Reactive compositions for polyurethane foams and their use in automotive parts

Abstract

The present invention relates to reactive compositions, semi-rigid polyurethane foams obtained therefrom, filled cavities, and their use in automotive parts.

Description

Technical Field

[0001] The present invention relates to reactive compositions, semi-rigid polyurethane foams obtained therefrom, filled cavities, and their use in automotive parts.

Background Art

[0002] Polyurethane cavity filling foams, especially those having a low density, are suitable for suppressing noise transmission through the vehicle body structure of automobiles instead of inserted baffles because they offer advantages in terms of cost and performance. However, concerns about exposure are recognized in relation to the release of isocyanate (MDI) from the foaming reaction to workers in automotive assembly areas. Many attempts to reduce isocyanate release in MDI have aimed to reduce the monomer content by forming an NCO-terminated prepolymer of MDI containing isocyanate-reactive components.

[0003] EP1679327(A1) describes a flexible PU foam, a sheet pad containing the PU foam, and a sound-absorbing material. This specification measures the sound-absorbing performance of the PU foam according to ISO10534-2. The sound-absorbing value measures the ability to reduce reverberation in an environment where the surface reflects sound. In fact, the sound-absorbing coefficient is a dimensionless ratio of the acoustic energy absorbed by a given surface to the acoustic energy incident on that surface. The PU foam described in this specification is based on toluene diisocyanate and contains an isomer mixture of 2,4- and 2,6-isomers, and the molding time is as long as 6 minutes.

[0004] US5,817,860A describes a polyisocyanate prepolymer composition containing a reaction product of an organic polyisocyanate, a monohydric alcohol, and a polyol. The monomer isocyanate content in the prepolymer composition was 10% by weight. A foam having a free rise density of 35.24 kg / m 3 was obtained from the prepolymer composition at a volume mixing ratio of 24:1.

[0005] Another US8,455,679(B2) describes a prepolymer system having a monomer isocyanate content of 10 wt% or less of the prepolymer system. The prepolymer system includes a diluent component obtained as a reaction product of a monohydric isocyanate-reactive component and an isocyanate component, and a prepolymer component different from the diluent component. Maintaining a volume mixing ratio of 24:1, about 35.24 kg / m 3 of density foam was obtained.

[0006] Existing polyurethane (PU) foams for NVH (noise, vibration, and harshness), also called NVH foams, exhibit a reduction in isocyanate emissions. However, these NVH foams result in an increase in amine emissions and are obtained at high mixing ratios and process temperatures. Furthermore, the polyol components of these NVH foams have storage stability problems, making the resulting foams dimensionally unstable. In the current situation, storage stability is indicated by chemical stability and phase stability.

[0007] The B-side component containing a self-catalytic polyol such as those described in WO2018 / 136258 provides stability in the foam but exhibits a high mixing ratio and thus results in a high-density foam.

[0008] Accordingly, an object of the present invention is to provide a reactive composition containing an isocyanate-reactive component or a B-side component that provides a stable, low-density semi-rigid polyurethane foam having acceptable isocyanate and amine emission levels, is processable at low mixing ratios and low temperatures, and is thereby suitable for cost-effective automotive applications. SUMMARY OF THE INVENTION

[0009] Surprisingly, it has been found that the above object is achieved by providing a reactive composition comprising an isocyanate component containing methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and an isocyanate-reactive component comprising a blend of a self-catalytic polyol having a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, another polyol having a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, a crosslinking agent, an amine catalyst, a surfactant and water.

[0010] Accordingly, in one aspect, the present invention relates to a reactive composition for producing a semi-rigid polyurethane foam, the composition comprising (A) an isocyanate component containing methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and (B) an isocyanate-reactive component comprising (a) 20% to 75% by weight of at least one self-catalytic polyol having an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, (b) 10% to 90% by weight of at least one polyol having an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, (c) 0.1% to 5.0% by weight of at least one crosslinking agent, (d) 0.01% to 5.0% by weight of at least one amine catalyst, (e) 0.1% to 5.0% by weight of at least one surfactant, and (f) 1.0% to 15.0% by weight of water, wherein the percentages by weight are based on the total weight of the isocyanate-reactive component and include the isocyanate-reactive component. Weight percentages are based on the total weight of the isocyanate-reactive component and include the isocyanate-reactive component.

[0011] In another aspect, the present invention relates to a process for preparing a semi-rigid polyurethane foam, the process comprising (S1) mixing the above reactive composition, and (S2) Curing the reactive composition to obtain a polyurethane foam having a foam density of less than 40 kg / m as determined according to ASTM D1622, 3 and obtaining a polyurethane foam having a foam density of less than 40 kg / m as determined according to ASTM D1622, The reactive composition has a tack-free time of less than 15 seconds.

[0012] In yet another aspect, the present invention relates to the above semi-rigid polyurethane foam.

[0013] In yet another aspect, the present invention relates to a process for filling a cavity, the process comprising: (M1) Injecting the above reactive composition into a cavity defined by at least two sides; (M2) Curing the reactive composition such that the reactive composition expands to connect the sides of the cavity.

[0014] In yet another aspect, the present invention relates to a filled cavity obtained by the above process.

[0015] In another aspect, the present invention relates to a molded article comprising the above filled cavity.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] Before describing the compositions and formulations of the present invention, it should be understood that since such compositions and formulations can of course vary, the present invention is not limited to the specific compositions and formulations described. It should also be understood that the terms used herein are not intended to be limiting, as the scope of the present invention is limited only by the appended claims.

[0017] As used herein, the terms "comprising", "comprises", and "comprised of" are synonymous with "including", "includes", or "containing", "contains", are inclusive or open-ended, and do not exclude additional, unrecited members, elements, or method steps. It will be understood that the terms "comprising", "comprises", and "comprised of" as used herein include the terms "consisting of", "consists of", and "consisting of".

[0018] Furthermore, the terms "first", "second", "third", or "a", "b", "c", "d", etc. and the like in the description and claims are used to distinguish between similar elements and do not necessarily describe a sequential or chronological order. Such terms are interchangeable under appropriate circumstances, and it should be understood that the embodiments of the invention described herein can be practiced in an order other than that described or illustrated herein. In the case of the terms "first", "second", "third", or "(A)", "(B)", and "(C)", or "(a)", "(b)", "(c)", "(d)", "i", "ii", etc. related to method or use or analysis steps, there is no consistency of time or time interval between the steps, that is, the steps are executed simultaneously or there may be a time interval of seconds, minutes, hours, days, weeks, months, or years between such steps unless specifically indicated in the context as described above or below in this specification.

[0019] In the following sections, various aspects of the present invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects, unless the contrary is clearly indicated. In particular, any feature shown as being preferred or advantageous may be combined with any other feature or features shown as being preferred or advantageous.

[0020] References throughout this specification to "an embodiment" or "embodiment" mean that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "in an embodiment" or "an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, although they may. Further, in one or more embodiments, as will be apparent to those skilled in the art from this disclosure, the particular features, structures, or characteristics may be combined in any suitable manner. Additionally, although some embodiments described herein include some features but not other features included in other embodiments, combinations of features of different embodiments are intended to be within the scope of the present invention and to form different embodiments as will be understood by those skilled in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

[0021] Further, ranges defined throughout the specification include the end values, i.e., a range of 1 to 10 means both 1 and 10 are included in the range. To avoid misunderstanding, Applicant hereby states that, to the extent applicable law allows, Applicant reserves the right to any equivalents.

[0022] One aspect of the present invention is Embodiment 1 relating to a reactive composition for producing a semi-rigid polyurethane foam, the composition comprising (A) an isocyanate component comprising methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and (B) an isocyanate-reactive component, wherein (a) At least one self-catalytic polyol of 20 wt% to 75 wt% having an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, (b) At least one polyol of 10 wt% to 90 wt% having an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, (c) At least one crosslinking agent of 0.1 wt% to 5.0 wt%, (d) At least one amine catalyst of 0.01 wt% to 5.0 wt%, (e) At least one surfactant of 0.1 wt% to 5.0 wt%, and (f) 1.0 wt% to 15.0 wt% of water, containing, wt% is based on the total weight of the isocyanate-reactive components, including the isocyanate-reactive components and.

[0023] In this context, a semi-rigid polyurethane (or PU) foam is characterized by a foam density of less than 40 kg / m 3 determined according to ASTM D1622.

[0024] In one embodiment, the isocyanate-reactive component (B) and the isocyanate component (A) in Embodiment 1 are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.0. In this context, the weight ratio (B):(A) can alternatively be referred to as the mixing ratio or mixing ratio. In another embodiment, the weight ratio (B):(A) in Embodiment 1 is 1.0:2.0 to 2.0:1.0, or 1.0:2.0 to 1.0:1.0. In yet another embodiment, the weight ratio (B):(A) in Embodiment 1 is 0.8:1.0 to 1.0:1.0. The weight ratio is determined as the ratio of the total of the self-catalytic polyol (a), polyol (b), crosslinking agent (c), amine catalyst (d) and surfactant (e) in the isocyanate-reactive component (B) to the isocyanate in the isocyanate component (A).

[0025] In another embodiment, the isocyanate-reactive component (B) and the isocyanate component (A) in Embodiment 1 are present at a volume mixing ratio (B):(A) of 1.0:3.0 to 3.0:1.0. The volume mixing ratio is determined as the ratio of the isocyanate-reactive component (B) to the isocyanate component (A). In one embodiment, the volume mixing ratio is 1.0:2.0 to 2.0:1.0. In another embodiment, it is 1.0:1.0.

[0026] In one embodiment, the isocyanate component (A) and the isocyanate-reactive component (B) in the embodiment are present at an index of 40 to 200. In another embodiment, the index is 40 to 180, or 40 to 160. In yet another embodiment, the index is 40 to 150, or 45 to 150, or 45 to 140. In yet another embodiment, the index is 45 to 130, or 50 to 130, or 50 to 120, or 50 to 110. The isocyanate index represents the molar ratio of the NCO groups to the isocyanate-reactive groups. An index of 100 is related to a 1:1 ratio.

[0027] In this context, the isocyanate component (A) may alternatively be referred to as the A-side component, while the isocyanate-reactive component (B) may also be referred to as the B-side component.

[0028] Isocyanate component (A) In one embodiment, the isocyanate component (A) in Embodiment 1 includes an aromatic isocyanate or an aliphatic isocyanate. It should be understood that the isocyanate includes both monomeric and polymeric forms of aliphatic or aromatic isocyanates. The term "polymer" refers, independently of each other, to polymer grades of aliphatic or aromatic isocyanates containing different oligomers and homologues.

[0029] In one embodiment, the aliphatic isocyanate is selected from tetramethylene 1,4 - diisocyanate, pentamethylene 1,5 - diisocyanate, hexamethylene 1,6 - diisocyanate, decamethylene diisocyanate, 1,12 - dodecane diisocyanate, 2,2,4 - trimethyl - hexamethylene diisocyanate, 2,4,4 - trimethyl - hexamethylene diisocyanate, 2 - methyl - 1,5 - pentamethylene diisocyanate, cyclobutane - 1,3 - diisocyanate, 1,2 -, 1,3 - and 1,4 - cyclohexane diisocyanate, 2,4 - and 2,6 - methylcyclohexane diisocyanate, 4,4’ - and 2,4’ - dicyclohexyl diisocyanate, 1,3,5 - cyclohexane triisocyanate, isocyanatomethylcyclohexane isocyanate, isocyanatoethylcyclohexane isocyanate, bis(isocyanatomethyl) - cyclohexane diisocyanate, 4,4’ - diisocyanate dicyclohexylmethane, pentamethylene 1,5 - diisocyanate, isophorone diisocyanate and mixtures thereof.

[0030] In one embodiment, the isocyanate component (A) in Embodiment 1 contains an aromatic isocyanate. In another embodiment, the isocyanate component (A) in Embodiment 1 consists of only an aromatic isocyanate.

[0031] Suitable aromatic isocyanates are selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate, 1-methyl-3,5-diethylphenylene-2,4-diisocyanate, 1,3,5-triethylphenylene-2,4-diisocyanate, 1,3,5-triisopropylphenylene-2,4-diisocyanate, 3,3′-diethyl-bisphenyl-4,4′-diisocyanate, 3,5,3′,5′-tetraethyl-diphenylmethane-4,4′-diisocyanate, 3,5,3′,5′-tetraisopropyldiphenylmethane-4,4′-diisocyanate, 1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate, 1,3,5-triethylbenzene-2,4,6-triisocyanate, 1-ethyl-3,5-diisopropylbenzene-2,4,6-triisocyanate, tolidine diisocyanate and 1,3,5-triisopropylbenzene-2,4,6-triisocyanate.

[0032] In another embodiment, the aromatic isocyanate is selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate, 1-methyl-3,5-diethylphenylene-2,4-diisocyanate. In yet another embodiment, the aromatic isocyanate is selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate. In yet another embodiment, the aromatic isocyanate is selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate. In a further embodiment, the isocyanate comprises methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate.

[0033] Methylene diphenyl diisocyanate is available as three different isomers, namely 2,2'-methylene diphenyl diisocyanate (2,2'-MDI), 2,4'-methylene diphenyl diisocyanate (2,4'-MDI) and 4,4'-methylene diphenyl diisocyanate (4,4'-MDI). Methylene diphenyl diisocyanate can be classified into monomeric methylene diphenyl diisocyanate and polymeric methylene diphenyl diisocyanate called industrial methylene diphenyl diisocyanate. The polymeric methylene diphenyl diisocyanate contains oligomeric species and methylene diphenyl diisocyanate isomers. Therefore, the polymeric methylene diphenyl diisocyanate may contain a single methylene diphenyl diisocyanate isomer or a mixture of isomers of two or three methylene diphenyl diisocyanate isomers, and the balance is oligomeric species. The polymeric methylene diphenyl diisocyanate tends to have an isocyanate functionality exceeding 2.0. The isomer ratio and the amount of oligomeric species can be varied widely in these products. For example, the polymeric methylene diphenyl diisocyanate may typically contain 30% to 80% by weight of methylene diphenyl diisocyanate isomers, and the balance is the oligomeric species. The methylene diphenyl diisocyanate isomers are often a mixture of 4,4'-methylene diphenyl diisocyanate, 2,4'-methylene diphenyl diisocyanate and a very low level of 2,2'-methylene diphenyl diisocyanate.

[0034] In one embodiment, there is no isocyanate other than methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate in the isocyanate component (A) in Embodiment 1.

[0035] In yet another embodiment, the isocyanate component (A) in Embodiment 1 includes, as described above, polymeric methylene diphenyl diisocyanate. For example, but not limited to, commercially available isocyanates available under trade names such as Lupranat® by BASF can also be used for the purposes of the present invention.

[0036] Isocyanate-reactive component (B) In one embodiment, the isocyanate-reactive component (B) in Embodiment 1 is (a) 20 wt% to 75 wt% of at least one self-catalytic polyol having an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, (b) 10 wt% to 90 wt% of at least one polyol having an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, (c) 0.1 wt% to 5.0 wt% of at least one crosslinking agent, (d) 0.01 wt% to 5.0 wt% of at least one amine catalyst, (e) 0.1 wt% to 5.0 wt% of at least one surfactant, and (f) 1.0 wt% to 15.0 wt% of water, and wt% is based on the total weight of the isocyanate-reactive component.

[0037] Self-catalytic polyol (a) In this context, a self-catalytic polyol is a polyol having self-catalytic activity. These polyols having intrinsic catalytic activity are chemically incorporated into the polyurethane (PU) structure. As a direct result, the amount of amine required as a catalyst is significantly reduced, and naturally, the release of amine is also significantly reduced. Self-catalytic polyols provide a fast gelation time.

[0038] In one embodiment, the self-catalytic polyol (a) in Embodiment 1 is a polyether polyol obtained by reacting an amine-containing starter molecule and an alkylene oxide. Suitable amine-containing starter molecules are 3,3'-diamino-N-methyldipropylamine, 2,2'-diamino-N-methyldiethylamine, 2,3-diamino-N-methyl-ethylpropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 3,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine.

[0039] In another embodiment, the amine-containing starter molecule is selected from 1,3-phenylenediamine, 1,4-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 3,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine. In yet another embodiment, it is selected from 2,4-toluenediamine, 3,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine. In yet another embodiment, it is selected from 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine. In a further embodiment, the amine-containing starter molecule comprises ethanolamine.

[0040] In one embodiment, the alkylene oxide is selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, isomers, and mixtures thereof. In another embodiment, it is selected from ethylene oxide and propylene oxide.

[0041] The amount of the autocatalytic polyol (a) depends on the desired reactivity profile required. In one embodiment, the autocatalytic polyol (a) in Embodiment 1 is present in an amount of 25% to 75% by weight based on the total weight of the isocyanate-reactive component (B). In another embodiment, it is present in an amount of 25% to 70% by weight, or 30% to 70% by weight, or 30% to 65% by weight. In yet another embodiment, it is present in an amount of 32% to 65% by weight, or 32% to 60% by weight, or 35% to 60% by weight, or 35% to 55% by weight, or 38% to 55% by weight. In a further embodiment, it is present in an amount of 38% to 50% by weight, or 40% to 50% by weight.

[0042] Polyol (b) The isocyanate-reactive component (B) also includes a polyol (b) different from the autocatalytic polyol (a). In one embodiment, the average functionality is 2.2 to 5.0, and the hydroxyl value is 20 mg KOH / g to 100 mg KOH / g. In another embodiment, the average functionality is 2.4 to 3.2, and the hydroxyl value is 25 mg KOH / g to 50 mg KOH / g.

[0043] The presence of the polyol (b) together with the autocatalytic polyol (a) in the reactive composition provides a fast gelling time along with the softness and flexibility of the PU foam.

[0044] In one embodiment, the polyol (b) in Embodiment 1 is selected from polyester polyols, polyether polyols, and polyether ester polyols. In other words, the polyol (b) in Embodiment 1 consists of at least one selected from polyester polyols, polyether polyols, and polyether ester polyols.

[0045] In another embodiment, other polyols, except those selected from polyester polyols, polyether polyols, and polyether ester polyols, do not exist as the polyol (b) in Embodiment 1.

[0046] Suitable polyether polyols can be obtained by anionic polymerization using known methods, for example, using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide as a catalyst and adding at least one amine-containing starter molecule, or by cationic polymerization using a Lewis acid such as antimony pentachloride, boron trifluoride etherate, or fuller's earth as a catalyst and one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety.

[0047] The starter molecules of the polyether polyol include amine-containing starter molecules and hydroxyl-containing starter molecules. Suitable amine-containing starter molecules include, for example, aliphatic and aromatic diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, phenylenediamine, toluenediamine, diaminodiphenylmethane and their isomers.

[0048] Other suitable starter molecules further include alkanolamines such as ethanolamine, N-methylethanolamine and N-ethylethanolamine, dialkanolamines such as diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, and trialkanolamines such as triethanolamine, and ammonia.

[0049] In one embodiment, the amine-containing starter molecule is selected from ethylenediamine, phenylenediamine, toluenediamine and their isomers. In other embodiments, the amine-containing starter molecule includes ethylenediamine.

[0050] The hydroxyl-containing starter molecule is selected from sugars, sugar alcohols such as glucose, mannitol, sucrose, pentaerythritol, sorbitol, polyphenols, resols, oligomeric condensation products formed from, for example, phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol, and their condensation products such as polyethylene glycol and polypropylene glycol, for example, diethylene glycol, triethylene glycol, dipropylene glycol, and water or combinations thereof.

[0051] In one embodiment, the hydroxyl-containing starter molecule is selected from sugars and sugar alcohols such as sucrose, sorbitol, glycerol, pentaerythritol, trimethylolpropane, and mixtures thereof. In another embodiment, the hydroxyl-containing starter molecule is selected from sucrose, glycerol, pentaerythritol, and trimethylolpropane. In yet another embodiment, the hydroxyl-containing starter molecule comprises glycerol.

[0052] Suitable alkylene oxides having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide. The alkylene oxides can be used alone, continuously in alternation, or as a mixture. In one embodiment, the alkylene oxide is propylene oxide and / or ethylene oxide. In other embodiments, the alkylene oxide is a mixture of ethylene oxide and propylene oxide containing more than 50% by weight of propylene oxide.

[0053] In one embodiment, the polyol (b) in Embodiment 1 comprises a polyether polyol based on glycerol having terminal capping with ethylene oxide and propylene oxide, and has an average functionality of 3.0 and a hydroxyl value of 27 mg KOH / g.

[0054] The polyester polyol according to the present invention is based on the reaction product of a carboxylic acid or anhydride and a hydroxyl group-containing compound. Suitable carboxylic acids or anhydrides have 2 to 20 carbon atoms, or 4 to 18 carbon atoms, for example, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, oleic acid, phthalic anhydride. In particular, it contains phthalic acid, isophthalic acid, terephthalic acid, oleic acid and phthalic anhydride or combinations thereof.

[0055] Suitable hydroxyl-containing compounds are selected from ethanol, ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,4-glycol, butylene-2,3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-propane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methylglycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyethylene-propylene glycol, dibutylene glycol and polybutylene glycol.

[0056] Suitable polyether ester polyols are obtainable as the reaction product of i) at least one hydroxyl-containing starter molecule, ii) one or more fatty acids, fatty acid monoesters or mixtures thereof, and iii) one or more alkylene oxides having 2 to 4 carbon atoms.

[0057] The starter molecules of component (i) are generally selected such that the average functionality of component (i) is from 2.2 to 5.0. Optionally, a mixture of suitable starter molecules can be used.

[0058] In one embodiment, the hydroxyl-containing starter molecules of component (i) are selected from sugars, sugar alcohols (glucose, mannitol, sucrose, pentaerythritol, sorbitol), polyphenols, resols, for example, oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol, and their condensation products such as polyethylene glycol and polypropylene glycol, for example, diethylene glycol, triethylene glycol, dipropylene glycol, water and mixtures thereof. In other embodiments, the hydroxyl-containing starter molecules of component (i) are selected from sugars and sugar alcohols, for example, sucrose and sorbitol, glycerol, and mixtures of said sugars and / or sugar alcohols with glycerol, water and / or glycols, for example, diethylene glycol and / or dipropylene glycol.

[0059] The fatty acid or fatty acid monoester (ii) is selected from polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, hydroxyl-modified fatty acids, and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, stearic acid, palmitic acid, vaccenic acid, petroselinic acid, gadleic acid, erucic acid, nervonic acid, linoleic acid, α- and γ-linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodonic acid, cervonic acid and mixtures thereof. The fatty acid can be used as a pure fatty acid. In this regard, it is preferred to use fatty acid methyl esters such as, for example, biodiesel or methyl oleate.

[0060] Biodiesel should be understood to mean fatty acid methyl esters within the scope of the meaning of the EN14214 standard of 2010. The main components of biodiesel generally produced from rapeseed oil, soybean oil or palm oil are saturated C 16 -C 18 methyl esters of fatty acids and methyl esters of mono-unsaturated or poly-unsaturated C 18 fatty acids such as oleic acid, linoleic acid and linolenic acid.

[0061] Suitable alkylene oxides (iii) having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3-butylene oxide and / or styrene oxide. The alkylene oxides can be used alone, continuously alternately, or as a mixture.

[0062] In one embodiment, the polyol (b) in Embodiment 1 is present in an amount of 10% to 90% by weight, based on the total weight of the isocyanate-reactive component (B). In another embodiment, it is present at 10% to 85% by weight, or 15% to 85% by weight, or 15% to 80% by weight, or 20% to 80% by weight. In yet another embodiment, it is present at 20% to 75% by weight, or 25% to 75% by weight, or 25% to 70% by weight, or 30% to 70% by weight, or 30% to 65% by weight. In yet another embodiment, it is present at 32% to 65% by weight, or 32% to 60% by weight, or 35% to 60% by weight, or 35% to 55% by weight, or 38% to 55% by weight. In a further embodiment, it is present at 38% to 50% by weight, or 40% to 50% by weight.

[0063] Crosslinking agent (c) In one embodiment, the crosslinking agent (c) in Embodiment 1 includes a compound containing at least two isocyanate-reactive groups and having a molecular weight of 30 g / mol to 150 g / mol. In another embodiment, the crosslinking agent has a molecular weight of 30 g / mol to 125 g / mol, or 30 g / mol to 75 g / mol.

[0064] In another embodiment, the crosslinking agent (c) in Embodiment 1 is selected from monoethanolamine, diethanolamine, triethanolamine, glycerin, trimethylolpropane, and pentaerythritol. In yet another embodiment, the crosslinking agent (c) in Embodiment 1 includes diethanolamine.

[0065] In one embodiment, the crosslinking agent (c) in Embodiment 1 is present in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B). In another embodiment, it is present at 0.2 wt% to 5.0 wt%, or 0.2 wt% to 4.5 wt%, or 0.2 wt% to 4.0 wt%. In yet another embodiment, it is present at 0.3 wt% to 4.0 wt%, or 0.3 wt% to 3.5 wt%, or 0.4 wt% to 3.5 wt%. In yet another embodiment, it is present at 0.4 wt% to 3.0 wt%, 0.4 wt% to 2.5 wt%, or 0.5 wt% to 2.5 wt%.

[0066] Amine catalyst (d) In one embodiment, the amine catalyst (d) in Embodiment 1 is a tertiary amine. In addition to the self-catalytic polyol (a), the presence of a tertiary amine catalyst results in an overall increase in the foam formation reaction. Thus, the reactive composition of Embodiment 1 provides an increase in the rate of PU foam formation, which is dimensionally stable. The term "dimensional stability" refers to the physical stability of the PU foam. In other words, the PU foam shows very minor changes (volume change of less than 1.5%) or no change when exposed to test conditions.

[0067] In another embodiment, the amine catalyst (d) in Embodiment 1 is selected from trimethylamine, triethylamine, dimethylethanolamine, N-methylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N′,N′-tetramethylene-1,4-butanediamine, N,N-dimethylpiperazine, bis(dimethylaminoethyl)ether, bis(2-dimethylaminoethyl)ether, morpholine, 4,4’-(oxydi-2,1-ethanediyl)bis, triethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, N-acetyl-N,N-dimethylamine, N-coco-morpholine, N,N-dimethylaminomethyl-N-methylethanolamine, N,N,N’-trimethyl-N’-hydroxyethylbis(aminoethyl)ether, N,N-bis(3-dimethyl-aminopropyl)N-isopropanolamine, (N,N-dimethyl)amino-ethoxyethanol, N,N,N’,N’-tetramethylhexanediamine, 1,8-diazabicyclo-5,4,0-undecene-7, N,N-dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopropyldipropanolamine, bis(dimethylaminopropyl)amino-2-propanol, tetramethylaminobis(propylamine), (dimethyl(aminoethoxyethyl))((dimethylamine)ethyl)ether, tris(dimethylaminopropyl)amine, dicyclohexylmethylamine, bis(N,N-dimethyl-3-aminopropyl)amine, and 1,2-ethylenepiperidine and methyl-hydroxyethylpiperazine, 1,4-diazabicyclo[2.2.2]octane-2-methanol and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine.

[0068] In another embodiment, the amine catalyst (d) in Embodiment 1 is selected from N,N,N'-trimethyl-N'-hydroxyethylbis(aminoethyl)ether, N,N-bis(3-dimethylaminopropyl)N-isopropanolamine, (N,N-dimethyl)amino-ethoxyethanol, N,N,N',N'-tetramethylhexanediamine, 1,8-diazabicyclo-5,4,0-undecene-7, N,N-dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopropyldipropanolamine, bis(dimethylaminopropyl)amino-2-propanol, tetramethylaminobis(propylamine), (dimethyl(aminoethoxyethyl))((dimethylamine)ethyl)ether, tris(dimethylaminopropyl)amine, dicyclohexylmethylamine, bis(N,N-dimethyl-3-aminopropyl)amine, and 1,2-ethylenepiperidine and methyl-hydroxyethylpiperazine, 1,4-diazabicyclo[2.2.2]octane-2-methanol and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine.

[0069] In yet another embodiment, the amine catalyst (d) in Embodiment 1 is selected from N,N,N'-trimethyl-N'-hydroxyethylbis(aminoethyl)ether, N,N-bis(3-dimethylaminopropyl)N-isopropanolamine, 1,4-diazabicyclo[2.2.2]octane-2-methanol and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine. In another embodiment, mixtures of these amine catalysts (d) can also be used.

[0070] In one embodiment, the amine catalyst (d) in Embodiment 1 is present in an amount of 0.01 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B). In the case of a mixture, each of the amine catalysts described herein is present in an amount of 0.01 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B).

[0071] Surfactant (e) In this context, the surfactant (e) does not contain any reactive functional groups with respect to NCO. In other words, the surfactant (e) does not contain free hydroxyl groups.

[0072] In one embodiment, the surfactant (e) in Embodiment 1 is a nonionic surfactant. In another embodiment, the nonionic surfactant includes polyether polysiloxane and / or polyether siloxane.

[0073] In another embodiment, the polyether polysiloxane has the general formula (I)

Chemical formula

[0074] As used herein, the term "alkyl" refers to an acyclic saturated aliphatic group containing a straight-chain or branched-chain alkyl saturated hydrocarbon radical represented by the general formula C p H 2p+1 wherein p represents the number of carbon atoms such as 1, 2, 3, 4, etc.

[0075] In one embodiment, alkyl refers to an unsubstituted, straight-chain or branched-chain C1-C 30 alkyl group. Unsubstituted straight-chain C1-C 30 alkyl includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl. In another embodiment, it is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.

[0076] The term "alkenyl" refers to an unsubstituted straight-chain acyclic unsaturated aliphatic group containing a straight-chain alkenyl unsaturated hydrocarbon radical represented by the general formula C p H 2p-1 wherein p represents the number of carbon atoms such as 1, 2, 3, 4, etc.

[0077] In one embodiment, the alkenyl is selected from unsubstituted linear C2-C of 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 1-nonadecenyl, 2-nonadecenyl, 1-eicosenyl, 2-eicosenyl, 2-henicosenyl, 2-docosenyl, 2-tricosenyl, 2-tetracosenyl, 2-pentacosenyl, 2-hexacosenyl, 2-octacosenyl, 2-nonacosenyl and 2-triacontenyl. 30 refers to alkenyl. In another embodiment, it is selected from 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl and 1-octadecenyl. In another embodiment, it is selected from unsubstituted linear C2-C of 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecenyl and 2-pentadecenyl. 30Alkenyl. In yet another embodiment, an unsubstituted straight-chain C2-C selected from 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl and 2-heptenyl 30 Alkenyl.

[0078] The term "cycloalkyl" refers to an unsubstituted or branched C3-C having a monocyclic or bicyclic 3- to 10-membered saturated alicyclic radical 10 Referring to cycloalkyl. Unsubstituted or branched C3-C 10 Cycloalkyl is a monocyclic or bicyclic C3-C 10 Compound. Unsubstituted or branched C3-C 10 Representative examples of monocyclic and bicyclic cycloalkyls are selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl and bicyclo[3.1.1]heptyl. C3-C 10 Monocyclic and bicyclic cycloalkyls may be further branched with one or more of the same or different alkyl groups as described above. Branched C3-C 10 Representative examples of monocyclic and bicyclic cycloalkyls include, but are not limited to, methylcyclohexyl, dimethylcyclohexyl, etc.

[0079] The term "aryl" preferably refers to a monocyclic, bicyclic or tricyclic hydrocarbon ring system having 6 to 14 carbon atoms, at least one carbon ring having a 4p + 2π electron system, where "p" is the number of aromatic rings. The aryl moiety may be unsubstituted, monosubstituted, or polysubstituted with the same or different groups. Examples of the aryl moiety include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl or anthracenyl.

[0080] The term "heteroaryl" refers to an aromatic monocyclic, bicyclic or tricyclic hydrocarbon having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms, or 5, 6, 9 or 10 atoms, wherein 1 to 4 carbon atoms are replaced by the same or different heteroatoms including oxygen, sulfur and nitrogen. The heteroaryl moiety may independently contain 1, 2, 3, 4 or 5, or 1, 2, or 3 heteroatoms selected from oxygen, sulfur and nitrogen. The heteroaryl moiety may be unsubstituted or mono-substituted, or multiply-substituted with the same or different substituents. Representative examples of suitable heteroaryl moieties are selected from furyl, pyridyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidinyl, pyrrolyl, isoxazolyl, triazolyl, tetrazolyl, pyridazinyl, isothiazolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, quinolinyl and isoquinolinyl.

[0081] The term "alkylene" refers to an acyclic saturated hydrocarbon chain that combines different moieties. Representative examples of alkylene groups are -CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH(CH2CH3)-, -CH2-CH(n-C3H7)-, -CH2-CH(n-C4H9)-, -CH2-CH(n-C5H 11 )-, -CH2-CH(n-C6H 13 )-, -CH2-CH(n-C7H 15 )-, -CH2-CH(n-C8H 17 )-, -CH(CH3)-CH(CH3)-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, -C(CH3)2-, -CH2-C(CH3)2-CH2-, and -CH2-[C(CH3)2]2-CH2-. In one embodiment, C2-C 10 alkylene is selected from one or more of -CH2-CH2-, CH2-CH(CH3)-, -CH2-CH(CH2CH3)-, -CH2-CH(n-C3H7)-, -CH2-CH(n-C4H9)-, -CH2-CH(n-C6H 13 )-, and -(CH2)4-.

[0082] In one embodiment, the polyether polysiloxane of general formula (I) is a polyether polysiloxane of general formula (I)(a)

Chemical formula

[0083] In one embodiment, R2 and R3 are each independently alkyl selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. In another embodiment, it is selected from methyl, ethyl, propyl, butyl, pentyl and hexyl. In yet another embodiment, R2 and R3 are the same and are selected from methyl, ethyl, propyl, butyl, pentyl and hexyl. In yet another embodiment, R2 and R3 contain methyl.

[0084] In another embodiment, n is an integer from 1 to 8, or 1 to 6, or 1 to 4 in general formula (I)(a).

[0085] In another embodiment, x and y are each independently an integer from 1 to 10,000, or 1 to 5,000, or 1 to 1,000, or 1 to 500, or 10 to 500, or 10 to 250, or even 10 to 100 in general formula (I)(a).

[0086] In this context, as understood by those skilled in the art, the linkages represented by x and y are distributed to form a block polymer structure or a random polymer structure.

[0087] In another embodiment, the nonionic surfactant comprises a polyether siloxane represented by general formula (II)

Chemical formula

[0088] In one embodiment, the polyether siloxane has the general formula (II)(a)

Chemical formula

[0089] In one embodiment, the surfactant (e) in Embodiment 1 is present in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B). In another embodiment, it is present in an amount of 0.1 wt% to 4.5 wt%, or 0.1 wt% to 4.0 wt%, or 0.1 wt% to 3.5 wt%. In yet another embodiment, it is present in an amount of 0.1 wt% to 3.0 wt%, or 0.2 wt% to 3.0 wt%, or 0.2 wt% to 2.5 wt%. In yet another embodiment, it is present in an amount of 0.2 wt% to 2.0 wt%, or 0.2 wt% to 1.5 wt%, or 0.2 wt% to 1.0 wt%. In a further embodiment, it is present in an amount of 0.2 wt% to 0.5 wt%.

[0090] Water (f) The isocyanate-reactive component (B) also contains water (f) which serves as a blowing agent. In one embodiment, the water (f) in Embodiment 1 is present in an amount of 1.0 wt% to 15.0 wt% based on the total weight of the isocyanate-reactive component (B). In another embodiment, it is present in an amount of 2.0 wt% to 15.0 wt%, or 2.0 wt% to 13.0 wt%, or 3.0 wt% to 13.0 wt%. In yet another embodiment, it is present in an amount of 3.0 wt% to 11.0 wt%, or 4.0 wt% to 11.0 wt%, or 5.0 wt% to 11.0 wt%. In yet another embodiment, it is present in an amount of 6.0 wt% to 11.0 wt%, or 7.0 wt% to 11.0 wt%.

[0091] Additive (g) The reactive composition of Embodiment 1 further contains an additive (g) selected from a cell opener, a flame retardant, a dye, a pigment, an IR absorbing material, a stabilizer, a plasticizer, an antistatic agent, an antifungal agent, an antibacterial agent, a hydrolysis control agent, a curing agent, an antioxidant, an alkylene carbonate, a carbonamide and a pyrrolidone. The additive (g) may be present in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B). Further details regarding the additives can be found, for example, in Szycher’s Handbook of Polyurethanes, 2 nd edition, 2013.

[0092] In one embodiment, the isocyanate-reactive component (B) in Embodiment 1 further contains an additive (g) as described herein. In another embodiment, the isocyanate-reactive component (B) in Embodiment 1 contains a cell opener in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the isocyanate-reactive component (B).

[0093] In another embodiment, the isocyanate component (A) and the isocyanate-reactive component (B) in Embodiment 1 are storage stable for several weeks or even several months. In one embodiment, the reactive composition of Embodiment 1 can be used for on-site injection applications and spraying applications. In one embodiment, the reactive composition described herein is useful for on-site injection applications where the reactive composition is dispensed into a cavity, foams within the cavity to fill it, and provides structural and / or insulating properties to the assembly. The term "on-site injection" refers to the fact that the foam is created in one step and not assembled at a predetermined location in a separate manufacturing step later, but is produced at the required location. Further, the term "cavity" refers to any shaped empty or hollow space defined by at least two sides into which the reactive composition can be dispensed under conditions such that expansion and curing of the composition occurs to form a PU foam. Suitable examples of cavities include, but are not limited to, the empty or hollow spaces of automobiles.

[0094] Preparation process of semi-rigid PU foam Another aspect of the present invention is Embodiment 2 regarding a process for preparing a semi-rigid PU foam, the process comprising (S1) mixing the reactive composition of Embodiment 1; (S2) curing the reactive composition to obtain a PU foam having a foam density of less than 40 kg / m 3 determined according to ASTM D1622, The reactive composition has a tack-free time of less than 15 seconds.

[0095] In one embodiment, the isocyanate-reactive component (B) and the isocyanate component (A) in the reactive composition of Embodiment 2 are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.0 as described in Embodiment 1.

[0096] In one embodiment, the isocyanate component (A) and the isocyanate-reactive component (B) that generate the reactive composition in Embodiment 1 are stored in different containers. Suitable storage containers include pressurized containers where the pressure conditions suitable for handling the isocyanate component (A) and the isocyanate-reactive component (B) are effective. This can be, for example, a pressure of at least 0.01 MPa, or 0.01 MPa to 7 MPa, or 3 MPa to 6 MPa at room temperature. The term "room temperature" refers to a temperature of 25 ± 3°C.

[0097] In another embodiment, in step (S1) of Embodiment 2, the reactive composition is mixed by supplying each of the isocyanate component (A) and the isocyanate-reactive component (B) as two separate streams stored in different containers. For this purpose, a mixing device can be used. Suitable mixing devices for the purposes of the present invention, for example, mixing heads, are known to those skilled in the art. Each stream preferably enters the mixing device separately, but the isocyanate component (A) and the isocyanate-reactive component (B) can be sufficiently mixed by suitable mixing means, for example, a static mixer. Further, the mixing can be continuous or discontinuous. The isocyanate component (A) and the isocyanate-reactive component (B) are mixed at an isocyanate index of 40 to 200 as described herein.

[0098] In another embodiment, the mixing in step (S1) of Embodiment 2 can be controlled by suitable means known to those skilled in the art, for example, simply by switching on and off, or even by process control software equipped with a flow meter, and as a result, parameters such as the mixing ratio, temperature, and pressure can be controlled.

[0099] In another embodiment, the mixing in step (S1) of Embodiment 2 is as follows (S11) a sub-step of supplying a first stream containing the isocyanate component (A); (S12) a sub-step of supplying a second stream containing the isocyanate-reactive component (B); (S13) A sub-step of mixing the first stream and the second stream in the mixing chamber of the mixing device to thereby obtain a reactive composition.

[0100] In one embodiment, the mixing chamber comprises several inlets and outlets. The first stream and the second stream are separately supplied to the mixing chamber via nozzles. Suitable nozzles for supplying the streams in the mixing chamber are known to those skilled in the art. In one embodiment, each nozzle of the first stream and the second stream has a diameter in the range of 0.02 inches to 0.06 inches. In another embodiment, the mixing device is operated at a temperature below 80°C. In yet another embodiment, the temperature is 30°C to 80°C.

[0101] In another embodiment, it is also possible to use three or more streams, for example, three, four, five or six separate streams. Each of these streams is different and may contain one or more of the components such as isocyanate, self-catalytic polyol (a), polyol (b), crosslinking agent (c), amine catalyst (d), surfactant (e), water (f) and additive (g) as described herein. Such a process is known as a multi-component process.

[0102] In another embodiment, optionally, the mixing device can further comprise at least one measurement and control unit for establishing the pressure of each stream in the mixing chamber.

[0103] In another embodiment, the curing of the reactive composition is carried out in step (S2) of embodiment 2. For this purpose, the reactive composition of step (S1) can be injected into, for example, a cavity where foaming of the reactive composition occurs. The term "injected" refers to injecting or spraying the reactive composition into the cavity.

[0104] In one embodiment, a temperature below 80°C is maintained in step (S2) of Embodiment 2. In another embodiment, the temperature is between 35°C and 70°C. In yet another embodiment, it is between 45°C and 65°C. The PU foam is obtained with a tack-free time of less than 12 seconds and has a foam density of 15 kg / m 3 ~40 kg / m 3 . Due to the short tack-free time, no or very little reactive composition spills from the mixing head.

[0105] Semi-rigid PU foam Another aspect of the present invention is Embodiment 3 regarding the semi-rigid PU foam obtained by the process of Embodiment 2. In one embodiment, the semi-rigid PU foam has a foam density of less than 40 kg / m determined according to ASTM D1622. 3

[0106] In one embodiment, the semi-rigid PU foam of Embodiment 3 is storage-stable and dimensionally stable over several weeks or even months, resulting in acceptable isocyanate and amine release levels. The release levels of isocyanate and amine can be measured using any standard technique known to those skilled in the art. In one embodiment, the isocyanate level in the air can be determined using the technique of OSHA47. The reactive composition of Embodiment 1 results in an isocyanate level in the air of less than 0.5 ppb with ventilation and less than 2 ppb without ventilation. Further, the amine release, particularly the diethanolamine level, is less than 0.1 ppm in the air determined using OSHA60.

[0107] In another embodiment, the semi-rigid PU foam of Embodiment 3 can adhere to various surfaces, including the surfaces of those composed of one or more metals, carbon fibers, plastics, and / or polymers.

[0108] The semi-rigid PU foam described in this specification is useful in NVH applications in automobiles, particularly in areas such as dashboards, headliners, instrument panel trims, underlays, and mats, but not limited to these.

[0109] Hollow filling process Another aspect of the present invention is Embodiment 4 regarding a process for filling a cavity, the process comprising: (M1) injecting the reactive composition of Embodiment 1 into a cavity defined by at least two sides; (M2) curing the reactive composition so that the reactive composition expands to connect the sides of the cavity.

[0110] In one embodiment, the isocyanate-reactive component (B) and the isocyanate component (A) in the reactive composition of Embodiment 4 are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.0, as described in Embodiment 1. In another embodiment, the isocyanate-reactive component (B) and the isocyanate component (A) in the reactive composition of Embodiment 4 are present in a volume mixing ratio (B):(A) of 1.0:3.0 to 3.0:1.0, as described in Embodiment 1.

[0111] In one embodiment, the cavity of Embodiment 4 is completely filled with the reactive composition. In another embodiment, the cavity of Embodiment 4 is partially filled with the reactive composition to increase rigidity or reinforcement in certain local regions.

[0112] In another embodiment, the reactive composition can be injected into the cavity, for example, by the process described in Embodiment 2. Since the reactive composition is essentially adhesive, it adheres to the inner surface of the cavity and is then cured. Suitable curing conditions as in Embodiment 2 result in foaming of the reactive composition to form a semi-rigid PU foam.

[0113] Filled cavity Another aspect of the present invention is Embodiment 5 regarding the filled cavity obtained by the process of Embodiment 4.

[0114] In one embodiment, the filled cavity is a cavity of a vehicle body. The acoustic performance of the semi-rigid PU foam in the filled cavity of Embodiment 5 can be determined using the technique of SAE J2846 that measures the noise reduction amount (insertion loss) when the material is introduced into the cavity for noise control purposes. The filled cavity of the present invention, particularly the semi-rigid PU foam in the filled cavity, has an acceptable insertion loss when compared with the semi-rigid PU foam of the current state of the art.

[0115] In this context, the insertion loss is the reduction of the noise level at a given location by placing a noise control device in the acoustic path between the sound source and that location. The insertion loss of a given material is its ability to reduce the sound passing through that material. The insertion is determined using SAE J2846.

[0116] Molded article Another aspect of the present invention is Embodiment 6 regarding a molded article including the filled cavity of Embodiment 5 or the cavity obtained in Embodiment 4. In one embodiment, the molded article is an automotive part.

[0117] The present invention is illustrated in more detail by the following embodiments and combinations of embodiments obtained from the corresponding dependent references and links.

[0118] I. A reactive composition for producing a polyurethane foam, the composition comprising (A) an isocyanate component, and (B) an isocyanate-reactive component, wherein (a) at least one self-catalytic polyol having an average functionality of 2.0 to 8.0 and a hydroxyl value of 300 mg KOH / g to 800 mg KOH / g, (b) at least one polyol having an average functionality of 2.0 to 8.0 and a hydroxyl value of 15 mg KOH / g to 200 mg KOH / g, (c) At least one crosslinking agent, (d) At least one amine catalyst, (e) At least one surfactant, and (f) water, and an isocyanate-reactive component.

[0119] II. The reactive composition according to Embodiment I, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.0.

[0120] III. The reactive composition according to Embodiment I or II, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 1.0:2.0 to 2.0:1.0.

[0121] IV. The reactive composition according to any one of Embodiments I to III, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 0.8:1.0 to 1.0:1.0.

[0122] V. The reactive composition according to any one of Embodiments I to IV, wherein the isocyanate component (A) and the isocyanate-reactive component (B) are present at an isocyanate index of 40 to 200.

[0123] VI. The reactive composition according to any one of Embodiments I to V, wherein the isocyanate component (A) contains an aromatic isocyanate or an aliphatic isocyanate.

[0124] VII. The reactive composition according to any one of Embodiments I to VI, wherein the isocyanate component (A) has an isocyanate functionality of 1.9 to 4.0.

[0125] VIII. The aromatic isocyanate is selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4,6-tolylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate, 1-methyl-3,5-diethylphenylene-2,4-diisocyanate, 1,3,5-triethylphenylene-2,4-diisocyanate, 1,3,5-triisopropylphenylene-2,4-diisocyanate, 3,3'-diethyl-bisphenyl-4,4'-diisocyanate, 3,5,3',5'-tetraethyl-diphenylmethane-4,4'-diisocyanate, 3,5,3',5'-tetraisopropyldiphenylmethane-4,4'-diisocyanate, 1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate, 1,3,5-triethylbenzene-2,4,6-triisocyanate, 1-ethyl-3,5-diisopropylbenzene-2,4,6-triisocyanate, tolidine diisocyanate, 1,3,5-triisopropylbenzene-2,4,6-triisocyanate and combinations thereof, and the reactive composition according to Embodiment VI.

[0126] IX. The aromatic isocyanate contains methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and the reactive composition according to any one of Embodiments VI to VIII.

[0127] X. At least one self-catalytic polyol (a) has an average functionality of 2.5 to 5.0 and a hydroxyl value of 400 mg KOH / g to 700 mg KOH / g, and the reactive composition according to any one of Embodiments I to IX.

[0128] XI. A reactive composition according to any one of Embodiments I to X, wherein at least one self-catalytic polyol (a) has an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g.

[0129] XII. A reactive composition according to any one of Embodiments I to XI, wherein at least one self-catalytic polyol (a) is a polyether polyol obtained by reacting an amine-containing starter molecule and an alkylene oxide.

[0130] XIII. The reactive composition according to Embodiment XII, wherein the amine-containing starter molecule is selected from 3,3'-diamino-N-methyldipropylamine, 2,2'-diamino-N-methyldiethylamine, 2,3-diamino-N-methyl-ethylpropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 3,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine.

[0131] XIV. The reactive composition according to Embodiment XII or XIII, wherein the amine-containing starter molecule contains ethanolamine.

[0132] XV. The reactive composition according to any one of Embodiments XII to XIV, wherein the alkylene oxide is selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, isomers, and mixtures thereof.

[0133] XVI. The reactive composition according to any one of Embodiments XII to XV, wherein the alkylene oxide is selected from ethylene oxide and propylene oxide.

[0134] XVII. A reactive composition according to any one of Embodiments I to XVI, wherein at least one self-catalytic polyol (a) is present in an amount of 10% to 90% by weight based on the total weight of the isocyanate-reactive component (B).

[0135] XVIII. A reactive composition according to any one of Embodiments I to XVII, wherein at least one polyol (b) is different from at least one self-catalytic polyol (a).

[0136] XIX. A reactive composition according to any one of Embodiments I to XVIII, wherein at least one polyol (b) has an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g.

[0137] XX. A reactive composition according to any one of Embodiments I to XIX, wherein at least one polyol (b) has an average functionality of 2.4 to 3.2 and a hydroxyl value of 25 mg KOH / g to 50 mg KOH / g.

[0138] XXI. A reactive composition according to any one of Embodiments I to XX, wherein at least one polyol (b) is selected from polyester polyols, polyether polyols, and polyether ester polyols.

[0139] XXII. A reactive composition according to any one of Embodiments I to XXI, wherein at least one polyol (b) contains a polyether polyol.

[0140] XXIII. A reactive composition according to any one of Embodiments I to XXII, wherein at least one polyol (b) is present in an amount of 10% to 90% by weight based on the total weight of the isocyanate-reactive component (B).

[0141] XXIV. The reactive composition according to any one of Embodiments I to XXIII, wherein at least one crosslinking agent (c) comprises a compound containing at least two isocyanate-reactive groups and having a molecular weight of 30 g / mol to 150 g / mol.

[0142] XXV. The reactive composition according to any one of Embodiments I to XXIV, wherein at least one crosslinking agent (c) is selected from monoethanolamine, diethanolamine, triethanolamine, glycerin, trimethylolpropane, and pentaerythritol.

[0143] XXVI. The reactive composition according to any one of Embodiments I to XXV, wherein at least one crosslinking agent (c) comprises diethanolamine.

[0144] XXVII. The reactive composition according to any one of Embodiments I to XXVI, wherein at least one crosslinking agent (c) is present in an amount of 0.1% by weight to 5.0% by weight based on the total weight of the isocyanate-reactive component (B).

[0145] XXVIII. The reactive composition according to any one of Embodiments I to XXVII, wherein at least one amine catalyst (d) is a tertiary amine.

[0146] XXIX. At least one amine catalyst (d) is selected from trimethylamine, triethylamine, dimethylethanolamine, N-methylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N′,N′-tetramethylene-1,4-butanediamine, N,N-dimethylpiperazine, bis(dimethylaminoethyl)ether, bis(2-dimethylaminoethyl)ether, morpholine, 4,4’-(oxydi-2,1-ethanediyl)bis, triethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, N-acetyl-N,N-dimethylamine, N-coco-morpholine, N,N-dimethylaminomethyl N-methylethanolamine, N,N,N’-trimethyl-N’-hydroxyethylbis(aminoethyl)ether, N,N-bis(3-dimethyl-aminopropyl)N-isopropanolamine, (N,N-dimethyl)amino-ethoxyethanol, N,N,N’,N’-tetramethylhexanediamine, 1,8-diazabicyclo-5,4,0-undecene-7, N,N-dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopropyldipropanolamine, bis(dimethylaminopropyl)amino-2-propanol, tetramethylaminobis(propylamine), (dimethyl(aminoethoxyethyl))((dimethylamine)ethyl)ether, tris(dimethylaminopropyl)amine, dicyclohexylmethylamine, bis(N,N-dimethyl-3-aminopropyl)amine, and 1,2-ethylenepiperidine and methyl-hydroxyethylpiperazine, 1,4-diazabicyclo[2.2.2]octane-2-methanol and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, the reactive composition according to any one of Embodiments I to XXVIII.

[0147] XXX. At least one amine catalyst (d) is present in an amount of 0.01% to 5.0% by weight based on the total weight of the isocyanate-reactive component (B), the reactive composition according to any one of Embodiments I to XXIX.

[0148] XXXI. The reactive composition according to any one of Embodiments I to XXX, wherein at least one surfactant (e) is a nonionic surfactant.

[0149] XXXII. The reactive composition according to Embodiment XXXI, wherein the nonionic surfactant comprises a polyether polysiloxane and / or a polyether siloxane.

[0150] XXXIII. The reactive composition according to Embodiment XXXI or XXXII, wherein the nonionic surfactant comprises a polyether polysiloxane.

[0151] XXXIV. The reactive composition according to any one of Embodiments XXXI to XXXIII, wherein the polyether polysiloxane is a polyether polysiloxane of general formula (I),

Chemical formula

[0152] XXXV. The reactive composition according to embodiment XXXIV, wherein the polyether polysiloxane of general formula (I) is a polyether polysiloxane of general formula (I)(a),

Chemical formula

[0153] XXXVI. The reactive composition according to any one of embodiments I to XXXV, wherein at least one surfactant (e) is present in an amount of 0.1% by weight to 5.0% by weight based on the total weight of the isocyanate-reactive component (B).

[0154] XXXVII. The reactive composition according to any one of embodiments I to XXXVI, wherein water (f) is present in an amount of 1.0% by weight to 15.0% by weight based on the total weight of the isocyanate-reactive component (B).

[0155] XXXVIII. The reactive composition according to any one of embodiments I to XXXVII, further comprising at least one additive (g).

[0156] XXXIX. The reactive composition according to embodiment XXXVIII, wherein the additive (g) is selected from a bubble release agent, a flame retardant, a dye, a pigment, an IR absorbing material, a stabilizer, a plasticizer, an antistatic agent, an antifungal agent, an antibacterial agent, a hydrolysis control agent, a curing agent, an antioxidant, an alkylene carbonate, a carbon amide, and a pyrrolidone.

[0157] XL. The reactive composition according to embodiment XXXVIII or XXXIX, wherein the additive (g) is present in an amount of 0.1% to 5.0% by weight based on the total weight of the isocyanate-reactive component (B).

[0158] XLI. A process for preparing a polyurethane foam, the process comprising: (S1) mixing the reactive composition according to any one of embodiments I to XL; and (S2) curing the reactive composition to obtain a polyurethane foam having a foam density of less than 40 kg / m determined according to ASTM D1622. 3 The reactive composition has a tack-free time of less than 15 seconds. The reactive composition has a tack-free time of less than 15 seconds.

[0159] XLII. The process according to embodiment XLI, wherein in step (S2), a temperature of less than 80 °C is maintained.

[0160] XLIII. The process according to embodiment XLI or XLII, wherein in step (S2), a temperature of 35 °C to 70 °C is maintained.

[0161] XLIV. The process according to any one of embodiments XLI to XLIII, wherein in step (S2), a temperature of 45 °C to 65 °C is maintained.

[0162] XLV. The process according to any one of embodiments XLI to XLIV, wherein the tack-free time is less than 12 seconds.

[0163] XLVI. The polyurethane foam has a density of 15 kg / m determined according to ASTM D1622.3 ~40 kg / m 3 and having a foam density of, the process according to any one of Embodiments XLI to XLV.

[0164] XLVII. A process according to any one of Embodiments XLI to XLVI, wherein the isocyanate component (A) and the isocyanate-reactive component (B) are mixed at an isocyanate index of 40 to 200.

[0165] XLVIII. A polyurethane foam obtained by the process according to any one of Embodiments XLI to XLVII.

[0166] XLIX. The polyurethane foam according to Embodiment XLVIII, wherein the polyurethane foam is a semi-rigid polyurethane foam.

[0167] L. A process for filling a cavity, the process comprising: (M1) injecting a reactive composition according to any one of Embodiments I to XL into a cavity defined by at least two sides; (M2) curing the reactive composition such that the reactive composition expands to connect the sides of the cavity.

[0168] LI. The process according to Embodiment L, wherein in step (M2), a temperature of less than 80 °C is maintained.

[0169] LII. In step (M2), the reactive composition expands to form a polyurethane foam having a foam density of less than 40 kg / m determined according to ASTM D1622, the process according to Embodiment L or 3 LI.

[0170] LI.

[0171] LIII. A filled cavity obtained by the process according to any one of Embodiments L to LII.

[0172] LIV. The filled cavity according to embodiment LIII, wherein the filled cavity is a vehicle body cavity.

[0173] LV. A molded article comprising a filled cavity obtained by the process according to embodiment LIII or LIV, or according to any one of embodiments L to LII.

[0174] LVI. The molded article according to embodiment LV, wherein the molded article is an automotive part.

[0175] LVII. A reactive composition for producing a semi-rigid polyurethane foam, the composition comprising (A) an isocyanate component comprising methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and (B) an isocyanate-reactive component, comprising (a) 20% to 75% by weight of at least one self-catalytic polyol having an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, (b) 10% to 90% by weight of at least one polyol having an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, (c) 0.1% to 5.0% by weight of at least one crosslinking agent, (d) 0.01% to 5.0% by weight of at least one amine catalyst, (e) 0.1% to 5.0% by weight of at least one surfactant, and (f) 1.0% to 15.0% by weight of water, wherein the percentages by weight are based on the total weight of the isocyanate-reactive components and include the isocyanate-reactive components. The percentages by weight are based on the total weight of the isocyanate-reactive components and include the isocyanate-reactive components and the isocyanate component.

[0176] LVIII. The reactive composition according to embodiment LVII, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.0.

[0177] LIX. The reactive composition according to embodiment LVII or LVIII, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 0.8:1.0 to 1.0:1.0.

[0178] LX. The reactive composition according to any one of embodiments LVII to LIX, wherein the isocyanate component (A) and the isocyanate-reactive component (B) are present at an isocyanate index of 40 to 200.

[0179] LXI. The reactive composition according to any one of embodiments LVII to LX, wherein at least one self-catalytic polyol (a) is a polyether polyol obtained by reacting an amine-containing starter molecule and an alkylene oxide.

[0180] LXII. The reactive composition according to embodiment LXI, wherein the amine-containing starter molecule contains ethanolamine.

[0181] LXIII. The reactive composition according to embodiment LXI, wherein the alkylene oxide is selected from ethylene oxide and propylene oxide.

[0182] LXIV. The reactive composition according to any one of embodiments LVII to LXIII, wherein at least one polyol (b) has an average functionality of 2.4 to 3.2 and a hydroxyl value of 25 mg KOH / g to 50 mg KOH / g.

[0183] LXV. The reactive composition according to any one of embodiments LVII to LXIV, further comprising at least one additive (g).

[0184] LXVI. The reactive composition according to embodiment LXV, wherein the additive (g) is selected from a defoaming agent, a flame retardant, a dye, a pigment, an IR absorbing material, a stabilizer, a plasticizer, an antistatic agent, an antifungal agent, an antibacterial agent, a hydrolysis control agent, a curing agent, an antioxidant, an alkylene carbonate, a carbon amide, and a pyrrolidone.

[0185] LXVII. A process for preparing a semi-rigid polyurethane foam, the process comprising: (S1) mixing the reactive composition according to any one of Embodiments LVII to LXVI; (S2) curing the reactive composition to obtain a semi-rigid polyurethane foam having a foam density of less than 40 kg / m 3 determined according to ASTM D1622, The reactive composition has a tack-free time of less than 15 seconds.

[0186] LXVIII. The process according to Embodiment LXVII, wherein in step (S2), a temperature of less than 80 °C is maintained.

[0187] LXIX. A semi-rigid polyurethane foam obtained by the process according to Embodiment LXVII or LXVIII.

[0188] LXX. A process for filling a cavity, the process comprising: (M1) injecting the reactive composition according to any one of Embodiments LVII to LXVI into a cavity defined by at least two sides; (M2) curing the reactive composition so that the reactive composition expands to connect the sides of the cavity.

[0189] LXXI. A filled cavity obtained by the process according to Embodiment LXX.

[0190] LXXII. The filled cavity according to Embodiment LXXI, wherein the filled cavity is a vehicle body cavity.

[0191] LXXIII. A molded article comprising the filled cavity according to Embodiment LXXI or LXXII, or obtained by the process according to Embodiment LXX.

Examples

[0192] The invention according to this claim is illustrated by the following non-limiting examples.

[0193] [Table 1]

[0194] [Table 2]

[0195] The tack-free time was determined by gently tapping the tongue depressor on the surface of the semi-rigid PU foam until the material no longer moved onto the tongue depressor.

[0196] The shear holding force was determined using a 100 mm × 300 mm steel panel. The panel was placed in a jig with spacers, and the reactive composition was foamed in a 100 mm × 150 mm × 25 mm cavity to obtain a test piece. A test load was applied in the central direction of the test piece together with the spacers, and the test piece was pulled at a tensile speed of 50 mm / min until it was broken.

[0197] General synthesis of the reactive composition Using the above components, an isocyanate component (A) and an isocyanate-reactive component (B) were prepared. The two components were each treated via a GRACO HFR mixing device at a temperature of 60°C and a pressure in the range of 4.0 MPa to 5.5 MPa at a flow rate of 120 ml / sec for IE1 and 80 ml / sec for IE2. An overview of the components used and their amounts (all in weight %) is shown in Table 1.

[0198] [Table 3]

[0199] Comparative Example (CE) The composition of the present invention (IE1) was compared with the prepolymer composition described in Table III of US8,455,679 (B2). The mixing ratio (B:A by volume) was maintained at 1.0:24.0 (equivalent mixing ratio 1.0:27.0 by weight).

[0200] The results of testing the acoustic performance of the foam articles are summarized in Table II. The size of the cavity in SAE J2846 was 75 mm (length) × 75 mm (width) × 250 mm (height), and the foam was filled up to the deposition covering the upper part of the cavity.

[0201] [Table 4]

[0202] Acoustic performance is frequency-dependent, and since porous materials generally have excellent sound absorption characteristics at high values (>1000 Hz), the insertion loss increases at high frequencies. The overall trend of the insertion loss of IE1 is the same as that of CE. Furthermore, as summarized in Table III, the characteristics of the foam obtained by the formulation of the present invention are more or less similar to those of the comparative foam materials, but the present invention provides a foam obtained at a lower mixing ratio. This results in cost-effective foaming.

[0203] [Table 5]

Claims

1. A reactive composition for producing a semi-rigid polyurethane foam, wherein the composition comprises (A) an isocyanate component containing methylene diphenyl diisocyanate and / or polymeric methylene diphenyl diisocyanate, and (B) an isocyanate-reactive component, wherein (a) 25% to 75% by weight of at least one self-catalytic polyol having an average functionality of 2.8 to 3.5 and a hydroxyl value of 450 mg KOH / g to 600 mg KOH / g, (b) 10% to 70% by weight of at least one polyol having an average functionality of 2.2 to 5.0 and a hydroxyl value of 20 mg KOH / g to 100 mg KOH / g, (c) 0.1% to 5.0% by weight of at least one crosslinking agent, (d) 0.01% to 5.0% by weight of at least one amine catalyst, (e) 0.1% to 5.0% by weight of at least one surfactant, and (f) 1.0% to 15.0% by weight of water, and said weight percentages are based on the total weight of the isocyanate-reactive component, and the reactive composition comprises an isocyanate-reactive component.

2. The reactive composition according to claim 1, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 1.0:3.0 to 3.0:1.

0.

3. The reactive composition according to claim 1 or 2, wherein the isocyanate-reactive component (B) and the isocyanate component (A) are present in a weight ratio (B):(A) of 0.8:1.0 to 1.0:1.

0.

4. The reactive composition according to any one of claims 1 to 3, wherein the isocyanate component (A) and the isocyanate-reactive component (B) are present at an isocyanate index of 40 to 200.

5. The reactive composition according to any one of claims 1 to 4, wherein the at least one self-catalytic polyol (a) is a polyether polyol obtained by reacting an amine-containing starter molecule and an alkylene oxide.

6. The reactive composition according to claim 5, wherein the amine-containing starter molecule contains ethanolamine.

7. The reactive composition according to claim 5, wherein the alkylene oxide is selected from ethylene oxide and propylene oxide.

8. The reactive composition according to any one of claims 1 to 7, wherein the at least one polyol (b) has an average functionality of 2.4 to 3.2 and a hydroxyl value of 25 mg KOH / g to 50 mg KOH / g.

9. The reactive composition according to any one of claims 1 to 8, further comprising at least one additive (g).

10. The reactive composition according to claim 9, wherein the additive (g) is selected from a defoaming agent, a flame retardant, a dye, a pigment, an IR absorbing material, a stabilizer, a plasticizer, an antistatic agent, an antifungal agent, an antibacterial agent, a hydrolysis control agent, a curing agent, an antioxidant, an alkylene carbonate, a carbon amide, and a pyrrolidone.

11. The semi-rigid polyurethane foam has a foam density of less than 40 kg / m 3 as determined according to ASTM D1622, and the reactive composition according to claim 1.

12. A process for preparing a semi-rigid polyurethane foam, the process comprising: (S1) mixing the reactive composition according to any one of claims 1 to 11; and (S2) curing the reactive composition to obtain a semi-rigid polyurethane foam having a foam density of less than 40 kg / m ３ as determined according to ASTM D1622, and including. A process wherein the reactive composition has a tack-free time of less than 15 seconds.

13. The process according to claim 12, wherein in step (S2), a temperature of less than 80 °C is maintained.

14. A semi-rigid polyurethane foam obtained by the process according to claim 12 or 13.

15. A process for filling a cavity, the process comprising: (M1) injecting the reactive composition according to any one of claims 1 to 11 into a cavity defined by at least two sides; (M2) curing the reactive composition so that the reactive composition expands to connect the sides of the cavity.

16. An article comprising a cavity and a filling in the cavity obtained by the process according to claim 15.

17. The article comprising a cavity and a filling in the cavity according to claim 16, wherein the filled cavity is a vehicle body cavity.

18. A molded article comprising an article comprising a cavity and a filling in the cavity according to claim 16 or 17, or obtained by the process according to claim 15.

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