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    • 专利摘要:
    STRUCTURAL POLYURETHANE ADHESIVE, CONNECTION METHOD AND ARTICLE The invention relates to a two-component polyurethane adhesive having high strength and elasticity at a particularly low glass transition temperature, suitable as a structural adhesive. The adhesive according to the invention contains a triol, a diol, a polyamine, a polyisocyanate and a polyurethane polymer having isocyanate groups in certain ratios and a Fe (III) or Ti (IV) or Zr chelate complex catalyst (IV) or Hf (IV).
    公开号:BR112015004214B1
    申请号:R112015004214-7
    申请日:2013-09-10
    公开日:2021-03-02
    发明作者:Urs Burckhardt；Steffen Kelch；Rita Cannas
    申请人:Sika Technology Ag；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [1] The invention relates to the field of two-component polyurethane adhesives, in particular structural polyurethane adhesives. PREVIOUS TECHNIQUE
    [2] Two-component polyurethane compositions based on polyols and polyisocyanates have long been used as elastic adhesives. They heal quickly after mixing and can therefore absorb and transfer forces after a short period of time.
    [3] Structural adhesives, also referred to as structural adhesives and assembly adhesives, are used in the manufacturing industry to bond components together in such a way that the adhesive bond is part of a permanent durable construction. Such adhesives are typically resistant and flexible and must meet high standards in terms of processability, strength and adhesive forces.
    [4] For many bonded constructions, it is important that the strength, for example, the modulus of elasticity, of the adhesive is as uniform as possible throughout its entire temperature range of use, particularly in the temperature range of approximately - 35 ° C to approximately + 80 ° C, so that the mechanical behavior of the adhesive connection can be properly taken into account in the construction calculation. Particularly desirable are the tough, high-strength elastic adhesives, which have the lowest glass transition temperature possible. These adhesives must be easily processable, usable even in higher layer thicknesses of up to 10 mm and more, and capable of being cured without problem for final strength, both at room temperature and in an accelerated heat curing process, and they must exhibit good bonding to metallic and non-metallic substrates. Description of the invention
    [5] Therefore, the object of the present invention is to provide a polyurethane adhesive that combines a high strength with a particularly low glass transition temperature and, consequently, which is excellently suitable as a structural adhesive.
    [6] It was surprisingly found that a polyurethane adhesive according to claim 1. Due to its special composition, the adhesive has good processability with high stability after mixing the components, good initial, fast and, at the same time, interference-free curing, as well as very high resistance in the cured state. In particular, the adhesive has excellent mechanical behavior, that is, rigid elastic properties with high strength and good extensibility, which remain largely constant over the temperature range of -35 ° C to + 85 ° C. It is particularly surprising that, as a result of the action of a special catalyst, the adhesive achieves a markedly lower glass transition temperature than is the case with other polyurethane catalysts.
    [7] Additional aspects of the invention are the subject of additional independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways of conducting the invention
    [8] The object of the invention is a polyurethane adhesive consisting of a first and a second component, where - the first component contains a) at least one A1 triol with a molecular weight in the range of 1000 to 10000 g / mol, b) at least one diol A2 with two primary hydroxyl groups and a molecular weight in the range of 60 to 150 g / mol, and c) at least one aliphatic polyamine A3 with a molecular weight in the range of 60-500 g / mol; - the second component contains d) at least one polyisocyanate B1 and e) at least one polyurethane polymer B2 with isocyanate groups; - and the polyurethane adhesive also contains f) at least one catalyst K in the form of a metal chelate complex, in which the metal is selected from the group consisting of Fe (III), Ti (IV), Zr ( IV) and Hf (IV); - In which triol A1, diol A2 and polyamine A3 are present in an amount such that g) the ratio V1 of the number of OH groups and the number of NH2 groups of (A2 + A3) / A1 is in the range of 3 to 15, eh) the V2 ratio of the number of OH groups and the number of NH2 groups of A2 / A3 is in the range of 2 to 30.
    [9] The prefix “poly” in the names of substances such as “polyol”, “polyisocyanate”, “polyether” or “polyamine” in this document indicates that the respective substance formally contains more than one of the functional groups that occur in the name per molecule.
    [10] The term “polyurethane polymer” encompasses all polymers that are produced according to the so-called diisocyanate polyaddition method. The term "polyurethane polymer" also encompasses polyurethane polymers with isocyanate groups, as can be obtained by reacting polyisocyanates and polyols and polyisocyanates which are represented and are also often referred to as prepolymers.
    [11] In this document, "molecular weight" is always understood to refer to the average molecular weight in the case of polymers.
    [12] An OH group that is attached to a C atom with two hydrogen atoms is referred to as a "primary hydroxyl group."
    [13] In this document, the term "phase separation" describes the process of demixing highly ordered ("crystalline") regions, also referred to as "hard segments" and less ordered ("amorphous regions"), also referred to as "segments "during the curing of the polyurethane adhesive.
    [14] In this document, "open time" refers to the time in which the parts to be connected must be joined after the components are mixed.
    [15] In this document, "glass transition temperature" indicates the glass transition temperature, determined by means of dynamic mechanical thermoanalysis (DMTA), the temperature of which is read at a maximum value of the loss ratio G '' / module of storage G '.
    [16] In this document, the term "strength" refers to the strength of the cured adhesive, where strength is understood to mean, in particular, the tensile strength and the modulus of elasticity (modulus E) in elongation vary up to 10% .
    [17] In this document, "room temperature" refers to a temperature of 25 ° C.
    [18] The term "storage-stable" refers to the property of a composition being able to be stored in a suitable container for several weeks to several months at room temperature, without its application or use properties changing substantially due to storage .
    [19] Like Al triol, polyoxyalkylene triois, also known as polyether triois, are particularly suitable. They are the products of the polymerization of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide or mixtures thereof. Typically, they are polymerized using a starting molecule with three active hydrogen atoms, such as, for example, glycerol, 1,1,1-trimethyloletane, 1,1,1-trimethylolpropane or mixtures thereof.
    [20] As the Al triol, polyoxypropylene triols, polyoxyethylene triples and polyoxypropylene-polyoxyethylene triples are preferred.
    [21] It is particularly preferable for the Al triol to have primary hydroxyl groups. As a result, the polyurethane adhesive is less susceptible to undesirable reactions from isocyanate groups with water that may be present, which can result in the formation of bubbles and incomplete curing.
    [22] As an Al triol, so-called "EO-capped" polyoxypropylene triois (capped with ethylene oxide) are particularly preferred. The latter are special polyoxypropylene-polyoxyethylene triois, which are obtained, for example, by another alkoxylation of pure polyoxypropylene triois with ethylene oxide after the completion of the polypropoxylation and which as a result comprise primary hydroxyl groups.
    [23] Triol Al preferably has an average OH functionality in the range of 2.2 to 3. With such Al triois, adhesives with good mechanical properties are obtained.
    [24] Triol Al preferably has a molecular weight in the range of 3000-8000 g / mol, particularly preferably 4000-6000 g / mol. Such a triol has a good combination of high functionality and chain length, so that an adhesive with good mechanical properties is obtained with it.
    [25] Al triol is preferably used in an amount of 30 to 70% by weight relative to the total weight of the first component.
    [26] As diol A2, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and diethylene glycol are particularly suitable. These diols are easy to obtain and contain primary hydroxyl groups with almost no steric hindrance, which are particularly reactive with isocyanate groups.
    [27] Diol A2 is preferably a linear diol selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. These diols are particularly easy to handle because they are little hydrophilic and are liquid at room temperature, and, during curing of the adhesive, they promote high strength with good extensibility over a wide range of temperatures. Among them, 1,4-butanediol is more preferred.
    [28] 1,5-pentanediol is also especially preferred. When used in conjunction with catalyst K, particularly high E modules and very low glass transition temperatures are achieved.
    [29] As aliphatic polyamine A3, amines having two or three aliphatic amino groups are suitable, in particular the following commercial polyamines: - Primary aliphatic, cycloaliphatic or arylaliphatic diamines, such as, in particular, ethylenediamine, 1,2-propanediamine, 1 , 3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,3-pentanediamine (DAMP), 1, 5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (Cll neodylamine), 1,6-hexanediamine, 2,5-dimethyl-1,6 -hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine , 1,12-dodecanediamine, 1,2-, 1,3- and 1,4-diaminocyclohexane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), bis (4-aminocyclohexyl) methane (H12- MDA), bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3,5-dimethylcyclohexi l) methane, bis (4-amino-3-ethyl-5-methylcyclohexyl) methane (M-MECA), l-amino-3-aminomethyl-3,5,5-trimethylcyclo (= isophoronadiamine or IPDA), 2- and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3- and 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA ), 3 (4), 8 (9) -bis (aminomethyl) tricycle [5.2.1.02'6] decane, 1,8-methanediamine and 1,3- and 1,4-bis (aminomethyl) benzene; - primary aliphatic diamines containing an ether group, such as, in particular, bis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecan-l, 10-diamine, 4,7- dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine and higher oligomers of these diamines , 3,9-bis (3-aminopropyl) -2,4,8,10- tetraoxaspiro- [5.5] undecane, bis (3-aminopropyl) polytetrahydrofurans and other polytetrahydrofuranodiamines, Jeffamine® RFD-270 (from Huntsman ), as well as polyoxyalkylene diamines ("polyether diamines"). The latter represent amine products for polyoxyalkylene diols and are available, for example, under the name Jeffamine® (from Huntsman), under the name Polyetheramine (from BASF) or under the name of PC Amine® (from Nitroil). Particularly suitable polyoxyalkylene diamines are Jeffamine® D-230, Jeffamine® D-400, Polyetheramine D 230, Polyetheramine D 400, PC Amine® DA 250 and PC Amine® DA 400; and - polyoxyalkylene triamines ("polyether triamines"), which represent the amination products of polyoxyalkylene triois and which are available, for example, under the trade name Jeffamine® (from Huntsman), under the name Polyetheramine (from BASF) or under the name PC Amine® (from Nitroil), such as, in particular, Jeffamine® T-403, Polyetheramine T403, and PC Amine® TA 403.
    [30] It is particularly preferred for polyamine A3 to be selected from the group consisting of 1,5-diamino-2-methylpentane, 2,2,4- and 2,4,4-trimethylhexanomethylenediamine, 1,8-octanediamine , 1,10-decanediamine, 1,12-dodecanediamine, 1-amino-3-aminomethyl1-3,5,5-trimethylcyclohexane, 2- and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -bis- (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) - bis ( aminomethyl) tricycle [5.2.1. O2'6] decane, bis (2-aminoethyl) ether, 3,6-dioxoxane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 1,3-bis (aminomethyl) benzene and 1,4-bis (aminomethyl) benzene.
    [31] These polyamines, in the reaction with isocyanates, lead to urea groups that undergo particularly satisfactory phase separation. Adhesives produced with them have particularly high strengths, in particular high modulus of elasticity, and a not very pronounced dependence on the mechanical properties of temperature.
    [32] Among them, 1,3-bis (aminomethyl) cyclohexane and 1,3-bis (aminomethyl) benzene are preferred; 1,3-bis (aminomethyl) benzene is more preferred. With these polyamines, adhesives cured particularly with very high resistance forms.
    [33] The selection of triol Al, diol A2 and polyamine A3 and their use in certain proportions carefully adjusted to each other gives good processing properties and excellent resistance to the adhesive, in which the amorphous and crystalline regions are present with very good demixing.
    [34] Ratio VI is preferably 3-10. These adhesives have a particularly low glass transition temperature.
    [35] The VI ratio is particularly preferably 39. These adhesives have a particularly low glass transition temperature.
    [36] Ratio VI is preferably 4-15. These adhesives have a high modulus of elasticity.
    [37] The VI ratio is particularly preferably 515. These adhesives have a particularly high modulus of elasticity.
    [38] The VI ratio is preferably in the range of 4 to 10, in particular 5 to 9. These adhesives have a particularly low glass transition temperature and at the same time a particularly high modulus of elasticity.
    [39] The V2 ratio is preferably 2-15. Such adhesives have a certain stability, with a long open time.
    [40] The V2 ratio is a particularly preferably 2-10 mode. Such adhesives have good stability with an easily manageable open time.
    [41] The V2 ratio is preferably 4.5-30 or higher. Such adhesives have very good stability, with a short open time.
    [42] The V2 ratio is a particularly preferably 5-30 mode. Such adhesives have good stability with an easily manageable open time.
    [43] The V2 ratio is preferably in the range of 4.5 to 15, in particular in the range of 5 to 10. Such adhesives show a good combination of good stability in the application time and an easily manageable open time.
    [44] As a polyisocyanate Bl, monomeric di- or triisocyanates, as well as monomeric oligomers, polymers and dior triisocyanates derivatives, as well as any mixtures thereof, are suitable.
    [45] Suitable aromatic monomeric di- or triisocyanates are, in particular, 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers (MDI), mixtures of MDI and MDI homologues (polymer MDI or PMDI), 1,3- and 1,4-phenylene, diisocyanate, 2, 3,5,6-tetramethyl- 1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisidine di - isocyanate (DADI), 1,3,5-tris- (isocyanatomethyl) benzene, tris- (4-isocyanatophenyl) methane and tris- (4-isocyanatophenyl) thiophosphate.
    [46] Suitable aliphatic monomeric di- or triisocyanates are, in particular, 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine and ester lysine diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-methyl-2,4- and -2,6-diisocyanatocyclohexane and any mixtures of these isomers (HTDI or HeTDI), l-isocyanate ~ 3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (= isophorone diisocyanate or IPDI), perhydro -2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI or H12MDI), 1,4-diisocyanate-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI ), m- and p-tetramethyl-1,3- and -1,4- xylylene diisocyanate (m- and p-TMXDI), bis (1-isocyanate-1-methylethyl) naphthalene, dimeric fatty acid isocyanates and trimers, such as 3,6-bis (9- isocyanatononyl) -4,5-di- (1-heptenyl) cyclohexene (dimeryl diisocyanate) and a, ot, a ', a', α '', α '' - hexamethy1-1,3,5-mesitylene tri -isocyanate.
    [47] Suitable oligomers, polymers and the monomeric di- and tri-isocyanate derivatives mentioned are derived particularly from MDI, TDI, HDI and IPDI. Of these, commercial types are particularly suitable, especially HDI-biurets such as Desmodur® N 100 and N 3200 (from Bayer), Tolonate® HDB and HDB-LV (from Rhodia) and Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur® N 3300, N 3600 and N 3790 BA (all from Bayer), Tolonate® HDT, HDT-LV and HDT-LV2 (from Rhodia), Duranate® TPA-100 and THA-100 (from Asahi Kasei) and Coronate® HX (from Nippon Polyurethabe); HDI uretodiones such as Desmodur® N 3400 (from Bayer); HDI imino-oxadiazindiones such as Desmodur® XP 2410 (from Bayer); HDI allophanates, such as HDI Desmodur® VP LS 2102 (from Bayer); IPDI isocyanurates, such as, for example, in solution such as Desmodur® Z 4470 (from Bayer) or in solid form, such as Vestanat® T1890 / 100 (from Degussa); TDI oligomers such as Desmodur® IL (from Bayer); as well as mixed isocyanurates based on TDI / HDI, such as Desmodur® HL (from Bayer). In addition, they are particularly suitable forms of MDI that are liquid at room temperature (so-called "modified MDI"), which represent mixtures of MDI with MDI derivatives, such as, in particular, carbodiimide MDI or urethane MDI or urethane MDI, known under trade names such as Desmodur® CD, Desmodur® PF, Desmodur® PC (all from Bayer) or Isonate® M 143 (from Dow), as well as mixtures of MDI and MDI (polymer MDI or PMDI) counterparts, available under trade names such as Desmodur® VL, Desmodur® VL50, Desmodur® VL RIO, Desmodur® VL R20, Desmodur® VH 20 N and Desmodur® VKS 20F (all from Bayer), Isonate® M 309, Voranate® M 229 and Voranate® M 580 (all from Dow) or Lupranat® M 10 R (from BASF). The oligomeric polyisocyanates mentioned above, in practice, in general, represent mixtures of substances with different degrees of oligomerization and / or chemical structures. Preferably, they have an average NCO functionality of 2.1 to 4.0.
    [48] As polyisocyanate Bl, forms of MDI that are liquid at room temperature are preferred. They are, in particular, the so-called polymeric MDI, as well as MDI with content of oligomers or derivatives thereof. The content of MDI (= 4,4 ', 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers) of such liquid forms of MDI is at least 50 to 95% in particular in particular weight, in particular, 60 to 90% by weight.
    [49] Particularly preferred as polyisocyanate Bl are forms of MDI which are liquid at room temperature and which comprise a content of 4,4'-diphenylmethane diisocyanate of at least 40% by weight, preferably at least 50% by weight, in particular at least 60% by weight. Such polyisocyanates Bl allow rapid curing.
    [50] As polyisocyanate Bl, polymeric MDI and in particular types of MDI that are liquid at room temperature and that contain levels of MDI-carbodiimides or adducts thereof are particularly preferred.
    [51] With these Bl polyisocyanates, especially good processing properties and particularly high strengths are obtained.
    [52] Polyurethane polymer B2 preferably has 50-95% by weight, in particular 70-90% by weight, polyoxyalkylene units, especially preferably polyoxyethylene and / or polyoxypropylene units, in particular polyoxypropylene units. Said polyurethane polymer has a low viscosity and allows good extensibility.
    [53] Polyurethane polymer B2 preferably has an average molecular weight of 1000 to 20000 g / mol, particularly and preferably from 2000 to 10,000 g / mol.
    [54] The polyurethane polymer B2 of polyurethane preferably has an average NCO functionality in the range of 1.7 to 3, in particular 1.8 to 2.5. Said polyurethane polymer allows good processing properties and good mechanical properties in the cured state.
    [55] Polyurethane polymer B2 preferably has an average NCO functionality of 2.05 to 2.5. Said polyurethane polymer allows good extensibility with high strength.
    [56] Polyurethane polymer B2 preferably has a content of free isocyanate groups from 1 to 10% by weight, especially preferably from 1 to 5% by weight.
    [57] Polyurethane polymer B2 preferably comprises urethane groups and free isocyanate groups, which are derived from 4,4'-diphenylmethane diisocyanate.
    [58] With this, during curing of the adhesive, particularly good rigid segments and therefore particularly high strengths are obtained.
    [59] A polyurethane B2 polymer that has suitable isocyanate groups can be obtained by reacting at least one polyisocyanate with at least one polyol. This reaction can occur by the reaction of the polyol and the polyisocyanate, using usual methods, for example, at temperatures of 50 ° C to 100 ° C, optionally with the simultaneous use of appropriate catalysts, in which the polyisocyanate is measured in such that its isocyanate groups in relation to the polyol hydroxyl groups are present in stoichiometric excess. The polyisocyanate is advantageously measured in such a way that an NCO / OH ratio of 1.3 to 5, in particular 1.5 to 3, is maintained. "NCO / OH ratio" means the ratio of the number of isocyanate groups used to the number of hydroxyl groups used. In polyurethane polymer B2, after the reaction of all hydroxyl groups of the polyol, it is preferable for a content of free isocyanate groups of 1 to 10% by weight, especially preferably from 1 to 5% by weight, to remain.
    [60] Polyurethane polymer B2 has an average molecular weight preferably of 500 g / mol or greater. In particular, polyurethane polymer B2 has an average molecular weight of 1000 to 20,000 g / mol, preferably 2000 to 10,000 g / mol.
    [61] In addition, polyurethane polymer B2 preferably has an average NCO functionality in the range of 1.7 to 3, in particular 1.8 to 2.5.
    [62] Said polyurethane polymer allows good processing properties and good mechanical properties in the cured state.
    [63] As a polyol to produce a B2 polyurethane polymer, the following commercial polyols or mixtures thereof are particularly suitable: - polyoxyalkylene polyols, also referred to as polyether polyols or oligoether alcohols, which are polymerization products of ethylene oxide, oxide of 1 , 2-propylene, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized using a starting molecule having two or more active hydrogen atoms, such as, for example, water, ammonia or compounds having various OH or NH groups, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomer of dipropylene glycols and tripropylene glycols, isomeric butanediols, pentanediols, hexanediols, hepatanediols, octanodiols, nonanodiols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethyloletane, 1,1,1- trimethylolpropane, glycerine 1, aniline, as well as mixtures of the aforementioned compounds. It is also possible to use polyoxyalkylene polyols that have a low degree of unsaturation (measured according to ASTM D-2849-69 and indicated in milliequivalents of unsaturation per gram of polyol (mEq / g)), produced, for example, using the so-called double metal cyanide catalysts (DMC catalysts), as well as polyoxyalkylene polyols with a higher degree of unsaturation, produced, for example, using anionic catalysts such as NaOH, KOH, CsOH or alkaline alcoholates.
    [64] Particularly suitable are polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene di- and -triols.
    [65] Particularly suitable are polyoxyalkylene diols and triols with a degree of unsaturation of less than 0.02 mEq / g with a molecular weight in the range from 1000-30,000 g / mol, as well as polyoxypropylene diols and triples with a weight molecular weight of 400-8000 g / mol.
    [66] Especially suitable are so-called polyoxypropylene polyols covered at the end with ethylene oxide ("capped at the end with EO"). - Styrene-acrylonitrile or polyether polyols grafted with acrylonitrile-methylmethacrylate. - Polyester polyols, also referred to as oligoesterols, produced according to known methods, in particular, polycondensation of hydroxycarboxylic acids or polycondensation of aliphatic and / or aromatic polycarboxylic acids with bivalent or polyvalent alcohols.
    [67] Particularly suitable polyester polyols are those produced from bivalent to trivalent, in particular bivalent alcohols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,12-hydroxystearyl alcohol, 1,4- cyclohexanedimethanol, fatty acid dimer diol (diol dimer), hydroxypivalic acid neopentyl glycol esters, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, with organic di- or tricarboxylic acids, in particular dicarboxylic acids, or their compounds anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, submeric acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, fatty acid dimer, phthalic acid, anhydride phthalic acid, isophthalic acid, acid terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic acid anhydride, or mixtures of the aforementioned acids, as well as polyester polyols from lactones, such as, for example, from ε-caprolactone and initiators, such such as the aforementioned bivalent or trivalent alcohols.
    [68] Polyester polyols which are particularly suitable are polyester diols. - Polycarbonate polyols, which can be obtained by reacting, for example, the aforementioned alcohols - used for the construction of polyester polyols - with dialkyl carbonates, diaryl or phosgene carbonates. - At least two block copolymers containing hydroxyl group comprising at least two different blocks with a structure of polyether, polyester and / or polycarbonate, of the type described above, in particular polyether polyester polyols. - Polyacrylate and polymethacrylate polyols. - Polyhydroxy fats and functional oils, for example, natural fats and oils, in particular castor oil; or polyols - the so-called oleochemical polyols - obtained by chemical modification of natural fats and oils, for example, epoxy polyesters or epoxy polyethers obtained by epoxidation of unsaturated oils and subsequent opening of the ring with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural fats and oils by degradation processes, such as alcoholysis or ozonolysis and subsequent chemical bonding, for example, by transesterification or dimerization of the degradation products thus obtained or their derivatives. Suitable breakdown products of natural fats and oils are, in particular, fatty acids and fatty alcohols, as well as fatty acid esters, in particular methyl esters (FAME), which can be derivatized, for example, by hydroformylation and hydrogenation to form esters of hydroxylated fatty acid. - polyhydrocarbon polyols, also known as oligohydrocarbons, such as, for example, functional polyhydroxy polyolefins, polyisobutylene, polyisoprene; copolymers of ethylene-propylene polyhydroxy functional, ethylene-butylene- or ethylene-propylene-diene, which are produced, for example, by the company Kraton Polimers; The functional polyhydroxy polymers of dienes, in particular, of 1,3-butadiene, which can be produced, in particular also by anionic polymerization; Functional polyhydroxyl copolymers prepared from dienes such as 1,3-butadiene or mixtures of diene, and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example, copolymers of functional polyhydroxy acrylonitrile / butadiene, which can be produced, for example, from epoxides or amino alcohols and acrylonitrile / butadiene copolymers terminated with carboxyl (commercially available, for example, under the name Hypro® (formally Hycar®) CTBN and CTBNX and ETBN from Nanoresins AG, Germany or Emerald Performance Materials LLC); as well as hydrogenated polyhydroxyl functional polymers or diene copolymers.
    [69] As the polyol for the preparation of a B2 polyurethane polymer, polyoxyalkylene polyols, polyester polyols, polycarbonate polyols and polyacrylate polyols are preferred. Particularly preferred are polyoxyethylene polyols, in particular polyoxypropylene polyols and mixed polyoxyethylene-polyoxypropylene polyols.
    [70] The polyol for producing a B2 polyurethane polymer preferably has a molecular weight of 500-20,000 g / mol, in particular 1000-8000 g / mol.
    [71] The polyol for producing a polyurethane polymer B2 is preferably a diol or a mixture of at least one diol and at least one triol, in particular a mixture of at least one diol and at least one triol.
    [72] Together with the polyol, the content of low molecular weight or bivalent or polyvalent alcohols can be used simultaneously for the manufacture of polyurethane polymer B2, in particular 1,2-ethanediol, 1,2-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomer of dipropylene glycols and tripropylene glycols, the isanomers of butanedioles, pentanedioles, hexanedioles, hepatanedioles, octanedioles, nonanedioles, decanodiols, undecanoedioles, 1,3- and 1,4-cyclohexane, ethanol and hexane fatty dimers, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher grade alcohols, low molecular weight products alkoxylation of the aforementioned bivalent and polyvalent alcohols, as well as mixtures of the aforementioned alcohols.
    [73] As a polyisocyanate to produce a B2 polyurethane polymer, the following commercial polyisocyanates or mixtures thereof are particularly suitable:
    [74] 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane-diisocyanate and any mixtures of these isomers (MDI), 1,3- and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI) , 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), 1,3,5-tris- (isocyanatomethyl) benzene, 2-methylpentamethylene-1,5-diisocyanate, 1,6-di -hexamethylene isocyanate (HDI), 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene-diisocyanate (TMDI), 1,10-decamethylene-diisocyanate, 1,12- dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3- and-1,4-diisocyanate, 1-methyl-2,4- and -2,6-diisocyanatocyclohexane and any mixtures of these isomers (HTDI or H6TDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI), perhydro 2,4'- and 4,4'-diphenylmethane diisocyanate (HMDI or H12MDI), 1,4-diisocyanate-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-b is (isocyanatomethyl) cyclohexane, m- and p-xylylene diisocyanate (m-ep-XDI) and m- and p-tetramethyl-1,3- and -1,4-xylylene (m- and p-TMXDI). MDI, TDI, HDI and IPDI are preferred. MDI is particularly preferred. 4,4'-diphenylmethane diisocyanate is more preferred. Using this MDI dimer, during curing with A2 diols and A3 polyamines, particularly rigid segments and thus particularly with high strengths are obtained. The polyisocyanate Bl and the polyisocyanate used for the preparation of the polyurethane prepolymer B2 are preferably different types of polyisocyanate.
    [75] Polyisocyanate Bl and polyisocyanate used for the preparation of polyurethane prepolymer B2 are preferably different types of polyisocyanates.
    [76] Polyisocyanate Bl is particularly preferably an MDI that is liquid at room temperature, and the polyisocyanate used for the preparation of polyurethane polymer B2 is preferably 4,4'-diphenylmethane diisocyanate, which is normally solid at room temperature. Here, the second component is a liquid at room temperature, which allows for simple processing, and allows for particularly good mechanical properties. A defined mixture of polyisocyanate Bl and polyurethane polymer B2 can be achieved by first producing polyurethane polymer B2 separately before it is mixed with polyisocyanate Bl.
    [77] Thus, the preparation of the polyurethane polymer, preferably B2, is not carried out in the presence of the polyisocyanate Bl.
    [78] The weight ratio between polyisocyanate Bl and polyurethane polymer B2 is preferably 0.25 to 4, preferably 0.25 to 2, particularly preferably 0.3 to 1.5, and especially 0.4 to 1.0. Said second component generates adhesives with good processing capacity, high resistance and high extension.
    [79] The polyurethane adhesive contains at least one K catalyst in the form of a metal chelate complex, in which the metal is selected from the group consisting of Fe (III), Ti (IV), Zr (IV) and Hf (IV).
    [80] In this document, metal carboxylates and metal alcoholates are not referred to as metal chelate complexes, unless they comprise at least one chelate binder.
    [81] Suitable chelate binders on catalyst K are, in particular- 1, 3-ketonates, in particular (2,4-pentanedionate), 2,2,6,6-tetramethyl-3,5-heptanedionate acetylacetonate, 1 , 3-diphenyl-1,3-propanedionate (dibenzoyl methanate), 1-phenyl-1,3-butanedionate and 2-acetylcyclohexanonate; - 1, 4-toesterates, in particular methylacetoacetate, atylacetoacetate, ethyl-2-methylacetoacetate, ethyl-2-ethylacetoacetate, ethyl-2-hexylacetoacetate, ethyl-2-phenylacetoacetate, propylacetoacetate, isopropylacetoacetate, butylacetate, butyl -oxovalerate, ethyl-3-oxohexanoate and 2-oxocyclohexanecarboxylic acid ethyl ester, and - 1,5-toamidates, in particular N, N-diethyl-3-oxobutane amidate, N, N-dibutyl-3-oxobutane amidate , N, N-bis (2-ethylhexyl) -3-oxobutane amidate, N, N bis (2-methoxyethyl) -3-oxobutane amidate, N, N-dibutyl-3-oxoheptane amidate, N, N-bis (2 -methoxyethyl) -3-oxoheptane amidate, N, N-bis (2-ethylhexyl) -2-oxocyclopentane carboxamidate, N, N-dibutyl-3-oxo-3-phenylpropane amidate, N, N-bis (2-methoxyethyl) -3-oxo-3-phenylpropane amidate and N-polyoxyalkylene-1,3-ketoamidates such as polyoxyalkylene amine acetoamidates with one, two or three amino groups and a molecular weight of up to 5000 g / mol, in particular SD types - 231, SD-401, S D-2001, ST-404, D-230, D-400, D-2000, T-403, M-600 and XTJ-581 available from Huntsman under the trade names Jeffamine®.
    [82] In the polyurethane adhesive, catalyst K produces a rapid cure, which occurs with surprisingly few disturbances; in particular, bubbles form less frequently than with other catalysts according to the prior art. In addition, catalyst K surprisingly influences the polyurethane adhesive in such a way that, after curing, the latter has a significantly lower transition temperature vitreous than if other catalysts according to the prior art are used, such as 1,4-diazobicyclo [2.2.2] octane (DABCO) or dibutyltin dilaurate, for example. For a structural adhesive, a low glass transition temperature is very advantageous, as the adhesive remains more constant during cooling in terms of its mechanical properties and once it reaches the point where it becomes less quickly where it becomes very hard and even brittle . In conventional structural adhesives based on two-component polyurethane compositions, the glass transition temperature is typically in the vicinity of -30 ° C or higher. Once such temperature values are reached under extreme winter conditions, a shift below the glass transition temperature by a few degrees Celsius may be sufficient to make a reliable use of this adhesive possible, even under these conditions.
    [83] Catalyst K preferably comprises at least one chelating linker selected from the group consisting of 1,3-diketonate, 1,3-ketoesterate and 1,3-ketoamidate.
    [84] In addition to at least one of said chelate binders, the metal-chelate complex may comprise additional binders that do not form chelates, in particular alcoholates such as methanolate, ethanolate, propanolate, isopropanolate, butanolate, tert-butanolate, isobutanolate , pentanolate, neopentanolate, hexanolate, octanolate or 2-ethylhexanolate; as well as carboxylates such as formate, acetate, propionate, ethyl butanoate, isobutanoate, ethyl pentanoate, hexanoate, cyclohexanoate, heptanoate, octanoate, 2-ethylhexanoate, nonanoate, decanoate, neodecanoate, undecanoate, dodecanoate, lact , oleate, citrate, benzoate, salicylate and phenylacetate.
    [85] K catalysts are particularly preferably represented by the following metal-chelate complexes: iron (III) tris (acetylacetonate), iron (III) tris (1,3-diphenylpropane-1,3-dionate), iron (III) tris (ethylacetoacetate), iron (III) tris (tert-butylacetoacetate), iron (III) tris (ethyl-3-oxo-valerate), iron (III) tris (ethyl-3-oxo-hexanoate), iron (III) tris (N, N-diethyl-3-oxobutane amidate), iron (III) tris (N, N-dibutyl-3-oxobutane amidate), iron (III), tris (N, N-bis (2-ethylhexyl) - 3-oxobutane amidate), iron (III) tris (N, N-bis (2 methoxyethyl) -3-oxobutane amidate), iron (III) tris (N, N-dibutyl-3-oxohepatane amidate), iron (III) tris (N, N-bis (2-methoxyethyl) -3-oxohepatane amidate), iron (III) tris (N, N-bis (2-ethylhexyl) -2-oxo-cyclopentane carboxamidate) and iron (III) tris ( N, N-dibutyl-3-oxo-3-phenylpropane amidate); titanium (IV), bis (acetylacetonate) diisopropylate, titanium (IV) bis (acetylacetonate) diisobutylate, titanium (IV) bis (acetylacetonate) -bis (2-ethylhexylate), titanium (IV) bis (1,3 -diphenylpropane-1,3-dionate) diisopropylate, titanium (IV) bis (1,3-diphenylpropane 1,3-dionate) diisobutylate, titanium (IV) bis (1,3-diphenylpropane-1,3) dionate) -bis (2-ethylhexylate), titanium (IV) bis (ethylacetoacetate) diisopropylate, titanium (IV) bis (ethylacetoacetate) diisobutylate, titanium (IV) bis (ethylacetoacetate) -bis (2-ethylhexylate), titanium (IV) bis (tert-butylacetoacetate) diisopropylate, titanium (IV) bis (tert-butylacetoacetate) diisobutylate, titanium (IV) bis (tert-butylacetoacetate) -bis (2-ethylhexylate), titanium (IV) bis (ethyl-3-oxo-valerate) diisopropylate, titanium (IV) bis (ethyl-3-oxo-valerate) diisobutylate, titanium (IV) bis (ethyl-3-oxo-valerate) -is (2 -ethylhexylate), titanium (IV) bis (ethyl-3-oxohexanoate) diisopropylate, titanium (IV) bis (ethyl-3-oxohexanoate) diisobutylate, titanium (IV) bis (et yl-3-oxo-hexanoate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) diisopropylate, titanium (IV) bis (N, N-diethyl-3 -oxobutane amidate) diisobutylate, titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-dibutyl-3-oxobutane amidate) diisopropylate, titanium (IV) bis (N, N-dibutyl-3-oxobutane amidate) diisopropylate, titanium (IV) bis (N, N-dibutyl-3-oxobutane amidate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-dibutyl-3-oxohepatane amidate) diisopropylate, titanium (IV) bis (N, N-dibutyl-3-oxohepatane amidate) diisobutylate, titanium (IV) bis (N, N-dibutyl-3-oxohepatane amidate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-bis (2-ethylhexyl) -3-oxobutane amidate) diisopropylate, titanium (IV) bis (N , N-bis (2-ethylhexyl) -3-oxobutane amidate diisobutylate), titanium (IV) bis (N, N-bis (2-ethylhexyl) -3-oxobutane amidate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-bis (2-ethylhexyl) -2-oxo-cyclopentane carboxamidate) diisopropylate, titanium (IV) b is (N, N-bis (2-ethylhexyl) -2-oxo-cyclopentane carboxamidate) diisobutylate, titanium (IV) bis (N, N-bis (2-ethylhexyl) -2-oxo-cyclopentane carboxamidate) -bis (2-ethylhexylate), titanium (IV) bis (N, N-dibutyl-3-oxo-3-phenylpropanamidate) diisopropylate, titanium (IV) bis (N, N-dibutyl-3-oxo-3-phenylpropanamidate) diisobutylate and titanium (IV) bis (N, N-dibutyl-3-oxo-3-phenylpropanamidate) -bis (2-ethylhexylate); zirconium (IV) tetrakis (acetylacetonate), zirconium (IV), tetrakis (1,3-diphenylpropane-1,3-dionate), zirconium (IV) tetrakis (1-phenylbutane-1,3-dionate), zirconium (IV) tetrakis (ethylacetoacetate), zirconium (IV) tetrakis (tert-butylacetoacetate), zirconium (IV) tetrakis (ethyl-3-oxo-valerate), zirconium (IV) tetrakis (ethyl-3-oxohexanoate), zirconium (IV) tetrakis (N, N-diethyl-3-oxobutane amidate), zirconium (IV) tetrakis (N, N-dibutyl-3-oxobutane amidate), zirconium (IV) tetrakis (N, N-dibutyl-3-oxohepatane amidate) , zirconium (IV) tetrakis (N, N-bis (2-ethylhexyl) -3-oxobutane amidate), zirconium (IV) tetrakis (N, N-bis (2-ethylhexyl) -2-oxo-cyclopentane carboxamidate) and zirconium (IV) tetrakis- (N, N-dibutyl-3-oxo-3-phenylpropanamidate); as well as the corresponding compounds with hafnium (IV) instead of zirconium (IV).
    [86] K catalysts are very particularly preferably selected from the group consisting of iron (III) tris (acetylacetonate), iron (III) tris (ethylacetoacetate), iron (III) tris (tert-butylacetoacetate), iron (III ) tris (N, N-diethyl-3-oxobutane amidate), titanium (IV) bis (acetylacetonate) diisopropylate, titanium (IV) bis (acetylacetonate) diisobutylate, titanium (IV) bis (acetylacetonate) -bis ( 2-ethylhexylate), titanium (IV) bis (ethylacetoacetate) diisopropylate, titanium (IV) bis (ethylacetoacetate) diisobutylate, titanium (IV) bis (ethylacetoacetate) -bis (2-ethylhexylate), titanium (IV) bis (tert-butylacetoacetate) diisopropylate, titanium (IV) bis (tert-butylacetoacetate) diisobutylate, titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) diisopropylate, titanium (IV) bis ( N, N-diethyl-3-oxobutane amidate) diisobutylate, titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) -bis (2-ethylhexylate), zirconium (IV) tetrakis (acetylacetonate), zirconium (IV) tetrakis (1,3-diphenylpropane-1,3, dionate), zirconium (IV) tetrakis (ethylacetoacetate), zirconium (IV) tetrakis (tert-butylacetoacetate), zirconium (IV) tetrakis (ethyl-3-oxo-valerate), zirconium (IV) tetrakis (ethyl-3-oxo- hexanoate), zirconium (IV) tetrakis (N, N-diethyl-3-oxobutane amidate), zirconium (IV) tetrakis (N, N-dibutyl-3-oxobutane amidate), zirconium (IV) tetrakis (N, N- dibutyl-3-oxohepatane amidate) and zirconium (IV) tetrakis (N, N-bis (2-ethylhexyl) -3-oxobutane amidate).
    [87] These K catalysts have good catalytic activity and are based on easily accessible starting materials.
    [88] Catalyst K in the polyurethane adhesive is preferably present in an amount such that the adhesive has an open time in the range of 1 minute to 2 hours, preferably 2 minutes to 1 hour, in particular preferably 5 to 30 minutes. The open time of the adhesive here is also influenced by the type of catalyst K, the amount and type of Al triois, A2 diols, A3 polyamines, Bl polyisocyanates, B2 polyurethane polymers present and additional substances, which are reactive with isocyanates and influenced by the existing air temperature and humidity.
    [89] Catalyst K can be present as a constituent of the first and / or as a constituent of the component in the polyurethane adhesive.
    [90] Catalyst K can be used as a powder, as a liquid or as a solution.
    [91] As a constituent of the first component, the polyurethane adhesive may additionally contain other substances capable of reacting with isocyanate groups.
    [92] In particular, the first component can contain at least one polyol and / or at least a low molecular weight polyvalent or divalent alcohol, which have been mentioned for the preparation of polyurethane polymer B2.
    [93] In addition, the polyurethane adhesive may contain additional catalysts that accelerate the reaction of hydroxyl groups with isocyanate groups, in particular, organic metallic tin, zinc and bismuth catalysts, for example, dibutyltin dilaurate or tertiary amines, or amidines, guanidines, for example, 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,8-diazabicyclo [5 • 4.0] undec-7-ene (DBÜ). The polyurethane adhesive preferably does not contain additional curing catalysts other than one or more K catalysts.
    [94] In addition, the polyurethane adhesive may contain a so-called latent curing agent, in particular polyaldimine.
    [95] In addition to the additional constituents mentioned conventionally used in two-component polyurethane compositions, the polyurethane may contain, in particular, the following: - plasticizers, particularly esters of carboxylic acids, such as phthalates, in particular dioctyl phthalate, di diisodecyl phthalateisononyl phthalate, adipates, in particular adipate dioctyl, azelates and sebacates, organic phosphoric acid and sulphonic esters or polybutenes; - solvents; - inorganic and organic fillers, in particular terrain, or precipitated calcium carbonates which are optionally coated with fatty acids, in particular stearates, barite (heavy spatum), talc, quartz metals, quartz sand, dolomite, wollastonite, kaolin, mica , aluminum oxides, aluminum oxides, silicic acids, in particular, highly dispersed silicic acids from pyrolysis processes, cements, plaster, flying ash, soot, in particular industrially produced soot (hereinafter referred to as "soot"), graphite, metallic powder, for example aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres; - Polyethylene fibers, for example; - Pigments, for example, titanium dioxide, zinc oxide or iron oxide; - Rheology modifying agents, in particular, thickeners or thixotropic agents, for example, phyllosilicates, such as bentonites, castor oil derivatives, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicic acids, and hydrophobically modified polyoxyethylene cellulose ethers; - Drying agents, such as, for example, molecular sieves, calcium oxide, highly reactive isocyanates, such as p-tosylisocyanate, monomeric diisocyanates, mono-oxazolidines such as Incozol® 2 (from Incorez), orthophoric acid esters alkoxysilanes such as tetraethoxysilane and organoalkoxysilanes such as, in particular, vinyl trimethoxysilane; - Adhesive promoters, for example, organoalkoxysilanes such as aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanatosilanes, carbamatosilanes, alkylsilanes, S- (alkylcarbonyl) mercaptosilanes and aldiminosilanes, as well as in oligones, especially in oligones 3- glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) - N '- [3- (trimethoxysilyl) propyl] ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanine -ureidopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, or the corresponding organosilanes with ethoxy groups, instead of the methoxy groups; - stabilizers against oxidation, heat, light and UV radiation; - flame retardant substances, for example, aluminum hydroxides, magnesium hydroxide, phosphoric acid esters; - surfactants, in particular cross-linking agents, leveling agents, air-removing agents or anti-foam agents; - biocides, algaecides, in particular fungicides or substances that inhibit the growth of fungi.
    [96] When using additional components of the polyurethane adhesive, it is advantageous to ensure that they do not strongly affect the storage stability of the respective components. If these substances are to be stored together with isocyanates, this means in particular that they must not contain water or, at most, traces of water. It may be suitable for chemically or physically drying out certain constituents before mixing.
    [97] The components of the polyurethane adhesive are advantageously formulated in such a way that the mixing ratio of the volumes between the first and second components is in the range of 1: 3 to 3: 1, in particular from 1: 2 to 2: 1 . This ratio is preferably about 1: 1.
    [98] The mixing ratio is preferably adjusted in such a way that, in the mixed polyurethane adhesive, the ratio between the number of isocyanate groups and the number of groups that are reactive with isocyanates, in particular, the sum of groups OH and NH2, before curing, is approximately in the range of 1.2 to 1, preferably 1.1 to 1.
    [99] The two components are typically produced separately from each other and at least for the second component, excluding moisture. The components are typically stored each in a separate container. Additional components of the polyurethane adhesive may be present as a constituent of the first or second component, wherein additional components that are reactive with isocyanate groups are preferably a constituent of the first component. A container suitable for storing the respective component is represented, in particular, by a drum, a bucket, a bag, a bucket, a can, a cartridge or a tube.
    [100] Before use, the two components are stored separately from each other and are mixed with each other only at the time of use or just before use. The components are advantageously supplied in a package consisting of two mutually separated chambers.
    [101] In another aspect, the invention comprises a package consisting of a package with two separate chambers, each of the chambers containing one of the two components of the polyurethane adhesive.
    [102] Preferred packages of this type are, on the one hand, double side-by-side cartridges or coaxial cartridges in which two tubular chambers are arranged side by side or one inside the other and closed with pistons in an airtight manner and moisture. When propelling these plungers, the components can be pressed out of the cartridge. The sides of the tube facing the pistons are modified, if necessary through an adapter, such that the chamber openings in the opening area are directly connected to each other through a separation wall. Advantageously, in the area of the outlet opening of the chambers, a filament is applied, so that a static mixer or a dynamic mixer can be connected firmly. Such packages are preferred in particular for small applications, in particular for filling quantities up to 1 liter.
    [103] For uses in larger quantities, in particular for uses in industrial manufacture, the two components are advantageously filled and stored in drums or buckets. During use, the components are pressed out by means of feed pumps and added by dosing through lines of a mixing apparatus that is conventionally used for two-component adhesives in industrial production.
    [104] Mixing is typically performed using static mixers or using dynamic mixers. During mixing, it must be ensured that the two components are mixed as homogeneously as possible. If the two components are poorly mixed, local deviations from the proportion of advantageous mixtures occur, which can have the effect of deteriorating mechanical properties. In order to be able to visually control the quality of the mixture, it can be advantageous for the two components having two different colors. The mixture is considered good, if the mixed adhesive has a homogeneous mixed color, with no visible stripes or streaks.
    [105] When the first component comes into contact with the isocyanate groups of the second component, healing begins with a chemical reaction. In the process, the amino groups of polyamine A3 and the hydroxyl groups of Al triol and of diol A2, and any other substances present, optionally, which are reactive with isocyanate groups, react with the isocyanate groups that are present. Excess isocyanate groups react with the moisture that is present. As a result of these reactions, polyurethane adhesives cure to form a solid material. This process is also referred to as crosslinking.
    [106] Another object of the invention is therefore also a cured polyurethane adhesive, obtained from curing a polyurethane adhesive, as described in this document.
    [107] Another aspect of the present invention relates to a method for bonding a first substrate to a second substrate, which comprises the steps of: - mixing the two components described above, - applying the mixed polyurethane adhesive to at least one of the surfaces of the substrate to be bonded, - bond the substrates to be bonded within the open time, - cure the polyurethane adhesive.
    [108] Here, the two substrates can consist of the same or different materials.
    [109] In this method, suitable substrates are, in particular, - glass, glass ceramics; - metals and metal alloys, such as aluminum, iron, steel and non-ferrous metals, as well as surface-finished metals and alloys, such as metals coated with chromium or coated with zinc, - coated and lacquered substrates, such as metals or alloys powder coated and lacquered metal sheets; - plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyesters, poly (methyl methacrylate) (PMMA), polyesters, resins epoxides, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) and ethylene / propylene / diene terpolymers (EPDM), in which the plastics can be treated on the surface preferably by means of plasma, corona or flame; - fiber reinforced plastic, such as carbon fiber reinforced plastics (CEP), glass fiber reinforced plastics (GFP) and sheet molding compounds (SMC); - wood, with resins; for example, phenol, melamine or epoxy resins, bonded wood materials, textile resin composite materials and additional so-called polymeric composites; as well as - concrete, mortar, brick, tile, plaster and natural stone, such as granite or marble.
    [110] In this method, one or both substrates is / are, preferably a metal or a ceramic or a glass fiber reinforced plastic or a carbon fiber reinforced plastic.
    [111] If necessary, substrates can be pre-treated before applying the adhesive. Such pretreatments include, inter alia, physical and / or chemical cleaning methods, as well as the application of an adhesive promoter, an adhesive promoter solution or an initiator.
    [112] From this method described for bonding, a product is formed, in which the adhesive establishes a non-positive bond of the two substrates to each other.
    [113] This article is, in particular, a structure, for example, a bridge, an industrial product or a consumer product, in particular a window, a rotor blade, a wind turbine or a means of transport, in in particular, a vehicle, preferably a motor vehicle, a bus, a truck, a train or a ship, as well as an airplane or a helicopter, or an additional part of said item.
    [114] An additional object of the invention is an item obtained from the method described above for bonding.
    [115] The polyurethane adhesive described has very good properties as a structural adhesive.
    [116] Here, the term structural adhesive is used to designate an adhesive that, in the cured state forms a portion of the supporting structure of the bonded components. The structural adhesive is thus an important connecting element of the construction within which it connects two components or substrates. Correspondingly stringent requirements are placed on its mechanical properties.
    [117] At room temperature, a cured structural adhesive preferably has a tensile strength greater than 5 MPa, particularly preferably more than 8 MPa, in particular greater than 10 MPa.
    [118] At room temperature, the cured structural adhesive preferably has an elongation at break of more than 100%, in particular more than 150%.
    [119] At room temperature, the cured structural adhesive preferably has an elastic modulus in the range of at least 20 MPa, particularly preferably at least 25 MPa, in particular at least 30 MPa.
    [120] The structural cured adhesive preferably has a glass transition temperature of less than -35 ° C, preferably less than -37 ° C, in particular less than - 40 ° C.
    [121] These mentioned values are measured as described in the following examples.
    [122] An important additional property of a structural adhesive is its good processing capacity. Here the two components, individually and at the time of mixing, must have a low viscosity so that they can be transported and mixed satisfactorily, but then they can build up very quickly to a viscosity such that a pseudoplastic, stable material it is obtained directly, so that layer thicknesses of up to 10 millimeters and more can be applied.
    [123] These requirements can be met particularly well with the described polyurethane adhesive. The presence of the special K catalyst during curing, in particular, makes it possible to achieve good mechanical properties at cold temperatures, as a result of its lower glass transition temperature effect.
    [124] Examples
    [125] In the following, examples of modalities are indicated, which is intended to better explain the described invention. Naturally, the invention is not limited to these examples of described modalities. 1. Substances used:


    [126] Zr-Ch2 was produced by mixing 9.36 g of zirconium (IV) tetrakis (isopropoxide) 70% by weight, in isopropanol and 17.94 g of 1,3-diphenyl-1,3-propanedione, stirring for 2 hours at 25 ° C, subsequently removing the volatile components in a vacuum, and finally dissolving the solid that is obtained in a mixture of 40 g of tetraethylene glycol dimethyl ether and 40 g of acetylacetone.
    [127] Fe-Chl was produced by mixing 4.4 g dry Fe (III) tris (acetylacetonate) and 9.3 g N, N-diethyl-3-oxobutanamide, heating under stirring for 3 hours at 90 ° C then removing the volatile components in a vacuum and finally cooling.
    [128] Bi-Chl was produced by mixing 1.25 g Coscat® 83 (bismuth (III) tris (neodecanoate) in neodecanoic acid, content of 16.0% bismuth by weight, from Erbslõh) and a solution of 0 , 44 g of 8-hydroxyquinoline in 3.27 diisodecyl phthalate, heating under stirring for 2 hours at 80 ° C, and subsequently cooling.
    [129] Bi-Ch2 was produced by mixing 7.75 g Coscat® 83 (bismuth (III) tris (neodecanoate) of neodecanoic acid, bismuth content 16.0% by weight, from Erbslõh) and 2.85 g of N, N-diethyl-3-oxobutanamide, heating under stirring for 2 hours at 80 ° C, and subsequently cooling.
    [130] Polymer-1 was produced by reacting 1300 g of polyoxypropylene diol (Acclaim® 4200 N from Bayer; OH number: 28.5 mg KOH / g), 2600 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02 from Shell; OH number: 35.0 mg KOH / g), 600 g of 4,4'-methylene diphenyl diisocyanate (Desmodur® 44 MC L from Bayer) and 500 g of diisodecyl phthalate, using known methods, at 80 ° C to form a polyurethane polymer coated at the NCO end with a content of free isocyanate groups of 2.05% by weight. 2. Preparation of polyurethane adhesives
    [131] For each adhesive, the ingredients listed in Tables 1 to 4 were transformed into the indicated quantities (in parts by weight) of the first component (component "1") using a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTekInc.) excluding moisture to form a homogeneous paste and were stored. Likewise, the ingredients indicated in Tables 1 to 4 of the second component (component "2") were processed and stored. Subsequently, the two components were processed by means of a centrifuge mixture with the exclusion of moisture to form a homogeneous paste and the said paste was immediately verified as follows:
    [132] As a measure of open time, "sticky-free time" was determined. For this purpose, several grams of adhesive were applied in a layer thickness of approximately 2 mm on the card and, under normal atmospheric conditions, the time until the first time that there were no residues remaining in the pipette after slightly hitting the surface of the adhesive with a pipette made of LDPE was determined.
    [133] For the determination of the mechanical properties, the adhesive was pressed onto a sheet coated with PTFE in order to form a film with a thickness of 2 mm, which was stored for 7 days under normal atmospheric conditions; several dumbbell-shaped samples with a length of 75 mm, with a bar length of 30 mm and a bar width of 4 mm, were perforated from the film, and these dumbbell-shaped samples were tested according to DIN standard EN 53504, at a tensile rate of 200 mm / min to determine the tensile strength (breaking strength), elongation at break and modulus E (at 0.5-50% elongation). The values for modulus E tensile strength were used as a measure of the strength of the composition.
    [134] To determine the glass transition temperature (Tg), the adhesive was pressed onto a film coated with PTFE to form a film with a thickness of 2 mm; this film was stored for 7 days, under normal atmospheric conditions; a disk-shaped sample having a diameter of 10 mm was drilled and using a Mettler DMA / SDTA 861e the Tg was determined (DMTA method, shear mode measurements, excitation frequency 10 Hz, heating rate 5 K / min). The sample was cooled in the process to -60 ° C and, with the determination of the storage module G '[MPa] of the loss module G' '[MPa], heated to 200 ° C. The Tg was read at a maximum value of the quotient G '' / G '.
    [135] The results are shown in Tables 1 to 4.
    [136] Adhesives Z-1 to Z-15 are examples according to the invention; adhesives Ref-1 to Ref-18 are examples of comparison.
    [137] Adhesives Zl, Z-2, Z-3 and Z-4 were applied 1 minute after the end of the mixing time of the two components to a small plate made of glass-reinforced plastic that had been degreased with isopropanol previously , and were then covered and pressed with a second identical small plate, so that an adhesive overlapping area of 15 x 45 mm with a layer thickness of 2 mm was formed, they were cured for 24 hours at 23 ° C and subsequently for 3 hours at 80 ° C, and after a conditioning time of 24 h at 23 ° C, the shear tensile strength according to DIN EN 14 65 was determined, in which case, in each case, a cohesive breaking pattern resulted.
    [138] Likewise, using adhesives Zl, Z-2, Z-3 and Z-4, in each case, two small plates made of carbon fiber reinforced in plastic were bonded, and the shear strength to tensile strength was determined, in which, in each case, a pattern of cohesive rupture resulted.
    [139] Ref-12 and Ref-13 comparison adhesives were liquid immediately after mixing the two components while the other adhesives, immediately after mixing, showed good stability.
    [140] The cured films Ref-3 and Ref-6 had many bubbles. The remaining cured films were either bubble-free or had only a few fine bubbles.
    Table 1: Composition (in parts by weight) and properties from Z-1 to Z-5 and Ref-1 to Ref-9
    Table 1: continuation

    Table 2: Composition (in parts by weight) and properties from Z-6 to Z-7 and Ref-10 to Ref-11

    Table 3: Composition (in parts by weight) and properties of

    Table 4: Composition (in parts by weight) and properties from Z-12 to Z-15 and Ref-16 to Ref-17
    权利要求:
    Claims (15)
    [0001]
    1. Polyurethane adhesive consisting of a first and a second component, characterized by the fact that a) the first component contains b) at least one A1 triol with a molecular weight in the range of 1000 to 10,000 g / mol, c) at least minus one diol A2 with two primary hydroxyl groups and a molecular weight in the range of 60 to 150 g / mol, and d) at least one aliphatic polyamine A3 with a molecular weight in the range of 60-500 g / mol; - the second component contains e) at least one polyisocyanate B1 and f) at least one polyurethane polymer B2 with isocyanate groups; - and the polyurethane adhesive also contains g) at least one catalyst K in the form of a metal chelate complex, in which the metal is selected from the group consisting of Fe (III), Ti (IV), Zr ( IV) and Hf (IV); - in which triol A1, diol A2 and polyamine A3 are present in an amount such that h) the ratio V1 of the number of OH groups and the number of NH2 groups (A2 + A3) / A1 is in the range of 3 to 15, ei) the ratio V2 of the number of OH groups and the number of NH2 groups of A2 / A3 is in the range of 2 to 30.
    [0002]
    2. Polyurethane adhesive according to claim 1, characterized in that the triol is a polyether triol.
    [0003]
    3. Polyurethane adhesive according to claim 1 or 2, characterized in that the triol comprises primary hydroxyl groups.
    [0004]
    Polyurethane adhesive according to any one of claims 1 to 3, characterized in that the diol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol.
    [0005]
    5. Polyurethane adhesive according to any one of claims 1 to 4, characterized in that the polyamine is selected from the group consisting of 1,5-diamino-2-methylpentane, 2,2,4- and 2, 4,4-trimethylhexanomethylenediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2- and 4-methyl-1,3 - diaminocyclohexane and mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -bis (aminomethyl) bicycle [2.2.1] heptane, 3 (4 ), 8 (9) -bis (aminomethyl) tricycle [5.2.1.02,6] decane, bis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10 -diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 1,3-bis (aminomethyl) benzene and 1 , 4-bis (aminomethyl) benzene.
    [0006]
    6. Polyurethane adhesive according to any one of claims 1 to 5, characterized in that the ratio V1 is in the range of 4 to 10.
    [0007]
    7. Polyurethane adhesive according to any one of claims 1 to 6, characterized in that the V2 ratio is in the range of 4.5 to 15.
    [0008]
    Polyurethane adhesive according to any one of claims 1 to 7, characterized in that the polyisocyanate B1 is a form of 4,4'-, 2,4'- and 2,2'-diphenylmethane di -isocyanate which is liquid at room temperature and any mixtures of these isomers (MDI), in the form of polymeric MDI or MDI with content of oligomers or derivatives.
    [0009]
    Polyurethane adhesive according to any one of claims 1 to 8, characterized in that the polyurethane polymer B2 comprises 50-95% by weight of polyoxyalkylene units.
    [0010]
    Polyurethane adhesive according to any one of claims 1 to 9, characterized in that the polyurethane polymer B2 comprises urethane groups and free isocyanate groups which are derived from 4,4'-diphenylmethane diisocyanate.
    [0011]
    Polyurethane adhesive according to any one of claims 1 to 10, characterized in that the catalyst K comprises at least one chelate binder selected from the group consisting of 1,3-diketonate, 1,3-ketoesterate and 1 , 3-ketoamidate.
    [0012]
    Polyurethane adhesive according to any one of claims 1 to 11, characterized in that the catalyst K is selected from the group consisting of iron (III) tris (acetylacetonate), iron (III) tris (ethylacetoacetate), iron (III) tris (tert-butylacetoacetate), iron (III) tris (N, N-diethyl-3-oxobutane amidate), titanium (IV) bis (acetylacetonate) diisopropylate, titanium (IV) bis (acetylacetonate) di -isobutylate, titanium (IV) bis (acetylacetonate) -bis (2-ethylhexylate), titanium (IV) bis (ethylacetoacetate) diisopropylate, titanium (IV) bis (ethylacetoacetate) diisobutylate, titanium (IV) bis (ethylacetoacetate) ) -bis (2-ethylhexylate), titanium (IV) bis (tert-butylacetoacetate) diisopropylate, titanium (IV) bis (tert-butylacetoacetate) diisobutylate, titanium (IV) bis (N, N-diethyl-3 - oxobutane amidate) diisopropylate, titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) diisobutylate, titanium (IV) bis (N, N-diethyl-3-oxobutane amidate) -bis (2 -ethylhexylate), zirconium (IV) tetrakis (acetylacetonate), zi rhonium (IV) tetrakis (1,3-diphenylpropane-1,3-dionate), zirconium (IV) tetrakis (ethylacetoacetate), zirconium (IV) tetrakis (tert-butylacetoacetate), zirconium (IV) tetrakis (ethyl-3-oxo -valerate), zirconium (IV) tetrakis (ethyl-3-oxohexanoate), zirconium (IV) tetrakis (N, N-diethyl-3-oxobutane amidate), zirconium (IV) tetrakis (N, N-dibutyl-3 -oxobutane amidate), zirconium (IV) tetrakis- (N, N-dibutyl-3-oxoheptane amidate) and zirconium (IV) tetrakis (N, N-bis (2-ethylhexyl) -3-oxobutane amidate).
    [0013]
    13. Method for bonding a first substrate to a second substrate, characterized in that it comprises the steps of: - mixing the two components of the polyurethane adhesive defined in any one of claims 1 to 12, - applying the mixed polyurethane adhesive to at least one of the substrate surfaces to be bonded, - bond the substrates to be cemented within the open time, - cure the polyurethane adhesive.
    [0014]
    Method according to claim 13, characterized by the fact that one or both substrates is / are a metal or a ceramic or a glass fiber reinforced plastic or carbon fiber reinforced plastic.
    [0015]
    15. Article, characterized by the fact that it is obtained by a method of connection defined in claim 13 or 14.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-22| B09A| Decision: intention to grant|
    2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12183893.2|2012-09-11|
    EP12183893.2A|EP2706075A1|2012-09-11|2012-09-11|Structural polyurethane adhesive with low glass transition temperature|
    PCT/EP2013/068731|WO2014040992A1|2012-09-11|2013-09-10|Structural polyurethane adhesive having a low glass transition temperature|
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