Moisture-curing polyurethane hot melt adhesive with high initial strength

Abstract

The present invention relates to a moisture-curable polyurethane hot-melt adhesive comprising at least 80% by weight, based on the total weight of the moisture-curable polyurethane hot-melt adhesive, of an isocyanate-terminated prepolymer obtainable by mixing a diisocyanate (a) with a compound (b) having at least two isocyanate-reactive groups and reacting the mixture to form an isocyanate-terminated prepolymer, wherein the compound (b) having at least two isocyanate-reactive groups comprises at least one polylactide (b1) obtainable by reacting a lactide with a linear, bifunctional starter molecule having 2 to 20 carbon atoms, and the isocyanate content of the isocyanate-terminated prepolymer is 1 to 5% by weight. The present invention also relates to a method for producing such a moisture-curable polyurethane hot-melt adhesive and a method for using it to bond substrates.

Description

[Technical field]

[0001] The present invention relates to a moisture-curable polyurethane hot melt adhesive comprising at least 80% by weight, based on the total weight of the moisture-curable polyurethane hot melt adhesive, of an isocyanate-terminated prepolymer obtainable by mixing a diisocyanate (a) with a compound (b) having at least two isocyanate-reactive groups and reacting the mixture to form an isocyanate-terminated prepolymer, wherein the compound (b) having at least two isocyanate-reactive groups comprises at least one polylactide (b1) obtainable by reacting lactide with a linear bifunctional starter molecule having 2 to 20 carbon atoms, and the isocyanate content of the isocyanate-terminated prepolymer is 1 to 5% by weight. and the starter molecule is selected from the group consisting of diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, and mixtures of two or more of these compounds. The present invention further relates to a method for producing such moisture-curable polyurethane hot melt adhesives and their use for bonding substrates. [Background technology]

[0002] Moisture-curing polyurethane hot melt adhesives are known and widely used. Typically, they comprise isocyanate-terminated prepolymers based on polyesters, obtained by reaction of an excess of diisocyanates, usually based on isomers of diphenylmethane diisocyanate, with polyesterols. Their main advantage is the combination of high early strength and the ability to react with water and thus cure effectively, producing a high effective bond once curing is complete.

[0003] Typical examples of polyesters used for the preparation of polyester-based isocyanate-terminated prepolymers for moisture-curing polyurethane hot melt adhesives are those that generally have a glass transition temperature T above 20°C. gand crystalline polyesterols (obtained by esterification of hexanediol and adipic acid) that are solid at 20° C. Such polyesterols are commercially available. An example of such an amorphous polyester polyol is sold under the trade name Dynacoll® 7130 by Evonik, and an example of a crystalline polyesterol is sold under the trade name Dynacoll® 7360 by Evonik.

[0004] In addition to these polyesters with a glass transition temperature or melting point above 20° C., other liquid polyesterols or polyetherols can also be used to prepare the isocyanate-terminated prepolymers. The moisture-curable polyurethane hot melt adhesives can also contain thermoplastic materials, such as thermoplastic polyurethanes, polyacrylates or others, preferably aliphatic resins, in addition to the isocyanate-terminated prepolymers, for optimization of process characteristics, open time, and early strength.

[0005] Currently, efforts are being made to increase the proportion of renewable raw materials in moisture-curable polyurethane hot melt adhesives.

[0006] To this end, US 20170002241 discloses the use of glycerol-containing polylactides and fatty acid glyceride-containing polylactides in the preparation of polyester-based isocyanate-terminated prepolymers. A disadvantage of the isocyanate-terminated prepolymers described in US 2017 / 0002241 is their low early strength. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US 20170002241 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a moisture-curable polyurethane adhesive having high early strength in which the isocyanate-terminated prepolymer contains a large amount of renewable raw materials. [Means for solving the problem]

[0009] The object of the present invention is achieved by a moisture-curable polyurethane hot melt adhesive comprising at least 80% by weight, based on the total weight of the moisture-curable polyurethane hot melt adhesive, of an isocyanate-terminated prepolymer obtainable by mixing a diisocyanate (a) with a compound (b) having at least two isocyanate-reactive groups and reacting the mixture to form an isocyanate-terminated prepolymer, wherein the compound (b) having at least two isocyanate-reactive groups comprises at least one polylactide (b1) obtainable by reacting lactide with a linear bifunctional starter molecule having 2 to 20 carbon atoms, and the isocyanate content of the isocyanate-terminated prepolymer is 1 to 5% by weight. and the starter molecule is selected from the group consisting of diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, and mixtures of two or more of these compounds. The present invention further relates to a method for producing such moisture-curable polyurethane hot melt adhesives and their use for bonding substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the context of the present invention, moisture-curing polyurethane hot melt adhesives are understood to mean mixtures containing isocyanate-containing prepolymers or isocyanate-containing prepolymers themselves, where the mixture comprises at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight of isocyanate-containing prepolymers. Furthermore, the moisture-curing polyurethane adhesives according to the invention may also comprise further additives, such as surface-active substances, such as release agents and / or defoamers, inhibitors, such as diglycol bis(chloroformate) or orthophosphoric acid, plasticizers, inorganic and / or organic fillers, such as sand, kaolin, chalk, barium sulfate, silica and carbon black, oxidation stabilizers, melting aids, such as thermoplastic polymers, dyes and pigments, such as stabilizers against hydrolysis, light, heat or discoloration, emulsifiers, flame retardants, ageing stabilizers and adhesion promoters, and also catalysts commonly used in polyurethane chemistry, such as 2,2-dimorpholinodiethyl ether.

[0011] In the context of the present invention, an isocyanate-terminated prepolymer is the reaction product of a diisocyanate (a) with a compound having at least two isocyanate-reactive groups and optionally a compound having one isocyanate-reactive group, where the diisocyanate is used in excess.

[0012] As diisocyanates for preparing isocyanate-containing prepolymers, all aliphatic, cycloaliphatic and aromatic difunctional isocyanates known from the prior art and any mixtures thereof can be used.Here, in addition to diisocyanates, it is also possible to use higher functional isocyanates.When higher functional isocyanates are used, their proportion is preferably less than 40% by weight, more preferably less than 20% by weight, particularly preferably less than 10% by weight, especially less than 1% by weight, based on the total weight of the isocyanates used.More preferably, no higher functional isocyanates are used.

[0013] Preferably, aromatic di- or polyfunctional isocyanates are used, such as diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanates (MDI), mixtures of monomeric and polycyclic homologues of diphenylmethane diisocyanates (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), naphthalene 1,5-diisocyanate (NDI), toluene 2,4,6-triisocyanate and toluene 2,4- and 2,6-diisocyanate (TDI), or mixtures thereof.

[0014] Particularly preferably, aromatic isocyanates are used, preferably selected from the group consisting of toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 2,4'-diisocyanate and diphenylmethane 4,4'-diisocyanate, and mixtures of these isocyanates. In particular, the diisocyanates used are aromatic isocyanates selected from the group consisting of diphenylmethane 2,4'-diisocyanate and diphenylmethane 4,4'-diisocyanate, and mixtures of these isocyanates. In the most preferred embodiment, the proportion of 4,4'-MDI is more than 50% by weight, more preferably more than 80% by weight, in particular more than 95% by weight, in each case based on the total weight of the isocyanates used.

[0015] The isocyanate-reactive compound (b) having at least two isocyanate-reactive groups used for the preparation of the isocyanate-containing prepolymer may be any compound having at least two isocyanate-reactive groups. It is preferable to use polyesterols, polyetherols or polyether-polyesterols, which can be obtained, for example, by alkoxylation of polyesters, in particular polyesterols. Here, the isocyanate-reactive compound (b) comprises at least one polylactide (b1), which can be obtained by reacting lactide with a bifunctional linear starter molecule having 2 to 20 carbon atoms. and the starter molecule is selected from the group consisting of diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, and mixtures of two or more of these compounds.The average OH functionality of the compounds (b) is preferably 1.8 to 2.2, more preferably 1.9 to 2.1 and in particular 2. Functionality is understood here to mean the theoretical functionality based on the starting materials.

[0016] Polyetherols are prepared from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical by known processes, for example anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and the addition of at least one starter molecule having 2 to 5, preferably 2 to 4, more preferably 2 to 3, especially 2 reactive hydrogen atoms in the form of bonds, or cationic polymerization with Lewis acids such as antimony pentachloride or boron trifluoride esters. Furthermore, the catalyst used may be a polymetal cyanide compound, the so-called DMC catalyst. Examples of suitable alkylene oxides include tetrahydrofuran, 1,3-propylene oxide, 1,2- and 2,3-butylene oxide, preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as a mixture. Preferably, 1,2-propylene oxide, ethylene oxide or a mixture of 1,2-propylene oxide and ethylene oxide is used.

[0017] Suitable starter molecules include water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2- or 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol and trimethylolpropane.

[0018] Polyether polyols, particularly preferably polyoxypropylene polyols or polyoxypropylene-polyoxyethylene polyols, can be obtained by alkoxylation of starter molecules having a functionality of 2.0 to 4.0, particularly preferably 2.0 to 3.0, more preferably 2.0 to 2.2, in particular 2.0, and have an average content of ethylene oxide of 20 to 70% by weight, preferably 25 to 60% by weight, in particular 30 to 50% by weight, based on the total weight of alkylene oxide. In a further preferred embodiment, the content of propylene glycol is more than 70% by weight, more preferably more than 85% by weight, in particular more than 95% by weight, based on the total weight of alkylene oxide used to prepare the polyetherol. Preferred polyetherols have a number average molecular weight of 400 to 9000 g / mol, preferably 1000 to 6000 g / mol, more preferably 1500 to 5000 g / mol, in particular 2000 to 4000 g / mol. Increasing the ethylene oxide content and decreasing the functionality without changing the molecular weight typically decreases the viscosity of the polyetherol.

[0019] The isocyanate-reactive compound (b) used may furthermore be a hydrophobic polyol having at least one hydrophobic hydrocarbon molecular moiety having at least 8 carbon atoms. The hydrophobic polyol employed in this case is preferably a hydroxyl-functionalized oleochemical compound, an oleochemical polyol. A large number of hydroxyl-functional oleochemical compounds are known which can be used. Examples include castor oil, fats and oils such as grape seed oil, black seed oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil, hemp oil, safflower oil, walnut oil modified with hydroxyl groups, and fatty acid esters modified with hydroxyl groups and based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, thymnodonic acid, clupanodonic acid and cervonic acid. Here, it is preferred to use castor oil and its reaction products with alkylene oxides or ketone-formaldehyde resins. The latter compound is, for example, sold by Bayer AG under the trade name Desmophen® 1150. In a particularly preferred embodiment, the isocyanate-reactive compound (b) having at least two isocyanate-reactive groups comprises a hydrophobic polyetherol or polyesterol.

[0020] Compound (b) may optionally comprise a chain extender and / or a crosslinker. The addition of the chain extender and / or crosslinker may take place before, together with or after the addition of the polyol. The chain extenders and / or crosslinkers used are preferably substances having a molecular weight of less than 400 g / mol, particularly preferably from 60 to 350 g / mol, where the chain extenders have two isocyanate-reactive hydrogen atoms and the crosslinkers have three isocyanate-reactive hydrogen atoms. These can be used alone or in the form of a mixture. When using chain extenders, 1,3- and 1,2-propanediol, dipropylene glycol, tripropylene glycol and 1,3-butanediol are particularly preferred.

[0021] If chain extenders, crosslinkers or mixtures thereof are used, these are expediently used in an amount of 1 to 30% by weight, preferably 1.5 to 20% by weight, in particular 2 to 10% by weight, based on the weight of the polyisocyanate, of the polymeric isocyanate-reactive compound and the chain extender and / or crosslinker. Preferably, no chain extenders and / or crosslinkers are used.

[0022] Polylactides (b1) can be obtained by reacting lactide with linear, bifunctional starter molecules having 2 to 20 carbon atoms. The starting molecule is It is selected from the group consisting of monoethylene glycol, diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and mixtures of two or more of these compounds. The linear starter molecule preferably comprises 1,6-hexanediol, and particularly preferably only 1,6-hexanediol is used as the linear starter molecule.

[0023] The reaction of the linear starter molecule with lactide is usually carried out in neat form, preferably using a metal catalyst, such as a tin catalyst or a so-called double metal cyanide catalyst (also called "DMC catalyst"), which is known and has already been generally described in the prior art.

[0024] Lactide can be used here in any form, for example L-lactide, D-lactide, meso-lactide or any mixture thereof. It is preferred to use L-lactide, D-lactide or meso-lactide, in each case preferably with a purity of more than 90% by weight. In addition to lactide, it is also possible to use other alkylene oxides, such as ethylene oxide, 1,3- or preferably 1,2-propylene oxide, or 1,2- or 2,3-butylene oxide, particularly preferably 1,2-propylene oxide. When using alkylene oxides in addition to lactide, it is preferably carried out in block structure. Particularly preferably, the alkylene oxide is used as an end block, i.e., it means that the starter molecule is reacted with lactide in a first step and then the resulting polymer undergoes chain extension with alkylene oxide in a second step. The proportion of lactide groups based on the total mass of groups in the polylactide (b1) added onto the starting molecule is 50 to less than 100 mass%, preferably 70 to 99.5 mass%. Particularly preferably, the proportion of lactide groups based on the total mass of groups in the polylactide (b1) added onto the starting molecule is 100 mass%. The hydroxyl value of the polylactide (b1) is preferably 35 to 230 mg KOH / g.

[0025] In a particularly preferred embodiment of the present invention, the compound (b) having at least two isocyanate-reactive groups comprises, in addition to the polylactide (b1), a further polyol (b2) different from the polylactide (b1). These include the abovementioned polyetherols, polyesterols, hydrophobic polyols and polyetherol-polyesterols, where the number-average molecular weight of the polyol (b2) is at least 500 g / mol. The compound (b2) preferably has a functionality of 2 to 4, more preferably 2 to 3, in particular 2. In the most preferred embodiment of the present invention, the polyol (b2) comprises a mixture of one or more polyether polyols (b2a) and one or more polyester polyols (b2b). The polyether polyols (b2a) and polyesterols (b2b) preferably have a number-average molecular weight of 1500 to 6000 g / mol, more preferably 2000 to 4000 g / mol. In particular, the polyester (b2b) is a polyester obtained starting from hexanediol, in particular 1,6-hexanediol, as diol component. The polyether (b2a) used is preferably a polyether which comprises at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 85% by weight, more preferably at least 95% by weight of propylene oxide, in particular exclusively propylene oxide, based on the alkylene oxide used to prepare the polyether (b2a). In a particularly preferred embodiment, the component (b2) does not comprise, in addition to the polyether (b2a) and the polyester (b2b), further compounds having at least two isocyanate-reactive groups.

[0026] The proportion of polylactide (b1) based on the total mass of the compound (b) having at least two isocyanate-reactive groups is preferably 5 to 90% by mass, particularly preferably 10 to 80% by mass, more preferably 15 to 50% by mass, in particular 20 to 40% by mass. The proportion of component (b2) is preferably 10 to 95% by mass, particularly preferably 20 to 90% by mass, more preferably 50 to 85% by mass, in particular 60 to 80% by mass, where the ratio of polyether (b2a) to polyester (b2b) is preferably 4:1 to 1:2, more preferably 3:1 to 1:1. Particularly preferably, component (b) contains, in addition to polyols (b1) and (b2), less than 10% by mass, more preferably less than 5% by mass, in particular none, of a compound having at least two isocyanate-reactive hydrogen atoms.

[0027] It is also possible to use compounds having only one isocyanate-reactive group for the preparation of the prepolymer according to the invention. These are preferably polyether monools obtained in a manner similar to the polyether monools described above, starting from monofunctional starter molecules, for example ethylene glycol monomethyl ether. The molecular weight of the polyether monools used here is preferably 100 to 1000 g / mol. When using polyether monools, the mass ratio of polyether monool to compound (b) is preferably 1:30 to 4:1, more preferably no compounds having only one isocyanate-reactive group are used.

[0028] Similarly, conventional polyurethane catalysts, preferably amine-containing polyurethane catalysts, can be optionally used to prepare the isocyanate-containing prepolymer. Such catalysts are described, for example, in "Kunststoffhandbuch [Plastics Handbook], Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd Edition, 1993, Chapter 3.4.1. The catalyst preferably comprises a strongly basic amine catalyst. Examples include amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiginoethylether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane, preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, and dimethylethanolamine. The catalysts can be used alone or in mixtures. Preferably, no catalyst is used in the preparation of the isocyanate-containing prepolymer.

[0029] In the preparation of the isocyanate-containing prepolymer, an excess of the above polyisocyanate is reacted with a compound having at least two isocyanate-reactive groups, optionally with a compound having one isocyanate-reactive group, to form a prepolymer at a temperature of, for example, 30° C. to 100° C., preferably about 80° C. In this process, the polyisocyanate is mixed with the compound having at least two isocyanate-reactive groups, optionally with a compound having one isocyanate-reactive group, preferably in a ratio of isocyanate groups to isocyanate-reactive groups of 1.5:1 to 15:1, preferably 1.8:1 to 8:1. The mixing ratio of the polyisocyanate, the polymeric compound having at least two isocyanate-reactive groups, optionally the compound having one isocyanate-reactive group, and optionally the chain extender and / or crosslinker is selected so that the isocyanate content (NCO content) of the prepolymer produced is in the range of 1 to 5% by weight, preferably 1.2 to 3% by weight, more preferably 1.5 to 2.5% by weight, in particular 1.6 to 2.0% by weight, based on the total weight of the isocyanate prepolymer produced. If necessary, volatile isocyanates can then be removed, preferably by thin-film distillation. The viscosity of the isocyanate prepolymer according to the invention is preferably 5 to 1000 Pas, more preferably 10 to 300 Pas, in particular 15 to 200 Pas, in each case at 40° C. This can be adjusted, for example, by adjusting the isocyanate index, the average functionality, and the polyols and isocyanates used. Such variations are known to those skilled in the art. The average isocyanate functionality of the isocyanate prepolymer is preferably 2.0 to 2.9, more preferably 2.0 to 2.2.

[0030] The use of melting auxiliaries such as thermoplastic polymers in the production of moisture-curable polyurethane hot melt adhesives is well known. In a preferred embodiment, the polyurethane hot melt adhesive according to the invention comprises a thermoplastic polymer that does not have isocyanate-reactive groups. All thermoplastics can be used here. The thermoplastics preferably have a melting point of 70 to 250°C, particularly preferably 80 to 220°C, more preferably 90 to 180°C, in particular 100 to 160°C. Examples of such thermoplastics include thermoplastic polyurethanes, polyacrylates or polyesters, particularly preferably thermoplastic polyurethanes and / or polyacrylates are used as thermoplastics.

[0031] The polyurethane hot melt adhesive according to the invention may be used for bonding substrates, for example by applying the moisture-curable polyurethane hot melt adhesive to at least one substrate at a temperature above 80 ° C, preferably between 90 and 200 ° C, more preferably between 100 and 150 ° C, applying a second substrate to the moisture-curable polyurethane hot melt adhesive, and curing the moisture-curable polyurethane hot melt adhesive at a temperature preferably below 100 ° C. Upon cooling to a temperature below 110 ° C, the polyurethane hot melt adhesive according to the invention shows very good adhesion and a rapid increase in viscosity, so that very good initial strength can be obtained in the adhesive bond. The polyurethane hot melt adhesive according to the invention also shows good adhesion and strength in the cured adhesive bond, as well as very good hydrolysis resistance, and has a high content of bio-based raw materials. The substrate may be materials such as wood, glass, metal, fibers, plastics, and natural materials such as fibers. It is particularly preferred to bond fibers to fiber-reinforced polyurethane plastics.

[0032] The present invention will now be described with reference to examples. EXAMPLES

[0033] The moisture-curable polyurethane adhesive according to the present invention (Example of the present invention) and a comparative example were produced, and the increase in viscosity during curing was investigated. For this purpose, the following starting materials were used.

[0034] Polyesterol 1: A polyesterol formed from hexanediol and adipic acid having a functionality of 2, a hydroxyl number of 30 mg KOH / g, and a melting point of 55° C., available from Evonik under the trade name Dynacoll® 7360.

[0035] Polyetherol: Polypropylene glycol with a functionality of 1:2 and a hydroxyl value of 56 mg KOH / g.

[0036] Polyetherol 2: Polypropylene glycol with a functionality of 2 and a hydroxyl value of 28 mg KOH / g.

[0037] Lactide polyols were prepared by reaction of OH-containing starters with Puralact L ((3S-cis)-3,6-dimethyl-1,4-dioxane-2,5-dione, CAS number 4511-42-6).

[0038] Lactide polyol 1: Polylactide having 1,6-hexanediol as the starting molecule, a functionality of 2, and a hydroxyl value of 56 mg KOH / g, produced at 175° C. with 100 ppm tin bis(2-ethylhexanoate) (amount of catalyst based on total mixture).

[0039] Lactide polyol 2: Polylactide having 1,6-hexanediol as the starting molecule, a functionality of 2, and a hydroxyl value of 56 mg KOH / g, produced (amount of catalyst based on total mixture) at 200° C. using a double metal cyanide catalyst (1000 ppm based on total mixture).

[0040] Lactide polyol 3: Polylactide having neopentyl glycol as the starter molecule, a functionality of 2, and a hydroxyl value of 56 mg KOH / g, prepared at 175° C. with 100 ppm tin bis(2-ethylhexanoate) (amount of catalyst based on total mixture).

[0041] Lactide polyol 4: Polylactide having neopentyl glycol as the starter molecule, a functionality of 2 and a hydroxyl number of 37 mg KOH / g, prepared at 175° C. with 100 ppm tin catalyst.

[0042] Acrylate polymer: a thermoplastic acrylate polymer having a number average molecular weight of 34000 g / mol and available under the trade name Elvacite® 2013 from Lucite International.

[0043] Isocyanate: An MDI mixture containing about 99% by weight 4,4'-MDI and about 1% by weight 2,4'-MDI.

[0044] Moisture-curable polyurethane adhesives were prepared by reacting starting materials in the weight ratios shown in Table 1 (values ​​are in parts by weight unless otherwise specified).

[0045] [Table 1]

[0046] The viscosity of the resulting moisture-curing polyurethane adhesive was measured at different temperatures according to ASTM D 3236 with a Brookfield viscometer equipped with a single measurement geometry SC27 spindle. These values ​​are shown in Table 2.

[0047] [Table 2]

[0048] The viscosity values ​​obtained for the inventive examples show that, due to the low viscosity, applications at temperatures above 100°C are possible without problems, but when cooled to temperatures below 100°C, the viscosity increases rapidly, resulting in high initial strength adhesive joints before complete curing of the adhesive. The comparative examples also show a similar increase in viscosity, but the increase in viscosity with decreasing temperature is smaller than for the inventive examples.

Claims

1. A moisture-curable polyurethane hot melt adhesive comprising at least 80% by weight, based on the total weight of the moisture-curable polyurethane hot melt adhesive, of an isocyanate-terminated prepolymer obtainable by mixing a diisocyanate (a) with a compound (b) having at least two isocyanate-reactive groups and reacting the mixture to form an isocyanate-terminated prepolymer, the compound (b) having at least two isocyanate-reactive groups comprising at least one polylactide (b1) obtainable by reacting lactide with a linear bifunctional starter molecule having 2 to 20 carbon atoms, the isocyanate content of the isocyanate-terminated prepolymer being 1 to 5% by weight, the starter molecule being selected from the group consisting of diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, and mixtures of two or more of these compounds; A moisture-curable polyurethane hot melt adhesive, wherein the proportion of polylactide (b1) based on the total mass of the compound (b) having at least two isocyanate reactive groups is 5% by mass to 90% by mass.

2. The moisture-curable polyurethane hot melt adhesive of claim 1, wherein the starter molecule is 1,6-hexanediol.

3. The polylactide (b1) is a copolymer, and the proportion of lactide groups based on the total mass of groups in the polylactide (b1) added to the starter molecule is 50% by mass to less than 100% by mass. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2.

4. 4. The moisture-curable polyurethane hot melt adhesive according to claim 3, wherein the polylactide (b1) is obtainable by reacting the starter molecule with lactide in a first step and with an alkylene oxide in a second step.

5. 3. The moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the proportion of lactide groups based on the total mass of groups in the polylactide (b1) added to the starter molecule is 100 mass%.

6. The moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 5, wherein the hydroxyl value of the polylactide (b1) is 35 to 230 mg KOH / g.

7. The moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 6, wherein a DMC catalyst is used in the production of the polylactide (b1).

8. The moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 7, wherein the diisocyanate is selected from the group consisting of 2,4-MDI, 4,4'-MDI and mixtures thereof.

9. 9. The moisture-curable polyurethane hot melt adhesive according to claim 1, further comprising a thermoplastic polymer having no isocyanate-reactive groups in addition to said isocyanate-terminated prepolymer.

10. 10. The moisture-curable polyurethane hot melt adhesive of claim 1, wherein the moisture-curable polyurethane hot melt adhesive also comprises auxiliaries and additives.

11. 1. A method for producing a moisture-curable polyurethane hot melt adhesive comprising an isocyanate-terminated prepolymer in an amount of at least 80% by weight, based on the total weight of the moisture-curable polyurethane hot melt adhesive, comprising mixing a diisocyanate (a) with a compound (b) having at least two isocyanate-reactive groups and reacting the mixture to obtain the isocyanate-terminated prepolymer, the compound (b) having at least two isocyanate-reactive groups comprising at least one polylactide (b1) obtainable by reacting lactide with a linear difunctional starter molecule having 2 to 20 carbon atoms, the quantitative proportions of diisocyanate (a) and compound (b) having at least two isocyanate-reactive groups are adjusted so that the resulting isocyanate-terminated prepolymer has an isocyanate content of 1 to 5% by weight, optionally mixing the resulting isocyanate-terminated prepolymer with a thermoplastic polymer and / or auxiliaries and additives, said starter molecules being selected from the group consisting of diethylene glycol, propanediol, neopentyl glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and mixtures of two or more of these compounds, The proportion of polylactide (b1) based on the total weight of the compound (b) having at least two isocyanate-reactive groups is 5% by weight to 90% by weight.

12. 11. A method of using a moisture curable polyurethane hot melt adhesive according to any one of claims 1 to 10 for bonding substrates by applying the moisture curable polyurethane hot melt adhesive to a substrate at a temperature above 80°C, applying a second substrate to the moisture curable polyurethane hot melt adhesive and curing the moisture curable polyurethane hot melt adhesive.

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