. Water resistance tests do not result in bubble formation as seen in HDI and IPDI trimmers. After weathering (CAM 180 and UV-A), this new system exhibits weather stability without significant loss of gloss or yellowing. Furthermore, these results can be obtained with lower catalyst loading, or even without catalyst, as shown in Examples 1a and 1b of the present invention. Example 6 (polyisocyanate 2) demonstrates that the polyisocyanate composition of the present invention can also be used in aqueous systems. Compared to the standard system using polyisocyanate 6 (Comparative Example 7), these systems have comparable hardness and offer the additional advantages of improved chemical resistance and faster drying, even in aqueous systems.

Claims

1. The material comprises at least one cross-linked cis-tetrahydrofuran-2,5-diyl-methylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate, and / or biuret structure. A polyisocyanate composition comprising and / or at least one crosslinked trans-tetrahydrofuran-2,5-diyl)-dimethylene unit and at least one isocyanurate, iminooxadiazinedione, allophanate, urethane, urea, uretdione, oxadiazinetrione, carbodiimide, thiourethane, thioallophanate and / or biuret structure.

2. The polyisocyanate composition according to claim 1, characterized by comprising at least one isocyanurate, iminooxadiazinedione, allophanate, uretdione and / or biuret structure, preferably at least one isocyanurate, iminooxadiazinedione, allophanate and / or uretdione structure, more preferably at least one isocyanurate, iminooxadiazinedione and / or allophanate 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, based on the total weight of the polyisocyanate composition, as determined in accordance with DIN EN ISO 11909:2007-05.

4. The polyisocyanate composition according to any one of claims 1 to 3, characterized in that it has a residual monomer 2,5-bis(isocyanatomethyl)tetrahydrofuran 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 the reaction of at least one cis-2,5-bis(isocyanatomethyl)tetrahydrofuran and / or trans-2,5-bis(isocyanatomethyl)tetrahydrofuran, which may be in the presence of at least one catalyst, and a further co-reactant selected from the group consisting of alcohols, thiols, amines, water, CO2, or further isocyanates having an NCO functional value > 1.

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

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

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

9. An article comprising at least one cured two-component system according to claim 7 or 8, or an article at least partially coated with the cured two-component system according to claim 7 or 8.

Images