Isocyanate-based foam and method for producing the same

Abstract

Isocyanate-based polymer foams are described that have (i) a limiting oxygen index (LOI) of 26.5% or greater, as measured in accordance with ASTM D2863-17A, and (ii) a total volatile organic content (TVOC) of 225 μg / g C or less, as measured in accordance with VDA 277. Preferably, the foams are made from a foamable composition that includes: an isocyanate; (1) a reactive compound having at least one hydrogen that is reactive with the isocyanate, and (2) one or both of a halogen and a phosphate moiety; a foaming agent that includes one or both of water and carbon dioxide; and a catalyst; wherein the reactive compound, if present, is present in an amount of from about 30% to about 95% of the total ISO equivalents, excluding water, in the foamable composition.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of Provisional Patent Application No. 62 / 922,801, filed on 30 August 2019 under Section 119(e) of the United States Patent Act, the contents of which are incorporated herein by reference. [Background technology]

[0002] In one aspect, the present invention relates to isocyanate foams. In another aspect, the present invention relates to a method for producing isocyanate foams. In yet another aspect, the present invention relates to isocyanate foams having improved flammability properties. In yet another aspect, the present invention relates to sprayable isocyanate foams having improved flammability properties.

[0003] Description of prior art Isocyanate polymers are well known in the art. Generally, those skilled in the art understand that isocyanate polymers include polyurethanes, polyureas, polyisocyanurates, and mixtures thereof.

[0004] The production of foamed isocyanate polymers is also known in the art. In fact, one of the advantages of isocyanate polymers compared to other polymer systems is that polymerization and foaming can occur in situ. This results in the ability to mold the polymer while it is being formed and expanding.

[0005] One conventional method for producing polyurethane foam is known as the "one-shot" technique. In this technique, isocyanates, suitable polyols, catalysts, water (acting as a reactive "foaming" agent and potentially added together with one or more physical foaming agents), and other additives are mixed simultaneously, for example, by collision mixing (e.g., under high pressure). Generally, when producing polyurea, the polyol is replaced with a suitable polyamine. Polyisocyanurates may be obtained by cyclic trimerization of the isocyanate component. Urethane-modified polyureas or polyisocyanurates are known in the art. In either scenario, the reactants are mixed very quickly and closely by suitable mixing techniques.

[0006] Low-density spray polyurethane foam (SPF) is a semi-rigid material with a sponge-like appearance that expands during introduction, creating small open cells filled with carbon dioxide. Due to its ability to expand during reaction, it fills cracks, fissures, and voids, and adheres to uneven surfaces or substrates to form air-filled thermal insulation materials.

[0007] When introduced or applied, SPF acts as an air barrier and sound absorber by preventing and absorbing air leaks. SPF is a thermal insulation material with a wide range of applications. One known application is spraying it onto the interior walls of mass transit vehicles, such as buses and trains.

[0008] Sprayed polyurethane foam has a much higher R-value than any other insulation product. The R-value simply represents the insulating power of a product. Independent laboratories have conducted various studies on the R-value of sprayed polyurethane foam compared to other materials such as fiberglass and cellulose, and have found that sprayed polyurethane foam with a typical R-value of 6-7 is highly advantageous.

[0009] Despite the progress made to date, there is still room for improvement. Specifically, known SPF is highly flammable and / or contains large amounts of volatile organic carbon compounds. These problems are particularly serious when SPF is applied to the interior walls of mass transit vehicles, such as buses and trains.

[0010] There is a continuing need for spray foams (polyurethane or other materials) that are less flammable and contain fewer volatile organic compounds. [Overview of the project]

[0011] An object of the present invention is to eliminate or mitigate at least one of the aforementioned drawbacks of the prior art.

[0012] Another objective of the present invention is to provide a novel isocyanate-based polymer foam.

[0013] Another object of the present invention is to provide a novel method for producing isocyanate-based polymer foams.

[0014] Therefore, in one aspect, the present invention provides an isocyanate polymer foam having: (i) a limiting oxygen index (LOI) of 26.5% or more as measured according to ASTM D2863-17a, and (ii) a total volatile organic matter content (TVOC) of 225 μg / g C or less as measured according to VDA 277.

[0015] In another respect, the present invention: (a) Isocyanates; (b)(1) at least one hydrogen that is reactive with an isocyanate, and (2) a reactive compound having one or both of a halogen and / or a phosphate moiety; (c) Foaming agents containing either water or carbon dioxide, or both; and (d) catalyst; We provide an isocyanate-based polymer foam produced from a foaming composition containing the following: Here, the amount of reactive compounds present in the foaming composition is approximately 30% to 95% of the total ISO equivalents excluding water.

[0016] In this specification, the term ISO equivalent is a percentage and may be determined as follows: Equivalent weight of a compound (%) = (Equivalent weight of the compound) / Total (Equivalent weight of all compounds in the resin mixture excluding water) × 100 Here: Isocyanate equivalent of the compound = (weight of the compound in the resin formulation) / equivalent weight of the compound That is the case.

[0017] Accordingly, the inventors have discovered a novel method for producing a sprayable foam composition that shows significant improvement over commercially available known SPFs. Specifically, the inventors have discovered that conventional polyols (described in detail below) may be removed from the foaming composition and replaced (or substantially completely replaced) with certain types of reactive compounds, resulting in an isocyanate-based polymer foam having a very desirable combination of LOI and TVOC without significant degradation of other physical properties. The reactive compound itself can be considered a flame retardant: (1) having at least one hydrogen that is reactive with the isocyanate, and (2) having one or both of a halogen and / or phosphate moiety. This definition of a reactive compound excludes conventional polyols used in the production of polyurethane foams. Thus, strictly speaking, the isocyanate-based polymer foams of the present invention may not be considered polyurethane foams (i.e., polymer foams produced from isocyanate as the main reactant and conventional polyols). The inventors have discovered LOI or TVOC can be improved in the limited way of modifying specific raw materials in known SPF formulations, but unless conventional polyols are replaced (or substantially completely replaced) with the reactive compounds described herein, the LOI and TVOC Both We further discovered that it is impossible to significantly improve this. [Modes for carrying out the invention]

[0018] On one side, the present invention relates to an isocyanate-based polymer foam which has: (i) a limiting oxygen index (LOI) of 26.5% or more measured according to ASTM D2863-17a, and (ii) a total volatile organic compound content (TVOC) of 225 μg / g C or less measured according to VDA 277.

[0019] A preferred embodiment of this aspect of the present invention may include any one or any combination of two or more of the following features: · The isocyanate-based polymer foam has an LOI of 26.5% to 35.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 35.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 34.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 33.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 32.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 31.0%; · The isocyanate-based polymer foam has an LOI of 27.5% to 31.0%; · The isocyanate-based polymer foam has an LOI of 27.0% to 30.0%; · The isocyanate-based polymer foam has an LOI of 27.5% to 30.0%; · The isocyanate-based polymer foam has an LOI of 28.0% to 30.0%; · The isocyanate-based polymer foam has a TVOC of 50 to 225 μg / g C; · The isocyanate-based polymer foam has a TVOC of 50 to 215 μg / g C; · The isocyanate-based polymer foam has a TVOC of 50 to 180 μg / g C; · The isocyanate-based polymer foam has a TVOC of 50 to 170 μg / g C; • Isocyanate polymer foams have a TVOC of 50-150 μg / g C; • Isocyanate polymer foams have a TVOC of 60-150 μg / g C; • Isocyanate polymer foams have a TVOC of 70-150 μg / g C; • Isocyanate polymer foams have a TVOC of 70-140 μg / g C; • Isocyanate polymer foams have a TVOC of 70-130 μg / g C; • Isocyanate polymer foams have a TVOC of 70-120 μg / g C; • Isocyanate polymer foams have a TVOC of 70-110 μg / g C; • Isocyanate polymer foams have a TVOC of 70-100 μg / g C; The density of isocyanate-based polymer foams is approximately 8.0 to 48 kg / m³. 3 and; The density of isocyanate-based polymer foams is approximately 16 to 40 kg / m³. 3 and; The density of isocyanate-based polymer foams is approximately 24 to 32 kg / m³. 3 and / or • Isocyanate-based polymer foams are: (a) Isocyanates; (b)(1) at least one hydrogen that is reactive with an isocyanate, and (2) a reactive compound having one or both of a halogen and / or a phosphate moiety; (c) Foaming agents containing either water or carbon dioxide, or both; and (d) catalyst; Manufactured from a foaming composition containing, Here, the amount of reactive compounds present in the foaming composition is approximately 30% to 95% of the total ISO equivalents excluding water.

[0020] In another respect, the present invention: (a) Isocyanates; (b)(1) at least one hydrogen that is reactive with an isocyanate, and (2) a reactive compound having one or both of a halogen and / or a phosphate moiety; (c) Foaming agents containing either water or carbon dioxide, or both; and (d) catalyst; Regarding isocyanate-based polymer foams produced from foaming compositions containing, Here, the amount of reactive compounds present in the foaming composition is approximately 30% to 95% of the total ISO equivalents excluding water.

[0021] Preferred embodiments of the foaming composition relating to all aspects of the present invention may include any one or more combinations of the following features: • The amount of reactive compounds present is approximately 40-90% of the total ISO equivalent excluding water; • The amount of reactive compounds present is approximately 45-85% of the total ISO equivalent excluding water; • Reactive compounds have one or more of the following parts: hydroxyl (R-OH), amino (R-NH2), and iminyl (R=NH); • The reactive compound is selected from the group consisting of halogenated aromatic esters, halogenated aromatic ethers, halogenated aliphatic esters, halogenated aliphatic ethers, halogenated phosphate esters, non-halogenated phosphate esters, and mixtures thereof; • The foaming composition is substantially free of polyols containing a hydroxyl-terminated skeleton selected from the group consisting of polyethers, polyesters, polycarbonates, polydienes, and polycaprolactones; • Isocyanates contain prepolymers; • Isocyanates include 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, furfrylidene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenyl-3,3'-dimethylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene, and 2,4-di Selected from the group consisting of s-triazine sorbates, 1-methyl-2,4-diisocyanate cyclohexane, p-phenylenediisocyanate, m-phenylenediisocyanate, 1,4-naphthalenediisocyanate, dianisidine diisocyanate, vitroleneisocyanate, 1,4-xylylenediisocyanate, 1,3-xylylenediisocyanate, bis-(4-isocyanatophenyl)methane, bis-(3-methyl-4-isocyanatetophenyl)methane, polymethylene polyphenyl polyisocyanates, and mixtures thereof; • The isocyanates are selected from the group consisting of (i) 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof; and (ii) mixtures of (i) with isocyanates selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof; The isocyanate is selected from the group essentially consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and mixtures thereof; • Isocyanates are present in amounts that provide an isocyanate index of approximately 60 to 200; • Isocyanates are present in amounts that provide an isocyanate index of approximately 80 to 160; • Isocyanates are present in amounts that provide an isocyanate index of approximately 100 to 150; Water is the only foaming agent present in the effervescent composition; · The amount of water present is from about 3.0 to about 15% by weight of the foaming composition excluding isocyanate; · The amount of water present is from about 4.0 to about 8.0% by weight of the foaming composition excluding isocyanate; and / or · The amount of water present is from about 4.0 to about 6.0% by weight of the foaming composition excluding isocyanate.

[0022] Isocyanate Isocyanates suitable for use in the reaction mixture are not particularly limited, and the selection thereof is left to those skilled in the art. Generally, isocyanate compounds suitable for use are of the general formula: Q(NCO) i (wherein i is an integer of 2 or more, and Q is an organic radical having a valence of i. Q may be a substituted or unsubstituted hydrocarbon group (e.g., an alkylene group or an arylene group)) and can be represented by. Further, Q is of the general formula: Q 1 -Z-Q 1 (wherein Q 1 is an alkylene or arylene group, and Z is selected from the group consisting of -O-, -O-Q 1 -, -CO-, -S-, -S-Q 1 -S-, -SO2- and -Q-N=C=N-Q-) and can be represented by. Examples of isocyanate compounds included in this definition include hexamethylene diisocyanate, 1,8-diisocyanate-p-methane, xylyl diisocyanate, (OCNCH2CH2CH2OCH2O)2, 1-methyl-2,4-diisocyanate cyclohexane, phenylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenyl-methane-4,4',4''-triisocyanate and isopropylbenzene-alpha-4-diisocyanate.

[0023] In another embodiment, Q may be a polyurethane radical having a valence of i. In this case, Q(NCO) i This is a compound commonly referred to as a prepolymer in the art. Generally, prepolymers may be produced by reacting a stoichiometric excess of an isocyanate compound (already defined) with an active hydrogen-containing compound (defined below), preferably a polyhydroxyl-containing material or the polyol described below. In this embodiment, the polyisocyanate may be used in a stoichiometric excess ratio of, for example, about 30% to about 200% with respect to the ratio of active hydrogen in the reactive compound. Since the method of the present invention may relate to the production of polyurea foam, it is understood in this embodiment that a polyurethane-modified polyurea can be produced using the prepolymer.

[0024] In another embodiment, isocyanate compounds suitable for use in the method of the present invention are dimers and trimers of isocyanates and diisocyanates, and are of the general formula: Q'[(NCO) i ] j (In the formula, i and j are integers greater than or equal to 2, and Q' is a polyfunctional organic radical.) A polymeric diisocyanate having, and / or as an additional component in the reaction mixture, the general formula: L(NCO) i (In the formula, i is an integer greater than or equal to 1, and L is a monofunctional or polyfunctional atom or radical.) Compounds having the can be selected. Examples of isocyanate compounds included in this definition include ethylphosphonic acid diisocyanate, phenylphosphonic acid diisocyanate, compounds containing the =Si-NCO group, sulfonamides (QSO2NCO), and isocyanate compounds derived from cyanic acid and thiocyanic acid.

[0025] For more information on suitable isocyanates, see, for example, British Patent No. 1,453,258.

[0026] Non-limiting examples of suitable isocyanates include: 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, furfrylidene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenyl-3,3'-dimethylmethane diisocyanate, carbodiimide-modified 4,4' - Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene, 2,4-diisocyanate-s-triazine, 1-methyl-2,4-diisocyanate-cyclohexane, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,4-naphthalene diisocyanate, dianisidine diisocyanate, vitrine diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, bis-(4-isocyanate phenyl)methane, bis-(3-methyl-4-isocyanate phenyl)methane, polymethylene polyphenyl polyisocyanate, and mixtures thereof. More preferred isocyanates are selected from the group comprising 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof, as well as polymeric MDIs also known as crude MDIs. Another more preferred isocyanate is selected from the group comprising 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, for example, a mixture comprising about 75 to about 85% by weight of 2,4-toluene diisocyanate and about 15 to about 25% by weight of 2,6-toluene diisocyanate.

[0027] Reactive compounds Unlike the production of conventional polyurethane foams, the main reactants in the foaming composition used to produce the isocyanate-based polymer foam of the present invention are: an isocyanate and (1) at least one hydrogen atom that is reactive with the isocyanate, and (2) a reactive compound having one or both of a halogen and / or a phosphate moiety. It is preferable that the foaming composition does not contain conventional polyols (described below) used in the production of polyurethane foams.

[0028] Preferably, the reactive compound is selected from the group consisting of halogenated aromatic esters, halogenated aromatic ethers, halogenated aliphatic esters, halogenated aliphatic ethers, halogenated phosphate esters, non-halogenated phosphate esters, and mixtures thereof.

[0029] Conventional polyols The following discussion focuses on so-called conventional polyols. The foaming composition used in the production of the isocyanate-based polymer foam of the present invention preferably does not contain conventional polyols, but in some embodiments, such polyols may be present in relatively small amounts.

[0030] "Small amount" refers to up to about 30% of the total ISO equivalent excluding water in the foaming composition, more preferably up to about 20% of the total ISO equivalent excluding water in the foaming composition, even more preferably up to about 10% of the total ISO equivalent excluding water in the foaming composition, and most preferably up to about 5% of the total ISO equivalent excluding water in the foaming composition.

[0031] The reaction mixture used in the production of the polyurethane foam of the present invention comprises a first polyol comprising a first polymer chain essentially consisting of propylene oxide units and alkylene oxide units selected from ethylene oxide, butylene oxide and mixtures thereof, wherein the weight ratio of propylene oxide units to alkylene oxide units is about 90:10 to about 25:75, the polymer chain is end-capped with ethylene oxide units, and the first polyol has a primary hydroxyl content of at least about 70% based on the total hydroxyl content of the first polyol. These characteristics of the first polyol are typical of polyols commonly used to produce molded foams.

[0032] The first polyol can be used alone or in combination with a second polyol comprising a second polymer chain essentially consisting of propylene oxide units and alkylene oxide units selected from ethylene oxide, butylene oxide, and mixtures thereof, with a weight ratio of propylene oxide units to alkylene oxide units of approximately 100:0 to approximately 60:40, and the polymer chain being end-capped with alkylene oxide units, and the second polyol having a secondary hydroxyl content of at least approximately 95% based on the total hydroxyl content of the second polyol. These characteristics of the second polyol are typical of polyols commonly used to produce slab (free-rise) foams.

[0033] Within these definitions relating to the first and second polyols, a polyol may be a hydroxyl-terminated skeletal portion selected from the group comprising polyethers, polyesters, polycarbonates, polydienes, and polycaprolactones. Preferably, the polyol is selected from the group comprising hydroxyl-terminated polyhydrocarbons, hydroxyl-terminated polyformals, fatty acid triglycerides, hydroxyl-terminated polyesters, hydroxymethyl-terminated polyesters, hydroxymethyl-terminated perfluoromethylenes, polyalkylene ether glycols, polyalkylene arylene ether glycols, and polyalkylene ether triols. More preferred polyols are selected from the group comprising adipic acid-ethylene glycol polyesters, poly(butylene glycol), poly(propylene glycol), and hydroxyl-terminated polybutadienes; for example, see British Patent No. 1,482,213 for preferred polyols. Preferably, the molecular weight of such polyether polyol is about 100 to about 10,000, more preferably about 100 to about 4,000, and most preferably about 100 to about 3,500.

[0034] In another embodiment, the second polyol may include polymer polyols known as graft copolymer polyols. As is known in the art, such polyols are generally polyether polyol dispersions filled with other organic polymers. Such polymer polyols are useful for improving the stiffness of load building or foams compared to using unmodified polyols. Non-limiting examples of useful polymer polyols include: chain-growth copolymer polyols (e.g., containing particulate poly(acrylonitrile), poly(styrene-acrylonitrile), and mixtures thereof), and / or step-growth copolymer polyols (e.g., polyurea (PolyHarnstoff) dispersions (PHD), polyisocyanate polyaddition (PIPA) polyols, epoxy dispersion polyols, and mixtures thereof). For more information on polymer polyols, see, for example, Chapter 2 of FLEXIBLE FOAM FUNDAMENTALS, Herrington et al. (1991) and the references cited therein. When polymer polyols are used, it is preferable to mix the polymer polyol with the base polyol. Generally, a mixture containing about 5 to about 50% by weight of polymer polyol relative to the unmodified polyol present in the mixture may be used.

[0035] The second polyol may be a so-called bio-derived polyol. In this specification, the term "bio-derived polyol" is a general term intended to include polyols derived from recycled resources such as vegetable oils or other bio-derived materials.

[0036] Preferred bio-derived polyols are those derived from vegetable oils. Non-limiting examples of preferred vegetable oils from which such polyols may be derived include soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, peanut oil, and combinations thereof. Partially hydrogenated vegetable oils and genetically modified vegetable oils are also useful and include high-oleic safflower oil, high-oleic soybean oil, high-oleic peanut oil, high-oleic sunflower oil, and high-erucic rapeseed oil (Japanese rose oil).

[0037] A preferred method for producing polyols of biological origin (e.g., from vegetable oils) involves reacting a vegetable oil (or a mixture of vegetable oils) with a peroxy acid to obtain an epoxidized vegetable oil. Essentially, some or all of the double bonds in the vegetable oil may be epoxidized. The epoxidized vegetable oil may be reacted with an alcohol and a catalytic amount of fluoroboric acid, and optionally further with water, to form a polyol. Such polyols have all secondary hydroxyl groups.

[0038] These bio-derived polyols may be used directly in the reaction mixture to produce isocyanate foams, such as polyurethane foams. Alternatively, bio-derived polyols may be reacted with the epoxidized vegetable oil in the presence of a fluoroboric acid catalyst, and possibly water, to form bio-derived polyols suitable for use in the reaction mixture, thereby producing isocyanate foams, such as polyurethane foams.

[0039] Examples of such manufacturing include, • U.S. Patent No. 6,686,435 (Petrovic et al.); • U.S. Patent No. 6,107,433 (Petrovic et al.); • U.S. Patent No. 6,573,354 (Petrovic et al.); and • U.S. Patent No. 6,433,121 (Petrovic et al.) It is described in [reference]. Alternatively, the epoxidation reaction may be carried out under conditions that result in a polyol having a residual double bond.

[0040] A suitable polyol is also a polyol derived from modified vegetable oil produced by hydroformylation. In this method, the vegetable oil is reacted with carbon monoxide and hydrogen in the presence of a Group VIII metal catalyst (e.g., rhodium catalyst) to obtain a hydroformylated vegetable oil. The hydroformylated vegetable oil is then hydrogenated to obtain a modified polyol derived from the vegetable oil. This method produces a polyol in which all groups are primary hydroxyl groups. These polyols may be used directly in the reaction mixture to produce isocyanate foams, such as polyurethane foams. Alternatively, these polyols may be reacted with the epoxidized vegetable oil in the presence of a fluoroboric acid catalyst, and possibly water, to form a polyol suitable for use in the reaction mixture to produce isocyanate foams, such as polyurethane foams.

[0041] Preferred bio-derived polyols are described in International Publication No. 2008 / 106769 (Stanciu et al.).

[0042] In the foaming composition used for the production of isocyanate polymer foams of the present invention, the catalyst is typically incorporated into the reaction mixture. The catalyst used in the reaction mixture is a compound capable of catalyzing polymerization and foaming reactions. Such catalysts are known, and their selection and concentration in the reaction mixture are within the pure view of those skilled in the art. For example, see U.S. Patents 4,296,213 and 4,518,778 for suitable catalyst compounds. Non-limiting examples of suitable catalysts include tertiary amines and / or organometallic compounds. In addition, as is known in the art, if the objective is to produce isocyanurates, Lewis acids must be used as catalysts alone or in combination with other catalysts. Naturally, it will be understood by those skilled in the art that combinations of two or more catalysts may be suitably used.

[0043] The reaction mixture used in the production of polyurethane foams typically further contains a foaming agent. As is known in the art, water can be used as an indirect or reactive foaming agent in the production of foamed isocyanate polymers. Specifically, water reacts with isocyanate to form carbon dioxide, which acts as an effective foaming agent in the final foamed polymer product. Alternatively, carbon dioxide may be generated by other means, such as an unstable compound that produces carbon dioxide (e.g., carbamates). The foaming agent preferred for use in the production of foamed isocyanate polymers of the present invention includes water.

[0044] It is well known in the art that, in the production of foamed isocyanate polymers (e.g., polyurethanes), the amount of water used as an indirect foaming agent is conventionally about 0.5 to about 40 or more parts by weight, preferably about 1.0 to about 10 parts by weight, based on 100 parts by weight of the total active hydrogen-containing compound content in the reaction mixture. As is well known in the art, the amount of water used in the production of foamed isocyanate polymers is usually limited by the fixed properties required of the foamed polymer, and by the tolerances for foam expansion toward self-structure formation, flame retardancy, etc.

[0045] Next, embodiments of the present invention will be described with reference to the following examples. These examples should not be construed as limiting the scope of the present invention. [Examples]

[0046] Various isocyanate polymer foams were produced using the compounds shown in Table 1. All compounds except water are commercially available from Xanathane Systems.

[0047] Various isocyanate polymer foams were produced using a variable ratio multi-component spraying system obtained from Bolair Fluid Handling Systems. This variable ratio system, manufactured by Glass-Craft Indianapolis, IN, was configured to supply isocyanate / resin (i.e., all raw materials) at weight ratios of 1 to 0.50 on both sides of the feed line.

[0048] The spraying system was equipped with separate primary heaters for both the isocyanate and the resin. The isocyanate and resin were supplied to a high-pressure heating line.

[0049] The spraying apparatus has two supply lines; line B has a Graco diaphragm transfer pump for resin, and line A also has a diaphragm transfer pump for isocyanate used in this example.

[0050] The fluids from line A and line B were mixed using a FUSION AP air-purge gun with a maximum operating pressure of 3,500 psi and a maximum fluid temperature of 93°C.

[0051] The spraying device is: Pressure at line A: 1,200 psi; Pressure at line B: 1,200 psi; The temperature of line A is -58°C; and Temperature on line B: 58℃ I set it to that.

[0052] The feeds from line A and line B were mixed in a 1:1 volume ratio and dispensed into a 130cm × 50cm × 13cm wooden box to obtain test foam packs. In addition, the feeds from line A and line B were mixed and sprayed onto a 130cm × 50cm × 0.3cm metal sheet at -20°C to 25°C to examine the adhesion of the foam to the surface of the metal sheet (simulating application to the frame of a vehicle, such as a bus). The system's reactivity profile was performed, and the cream time (seconds), gel time (seconds), rise time (seconds), and tack-free time (seconds) were measured.

[0053] The total volatile organic carbon (TVOC) content of foam samples was analyzed according to the procedure outlined in the VDA-277 standard, "Determination of Organic Emission of Non-metallic materials from vehicles Interior." The VDA-277 method uses gas chromatography and a flame ionization detector to measure the material's emission capacity and the total emission value of the released substances. The test was performed at 120°C using vapor space analysis (headspace technique). Sample sizes for TVOC testing ranged from 10 to 25 g.

[0054] The foam samples were also subjected to Limiting Oxygen Index (LOI) testing in accordance with ASTM D-2863 and JT / T-1905-2016 standards. The Limiting Oxygen Index (LOI) test is a widely used fire test response procedure for testing and quality control to determine the relative flammability of polymeric materials. The LOI, a numerical index, is defined as the minimum concentration of oxygen in the oxygen-nitrogen mixture required for a vertically placed specimen to burn downwards. Therefore, a higher LOI value indicates better flame retardancy. The LOI test method is generally reproducible with an accuracy of +0.5%. Originally designed for testing plastics, this method has been widely used to evaluate the relative flammability of rubber, fabrics, paper, coatings, and other materials. The sample size for the LOI test was 0.25 inches × 0.25 inches × 6 inches.

[0055] Example 1 - Comparative Example In Example 1, a foam sample was prepared from a commercially available spray foam compound from Xanathane Systems using the method described above. Therefore, Example 1 is merely a comparative example, and the foam produced therein is not within the scope of the present invention.

[0056] Table 2 shows some of the properties of the formulations used and the resulting foam.

[0057] Higher-density V2D spray foams exhibited desirable LOIs, but TVOCs were unacceptably high. The use of an auxiliary hydrocarbon foaming agent (Forane 365mfc) dramatically increased TVOC values, as observed in V2D spray foams.

[0058] The density of the foam is an important characteristic. Low-density V-300 spray foam had a high FR (flame retardant) load, meaning it used a large amount of FR, yet its LOI was 23.0%. This foam also had an unacceptably high TVOC (Tripartite Organic Compound).

[0059] V-100 spray foam was the only product with an acceptable TVOC. However, the LOI of this spray foam was unacceptably low.

[0060] The results of Example 1 demonstrate that it was not possible to produce isocyanate polymer foams with (i) a limiting oxygen index (LOI) of 26.5% or higher as measured according to ASTM D2863-17a, and (ii) a total volatile organic matter content (TVOC) of 225 μg / g C or less as measured according to VDA 277, from certain commercially available spray foam formulations.

[0061] Examples 2-4 - Comparative Examples In these examples, the aim was to produce foam samples with improved flammability (higher LOI) than the V-100 spray foam sample produced in Example 1, while maintaining TVOC. Specifically, the FR (flame retardant) load was increased and the amount of water was reduced.

[0062] Foam samples were prepared from commercially available raw materials by Xanathane Systems using the methods described above. The raw materials used in these examples are shown in Tables 3-5, and all parts are in parts by weight (unless otherwise specified).

[0063] As is evident from these tables, the formulations in Tables 3-5 contain relatively high amounts of so-called conventional polyether polyols. These polyether polyols do not fall under the definition of “reactive compound” as used herein (i.e., (1) having at least one hydrogen that is reactive with isocyanate, and (2) having one or both of a halogen and / or phosphate moiety). The only such raw material in Table 2 is XB2000. Therefore, Examples 2-4 are merely relative, and the foams produced therein do not fall within the scope of the present invention.

[0064] Tables 3-5 also show some of the properties of the obtained foams. As is clear from these tables, increasing the FR loading resulted in a desirable increase in LOI, but unfortunately, the density of each increased to unacceptable levels, as did the TVOC (i.e., far exceeding 225 μg / g C).

[0065] Examples 5-8 - Examples In these examples, the intention was to produce foam samples with improved flammability (LOI of 26.5% or more) and improved TVOC properties (TVOC of 225 μg / g C or less) compared to the foam samples produced in Examples 1-4. Specifically, the polyether polyol used to produce the polyurethane foam was removed, and the amount of "reactive compound" (as defined herein, a compound having (1) at least one hydrogen that is reactive with isocyanate, and (2) one or both of a halogen and / or phosphate moiety) XB2000 was increased.

[0066] Foam samples were prepared from commercially available raw materials by Xanathane Systems using the methods described above. The raw materials used in these examples are shown in Tables 6-8, and all parts are in parts by weight (unless otherwise specified).

[0067] Tables 6-8 also show some of the properties of the obtained foams. As is clear from these tables, a significant amount of modification of the polyether polyol used to produce the polyurethane foam to a “reactive compound” (as defined herein, (1) a compound having at least one hydrogen that is reactive with isocyanate, and (2) a compound having one or both of a halogen and / or phosphate moiety) XB2000 results in a very desirable combination of LOI and TVOC. Specifically, each foam sample had (i) a limiting oxygen index (LOI) of 26.5% or higher as measured according to ASTM D2863-17a, and (ii) a total volatile organic matter content (TVOC) of 225 μg / g C or lower as measured according to VDA 277.

[0068] Examples 9-10 - Examples In these examples, the aim was to produce foam samples with improved flammability (LOI of 26.5% or more) and improved TVOC properties (TVOC of 225 μg / g C or less) compared to the foam samples produced in Examples 1-4. Specifically, the polyether polyol used to produce the polyurethane foam was removed, and the amount of "reactive compound" (as defined herein, a compound having (1) at least one hydrogen that is reactive with isocyanate, and (2) one or both of a halogen and / or phosphate moiety) XB2000 was increased. These examples represent the most preferred embodiments of the present invention as currently envisioned by the inventors.

[0069] Foam samples were prepared from commercially available raw materials by Xanathane Systems using the methods described above. The raw materials used in these examples are shown in Tables 9-10, all values ​​being in parts by weight.

[0070] Tables 9-10 also show some of the properties of the obtained foams. As is clear from these tables, a significant amount of modification of the polyether polyol used to produce the polyurethane foam to a “reactive compound” (as defined herein, (1) a compound having at least one hydrogen that is reactive with isocyanate, and (2) a compound having one or both of a halogen and / or phosphate moiety) XB2000 results in a very desirable combination of LOI and TVOC. Specifically, each foam sample had (i) a limiting oxygen index (LOI) of 26.5% or higher as measured according to ASTM D2863-17a, and (ii) a total volatile organic matter content (TVOC) of 225 μg / g C or lower as measured according to VDA 277.

[0071] Although the present invention is described in relation to exemplary embodiments and examples, this description is not intended to be constrained. Therefore, exemplary embodiments, as well as various modifications of other embodiments of the invention, will be apparent to those skilled in the art by reference to this description. Accordingly, the appended claims are intended to encompass any such modifications or embodiments.

[0072] All publications, patents, and patent applications referred to herein are incorporated in their entirety to the same extent as individual publications, patents, or patent applications are specifically and comprehensively incorporated.

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3]

[0076] [Table 4]

[0077] Table 5

[0078] Table 6

[0079] Table 7

[0080] Table 8

[0081] Table 9

[0082] Table 10

Claims

1. (a) Isocyanates; (b) (1) at least one hydrogen that is reactive with an isocyanate, and (2) a reactive compound having one or both of a halogen and a phosphate moiety; (c) Foaming agents containing either water or carbon dioxide or both; and (d) catalyst; Manufactured from a foaming composition containing, Herein, the amount of the reactive compound present in the foaming composition is 30% to 95% of the total ISO equivalent excluding water, and (1) substantially free of polyols containing a hydroxyl-terminated skeleton selected from the group consisting of polyethers, polyesters, polycarbonates, polydienes, and polycaprolactones, and (2) the foaming composition is an isocyanate polymer foam having (i) a limiting oxygen index (LOI) of 26.5% or more as measured according to ASTM D2863-17a, and (ii) a total volatile organic matter content (TVOC) of 225 μg / g C or less as measured according to VDA 277.

2. The isocyanate-based polymer foam according to claim 1, wherein the amount of the reactive compound is 40 to 90% of the total ISO equivalents excluding water, or the amount of the reactive compound is 45 to 85% of the total ISO equivalents excluding water.

3. The reactive compound is the following part: hydroxyl(R-OH), amino(R-NH) ２ The isocyanate polymer foam according to claim 1 or 2, comprising one or more of ) and iminyl (R=NH).

4. The isocyanate-based polymer foam according to any one of claims 1 to 3, wherein the reactive compound is selected from the group consisting of halogenated aromatic esters, halogenated aromatic ethers, halogenated aliphatic esters, halogenated aliphatic ethers, halogenated phosphate esters, non-halogenated phosphate esters, and mixtures thereof.

5. The isocyanate-based polymer foam according to any one of claims 1 to 4, wherein the isocyanate comprises a prepolymer.

6. The isocyanate-based polymer foam according to any one of claims 1 to 5, wherein the isocyanate is selected from the group consisting essentially of (i) 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof; and (ii) a mixture of (i) and an isocyanate selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof.

7. The isocyanate-based polymer foam according to any one of claims 1 to 6, wherein the isocyanate is present in an amount that provides an isocyanate index of 60 to 200, the isocyanate is present in an amount that provides an isocyanate index of 80 to 160, or the isocyanate is present in an amount that provides an isocyanate index of 100 to 150.

8. The isocyanate polymer foam according to any one of claims 1 to 7, wherein water is present in the foaming composition as the sole foaming agent.

9. The isocyanate-based polymer foam according to claim 8, wherein the amount of water present is 3.0 to 15% by weight of the foaming composition excluding the isocyanate, the amount of water present is 4.0 to 8.0% by weight of the foaming composition excluding the isocyanate, or the amount of water present is 4.0 to 6.0% by weight of the foaming composition excluding the isocyanate.

10. Density of 8.0–48 kg / m³ ３ The density is 16-40 kg / m³. ３ It is, or its density is 24-32 kg / m³ ３ The isocyanate-based polymer foam according to any one of claims 1 to 9.

11. An isocyanate-based polymer foam according to any one of claims 1 to 10, wherein the LOI is 26.5% to 35.0%, the LOI is 27.0% to 35.0%, the LOI is 27.0% to 34.0%, the LOI is 27.0% to 33.0%, the LOI is 27.0% to 32.0%, the LOI is 27.0% to 31.0%, the LOI is 27.0% to 31.0%, the LOI is 27.0% to 30.0%, the LOI is 27.5% to 30.0%, or the LOI is 28.0% to 30.0%.

12. TVOC is 50-225 μg / g C, TVOC is 50-215 μg / g C, TVOC is 50-180 μg / g C, TVOC is 50-170 μg / g C, TVOC is 50-150 μg / g C, TVOC is 60-150 μg / g C, TVOC is 70-150 μg / g C, TVOC is 70-140 μg / g C, TVOC is 70-130 μg / g C, TVOC is 70-120 μg / g C, TVOC is 70-110 μg / g C, or TVOC is 70-100 μg / g C is an isocyanate-based polymer foam according to any one of claims 1 to 11.

Images