A semi-combustible polyurethane foam insulation material with excellent insulation properties and durability comprising an inorganic layered nanosheet modified with polyhedral oligomeric silsesquioxane, and a method for producing the same

Abstract

The present invention relates to a semi-flammable rigid polyurethane foam insulation material comprising an inorganic layered nanosheet (ILNS) modified with polyhedral oligomeric silsesquioxane (POSS) and a method for manufacturing the same. More specifically, the invention relates to a semi-noncombustible rigid polyurethane foam with excellent thermal insulation and durability, manufactured using a composition comprising a polyol, an isocyanate compound, a hybrid composite combining a functional POSS and an inorganic layered nanosheet, a flame retardant, a foaming agent, a surfactant, and a catalyst. The hybrid composite of the present invention can significantly improve thermal and mechanical stability by expanding the interlayer distance and forming a BNNS-POSS-BNNS bridge structure in which POSS is inserted between inorganic layers, with functional POSS bonded to the surface and between layers of inorganic layered nanosheets via covalent or siloxane bonds. Accordingly, not only can excellent dispersibility and interfacial stability be secured during the foaming process, but a highly flame-retardant structure is also formed, in which Si-OBN and Si-OPBN-based ceramic layer is generated during combustion, thereby reducing the peak heat release rate (PHRR) and total heat release (THR). In addition, the semi-noncombustible rigid polyurethane foam of the present invention reduces the amount of flame retardant used compared to existing flame-retardant systems while fully satisfying semi-noncombustible standards, and exhibits excellent core properties as an insulating material, such as compressive strength, dimensional stability, and thermal conductivity. Due to these structural and physical properties, the semi-fireproof rigid polyurethane foam of the present invention can be directly applied to various construction and industrial insulation structures, such as sandwich panels, roof panels, exterior insulation systems (replacing EPS and XPS), refrigeration and freezing panels, and insulation materials for tanks and pipes. In particular, the present invention provides a hybrid composite in the form of a polyol masterbatch, allowing it to be directly applied to existing foaming lines (continuous or batch type). It is a semi-fireproof insulation technology with very high commercial value, as it simultaneously achieves improved manufacturing process stability, increased productivity, and cost reduction.

Description

Technology Field

[0001] The present invention relates to a semi-flame-retardant polyurethane foam insulation material with excellent thermal insulation and durability comprising an inorganic layered nanosheet modified with polyhedral oligomeric silsesquioxane, and a method for manufacturing the same. More specifically, the invention relates to a composition for semi-flame-retardant rigid polyurethane foam comprising a polyol, an isocyanate compound, a hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst, a semi-flame-retardant rigid polyurethane foam, and a method for manufacturing the same. Background Technology

[0003] Rigid polyurethane foam is widely used in insulation, structural materials, and industrial panels, but it exhibits a high heat release rate (PHRR) upon combustion, generates smoke and toxic gases, and has poor thermal and dimensional stability.

[0004] To improve this, using flame retardants such as phosphorus-based flame retardants or expanded graphite enhances flame retardancy but leads to a problem of reduced mechanical performance.

[0005] Recently, thermal barrier technology using 2D inorganic nanosheets (hBN, MXene, graphene, etc.) has been attracting attention, but there are limitations to its practical application due to issues such as aggregation and dispersion of the inorganic layer and a lack of interfacial bonding with the polyurethane network.

[0006] Therefore, there is a need for technological development of new hybrid fillers that can improve flame retardancy, mechanical properties, thermal insulation, dimensional stability, and durability even at low content levels. Prior art literature

[0008] Korean Registered Patent No. 10-1340061 Korean Registered Patent No. 10-2397310 The problem to be solved

[0009] The present invention aims to provide semi-noncombustible rigid polyurethane foam and insulation materials with excellent flame retardancy, mechanical properties, thermal insulation, dimensional stability, and durability by using a hybrid composite prepared by reacting an inorganic layered nanosheet with a functional polyhedral oligomeric silsesquioxane. means of solving the problem

[0011] To achieve the above objectives, the present invention provides a composition for semi-flammable rigid polyurethane foam comprising a polyol, an isocyanate compound, a hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst.

[0012] In one embodiment of the present invention, the composition is characterized by comprising 20 to 70 weight% of a polyol, 20 to 70 weight% of an isocyanate compound, 0.1 to 10 weight% of a hybrid composite, 1 to 20 weight% of a flame retardant, 1 to 20 weight% of a foaming agent, 0.1 to 5 weight% of a surfactant, and 0.1 to 5 weight% of a catalyst.

[0013] In one embodiment of the present invention, the hybrid composite is characterized by being prepared by reacting an inorganic layered nanosheet with a functional polyhedral oligomeric silsesquioxane.

[0014] In one embodiment of the present invention, the inorganic layered nanosheet is characterized by using one or more of hexagonal boron nitride, clay, mica, montmorillonite, and layered silicate.

[0015] In one embodiment of the present invention, the functional polyhedral oligomeric silsesquioxane is characterized by comprising one or more functional groups selected from amino groups, epoxy groups, isocyanate groups, phosphonate groups, thiol groups, vinyl groups, acrylic groups, acrylate groups, and carboxyl groups.

[0016] In one embodiment of the present invention, the hybrid composite is characterized by having a functional polyhedral oligomeric silsesquioxane bonded to the surface of an inorganic layered nanosheet.

[0017] In one embodiment of the present invention, the hybrid composite is characterized in that a functional polyhedral oligomeric silsesquioxane is inserted between layers of inorganic nanosheets and bonded to each layer.

[0018] In one embodiment of the present invention, the interlayer spacing (d-spacing) of the inorganic layered nanosheets of the hybrid composite is extended to 0.34 to 1.00 nm.

[0019] In one embodiment of the present invention, the functional polyhedral oligomeric silsesquioxane is characterized by forming a BNNS-POSS-BNNS bridge structure connecting two or more inorganic layered nanosheets.

[0020] In one embodiment of the present invention, the inorganic layered nanosheet is characterized by being combined with a functional polyhedral oligomeric silsesquioxane in a state where catechol groups and amine groups are introduced to the surface through a polydopamine (PDA) primer treatment using dopamine.

[0021] In addition, the present invention comprises the step of surface treating an inorganic layered nanosheet;

[0022] Step of hydrolyzing functional polyhedral oligomeric silsesquioxane;

[0023] A step of preparing a hybrid composite by reacting a surface-treated inorganic layered nanosheet with a hydrolyzed functional polyhedral oligomeric silsesquioxane;

[0024] A step of preparing a composition by mixing a polyol, an isocyanate compound, the hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst; and

[0025] A method for manufacturing semi-flammable rigid polyurethane foam is provided, comprising the step of foaming the above composition to produce rigid polyurethane foam.

[0026] In one embodiment of the present invention, the hybrid composite is characterized in that a functional polyhedral oligomeric silsesquioxane is bonded to the surface of an inorganic layered nanosheet, and a functional polyhedral oligomeric silsesquioxane is inserted between the layers of the inorganic layered nanosheet and bonded to each layer.

[0027] In one embodiment of the present invention, the hybrid composite is characterized by being bonded with a polyurethane molecule.

[0028] In one embodiment of the present invention, the amino group, epoxy group, or isocyanate group of the functional polyhedral oligomeric silsesquioxane is characterized by forming a urea or urethane bond with a polyurethane network and being chemically fixed within the matrix.

[0029] In one embodiment of the present invention, the hybrid composite is characterized by being provided in the form of a masterbatch having a solid content of 10 to 40 weight% using a polyol as a dispersion medium.

[0030] In one embodiment of the present invention, the introduction of the hybrid composite stabilizes the cream-time and gel-time of the foaming process, thereby improving the production speed.

[0031] In one embodiment of the present invention, the hybrid composite is provided in the form of a masterbatch, so that it can be manufactured without an additional dispersion process.

[0032] In addition, the present invention provides a semi-flame-retardant rigid polyurethane foam manufactured by the above manufacturing method.

[0033] In one embodiment of the present invention, the semi-flame-retardant rigid polyurethane foam is characterized by having a peak heat release rate (PHRR) reduced by 10 to 50% compared to a semi-flame-retardant rigid polyurethane foam that does not contain a hybrid composite.

[0034] In one embodiment of the present invention, the semi-flame-retardant rigid polyurethane foam is characterized by having a compressive strength that increases by 5 to 20% compared to a semi-flame-retardant rigid polyurethane foam that does not contain a hybrid composite.

[0035] In one embodiment of the present invention, the introduction of a hybrid composite is characterized by reducing the total amount of flame retardant used by 5 to 30 percent while maintaining semi-flame retardant performance.

[0036] In one embodiment of the present invention, the thermal conductivity increase rate is 10% or less even when maintained for 90 days or more under storage conditions of 50°C or higher.

[0037] In addition, the present invention provides an insulating material comprising the above-mentioned semi-flammable rigid polyurethane foam.

[0038] In one embodiment of the present invention, the semi-noncombustible rigid polyurethane foam is characterized by forming a Si-OBN or Si-OPBN-based ceramic layer upon combustion.

[0039] In one embodiment of the present invention, it is characterized by being used in one or more of a sandwich panel, a roof panel, an external insulation system, a refrigeration panel, and a cold storage panel.

[0040] In one embodiment of the present invention, the thermal insulation material is characterized by satisfying KS F 2271, KS F 2277, or an international semi-noncombustible standard equivalent thereto.

[0041] In one embodiment of the present invention, the semi-fireproof rigid polyurethane foam is characterized by being molded into a pipe insulation material, a cold insulation material, a tank insulation material, a refrigerator insulation material, or an electronic product insulation material.

[0042] In one embodiment of the present invention, the semi-fireproof rigid polyurethane foam is characterized by being used as an exterior wall insulation material for buildings, replacing glass wool, mineral wool, EPS, or XPS. Effects of the invention

[0044] The present invention can provide semi-flame-retardant rigid polyurethane foam and insulation materials with excellent flame retardancy, mechanical properties, thermal insulation, dimensional stability, and durability by using a hybrid composite prepared by reacting an inorganic layered nanosheet with a functional polyhedral oligomeric silsesquioxane. Brief explanation of the drawing

[0046] Figure 1 shows the manufacturing process of a hybrid composite prepared by reacting an inorganic layered nanosheet of the present invention with a functional polyhedral oligomeric silsesquioxane. Figure 2 shows the semi-flammable rigid polyurethane foam of the present invention. Specific details for implementing the invention

[0047] The present invention will be described in detail below based on the following examples. The terms and examples used in this invention are merely illustrative to explain the invention more specifically and to aid the understanding of those skilled in the art, and the scope of the rights of the present invention should not be interpreted as being limited thereto.

[0048] Unless otherwise defined, technical and scientific terms used in this invention represent the meanings commonly understood by those skilled in the art to which this invention pertains.

[0050] The present invention relates to a composition for semi-flame-retardant rigid polyurethane foam comprising a polyol, an isocyanate compound, a hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst.

[0051] The above composition may include 20 to 70 wt% polyol, 20 to 70 wt% isocyanate compound, 0.1 to 10 wt% hybrid composite, 1 to 20 wt% flame retardant, 1 to 20 wt% foaming agent, 0.1 to 5 wt% surfactant, and 0.1 to 5 wt% catalyst.

[0052] If the content satisfies the above numerical range, thermal insulation and durability can be maximized.

[0054] The above polyols may include aliphatic polyols (glycerin, sorbitol, pentaerythritol, etc.), aromatic polyols (1,5-naphthalenediol, 4-methylbenzene-1,2-diol, etc.), polyether polyols (polypropylene glycol, polytetramethylene glycol, polyethylene glycol, etc.), polyester polyols, polycarbonate polyols, polybutadiene polyols, polyoxyethylpropyl glycol, polyoxytetraethylene glycol, polyoxyethylene glycol, etc.

[0056] The above isocyanate compounds may include metaxylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI), tetramethylxylene diisocyanate (TMXDI), hexahydrophthalic acid diisocyanate (HHDI), 4,4'-diphenylmethane diisocyanate (MDI), etc.

[0058] The above hybrid composite can be prepared by reacting an inorganic layered nanosheet (ILNS) and a functional polyhedral oligomeric silsesquioxane (POSS) (Fig. 1).

[0059] The above inorganic layered nanosheets may be one or more of hexagonal boron nitride (hBN), clay, mica, montmorillonite, and layered silicates.

[0060] The above functional polyhedral oligomeric silsesquioxane may include one or more functional groups selected from amino groups, epoxy groups, isocyanate groups, phosphonate groups, thiol groups, vinyl groups, acrylic groups, acrylate groups, and carboxyl groups.

[0061] In the above hybrid composite, functional polyhedral oligomeric silsesquioxane can be bonded to the surface of an inorganic layered nanosheet, and functional polyhedral oligomeric silsesquioxane can also be inserted between the layers of the inorganic layered nanosheet and bonded to each layer.

[0062] As an example, the hydroxyl group (-OH) of the inorganic layered nanosheet and the silanol group (-Si-OH) of the functional POSS can form a covalent bond through a reaction, thereby allowing the functional polyhedral oligomeric silsesquioxane to be bonded to the surface of the inorganic layered nanosheet.

[0063] In addition, functional POSS can be inserted between layers of inorganic nanosheets to form a bridge structure through covalent bonding with each layer.

[0064] That is, the above functional polyhedral oligomeric silsesquioxane can form a BNNS-POSS-BNNS bridge structure connecting two or more inorganic layered nanosheets.

[0065] By forming the above bridge structure, the distance between layers of the inorganic layered nanosheets increases and each layer is peeled off, thereby improving the dispersibility of the nanosheets within the polyurethane foam, which can improve the thermal insulation, mechanical properties, and durability of the polyurethane foam.

[0066] At this time, the interlayer distance (d-spacing) of the inorganic layer nanosheets of the above hybrid composite can be extended to 0.34~1.00 nm.

[0067] In addition, the functional groups of functional POSS can form covalent bonds with polyols, isocyanate compounds, polyurethanes, etc., and through this, the interfacial characteristics of polyurethanes and hybrid composites are improved, which can enhance the thermal insulation, mechanical properties, and durability of polyurethane foam.

[0068] In addition, the polyurethane foam of the present invention can improve heat and gas barrier properties and exhibit semi-non-combustible properties by having the inorganic layered nanosheets and POSS form a ceramic network layer of a Si-OBN structure or Si-OPBN structure upon pyrolysis or combustion.

[0070] The above flame retardant may be one or more of bromine-based flame retardants, antimony trioxide, phosphorus-based flame retardants, melamine cyanurate, melamine resin, magnesium hydroxide, and aluminum hydroxide.

[0071] The above-mentioned phosphorus-based flame retardants may include tris(chloroisopropyl)phosphate (TCPP), triethylphosphate (TEP), tris(2-carboxyethyl)phosphine (TCEP), etc.

[0073] One or more of the above blowing agents may be used from pentane, cyclopentane, 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, azodicarbonamide (ADCA), N,N-dinitrosopentamethylenetetramine, 4,4'-oxybis(benzenesulfonylhydrazide), diphenylsulfone-3,3'-disulfonylhydrazide, p-toluenesulfonylsemicarbazide, trihydrazinotriazine, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, and ammonium carbonate.

[0075] The above surfactant may be a silicone-based surfactant such as polydimethylsiloxane or silicone glycol copolymer.

[0076] The above silicone glycol copolymer may include a copolymer of polydimethylsiloxane and polyoxyalkylene ether, etc.

[0078] The above catalyst may be pentamethyldiethylenetriamine (PMDETA), di-(N,N-dimethylaminoethyl)ether (BDMEE), etc.

[0080] In addition, the present invention comprises the step of surface treating an inorganic layered nanosheet;

[0081] Step of hydrolyzing functional polyhedral oligomeric silsesquioxane;

[0082] A step of preparing a hybrid composite by reacting a surface-treated inorganic layered nanosheet with a hydrolyzed functional polyhedral oligomeric silsesquioxane;

[0083] A step of preparing a composition by mixing a polyol, an isocyanate compound, the hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst; and

[0084] The present invention relates to a method for manufacturing semi-fireproof rigid polyurethane foam, comprising the step of foaming the above composition to produce rigid polyurethane foam.

[0086] The step of surface treating the above-mentioned inorganic layered nanosheet can treat the inorganic layered nanosheet with plasma, ozone, hydrogen peroxide, polydopamine, etc.

[0087] Through the above surface treatment, functional groups such as hydroxyl groups, amino groups, carboxyl groups, amino groups, ketone groups, ester groups, and ether groups can be introduced to the surface of the inorganic layered nanosheet.

[0088] Functional groups introduced into inorganic layered nanosheets through surface treatment can form covalent bonds with functional POSS, polyols, isocyanates, polyurethanes, etc.

[0089] For example, hydroxyl groups (-OH) introduced into the inorganic layered nanosheet through surface treatment can form covalent bonds through reaction with the silanol groups (-Si-OH) of the functional POSS.

[0090] In addition, the above-mentioned inorganic layer nanosheet can be combined with functional polyhedral oligomeric silsesquioxane in a state where catechol groups and amine groups are introduced to the surface through polydopamine (PDA) primer treatment using dopamine.

[0092] The step of hydrolyzing the above functional polyhedral oligomeric silsesquioxane can convert the -Si(OR)3 group located at the terminal of the functional POSS into a -Si(OH)3 group through hydrolysis.

[0094] A hybrid composite can be prepared by reacting the above-mentioned surface-treated inorganic layered nanosheet with hydrolyzed functional polyhedral oligomeric silsesquioxane.

[0095] In the above hybrid composite, functional polyhedral oligomeric silsesquioxane can be bonded to the surface of an inorganic layered nanosheet, and functional polyhedral oligomeric silsesquioxane can also be inserted between the layers of the inorganic layered nanosheet and bonded to each layer.

[0096] As an example, the hydroxyl group (-OH) of the inorganic layered nanosheet and the silanol group (-Si-OH) of the functional POSS can form a covalent bond through a reaction, thereby allowing the functional polyhedral oligomeric silsesquioxane to be bonded to the surface of the inorganic layered nanosheet.

[0097] In addition, functional POSS can be inserted between layers of inorganic nanosheets to form a bridge structure through covalent bonding with each layer.

[0098] In addition, the functional groups of functional POSS can form covalent bonds with inorganic layered nanosheets, polyols, isocyanate compounds, polyurethanes, etc., and through this, the hybrid composite can be bonded to polyurethane chains or networks.

[0099] At this time, the nanosheet on the inorganic layer may include a structure partially exfoliated by ultrasonic dispersion, high-shear mixing, or surfactant-assisted exfoliation.

[0101] A composition can be prepared by mixing the above polyol, isocyanate compound, above hybrid composite, flame retardant, foaming agent, surfactant, and catalyst.

[0103] The step of manufacturing a rigid polyurethane foam by foaming the above composition may be performed by foaming the above composition at a temperature of 10 to 200°C and a pressure of 1 to 500 bar to manufacture the rigid polyurethane foam.

[0104] In addition, the present invention can be manufactured while maintaining process stability in a continuous foaming line or a batch foaming process.

[0105] The amino, epoxy, or isocyanate groups of the above functional polyhedral oligomeric silsesquioxane can be chemically immobilized within the matrix by forming urea or urethane bonds with the polyurethane network.

[0107] In addition, the hybrid composite of the present invention may be provided in the form of a masterbatch having a solid content of 10 to 40 weight% using a polyol as a dispersion medium.

[0108] Since the above hybrid composite is provided in the form of a masterbatch, it can be manufactured without an additional dispersion process.

[0109] In addition, the introduction of the above hybrid composite stabilizes the cream-time and gel-time of the foaming process, thereby improving the production speed.

[0111] In addition, the present invention relates to a semi-flame-retardant rigid polyurethane foam manufactured by the above manufacturing method (Fig. 2).

[0112] The semi-flame-retardant rigid polyurethane foam of the present invention may have a peak heat release rate (PHRR) reduced by 10 to 50% compared to semi-flame-retardant rigid polyurethane foam that does not contain a hybrid composite.

[0113] In addition, the semi-flame-retardant rigid polyurethane foam of the present invention may have a compressive strength that is 5 to 20 percent higher than that of a semi-flame-retardant rigid polyurethane foam that does not contain a hybrid composite.

[0114] The above semi-noncombustible rigid polyurethane foam can maintain semi-noncombustible performance while reducing the total amount of flame retardant used by 5 to 30 percent through the introduction of a hybrid composite.

[0115] In this case, the emission of volatile organic compounds (VOCs) can be reduced as the amount of flame retardant is reduced.

[0116] In addition, the above semi-fireproof rigid polyurethane foam may have a thermal conductivity increase rate of 10% or less even when maintained for 90 days or more under storage conditions of 50°C or higher.

[0117] In addition, the above-mentioned semi-fireproof rigid polyurethane foam can maintain an initial thermal conductivity in the range of 0.020 to 0.030 W / m·K.

[0119] In addition, the present invention relates to an insulating material comprising the above-mentioned semi-flammable rigid polyurethane foam.

[0120] The present invention can provide semi-flame-retardant rigid polyurethane foam and insulation materials with excellent flame retardancy, mechanical properties, thermal insulation, dimensional stability, and durability by using a hybrid composite prepared by reacting an inorganic layered nanosheet with a functional polyhedral oligomeric silsesquioxane.

[0121] The above semi-noncombustible rigid polyurethane foam can form a Si-OBN or Si-OPBN-based ceramic layer upon combustion.

[0122] In addition, the above insulation material can be used in one or more of sandwich panels, roof panels, exterior insulation systems, refrigeration panels, and cold storage panels.

[0123] In addition, the above insulation material may satisfy KS F 2271, KS F 2277, or equivalent international semi-noncombustible standards.

[0124] In addition, the above-mentioned semi-fireproof rigid polyurethane foam can be molded into pipe insulation, cold insulation, tank insulation, refrigerator insulation, or electronic product insulation.

[0125] In addition, the above-mentioned semi-fireproof rigid polyurethane foam can be used as exterior wall insulation for buildings, replacing glass wool, mineral wool, EPS, or XPS.

[0127] The present invention will be described in detail below through examples and comparative examples. The following examples are merely illustrative for the implementation of the present invention, and the scope of the present invention is not limited by the following examples.

[0129] (Example 1)

[0130] A composition was prepared by mixing 30.20 wt% polyester polyol, 58.17 wt% 4,4'-diphenylmethane diisocyanate (MDI), 3.60 wt% flame retardant (TCPP), 4.78 wt% foaming agent (pentane), 0.73 wt% surfactant (silicone-based compound), and 2.52 wt% catalyst (pentamethyldiethylenetriamine).

[0131] A rigid polyurethane foam was produced by foaming the above composition at a temperature of 30°C and a pressure of 100 bar.

[0133] (Example 2)

[0134] Hexagonal boron nitride (hBN) was plasma treated.

[0135] Functional polyhedral oligomeric silsesquioxane was hydrolyzed.

[0136] A hybrid composite was prepared by reacting plasma-treated inorganic layered nanosheets with hydrolyzed functional polyhedral oligomeric silsesquioxane.

[0138] A composition was prepared by mixing 30.20 wt% polyester polyol, 58.17 wt% 4,4'-diphenylmethane diisocyanate (MDI), 0.50 wt% of the hybrid composite, 3.60 wt% flame retardant (TCPP), 4.78 wt% foaming agent (pentane), 0.73 wt% surfactant (silicone-based compound), and 2.02 wt% catalyst (pentamethyldiethylenetriamine).

[0139] A rigid polyurethane foam was produced by foaming the above composition at a temperature of 30°C and a pressure of 100 bar.

[0141] Compared to Example 1, the rigid polyurethane foam had improved dimensional stability, increased compressive strength by 5-10%, and decreased heat release rate (PHRR) by 5-15%.

[0143] (Example 3)

[0144] Hexagonal boron nitride (hBN) was plasma treated.

[0145] Functional polyhedral oligomeric silsesquioxane was hydrolyzed.

[0146] A hybrid composite was prepared by reacting plasma-treated inorganic layered nanosheets with hydrolyzed functional polyhedral oligomeric silsesquioxane.

[0148] A composition was prepared by mixing 30.20 wt% polyester polyol, 58.17 wt% 4,4'-diphenylmethane diisocyanate (MDI), 1.00 wt% of the hybrid composite, 3.60 wt% flame retardant (TCPP), 4.78 wt% foaming agent (pentane), 0.73 wt% surfactant (silicone-based compound), and 0.52 wt% catalyst (pentamethyldiethylenetriamine).

[0149] A rigid polyurethane foam was produced by foaming the above composition at a temperature of 30°C and a pressure of 100 bar.

[0151] Compared to Example 1, the rigid polyurethane foam had a compressive strength improved by 10–20%, a heat release rate (PHRR) decreased by 15–25%, and a THR decreased by 10–20%.

Claims

Claim 1 A composition for semi-noncombustible rigid polyurethane foam comprising a polyol, an isocyanate compound, a hybrid composite, a flame retardant, a blowing agent, a surfactant, and a catalyst, wherein the composition comprises 20 to 70 wt% polyol, 20 to 70 wt% isocyanate compound, 0.1 to 10 wt% hybrid composite, 1 to 20 wt% flame retardant, 1 to 20 wt% blowing agent, 0.1 to 5 wt% surfactant, and 0.1 to 5 wt% catalyst, wherein the hybrid composite is prepared by reacting an inorganic layered nanosheet and a functional polyhedral oligomeric silsesquioxane, wherein the functional polyhedral oligomeric silsesquioxane is bonded to the surface of the inorganic layered nanosheet, and wherein the functional polyhedral oligomeric silsesquioxane is inserted between the layers of the inorganic layered nanosheet and bonded to each layer, and wherein the functional polyhedral oligomeric A composition for semi-flame-retardant rigid polyurethane foam characterized in that the functional group of silsesquioxane forms a covalent bond with an inorganic layered nanosheet, a polyol, an isocyanate compound, or a polyurethane, and when the polyurethane foam undergoes pyrolysis or combustion, the inorganic layered nanosheet and the functional polyhedral oligomeric silsesquioxane form a ceramic network layer of a Si-OBN structure or a Si-OPBN structure, thereby improving heat and gas barrier properties and exhibiting semi-flame-retardant properties. Claim 2 delete Claim 3 delete Claim 4 A composition for semi-flame-retardant rigid polyurethane foam according to claim 1, characterized in that the inorganic layered nanosheet is used from one or more of hexagonal boron nitride, clay, mica, montmorillonite, and layered silicate. Claim 5 A composition for semi-flame-retardant rigid polyurethane foam according to claim 1, wherein the functional polyhedral oligomeric silsesquioxane comprises one or more functional groups selected from amino groups, epoxy groups, isocyanate groups, phosphonate groups, thiol groups, vinyl groups, acrylic groups, acrylate groups, and carboxyl groups. Claim 6 delete Claim 7 delete Claim 8 A composition for semi-flame-retardant rigid polyurethane foam, characterized in that, in claim 1, the interlayer distance (d-spacing) of the inorganic layered nanosheets of the hybrid composite is extended to 0.34 to 1.00 nm. Claim 9 A composition for semi-flame-retardant rigid polyurethane foam according to claim 1, characterized in that the functional polyhedral oligomeric silsesquioxane forms a BNNS-POSS-BNNS bridge structure connecting two or more inorganic layered nanosheets. Claim 10 A composition for semi-flame-retardant rigid polyurethane foam according to claim 1, characterized in that the inorganic layered nanosheet is combined with a functional polyhedral oligomeric silsesquioxane in a state where catechol groups and amine groups are introduced to the surface through a polydopamine (PDA) primer treatment using dopamine. Claim 11 A step of surface-treating an inorganic layered nanosheet; a step of hydrolyzing a functional polyhedral oligomeric silsesquioxane; a step of preparing a hybrid composite by reacting the surface-treated inorganic layered nanosheet and the hydrolyzed functional polyhedral oligomeric silsesquioxane; a step of preparing a composition for semi-non-combustible rigid polyurethane foam by mixing a polyol, an isocyanate compound, the hybrid composite, a flame retardant, a foaming agent, a surfactant, and a catalyst; A method for manufacturing semi-fireproof rigid polyurethane foam comprising the step of foaming the composition for semi-fireproof rigid polyurethane foam to manufacture rigid polyurethane foam, wherein the step of surface treating the inorganic layered nanosheet involves treating the inorganic layered nanosheet with plasma, ozone, hydrogen peroxide, or polydopamine, wherein the hybrid composite is formed by binding a functional polyhedral oligomeric silsesquioxane to the surface of the inorganic layered nanosheet, wherein the hybrid composite is formed by inserting a functional polyhedral oligomeric silsesquioxane between the layers of the inorganic layered nanosheet and bonding it to each layer, wherein the functional group of the functional polyhedral oligomeric silsesquioxane forms a covalent bond with the inorganic layered nanosheet, polyol, isocyanate compound, or polyurethane, and wherein the composition comprises 20-70 wt% polyol, 20-70 wt% isocyanate compound, 0.1-10 wt% hybrid composite, 1-20 wt% flame retardant, and blowing agent A method for manufacturing a semi-flame-retardant rigid polyurethane foam comprising 1 to 20% by weight, 0.1 to 5% by weight of a surfactant, and 0.1 to 5% by weight of a catalyst, wherein the step of manufacturing the rigid polyurethane foam comprises foaming the composition for the semi-flame-retardant rigid polyurethane foam at a temperature of 10 to 200°C and a pressure of 1 to 500 bar to manufacture the rigid polyurethane foam, wherein, upon thermal decomposition or combustion, the inorganic layered nanosheet and functional polyhedral oligomeric silsesquioxane form a ceramic network layer having a Si-OBN structure or a Si-OPBN structure, thereby improving heat and gas barrier properties and exhibiting semi-flame-retardant properties. Claim 12 delete Claim 13 delete Claim 14 A method for manufacturing semi-fireproof rigid polyurethane foam, characterized in that, in claim 11, the hybrid composite is bonded with polyurethane molecules. Claim 15 A method for manufacturing semi-fireproof rigid polyurethane foam according to claim 11, characterized in that the amino group, epoxy group, or isocyanate group of the functional polyhedral oligomeric silsesquioxane forms a urea or urethane bond with the polyurethane network and is chemically fixed within the matrix. Claim 16 A method for manufacturing semi-flame-retardant rigid polyurethane foam, characterized in that, in claim 11, the hybrid composite is provided in the form of a masterbatch having a solid content of 10 to 40 weight% using a polyol as a dispersion medium. Claim 17 A method for manufacturing semi-fireproof rigid polyurethane foam, characterized in that, in claim 11, the introduction of the hybrid composite stabilizes the cream-time and gel-time of the foaming process and improves the production speed. Claim 18 A method for manufacturing semi-fireproof rigid polyurethane foam, characterized in that, in claim 16, the hybrid composite is provided in the form of a masterbatch, thereby enabling manufacturing without an additional dispersion process. Claim 19 Semi-noncombustible rigid polyurethane foam manufactured by the manufacturing method of claim 11. Claim 20 A semi-flame-retardant rigid polyurethane foam according to claim 19, characterized by a peak heat release rate (PHRR) reduced by 10 to 50% compared to a semi-flame-retardant rigid polyurethane foam that does not contain a hybrid composite. Claim 21 In claim 19, a semi-fireproof rigid polyurethane foam characterized by a compressive strength that increases by 5 to 20% compared to a semi-fireproof rigid polyurethane foam that does not contain a hybrid composite. Claim 22 In claim 19, a semi-noncombustible rigid polyurethane foam characterized by maintaining semi-noncombustible performance while reducing the total amount of flame retardant used by 5 to 30 percent through the introduction of a hybrid composite. Claim 23 A semi-noncombustible rigid polyurethane foam according to claim 19, characterized in that the increase rate of thermal conductivity is 10% or less even when maintained for 90 days or more under storage conditions of 50℃ or higher. Claim 24 Insulation material comprising the semi-noncombustible rigid polyurethane foam of Clause 19. Claim 25 In claim 24, the above-mentioned semi-noncombustible rigid polyurethane foam is an insulating material characterized by forming a Si-OBN or Si-OPBN-based ceramic layer upon combustion. Claim 26 In paragraph 24, an insulating material characterized by being used in one or more of sandwich panels, roof panels, external insulation systems, refrigeration panels, and cold storage panels. Claim 27 In claim 24, the insulation material is characterized by satisfying KS F 2271, KS F 2277, or an equivalent international semi-noncombustible standard. Claim 28 In claim 24, the insulation material is characterized in that the semi-noncombustible rigid polyurethane foam is molded into a pipe insulation material, a cold insulation material, a tank insulation material, a refrigerator insulation material, or an electronic product insulation material. Claim 29 In claim 24, the insulation material is characterized in that the semi-noncombustible rigid polyurethane foam is used as an exterior wall insulation material for buildings, replacing glass wool, mineral wool, EPS, or XPS.

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