Catalyst for forming polyurethane

Abstract

The present invention relates to novel carbamate or urethane compounds which can serve as catalysts for the reaction of at least one isocyanate compound with at least one isocyanate-reactive compound, in particular for the production of polyisocyanate addition products such as polyurethanes, especially for the production of polyurethane (PU) foams, wherein they exhibit excellent foaming properties.

Description

Technical Field

[0001] The present invention relates to novel urethane or carbamate and urea compounds obtained by the reaction of an isocyanate compound with at least one isocyanate-reactive compound, which compounds can be used as catalysts; a process for manufacturing such compounds; the use of such compounds as catalysts, in particular as catalysts for the reaction of at least one isocyanate compound with at least one isocyanate-reactive compound, in particular for the manufacture of polyisocyanate addition products such as polyurethanes, in particular for the manufacture of water-blown polyurethane (PU) foams, where they exhibit excellent foaming properties. Background Art

[0002] Polyurethane foams are manufactured by reacting a polyisocyanate (or a prepolymer thereof) with a compound containing two or more active hydrogens (chain extender, polyether polyol, polyester polyol, polyetheramine, etc.), usually in the presence of a blowing agent (chemical blowing agents such as water and physical blowing agents like pentane, cyclopentane, halogenated hydrocarbons, etc.), a catalyst (tertiary amines, organometallic derivatives of tin, bismuth, zinc, etc.), a silicone-based surfactant, and other auxiliaries. During the preparation of water-blown polyurethane foams, two main reactions are promoted by the catalyst between the reactants:

[0003] - The reaction of an isocyanate-reactive compound such as a polyol with an isocyanate, resulting in an increase in the polymer molecular weight, which leads to an increase in viscosity and gel strength, and this reaction is called the gelation reaction.

[0004] - The reaction of water with an isocyanate, resulting in the generation of CO2 gas that acts as a blowing agent, and this reaction is called the foaming reaction.

[0005] Tertiary amines are well-known PU catalysts. They do have varying degrees of activity in promoting the gelation reaction. This is especially true when the polyol has a high inherent reactivity. In some formulations, amine catalysts can be the only catalysts used. While organotin catalysts promote the gelation reaction, amine catalysts mainly affect the foaming reaction.

[0006] Most polyurethane foams emit volatile organic compounds. These emissions can consist, for example, of pollutants present in the raw materials, catalysts, degradation products or unreacted volatile starting materials or other additives. Amine emissions from polyurethane foams have become a major issue, particularly in automotive interior applications, in furniture or cushions, and the market is therefore increasingly demanding low-emission foams. The automotive industry in particular requires a significant reduction in volatile organic compounds (VOCs) and condensable compounds (fogging or FOG) in the foam. The VOC and FOG profiles of PU foams can be evaluated by the VDA 278 test. One of the main components of emissions from flexible molded foams is the amine catalyst.

[0007] Amine emissions can be reduced, inter alia, by: a) introducing reactive hydroxyl or amino groups into the tertiary amine molecular moiety, thereby enabling their attachment to the polymer network, or b) using tertiary amines with very low vapor pressures. Reactive amines are known to degrade fatigue properties such as moisture aging compression set. Furthermore, reactive amines promote undesirable chain termination, thereby reducing the amount of the potent and active amine catalytic moiety. Therefore, the development of efficient polyurethane catalysts with low emission profiles is one of the key goals of the modern polyurethane industry.

[0008] US 6423756 B1 describes IPDI-based bis-urethanes derived from tertiary amino groups as PU catalysts. The specific reactive tertiary amines described in this patent application are based on dimethylaminoethoxyethanol, dimethylaminoethanol, and bis(dimethylaminopropyl)amino-2-propanol. WO 2020011343 A1 describes IPDI-derived bis-urethanes using bicyclic tertiary amines.

[0009] Despite attempts in the prior art, there remains a need for catalyst compositions that are non-reactive, do not bind to the polymer network, and yet exhibit low emission properties. This invention describes novel compounds that can be used as catalysts that meet these requirements. Surprisingly, it was discovered that, despite having a higher molecular weight, these novel molecules are highly efficient and more differentiated foaming catalysts, comparable to many other known catalysts. Summary of the Invention

[0010] According to the present invention, there are therefore provided compounds obtained by reaction of an isocyanate compound with at least one isocyanate-reactive compound of formula (I), or salts thereof, and mixtures thereof:

[0011] (R) a -X(I)

[0012] in

[0013] R is selected from R 1and R 2 , wherein

[0014] R 1 is selected from R 3 、R 4 、R 5 、R 6 、R 14 and R 16 , wherein

[0015] R 3 represents a hydrocarbon group comprising at least two tertiary amino groups and at least one ether (-O-) group,

[0016] R 4 represents a hydrocarbon group comprising at least one monocyclic heterocyclic group,

[0017] R 5 represents a group of the formula:

[0018]

[0019] (The dotted line represents the binding site to X)

[0020] wherein R 17 represents an aliphatic hydrocarbon group having at least three carbon atoms, and R 7 and R 8 each independently represent a linear or branched aliphatic hydrocarbon residue, which may optionally be substituted by one or more tertiary amino groups and may optionally contain one or more ether (-O-) groups,

[0021] R 6 represents a group of the formula:

[0022]

[0023] (The dotted line represents the binding site to X)

[0024] wherein R 18 represents an aliphatic hydrocarbon group having at least two carbon atoms, R 19 represents an aliphatic hydrocarbon group having at least three carbon atoms, and R 9 -R 11 each independently represent a linear or branched aliphatic hydrocarbon residue,

[0025] R 14 represents a group of the formula:

[0026]

[0027] (The dotted line represents the binding site to X)

[0028] wherein R 15each independently selected from a hydrocarbyl group comprising at least one tertiary amino group and optionally comprising one or more ether (-O-) groups, and

[0029] R 16 represents an aromatic group substituted by at least two hydrocarbyl groups each comprising at least one tertiary amino group,

[0030] R 2 represents a hydrocarbyl group, preferably an aliphatic saturated hydrocarbyl group having up to 10 carbon atoms, more preferably an alkyl group having up to 10 carbon atoms, or hydrogen,

[0031] a is 2 or 3, and

[0032] X is selected from O, S, or N,

[0033] provided that the compound comprises at least one group R as defined above 1 and at least one group R is R as hydrogen 2 and R 1 may represent only one group R 5 .

[0034] Thus, when X represents O or S, a is 2, and when X represents N, a is 3. In order to be isocyanate-reactive, the compound of formula (I) must have at least one hydrogen atom bonded to X (R 2 is hydrogen). X is preferably O or N. When X is N, preferably there are two hydrogen atoms bonded to N, and one group R 1 , i.e., the isocyanate-reactive compound has a primary amino group and has the formula R 1 -NH2. Compounds of formula R 2 wherein R 1 R 2 NH represents a hydrocarbyl group are less preferred. When X is O or S, the compound thus has the formula R 1 -X-H, which is specifically a hydroxyl compound of the formula R 1 -OH and a mercapto compound of the formula R 1 -SH. Thus, basically, the compounds of formula (I) include any compound having the following formula: R 1 -NH2; R 1 R 2 NH, wherein R 2 represents a hydrocarbyl group; and R 1 XH, wherein R 1As defined above. The isocyanate-reactive compounds of formula (I) generally do not include any other isocyanate-reactive functional groups except for the isocyanate-reactive functional groups -OH, -SH, =NH or -NH2, i.e., they are generally monofunctional with respect to the reaction with the isocyanate groups of the isocyanate compounds.

[0035] Examples of such isocyanate-reactive compounds of formula (I) are, for example, selected from the following compounds:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] Particularly preferred compounds according to the invention are the reaction products of these isocyanate-reactive compounds with isophorone diisocyanate (IPDI) and hexamethylene-1,6-diisocyanate (HDI), most preferably with isophorone diisocyanate (IPDI). Such compounds particularly and most preferably include compounds in which both isocyanate groups of the diisocyanate have been reacted off, but may also include compounds in which only one isocyanate group has been reacted off and all molar ratios therebetween, as exemplified below for isophorone diisocyanate:

[0047]

[0048] wherein R is as defined above, and depending on whether X is S or O or N, b is 1 or 2.

[0049] In a specific preferred embodiment of the invention, R in formula (I) 1 is selected from R 3, i.e., a hydrocarbyl group comprising at least two tertiary amino groups and at least one ether (-O-) group. The hydrocarbyl group is preferably a saturated aliphatic hydrocarbyl group such as an alkyl group having up to 25 carbon atoms, which comprises at least one tertiary amino group as follows:

[0050] wherein all binding sites of the nitrogen atom (as represented by the dashed lines) are bonded to an aliphatic hydrocarbyl residue.

[0051] In a particularly preferred compound according to the invention, R in formula (I) 1 is selected from R 3 , R 3 is selected from saturated aliphatic hydrocarbyl groups having up to 20, preferably up to 15 carbon atoms and comprising at least two tertiary amino groups and at least one ether (-O-) group. In such preferred compounds, R in formula (I) 1 is suitably selected from R 3 , R 3 is selected from the following formula:

[0052]

[0053] (where the wavy line represents the bonding site to X)

[0054] where the group R 13 is independently selected from divalent linear, branched or cyclic hydrocarbyl groups, and two of A, B, C represent tertiary amino groups (for A and B, selected from -N(R 12 )- and for C, selected from -N(R 12 )2, where R 12 is an organic group, preferably an aliphatic hydrocarbyl group having up to 15 carbon atoms, preferably an alkyl group having up to 6 carbon atoms) and one of A, B, C represents an ether group (for A and B, selected from -O- and for C, selected from -OR 12 , where R 12 is as defined previously.

[0055] In a particularly preferred compound according to the invention, R in formula (I) 1 is selected from R 3 , R 3 is selected from the following formula:

[0056]

[0057] (where the wavy line represents the bonding site to X)

[0058] where x, y, and z are integers from 2 - 6, preferably 2 or 3, and where A, B, and C are as defined previously. Wherein R in formula (I) 1 is selected from R3 The isocyanate-reactive compounds according to the present invention can be exemplified by the following formula:

[0059]

[0060]

[0061] In such exemplified compounds, X represents O or N, and R 2 represents hydrogen. Wherein R 1 is selected from R 3 Particularly preferred isocyanate-reactive compounds are:

[0062]

[0063] In a further preferred embodiment, R in formula (I) 1 is selected from R 4 , that is, R 1 represents a hydrocarbon group including at least one monocyclic heterocyclic group. Preferably, R 1 =R 4 =an aliphatic hydrocarbon group having up to 20 carbon atoms substituted by at least one monocyclic heterocyclic group.

[0064] In particularly preferred isocyanate-reactive compounds, R in formula (I) 1 is selected from R 4 , R 4 is a saturated linear or branched hydrocarbon group having up to 10 carbon atoms, which may contain up to three heteroatoms such as N or O, which may optionally be substituted by one or more hydroxyl groups, and the hydrocarbon group is substituted by at least one of the following monocyclic heterocyclic groups: the monocyclic heterocyclic group is selected from saturated or unsaturated or aromatic optionally substituted 5-6 membered heterocycles preferably having 1 or 2 heteroatoms selected from N, O and S, preferably N and O, more preferably N. Particularly preferred monocyclic heterocyclic groups in R 4 are selected from pyrrolidinyl, piperidinyl, 4-alkylpiperazin-1-yl, imidazolyl, and morpholin-4-yl, preferably imidazolyl, more preferably R 4 is imidazol-1-yl.

[0065] Wherein particularly preferred isocyanate-reactive compounds in which R in formula (I) 1 is selected from R 4 are, for example, selected from:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073] In a preferred embodiment, R in formula (I) of the isocyanate-reactive compound 1 is selected from R 5 and R 6 , where

[0074] R 5 represents a group of the formula:

[0075]

[0076] (The dashed line represents the binding site to X)

[0077] where R 17 represents an aliphatic, preferably saturated hydrocarbon-based group having at least three carbon atoms and preferably at most 10, more preferably at most 6 carbon atoms, and R 7 and R 8 each represent a linear or branched aliphatic, preferably saturated hydrocarbon-based residue, which preferably has at most 10, preferably at most 6 carbon atoms, which may optionally be substituted by one or more tertiary amino groups, preferably di(C1-C6)alkylamino groups, and may optionally contain one or more ether (-O-) groups,

[0078] R 6 represents a group of the formula:

[0079]

[0080] where R 18 represents an aliphatic, preferably saturated hydrocarbon-based group having at least two carbon atoms and preferably having at most 10, more preferably at most 6 carbon atoms, R 19 represents an aliphatic, preferably saturated hydrocarbon-based group having at least three carbon atoms and preferably at most 10, more preferably at most 6 carbon atoms, and R 9 -R 11 each independently represent a linear or branched aliphatic, preferably saturated hydrocarbon-based residue, which preferably has 1-10 carbon atoms, more preferably 1-6 carbon atoms, still more preferably 1 carbon atom (methyl),

[0081] In a further preferred embodiment, R in formula (I) of the isocyanate-reactive compound1 Selected from R 5 and R 6 , wherein

[0082] R 5 represents a group of the formula:

[0083]

[0084] wherein n represents an integer of ≥ 3, preferably 3 - 10, more preferably 3 - 6, and even more preferably 3, and R 7 and R 8 each represent a linear or branched aliphatic, preferably saturated hydrocarbon residue, which preferably has 1 - 10 carbon atoms, more preferably 1 - 6 carbon atoms and even more preferably 1 carbon atom (methyl), which may optionally be substituted by one or more tertiary amino groups, preferably di(C1 - C6)alkylamino groups, and may optionally contain one or more ether (-O-) groups, and

[0085] R 6 represents a group of the formula:

[0086]

[0087] wherein o represents an integer of ≥ 2, preferably 2 - 10, more preferably 2 - 6 and even more preferably 2 or 3, p represents an integer of ≥ 3, preferably 3 - 10, more preferably 3 - 6 and even more preferably 3, and R 9 -R 11 each represent a linear or branched aliphatic hydrocarbon residue.

[0088] In a further preferred embodiment, R in formula (I) of the isocyanate - reactive compound 1 is selected from R 5 and R 6 , wherein

[0089] R 5 represents a group of the formula:

[0090]

[0091] wherein n represents an integer of 3 - 6, and R 7 and R 8 each represent a linear or branched alkyl group having up to 6 carbon atoms, preferably having 1 carbon atom (methyl), and

[0092] R 6 represents a group of the formula:

[0093]

[0094] where o represents an integer from 2 - 6, preferably 2 - 3, p represents an integer from 3 - 6, preferably 3, and R 9 -R 11 each represents a linear or branched alkyl group having up to 6 carbon atoms, preferably a methyl group.

[0095] In a further preferred embodiment, R in formula (I) of the isocyanate - reactive compound 1 is selected from R 5 and R 6 , and the isocyanate - reactive compound is selected from:

[0096]

[0097]

[0098] In a further preferred embodiment, R in formula (I) of the isocyanate - reactive compound 1 is selected from R 14 or R 16 :

[0099] R 14 represents a group of the formula:

[0100]

[0101] where R 15 are each independently selected from hydrocarbon groups, preferably aliphatic, preferably saturated hydrocarbon groups, which preferably have up to 10, even more preferably up to 6 carbon atoms, which include at least one tertiary amino group (especially a dialkylamino group, such as a dimethylamino group), and optionally include one or more ether (-O-) groups, and

[0102] R 16 represents an aromatic group, such as a C6 - C10 aromatic group, preferably a phenyl group, which is substituted by at least two hydrocarbon groups, preferably saturated aliphatic groups having up to preferably 6 carbon atoms each including at least one tertiary amino group (especially, a dialkylamino group, such as a dimethylamino group).

[0103] Wherein R in formula (I) 1 is selected from R 14 or R 16 The preferred isocyanate - reactive compounds are selected from:

[0104]

[0105]

[0106] The isocyanate-reactive compounds reacting with the isocyanate compound are particularly selected from the formulas (Ia) and (Ib):

[0107] R 1 -OH (Ia),

[0108] R 1 -NH-R 2 (Ib), and

[0109] R 1 -NH-R 1 (Ic),

[0110] wherein R 1 and R 2 are each as defined above. In the case where R 2 in formula (Ib) is hydrogen, a primary amine of the formula R 1 -NH2 (Id) is obtained, wherein R 1 is as defined above. Particularly preferred according to the invention are the compounds of formulas (Ia) and (Id), wherein R 1 is preferably selected from R 3 .

[0111] Preferably, the isocyanate compounds used for preparing the compounds of the present invention are selected from monoisocyanates and polyisocyanates (having two or more isocyanate groups), and mixtures thereof. The mixtures can include mixtures of monoisocyanates, mixtures of polyisocyanates, or mixtures of one or more monoisocyanates and one or more polyisocyanates. Preferred are polyisocyanates.

[0112] The monoisocyanates can be selected, for example, from aliphatic or aromatic isocyanates such as octadecyl isocyanate; octyl isocyanate; butyl and tert-butyl isocyanates; cyclohexyl isocyanate; adamantyl isocyanate; ethyl isocyanatoacetate; ethoxycarbonyl isocyanate; phenyl isocyanate; α-methylbenzyl isocyanate; 2-phenylcyclopropyl isocyanate; 2-ethylphenyl isocyanate; benzyl isocyanate; m- and p-tolyl isocyanates; 2-, 3-, or 4-nitrophenyl isocyanate; 2-ethoxyphenyl isocyanate; 3-methoxyphenyl isocyanate; 4-methoxyphenyl isocyanate; ethyl 4-isocyanatobenzoate; 2,6-dimethylphenyl isocyanate; 1-naphthyl isocyanate; and (naphthyl)ethyl isocyanate.

[0113] The polyisocyanate can be selected, for example, from aliphatic or aromatic polyisocyanates, preferably aliphatic polyisocyanates, which are preferably selected from isophorone diisocyanate (IPDI); toluene diisocyanate (TDI); diphenylmethane-2,4'-diisocyanate (2,4'-MDI); diphenylmethane-4,4'-diisocyanate (4,4'-MDI); hydrogenated diphenylmethane-4,4'-diisocyanate (H.12MDI); tetramethylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI); naphthalene-1,5-diisocyanate; 3,3'-dimethoxy-4,4'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-dimethyl-4,4'-biphenyl diisocyanate; phenylene diisocyanate; 4,4'-biphenyl diisocyanate; trimethylhexamethylene diisocyanate; tetramethylxylene diisocyanate; 4,4'-methylene-bis(2,6-diethylphenyl isocyanate); 1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane; 1,4-diisocyanatobutane; and cyclohexylene diisocyanate and its isomers or its derivatives, such as its biuret, isocyanurate, urethane, and oligomers, for example, the uretdione dimer of HDI; the trimethylolpropane trimer of TDI; the isocyanurate trimers of TDI, HDI, and IPDI; the biuret trimers of TDI, HDI, or IPDI; and the polyisocyanates as described above in which the isocyanate groups are partially reacted with at least one isocyanate-reactive compound that does not have a group R 1 and the isocyanate-reactive compound that does not have a group R 1 is preferably selected from OH-, NH-, and NH2-functional optionally substituted hydrocarbons, which may contain one or more heteroatoms, such as alcohols like methanol, tert-butanol, isopropanol, sec-butanol, OH-functional mono(ethylene) glycol ethers, OH-functional di(ethylene) glycol ethers, etc.

[0114] Trivalent or higher-valent aliphatic polyisocyanates include, in particular, the biurets, urethanes, carbamates, isocyanurates, and higher oligomers of diisocyanates, the diisocyanates being in particular hexamethylene diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI or isophorone diisocyanate), and / or bis(isocyanatocyclohexyl)-methane, etc. Specific examples of such polyisocyanates include, for example:

[0115] - the biurets and oligomers of hexamethylene diisocyanate, such as:

[0116]

[0117] which can be obtained, for example, as 100 commercially available;

[0118] - Isocyanurate trimers of hexamethylene diisocyanate, for example:

[0119]

[0120] which can be obtained commercially, for example, as N3300; or its higher oligomers such as pentamers:

[0121] or asymmetric trimers such as:

[0122] wherein R is an isocyanate-containing aliphatic residue derived from HDI or 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI or hydrogenated MDI);

[0123] - Isocyanurate trimers of isophorone diisocyanate, for example:

[0124]

[0125] which can be obtained commercially, for example, as Z4470 or Tolonate IDT 70B.

[0126] Other polyisocyanates can be prepared, for example, from polyhydroxy-functional compounds or polymers and preferably at least equimolar amounts of diisocyanates such as HDI, IPDI or HMDI to form the corresponding polyisocyanates.

[0127] Preferably, the isocyanate compound is a polyisocyanate selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and derivatives derived from IPDI and / or HDI such as their biurets, isocyanurates, urethanes, and oligomers, preferably isophorone diisocyanate (IPDI) or hexamethylene-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI) and hexamethylene-1,6-diisocyanate (HDI), and uretidione dimers; their trimethylolpropane trimers, isocyanurate trimers, and biuret trimers, preferably selected from isophorone diisocyanate (IPDI) and hexamethylene-1,6-diisocyanate (HDI). More preferably, the isocyanate compound comprises aliphatic polyisocyanates, preferably aliphatic diisocyanate compounds, particularly hexamethylene-1,6-diisocyanate (HDI) and isophorone diisocyanate (IPDI). Most preferably, the isocyanate compound is isophorone diisocyanate (IPDI).

[0128] In the compounds of the present invention, the isocyanate groups of the polyisocyanate are reacted completely or partially, preferably they are reacted completely with the isocyanate-reactive compounds of formula (I). That is, for example, in a diisocyanate compound, it is possible that, by selecting a suitable molar ratio of 1:1 of NCO / isocyanate-reactive functional groups (such as -OH, -SH, -NH2 or -NHR where R is a hydrocarbon group), only one of the two isocyanate groups reacts with the isocyanate-reactive compound. Thus, if the number of isocyanate groups in the polyisocyanate is represented as v, the molar number of the isocyanate-reactive groups in the isocyanate-reactive compound relative to the isocyanate groups in the polyisocyanate compound can be v or less than v. It is also possible to react a molar excess of the isocyanate-reactive compound (based on the isocyanate groups in the isocyanate compound), thereby preparing a mixture of the isocyanate-reactive compound and the compound according to the present invention. Such compositions of the compounds of the present invention are also included within the scope of the present invention and will be described in more detail hereinafter.

[0129] Depending on the isocyanate-reactive compound, the compounds according to the present invention can be selected from the following compounds: urethane (carbamate) compounds of formula (II):

[0130]

[0131] wherein R 1 is as defined above, x is 1 - 6 and R 20 is an optionally substituted hydrocarbon group having a valence of 1 - 6, which optionally contains one or more heteroatoms and which is bonded to the nitrogen atom of the carbamate group through a carbon atom,

[0132] and urea compounds of formula (III):

[0133]

[0134] wherein one R is R as defined above 1 and the other Rs are selected from R as defined above 1 or R 2 and x and R 20 are as defined above, wherein R 20 is bonded to the nitrogen atom of the urea group through a carbon atom.

[0135] The group R 20Derived from isocyanate compounds, including the mono-isocyanate compounds and poly-isocyanate compounds as described above. It is thus preferably a saturated, unsaturated or aromatic hydrocarbon radical which preferably has up to 40 carbon atoms, preferably up to 30 carbon atoms, more preferably up to 20 carbon atoms, which may include one or more heteroatoms, and even more preferably it is an aliphatic saturated hydrocarbon radical having up to 20 carbon atoms such as those with respect to HDI or IPDI.

[0136] Specific examples of the compounds according to the invention are, for example, the reaction products of HDI or IPDI with the isocyanate-reactive compounds of formula (I) as defined above, in particular those compounds in which both isocyanate groups have already reacted with the isocyanate-reactive compounds of formula (I).

[0137] Particularly preferred compounds according to the invention are selected from

[0138]

[0139] The invention further relates to a process for preparing the compounds according to the invention, which process comprises reacting at least one isocyanate compound with at least one isocyanate-reactive compound of formula (I) as defined above. Preferably such a process is carried out at a temperature of about 20 - 140 °C, more preferably about 40 - 120 °C, and most preferably about 60 - 100 °C, optionally in the presence of one or more diluents and one or more catalysts. Non-reactive diluents / solvents may include, for example, aprotic organic solvents (ethyl acetate, acetone, acetonitrile, ketones, halogenated alkanes, diethylene glycol dimethyl ether, dioxane, ethers - diethyl ether, methyl butyl ether, tetrahydrofuran, alkanes, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, benzene, xylene and their analogues or mixtures thereof) which can be used to dissolve or melt the said components before mixing them. Preferably, the reaction is carried out with vigorous stirring and the isocyanate compound is added to the isocyanate-reactive compound or vice versa under an inert atmosphere. The addition of the isocyanate compound is carried out slowly either continuously or in portions discontinuously. In view of the exothermic reaction, the temperature rises. Generally, it is preferred to carry out the reaction under an inert atmosphere (nitrogen, argon, etc.) to exclude moisture. After completion of the reaction, the diluent / solvent may be removed partially or completely to provide the final compounds, their mixtures or their concentrated solutions.

[0140] The invention further relates to a composition comprising one or more compounds according to the invention, which further comprises at least one diluent. Such diluents can be used in particular to reduce the viscosity of the said composition. Reactive diluents may include in particular those compounds which react in the polyurethane or polyurea formation reaction in which the compounds of the invention act as catalysts.

[0141] The diluent may include, in particular, an excess of the isocyanate-reactive compound of formula (I) or any other isocyanate-reactive compound or non-isocyanate-reactive compound, i.e., a diluent that does not react with isocyanate. In the case of using the isocyanate-reactive compound of formula (I), in particular, a molar excess of such isocyanate-reactive compound is used, which then acts as a diluent for the composition according to the invention. Regarding such isocyanate-reactive compounds of formula (I), reference may be made to the preferred embodiments described above. Any diluent including any other isocyanate-reactive compound different from formula (I) may also be added after the reaction of the at least one isocyanate compound of formula (I) and at least one isocyanate-reactive compound. Such isocyanate-reactive compounds different from formula (I) may include various types of amines or alcohols, and may also include known amine catalysts for polyurethane formation as explained below.

[0142] The non-reactive diluent / solvent may include, in particular, dialkyl sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, diisobutyl sulfoxide, etc.; N,N-dialkyl alkanolamides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, etc.; phosphonates such as O,O-dimethyl, O,O-diethyl, O,O-diisopropyl methyl phosphonate, O,O-bis(2-chloroethyl) vinyl phosphonate, etc.; aromatic solvents such as toluene, xylene, benzene, etc.; ether solvents such as diethyl ether, dioxane, diethylene glycol dimethyl ether, etc.; tetramethylene sulfone, 1-methyl-2-pyrrolidone, trialkyl phosphates such as trimethyl phosphate and triethyl phosphate, acetonitrile, etc., and organic carbonates like dimethyl carbonate, ethylene carbonate, propylene carbonate, or a combination thereof. The diluent / solvent may be used together with co-solvents such as fatty acids, vegetable oils, or a combination thereof. Preferred solvents include glycols such as ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, propane-1,2,3-triol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol. Those diluents / solvents may be used as a mixture or co-solvent with amines.

[0143] A particularly preferred diluent may be water, which may act as a blowing agent in the subsequent polyurethane or polyurea foam formation reaction in which the compounds of the present invention act as catalysts.

[0144] In a further preferred embodiment of the composition according to the invention, it may optionally comprise one or more additional amines or amine catalysts for forming the polyisocyanate addition product, for example amines different from the isocyanate-reactive compounds. Such catalysts include alkylamines such as bis(2-dimethylaminoethyl) ether, N,N-dimethylcyclohexylamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N',N''-pentamethyldipropylenetriamine, triethylenediamine, ethanolamines such as 2-aminoethanol, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methylethanolamine, N-ethylethanolamine, diisopropylamine, bis(2-hydroxypropyl)amine, 2-[2-(dimethylamino)ethoxy]ethanol, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, 3-dimethylamino-N,N-dimethylpropanamide, N,N'-dimorpholinodiethylether, N,N'-dimethylpiperazine, N-methylmorpholine, N-ethylmorpholine, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol, 3,3'-iminobis(N,N-dimethylpropylamine), 3-(dimethylamino)-1-propylamine, 3-(diethylamino)-1-propanol, 1-(3-hydroxypropyl)pyrrolidine, 1-(2-hydroxypropyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, 1-(3-hydroxypropyl)piperidine, 1-(2-hydroxypropyl)piperidine, 1-(3-aminopropyl)pyrrolidine, 1-(2-aminoethyl)pyrrolidine, 1-(3-aminopropyl)piperidine, 1-(2-aminoethyl)piperidine, 1-(pyrrolidin-1-yl)-2-propanamine, 1-(piperidin-1-yl)propane-2-amine, N-methoxyethylmorpholine, N-methylimidazole, 1-(3-aminopropyl)imidazole, 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol, N-methyldicyclohexylamine, 3-{[3-(dimethylamino)propyl]methylamino}propanol, tris(dimethylaminopropyl)amine, 2-{[3-(dimethylamino)propyl]methylamino}ethanol, N,N,N',N'-tetramethyl-hexamethylenediamine, N,N,N',N'-tetramethylethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N-methyl-N'-(2-dimethylamino)ethyl-piperazine, N,N'-bis[3-(dimethylamino)propyl]urea, N-[3-(dimethylamino)propyl]urea, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine.Preferred amines include alkylamines such as bis(2-dimethylaminoethyl) ether, N,N-dimethylaminopropylamine, N,N-dimethylcyclohexylamine, N,N,N',N',N''-pentamethyldiethylenetriamine, triethylenediamine, ethanolamines such as diethanolamine, 2-(2-dimethylaminoethoxy)ethanol, N-[2-(dimethylamino)ethyl]-N-methylethanolamine, dimethylethanolamine, or other amines such as 3-dimethylamino-N,N-dimethylpropanamide and N-ethylmorpholine, triethanolamine, 2-dimethylaminoethanol, N,N-dimethylaminopropylamine, diethanolamine, trimethylamine, triethylenediamine, bis(2-dimethylaminoethyl) ether.

[0145] A preferred composition according to the invention comprises one or more compounds according to the invention, which further comprises at least one conventional polyurethane-forming catalyst, preferably at least one conventional polyurethane foam-forming gel catalyst as described above.

[0146] Another preferred composition comprising one or more compounds according to the invention further comprises at least one carboxylic acid. In a preferred embodiment, the composition according to the invention comprises at least one carboxylic acid, such as those described in US 6,387,972 B1. Preferably the carboxylic acid is selected from monocarboxylic acid compounds such as benzoic acid, polycarboxylic acid compounds such as dicarboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and hydroxy-functional carboxylic acid compounds, in particular salicylic acid, citric acid. In a particularly preferred embodiment, the composition comprises at least one carboxylic acid selected from the following: salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and citric acid.

[0147] The compound or composition according to the invention is preferably used as a catalyst, in particular as a catalyst for catalyzing the reaction of at least one isocyanate compound with at least one isocyanate-reactive compound, i.e., as a catalyst for producing polyisocyanate addition products. Such polyisocyanate addition products particularly have one or more functional groups composed of groups selected from urethane groups and urea groups. The compound or composition according to the invention is preferably used as a catalyst for producing polyurethanes, particularly polyurethane foams, and most preferably as a foaming catalyst for producing polyurethane foams, which particularly catalyzes the foaming reaction of water with isocyanate, resulting in the generation of CO2 gas acting as a blowing agent.

[0148] Accordingly, the invention also relates to a catalyst comprising a compound or composition according to the invention, in particular, a catalyst composition comprising a compound of the invention and one or more additional catalysts each for producing polyisocyanate addition products.

[0149] Accordingly, the present invention also relates to a process for manufacturing an isocyanate addition product, which comprises reacting an isocyanate compound, in particular a polyisocyanate compound, with an isocyanate-reactive compound in the presence of a compound or composition according to any of the present invention. Such a process for manufacturing an isocyanate addition product particularly comprises reacting an isocyanate compound, preferably a polyisocyanate compound, with an isocyanate-reactive compound in the presence of a compound or composition according to the present invention in the presence of water. In this process for manufacturing an isocyanate addition product using a compound or composition according to the present invention as a catalyst, the isocyanate is preferably a polyisocyanate and the isocyanate-reactive compound is preferably a polyol, and this process is used for manufacturing polyurethanes, in particular polyurethane foams.

[0150] In the process for manufacturing an isocyanate addition product according to the present invention, the isocyanate addition product is preferably a polyurethane, more preferably a polyurethane foam, which is selected from cellular or non-cellular polyurethanes, and preferably this process optionally comprises a blowing agent, more preferably water.

[0151] The process for manufacturing an isocyanate addition product according to the present invention is preferably used for manufacturing polyurethanes, and this process optionally comprises adding a surfactant, a flame retardant, a chain extender, a crosslinking agent, an adhesion promoter, an antistatic additive, a hydrolysis stabilizer, a UV stabilizer, a lubricant, an antimicrobial agent, or a combination of two or more thereof.

[0152] In the process for manufacturing an isocyanate addition product according to the present invention, the compound or composition according to the present invention is present in an amount of about 0.005% by weight to about 5% by weight, based on the total weight of the entire composition including all components.

[0153] The present invention also relates to a foam-forming isocyanate addition product obtainable by the process for manufacturing an isocyanate addition product of the present invention. Particularly preferred foam-forming isocyanate addition products can be selected, for example, from blocks, molded foams, flexible foams, rigid foams, semi-rigid foams, spray foams, thermoformable foams, micro-cellular foams, footwear foams, open-cell foams, closed-cell foams, adhesives.

[0154] The process for manufacturing polyurethanes using a compound or composition according to the present invention as a catalyst is described in more detail below.

[0155] As used herein, the term "polyurethane" refers to the reaction product of an isocyanate containing two or more isocyanate groups with a compound containing two or more active hydrogens such as a polyol (polyether polyol, polyester polyol, copolymer polyol also referred to as graft polyol) and / or a polymer terminated with primary and secondary amines also referred to as polyamines. These reaction products are generally referred to by those skilled in the art as polyurethanes and / or polyureas. The reaction for forming porous and non-porous foams optionally includes a blowing agent. In the manufacture of polyurethane foams, the reaction includes a blowing agent and other optional components such as surfactants, flame retardants, chain extenders, crosslinkers, adhesion promoters, antistatic additives, hydrolysis and UV stabilizers, lubricants, antimicrobial agents, catalysts, and / or other specialty additives to make dense or porous polyurethane materials [The polyurethanes book, edited by David Randall and Steve Lee, John Willey & Sons, LTD, 2002]. The present catalyst material of the invention is particularly suitable for use in the manufacture of flexible, semi-flexible, and rigid foams using one-shot foaming, quasi-prepolymer, and prepolymer processes. The polyurethane manufacturing process of the present invention typically involves the reaction of, for example, a polyol (generally, a polyol having a hydroxyl value of about 10 - about 700), an organic polyisocyanate, a blowing agent, and optional additives known to those skilled in the art and one or more catalysts (at least one of which is selected from the subject tertiary amine compounds). As blowing agents and optional additives, flexible and semi-flexible foam formulations (hereinafter simply referred to as flexible foams) also generally include, for example, water, an organic low-boiling auxiliary blowing agent or an optional non-reactive gas, a silicone surfactant, an optional catalyst different from the catalyst according to the present invention, and an optional crosslinker. Rigid foam formulations often contain both a low-boiling organic material and water for foaming. The "one-shot foaming process" for manufacturing polyurethane foams is a one-step process in which all the ingredients necessary (or desired) for making a foamed polyurethane product, including a polyisocyanate, an organic polyol, water, catalysts (both of the present invention and different from the catalyst according to the present invention), a surfactant, an optional blowing agent, etc., are effectively mixed, poured onto a moving conveyor belt or into a mold of a suitable configuration, and cured [Chemistry and Technology of Polyols for Polyurethanes, Mihail Ionescu, Rapra Technology LTD. (2005)]. The one-shot process is in contrast to prepolymer and quasi-prepolymer processes [[Flexible polyurethane foams, Ron Herrington and Kathy Hock, Dow Plastics, 1997].In the prepolymer process, most prepolymers currently in use are isocyanate-tipped. When just enough polyisocyanate is added to react with all available hydroxyl sites, a strict prepolymer is formed. If there is an excess or residual isocyanate monomer, the product is called a quasi-prepolymer. The prepolymer or quasi-prepolymer is first prepared in the absence of any foaming components. In a second step, a high molecular weight polyurethane material is formed by reacting the prepolymer with water and / or a chain extender such as ethylene glycol, diethylene glycol, 1,4-butanediol, or a diamine in the presence of a catalyst.

[0156] The catalyst compounds and their compositions of the present invention can be used as a sole catalyst or in combination with one or more additional catalysts for forming polyisocyanate adducts such as the tertiary amine catalysts described above.

[0157] In addition, the catalyst compositions of the present invention can include two or more different compounds according to the present invention as described above. The catalyst compounds or their compositions of the present invention can be present in a reactive mixture for forming polyurethanes including all required components in an amount of about 0.005% - about 5% by weight of the total weight of the reactive composition; preferably about 0.01% - about 3.0%; or more preferably about 0.03% - about 1.00%. Other catalysts that can be used to manufacture polyurethane foams include, for example, tertiary amines such as the alkylamines described above, organometallic catalysts such as organotin catalysts, metal salt catalysts such as alkali metal or alkaline earth metal carboxylate catalysts, other delayed-action catalysts, or other known polyurethane catalysts. Organometallic catalysts or metal salt catalysts can also and often are used in polyurethane foam formulations. For example, for flexible slabstock foams, the generally preferred metal salt and organometallic catalysts are stannous octoate and dibutyltin dilaurate, respectively. For flexible molded foams, exemplary organometallic catalysts are dibutyltin dilaurate and dibutyltin dialkylthiolate. For rigid foams, exemplary metal salt and organometallic catalysts are potassium acetate, potassium octoate, and dibutyltin dilaurate, respectively. Metal salt or organometallic catalysts are typically used in small amounts in polyurethane formulations, typically in an amount of about 0.001 parts per hundred parts (pphp) - about 0.5 phpp based on the total weight of the composition.

[0158] The polyols useful in the process of the present invention for manufacturing polyurethanes, especially via a one-shot pouring foaming process, are of any type currently used in the art for preparing flexible slab foams, flexible molded foams, semi-flexible foams, and rigid foams. Such polyols are typically liquids at ambient temperature and pressure and include polyether polyols and polyester polyols having a hydroxyl value in the range of about 15 - about 700. The hydroxyl value is preferably between about 20 - about 60 for flexible foams, between about 100 - about 300 for semi-flexible foams, and between about 250 - about 700 for rigid foams.

[0159] For flexible foams, the preferred functionality of the polyol, i.e., the average number of hydroxyl groups per molecule of polyol, is about 2 - about 4 and most preferably about 2.3 - about 3.5. For rigid foams, the preferred functionality is about 2 - about 8 and most preferably about 3 - about 5.

[0160] Among the polyamines different from the compounds according to the present invention and useful in the process of the present invention for manufacturing polyurethanes, diamines such as piperazine, 2,5 - dimethylpiperazine, bis(4 - aminophenyl) ether, 1,3 - phenylenediamine, and hexamethylenediamine are preferred.

[0161] The polyfunctional isocyanate - reactive compounds, either alone or in mixture form as copolymers, useful in the process for manufacturing polyurethanes and / or polyureas in the presence of the catalyst compositions of the present invention include, for example, any of the following non - limiting classes of polyols:

[0162] (a) Polyether polyols obtained by the reaction of polyhydroxyalkanes with one or more alkylene oxides such as ethylene oxide, propylene oxide, etc.

[0163] (b) Polyether polyols obtained by the reaction of high - functionality alcohols, sugar alcohols, sugars, and / or high - functionality amines (if desired, in mixture with low - functionality alcohols and / or amines) with alkylene oxides such as ethylene oxide, propylene oxide, etc.

[0164] (c) Polyether polyols obtained by the reaction of phosphoric acid and polyphosphoric acid with alkylene oxides such as ethylene oxide, propylene oxide, etc.

[0165] (d) Polyether polyols obtained by the reaction of polyaromatic alcohols with alkylene oxides such as ethylene oxide, propylene oxide, etc.

[0166] (e) Polyether polyols obtained by the ring - opening polymerization of tetrahydrofuran.

[0167] (f) Polyether polyols obtained by the reaction of ammonia and / or amines with alkylene oxides such as ethylene oxide, propylene oxide, etc.

[0168] (g) Polyester polyols obtained by the reaction of a polyfunctional initiator such as a diol with a hydroxycarboxylic acid or its lactone such as hydroxycaproic acid or ε-caprolactone;

[0169] (h) Polyoxalurate polyols obtained by the direct reaction of an oxalate ester and a diamine such as hydrazine, ethylenediamine, etc. in a polyether polyol;

[0170] (i) Polyurea polyols obtained by the direct reaction of a diisocyanate and a diamine such as hydrazine, ethylenediamine, etc. in a polyether polyol.

[0171] For flexible foams, the preferred types of alkylene oxide adducts of polyhydroxyalkanes are ethylene oxide and propylene oxide adducts of aliphatic triols such as glycerol, trimethylolpropane, etc. For rigid foams, the preferred classes of alkylene oxide adducts are ethylene oxide and propylene oxide adducts of ammonia, toluenediamine, sucrose, and phenol-formaldehyde-amine resins (Mannich bases).

[0172] Grafted or polymer polyols are widely used in the manufacture of flexible foams and, together with standard polyols, are one of the preferred classes of polyols that can be used in the process of the present invention. Polymer polyols are polyols containing a stable dispersion of a polymer (e.g., in the above polyols a)-e) and more preferably type a) polyols). Other polymer polyols that can be used in the process of the present invention are polyurea polyols and polyoxalurate polyols.

[0173] The polyisocyanates that can be used in the polyurethane foam forming process of the present invention are organic compounds containing at least two isocyanate groups and will generally be any known aromatic or aliphatic polyisocyanates. Suitable organic polyisocyanates include, for example, hydrocarbon diisocyanates (e.g., alkylene diisocyanates and arylene diisocyanates), such as methylene diphenyl diisocyanate (MDI) and 2,4- and 2,6-toluene diisocyanate (TDI), as well as known triisocyanates and polymethylene poly(phenylene isocyanates) also referred to as polymer-type or crude MDI. For flexible and semi-flexible foams, the preferred isocyanates are generally, for example, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI) in weight ratios of about 80% and about 20% and about 65% and about 35% respectively based on the total weight of the TDI composition; mixtures of TDI and polymer-type MDI, preferably in weight ratios of about 80% TDI and about 20% crude polymer-type MDI to about 50% TDI and about 50% crude polymer-type MDI based on the total weight of the mixture composition; and all polyisocyanates of the MDI type. For rigid foams, the preferred isocyanates are, for example, polyisocyanates of the MDI type and preferably crude polymer-type MDI.

[0174] The amount of polyisocyanate included in the formulation is described in terms of the "isocyanate index" relative to the amounts of the other materials in the foam formulation used. The "isocyanate index" means the actual amount of polyisocyanate used divided by the stoichiometric amount of polyisocyanate theoretically required to react with all of the active hydrogens in the reaction mixture, multiplied by one hundred (100) [see Oertel, Polyurethane Handbook, Hanser Publishers, New York, N.Y. (1985)]. The isocyanate index of the reaction mixture used in the process of the present invention is typically between 60 and 140. More typically, the isocyanate index is: for flexible TDI foams, typically between 85 and 120; for molded TDI foams, usually between 90 and 105; for molded MDI foams, most often between 70 and 90; and for rigid MDI foams, usually between 90 and 130. Some examples of polyisocyanurate rigid foams are made at isocyanate indices up to 250 - 400.

[0175] In the polyurethane forming reaction according to the present invention using the compounds of the present invention as catalysts, water is preferably used as the reactive blowing agent in both flexible and rigid foams. In the manufacture of flexible slabstock foams, water can generally be used, for example, at a concentration between 2 - 6.5 parts per hundred parts (pphp) of the polyol blend, and more often between 3.5 - 5.5 pphp of the polyol blend. For TDI molded foams, the level of water typically ranges, for example, from 3 - 4.5 pphp of the polyol blend. For MDI molded foams, the level of water is, for example, more typically between 2.5 and 15 pphp. For rigid foams, the level of water ranges, for example, from 0.5 - 5 pphp of the polyol blend, and more often 0.5 - 2 pphp. Physical blowing agents such as blowing agents based on volatile hydrocarbons or halogenated hydrocarbons and other non-reactive gases can also be used in the manufacture of the polyurethane foams according to the present invention. A significant proportion of the rigid insulating foams manufactured are foamed with volatile hydrocarbons or halogenated hydrocarbons and the preferred blowing agents are hydrochlorofluorocarbons (HCFCs) as well as the volatile hydrocarbons pentane and cyclopentane. In the manufacture of flexible slabstock foams, water is the primary blowing agent; however, other blowing agents can be used as auxiliary blowing agents. For flexible slabstock foams, the preferred auxiliary blowing agents are carbon dioxide and dichloromethane (methylene chloride). Other blowing agents such as chlorofluorocarbons (CFCs) and trichlorofluoromethane (CFC-11) can also be used.

[0176] Flexible molded foams typically do not use inert co - blowing agents and, in any case, introduce fewer co - blowing agents compared to block foams. However, there is significant interest in using carbon dioxide in some molding technologies. MDI - molded foams in Asia and some developing countries use methylene chloride, CFC - 11, and other blowing agents. The amount of blowing agent varies according to the desired foam density and foam hardness, as recognized by those skilled in the art. When used, the amount of hydrocarbon - type blowing agents varies from, for example, trace amounts up to about 50 parts per hundred parts (pphp) of the polyol blend, and CO2 varies from, for example, about 1 to about 10 pphp of the polyol blend.

[0177] Cross - linkers can also be used in the manufacture of polyurethane foams. Cross - linkers are typically small molecules; usually less than 350 molecular weight, which contain hydrogen that is reactive towards reaction with isocyanates. The functionality of the cross - linker is greater than 3 and preferably between 3 and 5. The amount of cross - linker used can vary between about 0.1 pphp and about 20 pphp based on the polyol blend and the amount used is adjusted to achieve the desired foam stabilization or foam hardness. Examples of cross - linkers include glycerol, diethanolamine, triethanolamine, and tetra - hydroxyethyl ethylenediamine.

[0178] Silicone surfactants that can be used in the processes of the present invention include, for example, "hydrolyzable" polysiloxane - polyoxyalkylene block copolymers, "non - hydrolyzable" polysiloxane - polyoxyalkylene block copolymers, cyanoalkyl polysiloxanes, alkyl polysiloxanes, and polydimethylsiloxane oils. The type of silicone surfactant used and the amount required depend on the type of foam being manufactured, as recognized by those skilled in the art. The silicone surfactant can be used as such or dissolved in a solvent such as a glycol. For flexible block foams, the reaction mixture typically contains about 0.1 - about 6 pphp, and more often about 0.7 - about 2.5 pphp of the silicone surfactant. For flexible molded foams, the reaction mixture typically contains about 0.1 - about 5 pphp, and more often about 0.5 - about 2.5 pphp of the silicone surfactant. For rigid foams, the reaction mixture typically contains about 0.1 - about 5 pphp, and more often about 0.5 - about 3.5 pphp of the silicone surfactant. The amount of surfactant used is adjusted to achieve the desired foam cell structure and foam stabilization.

[0179] The temperature that can be used for manufacturing polyurethanes varies depending on the type of foam and the specific process used for manufacturing, as is well understood by those skilled in the art. Flexible slabstock foams are typically manufactured by mixing the reactants at an ambient temperature generally between about 20 °C and about 40 °C. The conveyor belt on which the foam rises and cures is substantially at ambient temperature, which can vary significantly depending on the geographical area where the foam is manufactured and the time of year. Flexible molded foams are typically manufactured by mixing the reactants at a temperature between about 20 °C and about 30 °C, and more often between about 20 °C and about 25 °C. The mixed starting materials are fed into a mold, typically by pouring. The mold is preferably heated to a temperature between about 20 °C and about 70 °C, and more often between about 40 °C and about 65 °C. Spray rigid foam starting materials are mixed and sprayed at ambient temperature. Molded rigid foam starting materials are mixed at a temperature in the range of about 20 °C - about 35 °C. A preferred process for manufacturing flexible slabstock foams, molded foams, and rigid foams according to the present invention is the "one-shot" process in which the starting materials are mixed and reacted in one step.

[0180] Accordingly, in one embodiment of the present invention, which relates to a process for manufacturing an isocyanate addition product according to the present invention, wherein the isocyanate addition product is a polyurethane, preferably a polyurethane foam, which is selected from porous or non-porous polyurethanes, and the process optionally includes a blowing agent. Such a process optionally includes adding a surfactant, a flame retardant, a chain extender, a crosslinking agent, an adhesion promoter, an antistatic additive, a hydrolysis stabilizer, a UV stabilizer, a lubricant, an antimicrobial agent, or any other conventional auxiliary additive used in the manufacture of polyurethanes, or a combination of two or more thereof. Accordingly, in one embodiment of the present invention, it also relates to a foam-forming isocyanate addition product formed by the process for manufacturing an isocyanate addition product as described above using the catalyst composition of the present invention. Such foam-forming isocyanate addition products are, for example, selected from slabstock, molded foam, flexible foam, rigid foam, semi-rigid foam, spray foam, thermoformable foam, footwear foam, open-cell foam, closed-cell foam, and adhesives.

[0181] While the scope of the present invention is defined by the appended claims, the following examples illustrate certain aspects of the present invention and, more specifically, describe the evaluation methods. The examples are presented for illustrative purposes and should not be construed as limiting the present invention. Examples

[0182] Catalyst Formation Example

[0183] First, an 80 wt% aqueous solution of C1 from US 6423756B1 (where C1 is the reaction product of dimethylaminoethoxyethanol and isophorone diisocyanate) was prepared and further used as an amine catalyst mainly having gel properties. The 80% aqueous solution of C1 was named C1.1.

[0184] Inventive Catalyst 1 (or IC1) [reaction product of 2 mol of N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether and 1 mol of isophorone diisocyanate]

[0185] Thus, a four-necked 250 mL round-bottom flask was equipped with a thermometer, a mechanical stirrer, and a reflux condenser. The flask was flushed with dry nitrogen. Under a nitrogen atmosphere, N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether (96.09 g, 0.505 mol) was added to the flask. Isophorone diisocyanate (55.58 g, 0.25 mmol) was added over 30 minutes while the reaction mixture was vigorously stirred and the temperature of the reaction mixture was kept below 80 °C. After the complete addition of isophorone diisocyanate, the reaction mixture was heated at 75 °C for 2.5 hours to give a clear, viscous product. 43.32 g of the product. 13 C and 1 1H NMR data confirmed the formation of Inventive Catalyst 1 (IC1, as shown below as the reaction product). 43.32 g of IC1 was dissolved in 10.83 g of water to obtain an 80 wt% aqueous solution IC1.1, which was used in polyurethane foam manufacture. Additionally, 71.70 g of IC1 was dissolved in 10.43 g of dipropylene glycol to obtain IC1.2, which was used in the polyurethane foaming reaction.

[0186]

[0187] Inventive Catalyst 2 (or IC2) [reaction product of 2 mol of 2-{2-[(3-aminopropyl)(methyl)amino]ethoxy}ethyl)dimethylamine (or N'-[2-[2-(dimethylamino)ethoxy]ethyl]-N'-methyl-propane-1,3-diamine) and 1 mol of isophorone diisocyanate]

[0188]

[0189] In a 10 mL glass vial equipped with a magnetic stirrer, 2.03 g (10 mmol) of 2-{2-[(3-aminopropyl)(methyl)amino]ethoxy}ethyl)dimethylamine was added under a nitrogen atmosphere and the vial was sealed with a septum cap. 1.11 g of isophorone diisocyanate (5.0 mmol) was added dropwise while vigorously stirring the reaction mixture. The mixture was stirred vigorously for ~5 minutes and the vial was placed on a heating block at 75 °C. After 2 hours, the vial was removed from the heating block and cooled to room temperature. A transparent glassy, highly viscous material was obtained. 13 C and 1 1H NMR data confirmed the formation of the inventive catalyst 2 (IC2, shown as the reaction product in the above protocol).

[0190] Foaming experiment:

[0191] Polyurethane foams were prepared according to the following procedure. 4950.00 g of a reactive polyether polyol ( (or HP) 1629; hydroxyl value 29.5 - 33.5 mg KOH / g), 49.50 g of an EO-rich cell opener (Voranol TM CP 1421; hydroxyl value 33 mg KOH / g), 32.67 g of a 90 wt% aqueous solution of diethanolamine (90% DEOA in water), 29.70 g of a silicone stabilizer ( Silicone L-3639S), 148.50 g of water and 39.60 g of a premix P1 of mainly gelling catalyst C1.1 (for the polyurethane foams presented in Table 1) were prepared: The mixture was thoroughly mixed in a plastic bucket using a paddle stirrer with a ring at 800 rpm for 20 minutes. From this premix, multiple single batches each weighing 291.67 g were placed in suitable mixing plastic containers and additional amounts of water and the corresponding catalysts (e.g., C1.1, IC1.1) were added according to the ratios given in Table 1 to obtain the adjusted final polyol blends.

[0192] For the foam systems presented in Table 2, a premix P2 was prepared by thoroughly mixing the mixture in a plastic bucket using a paddle stirrer with a ring at 800 rpm for 20 minutes without adding water and any catalyst. For those foam compositions, after preparing the premix, multiple single batches each weighing 281.22 g were placed in suitable mixing plastic containers. The required amounts of water and the corresponding catalysts (e.g., C1.1, IC1.1) were added according to the ratios given in Table 2 to obtain the final polyol blends.

[0193] To manufacture the foam pads, the polyol blend was thoroughly mixed in a plastic container for 30 seconds at 3000 rpm using a paddle stirrer with a ring. A limited amount of Suprasec 2447 isocyanate (MDI, NCO content 32.6%) was added according to the ratios given in Table 1 or 2 and the reactive mixture was mixed for 4 - 6 seconds. The reactive mixture was immediately poured into a 30×30×10 cm aluminum mold and the mold was immediately closed and clamped. The mold lid had four vent openings with a diameter of 0.4 mm at the four corners. The mold temperature was controlled at 55 °C via a hot water circulation thermostat. The mold was coated with a release agent PU - 1705M. The foam was demolded after 4 minutes. The processing and physical properties of the foam were evaluated as follows:

[0194]

[0195]

[0196] For reactive mixtures 1 - 4 (the composition of the chemical components is given in parts by weight or pbw), a summary of the PU foam composition and PU foam properties is shown in Table 1 below

[0197]

[0198] It was found that adding the inventive catalyst solution IC1.1 to the catalyst solution C1.1 significantly improved the foaming efficiency of the catalyst blend. Thus, the demold time for reactive mixture 1 was 78 seconds, while the demold time for reactive mixture 3 was 60 seconds, although the total weight of the active catalyst was the same (0.80 + 0.25 = 1.05 pbw) in those comparative experiments 1 and 3. In the same way, the comparison of the demold time of experiment 2 (52 seconds) with that of experiment 4 clearly demonstrated the higher foaming efficiency of the inventive catalyst solution IC1.1. Furthermore, it was found that the ILD values of the PU foams prepared by using the inventive catalyst solution IC1.1 tended to be advantageously higher compared to the PU foams manufactured by using only the prior art catalyst solution C1.1. This trend was demonstrated by the comparison of the ILD values of foams 2 and 4 manufactured at a higher catalyst usage level (0.80 + 0.75 = 1.55 pbw). In particular, compared to the PU foam obtained from the reactive mixture 2 in which C1.1 was used as the sole catalyst at a usage level of 1.55 pbw, the catalyst composition of 0.80 pbw C1.1 and 0.75 pbw IC1.1 (reactive mixture 4) provided a PU foam with a higher ILD value.

[0199] A summary of the experiments shown in Table 2 below presents the following comparison: between using only a single catalyst and between the inventive catalyst IC1.1 in solution and the prior art catalyst C1.1 in solution.

[0200]

[0201] * The foam is very soft, sticky and fragile after demolding, indicating incomplete curing, which is also clear from the lower FTC and thermal ILD values. The skin of the foam wrinkles after demolding. Therefore, it is not recommended to use the ILD value of this foam for further demonstration.

[0202] It was found that the foaming efficiency of the inventive catalyst IC1.1 is significantly higher compared to the prior art catalyst C1.1. Therefore, the departure time of the reactive mixture A1 catalyzed by IC1.1 is 83 seconds, while the departure time of the reactive mixture A3 catalyzed by the prior art catalyst C1.1 is significantly longer and is 143 seconds. In addition, compared to the PU foam A1, the foam A3 is very soft, sticky and fragile after demolding, which is clear from the lower FTC and thermal ILD values. The skin of the PU foam A3 wrinkles after demolding, thus confirming incomplete polymerization. In the same way, the comparison of the departure time of experiment A2 (44 seconds) with the departure time of experiment A4 clearly shows the better foaming efficiency of the inventive catalyst IC1. Moreover, in addition to the faster departure time, the beneficial higher thermal ILD and ILD values of the A2 PU foam compared to the A4 PU foam also show the better curing efficiency of the inventive catalyst IC1.1.

[0203] The following TDI-based polyurethane foams were prepared according to the following procedure. 1425.00 g of a reactive polyether polyol ( Polyol 1629; hydroxyl value 29.5 - 33.5 mg KOH / g), 1425.00 g of a styrene-acrylonitrile (SAN) polymer-modified reactive polyether polyol (with 43% SAN content) ( Polyol 1639; hydroxyl value 20 mg KOH / g), 34.20 g of a 90 wt% aqueous solution of diethanolamine (90% DEOA in water), 28.50 g of a silicone stabilizer ( Premix P3 of 85.50 g of Silicone L-3555 and 85.50 g of water: The mixture was thoroughly mixed in a plastic bucket for 20 minutes at 800 rpm using a paddle stirrer with a ring. Multiple single batches each weighing 315.60 g were weighed out from the premix P3 into suitable plastic containers for mixing, and additional amounts of water and the corresponding catalysts (such as C1.1, IC1.1) in solution were added according to the ratios given in Table 3 to obtain the final polyol blend. To manufacture the PU foam pad, the polyol blend was thoroughly mixed in a plastic container for 30 seconds at 3000 rpm using a paddle stirrer with a ring. A limited amount of Scuranate T80 isocyanate (TDI, NCO content 48.1%) was added according to the ratios given in Table 3 and the reactive mixture was mixed for 4 - 6 seconds. The reactive mixture was immediately poured into a 30×30×10 cm aluminum mold and the mold was immediately closed and clamped. The mold cover had 4 ventilation openings with a diameter of 0.4 mm at the four corners. The mold temperature was controlled at 65 °C via a hot water circulation thermostat. The mold was coated with the mold release agent Chem- PU-1705M. The foam was demolded after 5 minutes. The processing and physical properties of the foam were evaluated as described above.

[0204] Table 3 describes the reactive mixtures B1 - B4 of the PU foam composition in pbw and the physical properties of the corresponding PU foams.

[0205]

[0206]

[0207] *After demolding, the foam was very soft, sticky and fragile, indicating incomplete curing, which was also clear from the lower FTC and thermal ILD values. The skin of the foam wrinkled after demolding. Therefore, the ILD value of this foam is not recommended for further demonstration.

[0208] It was found that the foaming efficiency of the invented catalyst IC1.1 is significantly higher compared to the prior art catalyst C1.1. Therefore, the departure time of the reactive mixture B1 catalyzed by IC1.1 is 49 seconds, while the departure time of the reactive mixture B3 catalyzed by the prior art catalyst C1.1 is significantly longer and is 68 seconds. In addition, compared to foam B1, foam B3 is much softer, stickier and more fragile after demolding, which is evident from the lower FTC and thermal ILD values. After demolding, the skin of foam B3 becomes very wrinkled, thus confirming incomplete polymerization. In the same way, the comparison of the departure time of experiment B2 (33 seconds) with the departure time of experiment B4 clearly demonstrates the better foaming efficiency of the invented catalyst. In addition, in addition to the faster departure time, the beneficial trend of higher thermal ILD and ILD values of foam B2 compared to foam B4 also demonstrates the better curing efficiency of the invented catalyst IC1.1.

Claims

1. A compound obtained by reacting isophorone diisocyanate (IPDI) with at least one isocyanate-reactive compound having the formula (I), or a salt thereof, or a mixture thereof: (R) a -X(I) wherein R is selected from R 1 and R 2 , where R 1 selected from R 3 , wherein R 3 represents a hydrocarbyl group comprising at least two tertiary amino groups and at least one ether (-O-) group, R 2 represents a hydrocarbyl group or hydrogen, a is 2 or 3, and X is selected from O, S, or N, Provided that the compound comprises at least one group R 1 and at least one being R 2 and this R 2 is a group R that is hydrogen.

2. The compound according to claim 1, wherein R in the formula (I) of the isocyanate-reactive compound 1 is selected from R 3 , R 3 is selected from saturated aliphatic hydrocarbon-based groups having up to 20 carbon atoms and comprising at least two tertiary amino groups and at least one ether (-O-) group.

3. The compound according to claim 1, wherein R in the formula (I) of the isocyanate-reactive compound 1 is selected from R 3 , R 3 is selected from saturated aliphatic hydrocarbon-based groups having up to 15 carbon atoms and including at least two tertiary amino groups and at least one ether (-O-) group.

4. The compound according to any one of claims 1-3, wherein R in the formula (I) of the isocyanate-reactive compound 1 is selected from R 3 , R 3 is selected from the following formula: wherein the group R 13 is independently selected from divalent linear, branched or cyclic hydrocarbon groups, and two of A, B and C represent tertiary amino groups and one of A, B and C represents an ether group.

5. The compound according to claim 4, wherein two of A, B, and C represent tertiary amino groups, and for A and B, are selected from -N(R 12 )-, and for C, is selected from -N(R 12 )2, wherein R 12 is an organic group.

6. The compound according to claim 5, wherein R 12 is an alkyl group.

7. The compound according to claim 4, wherein one of A, B, and C represents an ether group, wherein for A and B, it is selected from -O-, and for C, it is selected from -OR 12 , wherein R 12 is an organic group.

8. The compound according to any one of claims 1 - 3, wherein R in formula (I) of the isocyanate - reactive compound 1 is selected from R 3 , R 3 is selected from the following formula: wherein x, y, and z are integers from 2 to 6, and two of A, B, C represent tertiary amino groups and one of A, B, C represents an ether group.

9. The compound according to claim 8, wherein x, y, and z are integers of 2 or 3.

10. The compound according to claim 8, wherein two of A, B, and C represent tertiary amino groups, wherein for A and B, selected from -N(R 12 )-, and for C, selected from -N(R 12 )2, wherein R 12 is an organic group.

11. The compound according to claim 10, wherein R 12 is an alkyl group.

12. The compound according to claim 8, wherein one of A, B, and C represents an ether group, wherein for A and B, it is selected from -O-, and for C, it is selected from -OR 12 , wherein R 12 is an organic group.

13. The compound according to any one of claims 1-3, wherein R in the formula (I) of the isocyanate-reactive compound 1 is selected from R 3 and wherein the isocyanate-reactive compound is selected from:

14. The compound according to any one of claims 1-3, wherein R in formula (I) of the isocyanate-reactive compound 1 is selected from R 3 and wherein the isocyanate-reactive compound is selected from:

15. The compound according to any one of claims 1 - 3, wherein the at least one isocyanate-reactive compound having the formula (I) is selected from formula (Ia) and (Ib): R 1 -OH (Ia), R 1 -NH-R 2 (Ib), and R 1 -NH-R 1 (Ic), wherein R 1 selected from R 3 , wherein R 3 denotes a hydrocarbyl group comprising at least two tertiary amino groups and at least one ether (-O-) group, and R 2 represents a hydrocarbon group or hydrogen.

16. The compound according to any one of claims 1 - 3, wherein the isocyanate groups of isophorone diisocyanate react completely or partially with the isocyanate-reactive compound of formula (I).

17. The compound according to claim 16, wherein the isocyanate groups of isophorone diisocyanate react completely with the isocyanate-reactive compound of formula (I).

18. The compound according to any one of claims 1 - 3, which is selected from 19. A process for manufacturing the compound according to any one of claims 1 - 18, the process comprising reacting isophorone diisocyanate and the at least one isocyanate-reactive compound having the formula (I).

20. The process according to claim 19, wherein the reaction is carried out at a temperature of 20 - 140 °C, optionally in the presence of one or more diluents and one or more catalysts.

21. The process according to claim 20, wherein the reaction is carried out at a temperature of 40 - 120 °C, optionally in the presence of one or more diluents and one or more catalysts.

22. The process according to claim 20, wherein the reaction is carried out at a temperature of 60 - 100 °C, optionally in the presence of one or more diluents and one or more catalysts.

23. A composition comprising one or more compounds according to any one of claims 1 - 18, which further comprises at least one diluent.

24. A composition comprising one or more compounds according to any one of claims 1 - 18, which further comprises at least one conventional polyurethane-forming catalyst.

25. The composition according to claim 24, which further comprises at least one conventional polyurethane foam-forming gel catalyst.

26. A composition comprising one or more compounds according to any one of claims 1 - 18, which further comprises at least one carboxylic acid.

27. The composition according to claim 26, wherein the carboxylic acid is selected from monocarboxylic acid compounds, polycarboxylic acid compounds, and hydroxy-functional carboxylic acid compounds.

28. The composition according to claim 27, wherein the polycarboxylic acid compound is a dicarboxylic acid compound.

29. The composition according to any one of claims 26 - 28, which further comprises at least one carboxylic acid selected from the following: salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and citric acid.

30. Use of a compound according to any one of claims 1-18 or a composition according to any one of claims 23-29 as a catalyst.

31. Use according to claim 30, as a catalyst for the reaction of at least one isocyanate compound with at least one isocyanate-reactive compound.

32. Use according to claim 30 or 31, as a catalyst for the production of polyisocyanate addition products.

33. Use according to claim 30 or 31, wherein the polyisocyanate addition product has one or more functional groups consisting of groups selected from urethane groups and urea groups.

34. Use according to claim 30 or 31, as a catalyst for the production of polyurethanes.

35. Use according to claim 34, as a catalyst for the production of polyurethane foams.

36. Use according to claim 30 or 31, as a catalyst for foaming in the production of polyurethane foams.

37. A catalyst comprising a compound according to any one of claims 1-18 or a composition according to any one of claims 23-29.

38. The catalyst according to claim 37, which comprises one or more additional catalysts for the production of polyisocyanate addition products.

39. A process for producing an isocyanate addition product, which comprises reacting an isocyanate compound with an isocyanate-reactive compound in the presence of a compound according to any one of claims 1-18 or a composition according to any one of claims 23-29.

40. A process for producing an isocyanate addition product, which comprises reacting an isocyanate compound with an isocyanate-reactive compound in the presence of a compound according to any one of claims 1-18 or a composition according to any one of claims 23-29 and in the presence of water.

41. The process for producing an isocyanate addition product according to claim 40, wherein the isocyanate is a polyisocyanate and the isocyanate-reactive compound is a polyol, and the process is for the production of polyurethanes.

42. The process for producing an isocyanate addition product according to claim 41, wherein the process is for the production of polyurethane foams.

43. The process for producing an isocyanate addition product according to claim 39 or 40, wherein the isocyanate addition product is a polyurethane selected from porous or non-porous polyurethanes, and the process optionally comprises a blowing agent.

44. The process for producing an isocyanate addition product according to claim 43, wherein the isocyanate addition product is a polyurethane foam.

45. The process for producing an isocyanate addition product according to claim 43, wherein the blowing agent is water.

46. A process for manufacturing an isocyanate addition product according to claim 39 or 40, wherein the process is for manufacturing a polyurethane, and the process optionally includes adding a surfactant, a flame retardant, a chain extender, a crosslinking agent, an adhesion promoter, an antistatic additive, a hydrolysis stabilizer, a UV stabilizer, a lubricant, an antimicrobial agent, or a combination of two or more thereof.

47. A process for manufacturing an isocyanate addition product according to claim 39 or 40, wherein the compound according to any one of claims 1-18 or the composition according to any one of claims 23-29 is present in an amount of 0.005 wt% - 5 wt%, based on the total weight of the entire composition including all components.

48. An isocyanate addition product that forms a foam, which can be obtained by the process for manufacturing an isocyanate addition product according to any one of claims 39-47.

49. The isocyanate addition product that forms a foam according to claim 48, which is selected from block foam, molded foam, flexible foam, rigid foam, semi-rigid foam, spray foam, thermoformable foam, microcellular foam, footwear foam, open-cell foam, closed-cell foam, adhesives.

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