Highly elastic low-monomer polyurethane foam

Abstract

The invention relates to a crosslinkable foamable composition with a low content of monomer isocyanates, containing, in each case with respect to the total composition: a) 50 to 90 wt.% of at least one prepolymer produced by reacting at least one linear unbranched C3 or C4 polyether diol and optionally up to 25 wt.%, with respect to all of the polyols used, of additional polyether polyols, and at least one monomer diisocyanate in an NCO / OH ratio of > 2 / 1 and subsequently removing excess monomer diisocyanate, b) 0.2 to 20 wt.% of an additive, and c) 9 to 40 wt.% of at least one propellant, wherein the at least one prepolymer has a residual monomer content of less than 0.5 wt.%, with respect to the prepolymer. The composition is suitable as a flexible single-component polyurethane foam which has a high load-bearing capacity and which has excellent elastic properties, a high degree of flexibility, and a good relaxation behavior but which does not require hazardous substance labeling.

Description

[0001] HIGHLY ELASTIC, LOW-MONOMER POLYURETHANE FOAM

[0002] Technical area

[0003] The invention relates to low-monomer one-component polyurethane foams and their use as one-component assembly foams, as well as aerosol cans containing these foams.

[0004] State of the art

[0005] One-component polyurethane foams (PUR foams) have long been known and are primarily used for sealing and insulating joints in construction and DIY. In such applications, the foam product is applied from an aerosol can (so-called OCF foams) and is used, for example, for the installation of door and window frames in buildings. To fill the joints between the frame and the wall, the initial viscosity of the foam must be low enough to ensure sufficient expansion of the foam in the joint. The one-component PUR foam solidifies through crosslinking reactions with moisture.

[0006] Today's one-component PUR foam compositions typically comprise a prepolymer formed from an isocyanate and a polyol component. A monomeric diisocyanate such as diphenylmethane diisocyanate (MDI) is typically used as the isocyanate component. Until now, a high content of monomeric diisocyanates was necessary to produce a polyurethane foam with sufficient strength and low viscosity. The lower viscosity enables good foamability and joint fillability, as well as satisfactory dispensing from the can at common processing temperatures, usually room temperature. Furthermore, the monomeric diisocyanate in conventional foams also contributes significantly to the foam's reactivity. Therefore, most one-component PUR foams still contain a significant content of monomeric diisocyanates.This causes processing problems in that volatile monomeric diisocyanates are released into the working atmosphere during the dispensing (foaming) of the contents of the aerosol can. This must be avoided due to the harmful effects of monomeric isocyanates. In response to this problem, the EU has enacted restrictive laws on the use of products containing more than 0.1% monomeric diisocyanates as part of Regulation (EC) No. 1907 / 2006 (REACH). This results in limitations on the use of non-low-monomer PUR foams.

[0007] These limitations have recently led to the development of more and more low-monomer, single-component PUR foams.

[0008] For example, WO 02 / 079292 describes adhesive polymers containing a prepolymer consisting of an isocyanate component, a polyol, and a low-viscosity component that is non-reactive with isocyanates and OH groups. The monomeric diisocyanates should constitute less than 2% of the composition. Phosphate esters, adipic esters, or phthalic esters are described as non-reactive, low-viscosity components for reducing viscosity.

[0009] WO 2012 / 010389 A1 discloses single-component, low-monomer polyurethane foams based on prepolymers prepared from polyester polyols and / or polyether polyols by reaction with an excess of aromatic diisocyanates and subsequent removal of excess monomeric diisocyanate. The polyols have a functionality of less than 2.5, the polyols have a molecular weight between 150 and 3000 g / mol, and the prepolymers have a monomeric diisocyanate content of less than 5 wt.%. These prepolymers can be used to produce relatively low-viscosity foams with good initial strength even without a high monomeric diisocyanate content.

[0010] However, the currently available one-component, low-monomer PUR foams and OCF foams have certain disadvantages. Moisture-curing, one-component foams from pressurized containers are almost always more or less rigid after curing and easily crack under strong or extreme mechanical stress. Under long-term conditions in gaps between buildings, this can lead to a loss of gap density and insulation. These phenomena are even more pronounced with low-monomer foams, as they generally have a lower crosslinking density and thus a higher tendency to crack.

[0011] Somewhat flexible OCF foams are only available on a pMDI basis (containing polymeric forms of MDI) with hazardous substance labeling and have very limited elasticity.

[0012] Therefore, there is still a need for a highly resilient, flexible OCF foam that has excellent elastic properties, high flexibility and good relaxation behavior, but does not require hazardous substance labeling and is low in monomers.

[0013] Description of the invention

[0014] The object of the present invention is to provide a novel, low-monomer PUR foam composition which overcomes the disadvantages of the prior art and is suitable as a highly resilient, flexible OCF foam which has excellent elastic properties, high flexibility and good relaxation behavior, but does not require hazardous substance labeling.

[0015] This object is achieved with a curable composition as described in claim 1. By using 50 to 90 wt. % of a prepolymer prepared from the reaction of at least one linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt. %, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate in an NCO / OH ratio of > 2 / 1 in a conventional one-component polyurethane foam composition, a foam product is obtained which is highly flexible in the foamed and cured state and exhibits high flexibility and good relaxation behavior. The crosslinkable foamable composition according to the invention is also low in monomers and does not require hazardous substance labeling. Further aspects of the invention are the subject of further independent claims.Particularly preferred embodiments of the invention are the subject of the dependent claims.

[0016] Ways to implement the invention

[0017] The invention relates to a crosslinkable, foamable composition with a low content of monomeric isocyanates, comprising, in each case based on the total composition: a) 50 to 90% by weight of at least one prepolymer prepared from the reaction of at least one linear, unbranched C3 or C4 polyether diol and optionally up to 25% by weight, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate in an NCO / OH ratio of > 2 / 1 and subsequent removal of excess monomeric diisocyanate, b) 0.2 to 20% by weight of additives, c) 9 to 40% by weight of at least one blowing agent, wherein the at least one prepolymer has a residual monomer content of less than 0.5% by weight, based on the prepolymer.

[0018] The term “molecular weight” refers to the molar mass (in grams per mole) of a molecule or a moiety of a molecule. The term “average molecular weight” refers to the number average molecular weight (M n ) a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. It is determined by gel permeation chromatography (GPC) against polystyrene as a standard, particularly with tetrahydrofuran as the mobile phase, refractive index detector, and evaluation starting at 200 g / mol.

[0019] Substance names beginning with “poly” such as polymercaptan, polyaldehyde, polyisocyanate or polyol refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0020] A composition is described as “storage-stable” if it can be stored at room temperature in a suitable container for a prolonged period, typically for at least 3 months up to 6 months or more, without its application or use properties being changed by storage to an extent relevant to its use.

[0021] A “monomeric diisocyanate” is an organic compound with two isocyanate groups separated by a divalent hydrocarbon radical with 4 to 15 carbon atoms.

[0022] "Aromatic" refers to an isocyanate group that is directly bonded to an aromatic carbon atom. Isocyanates with exclusively aromatic isocyanate groups are referred to as "aromatic isocyanates." A monomeric diisocyanate with aromatic isocyanate groups is referred to as "monomeric aromatic diisocyanate."

[0023] The "NCO content" refers to the content of isocyanate groups in weight percent. "Room temperature" refers to a temperature of 23 °C.

[0024] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application. Percentages by weight (wt%) refer to the mass fraction of a component of a composition or molecule relative to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0025] In the context of OCF foams according to the present invention, “elasticity” is understood to mean the maximum permanent elasticity, which describes the repeated compression and stretching capability of a foam and which can be measured according to DIN EN 17333-4, Chapter 4.4 (movement capability).

[0026] An essential component of the composition according to the invention are prepolymers prepared from the reaction of at least one linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt.%, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate. These are NCO-reactive prepolymers, which must be low in monomer content. The term "low in monomer" here means that the prepolymers have a residual monomer content of less than 0.5 wt.%, based on the prepolymer. These prepolymers should also have a suitable viscosity so that they can be processed as a foam, while also developing sufficiently high initial strength for use as an assembly foam.

[0027] Suitable prepolymers are prepared by reacting at least one linear, unbranched C3 or C4 polyether diol and, optionally, up to 25 wt.%, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate. In particular, essentially linear diols should be used.

[0028] The reaction of the at least one linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt.%, based on all polyols used, of further polyetherpolyols and the at least one monomeric diisocyanate is carried out in an NCO / OH ratio of > 2 / 1 and subsequent removal of excess monomeric diisocyanate.

[0029] The NCO / OH ratio is preferably in the range from 3 / 1 to 10 / 1, particularly preferably in the range from 3 / 1 to 8 / 1, in particular in the range from 4 / 1 to 7 / 1.

[0030] The linear, unbranched C3 or C4 polyetherdiols essential for the invention for producing the prepolymers can be, for example, polytetrahydrofurandiols, which are linear, unbranched C4 polyetherdiols.

[0031] Furthermore, polytrimethylene glycols, which are linear, unbranched C3 or C4 polyetherdiols, are suitable for the production of the prepolymers. Such polytrimethylene glycols can be produced from the polymerization of propanediol, in particular from bio-based propanediol. Such polytrimethylene glycols are commercially available under the trade name Velvetol® from WeylChem Allessa GmbH. Of the Velvetol® types, Velvetol® H250, Velvetol® H500, Velvetol® H1000, and Velvetol® H2000 are particularly preferred, which, depending on the type, have an average molecular weight M n, measured by gel permeation chromatography (GPC) against polystyrene as standard, in the range between 250 and 2000 g / mol.

[0032] Suitable polytetrahydrofuran diols for the preparation of the prepolymers are typically prepared from tetrahydrofuran by acid catalysis at 30 to 40 °C. Chemically, polytetrahydrofuran is polytetramethylene ether glycol (PTMEG). The polytetrahydrofuran diols are prepared in a manner known to those skilled in the art and are commercially available, for example, under the trade names Terathane® PTMEG from Tri-iso or PolyTHF® from BASF.

[0033] Preferably, the prepolymer is based at least or in particular exclusively on a polytrimethylene glycol diol and / or a polytetrahydrofuran diol, in particular with an average molecular weight M n, measured by gel permeation chromatography (GPC) against polystyrene as a standard, in the range of between 250 and 2000 g / mol, preferably between 500 and 1000 g / mol, in particular between 600 and 800 g / mol. A particularly preferred commercially available polytetrahydrofuran diol is Terathane® PTMEG 650 from Tri-iso. A particularly preferred commercially available polytrimethylene glycol diol is Velvetol® H500 from WeylChem Allessa GmbH.

[0034] In a preferred embodiment, the prepolymer is based at least or in particular exclusively on a polytetrahydrofuran diol, in particular with an average molecular weight M n , measured by gel permeation chromatography (GPC) against polystyrene as standard, in the range between 250 and 2000 g / mol, preferably between 500 and 1000 g / mol.

[0035] In another preferred embodiment, the prepolymer is based at least or in particular exclusively on a polytrimethylene glycol diol, in particular having an average molecular weight M n , measured by gel permeation chromatography (GPC) against polystyrene as standard, in the range of between 250 and 2000 g / mol, preferably between 500 and 1000 g / mol. In all embodiments, however, up to 25 wt. %, preferably up to 15 wt. %, in particular up to 10 wt. % or up to 5 wt. %, based on all polyols used, of further polyether polyols which are not linear, unbranched C3 or C4 polyetherdiols can optionally be used in the reaction. These can be, for example, polypropylene glycol (PPG) polyols, polyethylene glycol (PEG) polyols, or polypropylene glycol-polyethylene glycol copolyols. They are preferably polyether triols.

[0036] Suitable such further polyether polyols are, for example, reaction products of low molecular weight polyfunctional alcohols with alkylene oxides. The alkylene oxides preferably have 2 to 4 carbon atoms. Suitable examples are the reaction products of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with aliphatic diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, the isomeric butanediols, hexanediols, 2,2-dimethyl-1,3-propanediol, 2-methylpropanediol, 1,6-hexanediol or aromatic diols. Furthermore, the reaction products of polyfunctional alcohols, such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols with the alkylene oxides may also be suitable. The polyether polyols are prepared in a manner known to those skilled in the art and are commercially available. According to the invention, low molecular weight polyethers should preferably be selected, for example polyether polyols with an average molecular weight M nfrom 150 to 5,000 g / mol, in particular up to 3,000, preferably 200 to 2,000 g / mol, are suitable. Diols such as homopolymers of polyethylene glycol, propylene glycol, block or random copolymers of ethylene glycol and propylene glycol are particularly suitable. Triols and higher polyols, which are obtainable from the reaction of polyfunctional alcohols, such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols, and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, are also particularly suitable.

[0037] In a preferred embodiment, however, the prepolymer is prepared from the sole reaction of at least one polytrimethylene glycol diol and / or at least one polytetrahydrofuran diol and at least one monomeric diisocyanate, in particular a monomeric aromatic diisocyanate.

[0038] Common aliphatic and aromatic diisocyanates are suitable as diisocyanates for the production of NCO-containing prepolymers. These preferably have a molecular weight below 500 g / mol.

[0039] Suitable diisocyanates include, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl)fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1 ,6-Diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or isomer mixtures of TDI, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate (MDI) and their isomer mixtures.Furthermore, partially or fully hydrogenated cycloalkyl derivatives of MDI are used, for example fully hydrogenated MDI (H12-MDI), alkyl-substituted diphenylmethane diisocyanates, for example mono-, di-, tri- or tetraalkyldiphenylmethane diisocyanate and their partially or fully hydrogenated cycloalkyl derivatives.

[0040] Asymmetric isocyanates containing NCO groups with varying reactivity toward diols can also be used. Examples of suitable cycloaliphatic asymmetric diisocyanates include 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), or hydrogenation products of the aforementioned aromatic diisocyanates, for example, hydrogenated MDI in isomerically pure form, preferably hydrogenated 2,4'-MDI. Examples of preferred aromatic asymmetric diisocyanates are 1,3-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), either in pure isomeric form or as a mixture of several isomers, naphthalene 1,5-diisocyanate (NDI), diphenylmethane 2,4'-diisocyanate (MDI), and mixtures of 4,4'-diphenylmethane diisocyanate with the 2,4'-MDI isomer. Aromatic diisocyanates are preferably used, especially 4,4'-MDI.

[0041] One embodiment uses asymmetric isocyanates. A preferred embodiment reacts the polyols individually or as a mixture with an excess of symmetric diisocyanates.

[0042] The amounts of polyol and diisocyanate are always chosen so that an NCO-terminated prepolymer is obtained.

[0043] Monomeric aromatic diisocyanates are preferred.

[0044] Particularly suitable as a monomeric aromatic diisocyanate is 4,4'-diphenylmethane diisocyanate, optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate or mixtures thereof with 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI) or 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI).

[0045] Preferred among these is 4,4'-diphenylmethane diisocyanate (4,4'-MDI) or 2,4-toluene diisocyanate or 1,4-phenylene diisocyanate. Most preferred is 4,4'-diphenylmethane diisocyanate.

[0046] The prepolymer is obtained from the reaction of at least one monomeric diisocyanate and the linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt. %, based on all polyols used, of further polyether polyols in an NCO / OH ratio of more than 2 / 1, preferably at least 3 / 1. The NCO / OH ratio always refers to the NCO / OH ratio established at the beginning of the reaction (prepolymer preparation) via the mass fractions of polyols and polyisocyanates used.

[0047] The NCO / OH ratio is preferably in the range from 3 / 1 to 10 / 1, particularly preferably in the range from 3 / 1 to 8 / 1, in particular in the range from 4 / 1 to 7 / 1. The reaction is preferably carried out in the absence of moisture at a temperature in the range from 20 to 160°C, in particular 40 to 140°C, optionally in the presence of suitable catalysts.

[0048] The selected ratio of polyol to diisocyanate with respect to the NCO / OH ratio ensures that no significant increase in molecular weight (chain extension) of the prepolymers occurs. The resulting prepolymers, if based on diols, should contain between 1.7 and 2.3 NCO groups statistically, especially two NCO groups per molecular chain.

[0049] After the reaction, the excess monomeric diisocyanate remaining in the reaction mixture is removed down to the described residual content by means of a suitable separation process.

[0050] The preferred separation process is a distillative process, in particular thin-film distillation or short-path distillation, preferably under vacuum.

[0051] Particularly preferred is a multi-stage process in which the monomeric aromatic diisocyanate is removed in a short-path evaporator at a jacket temperature in the range of 120 to 200°C and a pressure of 0.001 to 0.5 mbar.

[0052] In the case of 4,4'-MDI, the preferred monomeric aromatic diisocyanate, distillative removal is particularly challenging. For example, care must be taken to prevent the condensate from solidifying and clogging the system.

[0053] Preferably, the reaction is carried out at a jacket temperature in the range of 160 to 200°C at 0.001 to 0.5 mbar and the removed monomer is condensed at a temperature in the range of 40 to 60°C.

[0054] Preferably, the reaction of the monomeric diisocyanate with the linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt. %, based on all polyols used, of further polyether polyols, followed by the removal of the majority of the monomeric diisocyanate remaining in the reaction mixture, takes place without the use of solvents or entraining agents. Preferably, the monomeric diisocyanate removed after the reaction is subsequently reused, i.e., reused for the production of isocyanate-containing prepolymer.

[0055] The prepolymer thus produced preferably has a viscosity at 20°C of at most 50 Pa s, in particular at most 40 Pa s, particularly preferably at most 30 Pa s. The viscosity is determined using a cone-plate viscometer with a cone diameter of 25 mm, cone angle of 1 °, cone tip-plate distance of 0.05 mm at a shear rate of 10 s' 1 .

[0056] The content of prepolymer in the composition according to the invention is in particular between 60 and 80 wt.%, preferably between 70 and 75 wt.%, based on the total composition.

[0057] Even if the composition uses prepolymers that contain a smaller amount of monomeric isocyanates, it may be advantageous to also add non-volatile oligomeric isocyanate derivatives. These can be, for example, aliphatic or aromatic isocyanurates, allophanates, and biurets. Polymeric aromatic isocyanates, such as p-MDI, can also be used. A key factor in the selection of these oligomeric isocyanate derivatives is that they are substances that exhibit a low vapor pressure at room temperature, for example, below 0.005 mbar at 25°C. These substances should therefore be essentially free of monomeric diisocyanates.

[0058] Furthermore, the composition according to the invention should also contain additives known in the field of polyurethane foams as foam precursors. Such additives are present in the composition according to the invention in an amount of 0.5 to 20 wt. %, based on the total composition. These additives can be, for example, plasticizers, stabilizers, adhesion promoters, dyes, fragrances, non-reactive polymers, catalysts, flame retardants, biocides, cell openers, and similar additives. It is advisable to keep the proportion of components that do not react in the polymer, such as plasticizers or flame retardants, as low as possible. Volatile components, especially solvents, should be avoided if possible.

[0059] Plasticizers can be contained in the foam precursor in amounts of up to 30% by weight, based on the total composition, preferably less than 5% by weight, in particular no plasticizers.

[0060] A composition according to the invention can contain, in addition to the reactive prepolymers, up to 25 wt. % of further non-reactive polymers. These are preferably solid polymers that do not contain any functional groups crosslinkable with isocyanate groups. They should be homogeneously miscible with the prepolymers. These additional polymers can be used to influence properties of the crosslinked foam material, such as hardness, elasticity, moisture absorption, etc. Suitable polymers of this type include, for example, poly(meth)acrylates, non-reactive polyurethanes, vinyl acetate copolymers, polyesters, or aromatic block copolymers.

[0061] For the purposes of this invention, the term "stabilizers" refers in particular to antioxidants, UV stabilizers, hydrolysis stabilizers, or foam stabilizers. Examples of these are commercially available sterically hindered phenols and / or thioethers and / or substituted benzotriazoles and / or amines of the "HALS" type (hindered amine light stabilizer). It is preferred for the purposes of the present invention to use a UV stabilizer that bears a silyl group and is incorporated into the final product during crosslinking or curing. Furthermore, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, or sterically hindered phenols can also be added.Examples of foam stabilizers include polyether siloxanes, such as copolymers of ethylene oxide and propylene oxide combined with a polydimethylsiloxane radical, polysiloxane-polyoxyalkylene copolymers branched via allophanate groups, other organopolysiloxanes, such as dimethylpolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, and / or paraffin oils. Oligomeric polyacrylates with polyoxyalkylene and / or fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure, and / or for stabilizing the cell structure.

[0062] In preferred embodiments of the composition according to the invention, at least one foam stabilizer is contained in an amount between 0.5 and 5 wt.%, based on the total composition, preferably at least one silicone-based foam stabilizer.

[0063] Preferably, the content of foam stabilizers in the composition is between 1 and 3 wt.%, preferably between 1.5 and 2.5 wt.%, based on the total composition.

[0064] If necessary, organofunctional silanes such as hydroxyfunctional, (meth)acryloxyfunctional, mercaptofunctional, aminofunctional, or epoxyfunctional silanes can be used as adhesion promoters. The amounts can range from 0 to 10 wt.%, preferably between 0.5 and 5 wt.%, based on the total composition.

[0065] The composition according to the invention preferably contains at least one catalyst. All known compounds capable of catalyzing isocyanate reactions can be used as catalysts. Examples include titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaulate (DBTL), dibutyltin diacetate and tin octoate, tin oxides such as dibutyltin oxide and dioctyltin oxide, organoaluminum compounds such as aluminum trisacetylacetonate and aluminum trisethylacetoacetate, chelate compounds such as titanium tetraacetylacetonate, amine compounds such as triethylenediamine, guanidines, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo-(5,4,0)-undecen-7 (DBU), 1,4-diazabicyclo[2,2,2]octane, N,N-dimethylpiperazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, Dimorpholinodimethyl ether, dimorpholinodiethyl ether (DMDEE) or mixtures thereof.The catalysts are preferably used in an amount of 0.01 to about 5 wt.% based on the total weight of the composition. In preferred embodiments, the composition according to the invention contains at least one catalyst in an amount between 0.1 and 5 wt.%, based on the total composition, preferably 2,2'-dimorpholinodiethyl ether.

[0066] The foamable composition according to the invention can also contain at least one, especially liquid, flame retardant. The flame retardant can be selected, for example, from the group consisting of halogenated (especially brominated) ethers or esters, organic phosphates, especially diethyl ethanephosphonate, triethyl phosphate, dimethylpropylphosphonate, diphenyl cresyl phosphate, and chlorinated phosphates, especially trismonochloropropyl phosphate, tris(2-chloroethyl)phosphate, tris(2-chloroisopropyl)phosphate, tris(1,3-dichloroisopropyl)phosphate, tris(2,3-dibromopropyl)phosphate, and tetrakis(2-chloroethyl)ethylenediphosphate, or mixtures thereof. A preferred embodiment selects flame retardants that do not contain hydroxyl groups, since these can reduce the content of reactive NCO groups. The mixture preferably contains the flame retardant in an amount of less than 30% by weight, preferably less than 10% by weight, in particular less than 5% by weight.

[0067] In some preferred embodiments, the composition contains

[0068] Contains trismonochloropropyl phosphate (TMCP) as a viscosity regulator and flame retardant, preferably in an amount of between 5 and 15 wt.%, based on the total composition.

[0069] A foamable composition according to the invention contains, in addition to the mixture of prepolymers and additives, at least one blowing agent. The blowing agent is present in an amount of 9 to 40 wt.%, based on the total composition.

[0070] In principle, a variety of highly volatile compounds can be used as propellants. These compounds are volatile and capable of evaporation at the application temperature, for example, at 20°C. Propellants are preferably selected from hydrocarbons and / or fluorocarbons, each containing 1-5 carbon atoms, and / or ethers with a molecular weight below 120 g / mol, such as dimethyl ether (DME), diethyl ether, dimethoxymethane, dimethoxyethane, and mixtures thereof, for example, a mixture of DME / propane / isobutane / n-butane.

[0071] In a particular embodiment, it is advantageous to contain at least a portion of polar propellants. If desired, non-polar propellants can also be used. Non-polar propellants are understood to be the well-known highly volatile hydrocarbons which have 1 to 5 carbon atoms. Polar propellants are understood to be substances which have a considerable vapor pressure at 20°C and a polarity known to a chemically trained person skilled in the art. These are compounds which, in addition to hydrocarbon units, contain further heteroatoms, in particular oxygen, fluorine or chlorine. Examples of such compounds are dimethyl ether (DME), diethyl ether, dimethoxymethane, dimethoxyethane, 1,1-difluoroethane (R152a) or 1,1,1,2-tetrafluoroethane (R134a). Such polar propellants can be contained individually or in a mixture.

[0072] The blowing agents are preferably used in amounts of 10 to 40 wt.%, preferably 15 to 35 wt.%, preferably between 20 and 30 wt.%, based on the total foamable mixture.

[0073] In particular, a high proportion of polar blowing agents can be advantageously used; for example, more than 25% of the amount of polar blowing agents are preferably present, especially more than 50%. DME and / or dimethoxymethane are particularly preferred as polar blowing agents.

[0074] In particularly preferred embodiments, the blowing agent is selected from dimethyl ether, diethyl ether, dimethoxymethane, propane, butane, and any mixtures of these blowing agents, with dimethyl ether preferably being present in an amount of at least 50% by weight, based on all blowing agents present in the composition. A particularly preferred embodiment of the foamable composition according to the invention contains 65 to 80% by weight, preferably 70 to 75% by weight, of prepolymers, 1.0 to 3.0% by weight, preferably 1.5 to 2.5% by weight, of foam stabilizers, 0.5 to 2.0% by weight, preferably 1 to 1.5% by weight, of catalysts, and 15 to 35% by weight, preferably 20 to 30% by weight, of blowing agent.

[0075] In the same or another preferred embodiment, the composition contains less than 0.1 wt.% monomeric diisocyanates, based on the total composition. Such a composition is particularly advantageous in terms of occupational safety and user-friendliness.

[0076] Due to the targeted, narrow selection of prepolymers, a foamed composition according to the invention exhibits unusually high permanent elasticity after crosslinking. This can be determined as the maximum permanent elasticity according to DIN EN 17333-4, Chapter 4.4 (movement capability). The permanent elasticity of the composition according to the invention, determined by this method after foaming, is up to 40%, whereas this property is less than 20% in comparable compositions based on conventional polyether polyols such as polypropylene glycol diols. Thus, the foamed and cured compositions according to the invention most surprisingly exhibit a previously unknown level of permanent elasticity, which cannot be achieved with conventional one-component foams.

[0077] The invention further provides a process for producing the foamable, crosslinkable compositions according to the invention. According to this process, a prepolymer composed of at least one linear, unbranched C3 or C4 polyetherdiol and optionally up to 25% by weight, based on all polyols used, of further polyether polyols is reacted with a molar excess of monomeric isocyanates. This excess should comprise an NCO / OH ratio of more than 2 / 1. After the reaction, the unreacted monomeric diisocyanate is removed, in particular distilled off, to a content of less than 0.5% by weight based on the prepolymer, preferably less than 0.3% by weight, in particular below 0.2% by weight. In a particular embodiment, the prepolymer is virtually free of monomeric isocyanates, i.e., contains less than 0.1% by weight. It is possible to reuse the distilled diisocyanate in the synthesis of the prepolymers.The isocyanates particularly suitable for this process are aromatic isocyanates, such as 2,4'- or 4,4'-MDI, or mixtures thereof. After reducing the monomers, the prepolymer can be filled into the packaging and mixed together with the other additives.

[0078] Furthermore, at least one propellant gas is added to this mixture. A mixture of polar and non-polar propellant gases is preferably used. This can be achieved by mixing the prepolymer / additive mixture with propellant gas, which is then filled into the appropriate disposable pressurized containers. It is also possible to add the prepolymers and additives individually to the appropriate container and then add the propellant gases. The components are mixed together in a known manner. The mixing of the components can also be assisted by heating, so that the processing steps proceed more quickly.

[0079] The present invention further provides a one-component aerosol can (disposable pressure container) containing a foamable composition according to the invention. The disposable pressure container (aerosol can) thus contains at least 50 to 90 wt. % of at least one prepolymer prepared from the reaction of at least one linear, unbranched C3 or C4 polyetherdiol and optionally up to 25 wt. %, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate in an NCO / OH ratio of > 2 / 1 and subsequent removal of excess monomeric diisocyanate, 0.2 to 20 wt. % of additives, and 9 to 40 wt. % of at least one blowing agent, wherein the at least one prepolymer has a residual monomer content of less than 0.5 wt. %, based on the prepolymer.To enable good processability of the mixture - especially the filling of the containers - the viscosity of the mixture with the non-volatile components (composition without propellant) is preferably in the range of 3000 to 150000 mPas (measured at 50°C). The mixtures, filled in disposable pressurized containers, are storage-stable for a period of at least 6 months, provided they are processed under anhydrous conditions. The composition according to the invention has a viscosity that enables good and easy application in the form of a spray application from a pressurized can. The applied composition foams. The foamable compositions according to the invention cure after dispensing from the aerosol can by reacting with the ambient air humidity to form fine-cell foams, so that the compositions are suitable for sealing, insulating and / or mounting, e.g.of joints, roof surfaces, windows and doors or for filling cavities.

[0080] A further subject matter of the present invention is therefore also the use of the composition according to the invention as assembly foam for filling cavities, in particular for soundproofing and / or thermal insulation in buildings and / or vehicles, for example for sealing, insulating and / or assembling joints, roof surfaces, windows and doors or for filling cavities, for example A-pillars in vehicles.

[0081] The foamable compositions according to the invention are particularly suitable for use as one-component canned foams. These are typically used as assembly or construction foams, i.e., they are filled into aerosol cans for production, storage, and transport, and are dispensed and foamed immediately upon use. The composition according to the invention makes it possible to produce isocyanate-reactive polyurethane foams that have a low monomer content and also exhibit very high permanent elasticity. The compositions according to the invention have a composition that exhibits sufficient viscosity to be foamable with known blowing agents. The foamable compositions according to the invention cure with the existing atmospheric humidity and produce small-cell, mechanically stable foams.The low content of free isocyanates ensures compliance with occupational health and safety requirements. The technical application properties of the foamed materials are at least equivalent to those of the state of the art. The mechanical properties, particularly the permanent elasticity of the cross-linked materials, are significantly improved compared to the state of the art.

[0082] Examples

[0083] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0084] The “standard climate” (“NK”) is defined as a temperature of 23±1 °C and a relative humidity of 50±5%.

[0085] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH.

[0086] Description of the measurement methods:

[0087] The content of monomeric diisocyanate was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization using N-propyl-4-nitrobenzylamine.

[0088] The maximum permanent elasticity was determined according to DIN EN 17333-4, Chapter 4.4 (movement capability). A foam sample is repeatedly compressed and stretched to determine the maximum permanent elasticity.

[0089] Production of polymers containing isocyanate groups:

[0090] Polymer P-1 :

[0091] A propylene glycol-initiated polyoxypropylene diol with an average molecular weight of 431 g / mol (Voranol® P 400, OH number 260 mg KOH / g, from Dow) was reacted with 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) with an NCO / OH ratio of 4 / 1 at 80 °C using a known method to form an NCO-terminated prepolymer. The volatile components, particularly unreacted 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 to 0.005 mbar, condensation temperature 47 °C), yielding a prepolymer with a monomeric 4,4'-diphenylmethane diisocyanate content of 0.04 wt. %.

[0092] Polymer P-2:

[0093] A polytetrahydrofuran diol with an average molecular weight of 650 g / mol (Terathane® PTMEG 650, OH number 172 mg KOH / g, from Tri-iso) was reacted with 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) with an NCO / OH ratio of 4 / 1 at 80 °C using a known method to form an NCO-terminated prepolymer. The volatile components, particularly unreacted 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 to 0.005 mbar, condensation temperature 47 °C), yielding a prepolymer with a monomeric 4,4'-diphenylmethane diisocyanate content of 0.05 wt. %.

[0094] Preparation of the example compositions as one-component canned foam: To 72 parts by weight of the respective prepolymer, 1.1 parts by weight of 2,2-dimorpholinodiethyl ether (DMDEE) (Jeffcat® DMDLS) were added as a catalyst, along with 2.0 parts by weight of a commercial silicone-based foam stabilizer. Subsequently, 25 parts by weight of a blowing agent mixture of propane / dimethyl ether (1:1) were added to this mixture. Filling into the pressurized cans takes place at elevated temperature. After cooling, a good flow of foam from the pressurized can is observed.

[0095] Example 1 (reference example) contains exclusively the polymer P-1 described above as prepolymer.

[0096] Example 2 (according to the invention) contains exclusively the polymer P-2 described above as prepolymer.

[0097] Results of maximum permanent elasticity Example 1 (reference example) showed a maximum permanent elasticity, measured according to the above method, of 17.5%.

[0098] Example 2 (according to the invention) had a maximum permanent elasticity, measured according to the above method, of 40%.

[0099] The results for maximum permanent elasticity surprisingly show that the inventive composition exhibits a significantly higher maximum permanent elasticity than the very similar reference composition, which is based on a polyetherurethane polymer based on a conventional polypropylene glycol polyol of similar molecular weight. This significant difference in maximum permanent elasticity enables one-component foam products with previously unattained elasticity properties, while also eliminating the need for harmful ingredients.

Claims

Patent claims:

1. Crosslinkable foamable composition with a low content of monomeric isocyanates, comprising, in each case based on the total composition: a) 50 to 90 wt.% of at least one prepolymer prepared from the reaction of at least one linear, unbranched C3 or C4 polyether diol and optionally up to 25 wt.%, based on all polyols used, of further polyether polyols and at least one monomeric diisocyanate in an NCO / OH ratio of > 2 / 1 and subsequent removal of excess monomeric diisocyanate, b) 0.2 to 20 wt.% of additives, c) 9 to 40 wt.% of at least one blowing agent, wherein the at least one prepolymer has a residual monomer content of less than 0.5 wt.%, based on the prepolymer.

2. Composition according to claim 1, characterized in that the NCO / OH ratio for the preparation of the prepolymer is between 3 / 1 and 7 / 1.

3. Composition according to one of claims 1 or 2, characterized in that foam stabilizers, catalysts, cell openers, flame retardants, non-reactive polymers, dyes or pigments, and / or UV stabilizers are included as additives.

4. Composition according to one of claims 1 to 3, characterized in that at least one catalyst is present in an amount between 0.1 and 5 wt.%, based on the total composition, preferably 2,2'-dimorpholinodiethyl ether.

5. Composition according to one of claims 1 to 4, characterized in that at least one foam stabilizer is present in an amount between 0.5 to 5 wt.%, based on the total composition, preferably at least one silicone-based foam stabilizer.

6. Composition according to one of claims 1 to 5, characterized in that the composition contains less than 0.1 wt.% of monomeric diisocyanates, based on the total composition.

7. Composition according to one of claims 1 to 6, characterized in that the content of prepolymer in the composition is between 60 and 80 wt.%, preferably between 70 and 75 wt.%, based on the total composition.

8. Composition according to claim 5, characterized in that the content of foam stabilizers in the composition is between 1 and 3 wt.%, preferably between 1.5 and 2.5 wt.%, based on the total composition.

9. Composition according to one of claims 1 to 8, characterized in that the prepolymer is based on an aromatic diisocyanate, preferably methylenediphenyl isocyanate (MDI), in particular diphenylmethane-4,4'-diisocyanate (4,4'-MDI).

10. Composition according to one of claims 1 to 9, characterized in that the prepolymer is based at least or in particular exclusively on a polytrimethylene glycol diol and / or a polytetrahydrofuran diol, in particular having an average molecular weight M n , measured by gel permeation chromatography (GPC) against polystyrene as standard, in the range between 500 and 1000 g / mol, preferably between 600 and 800 g / mol.

11. Composition according to one of claims 1 to 10, characterized in that the propellant is selected from dimethyl ether, diethyl ether, dimethoxymethane, propane, butane and any Mixtures of these propellants, preferably containing dimethyl ether in an amount of at least 50% by weight based on all propellants contained in the composition.

12. Composition according to one of claims 1 to 11, characterized in that the content of propellant in the composition is between 15 and 35 wt.%, preferably between 20 and 30 wt.%, based on the total composition.

13. Composition according to one of claims 1 to 12, characterized in that the composition contains trismonochloropropyl phosphate (TMCP) as viscosity regulator and flame retardant, preferably in an amount of between 5 and 15% by weight, based on the total composition.

14. A one-component aerosol can containing the composition according to any one of claims 1 to 13.

15. Use of the composition according to any one of claims 1 to 13 as assembly foam for filling cavities, in particular for soundproofing and / or thermal insulation in buildings and / or vehicles.