Polyol composition, polyurethane foam material and preparation method thereof

Abstract

The invention discloses a polyol composition, a polyurethane foam material and a preparation method thereof, the polyol composition is prepared by using a polyhydroxy compound as an initiator and catalyzing an epoxy compound and carbon dioxide through a supported DMC catalyst, and the supported DMC catalyst comprises a DMC catalyst supported on natural nano clay; the polyhydric alcohol composition contains nano clay, can directly react with diisocyanate and / or polyisocyanate to be converted into a polyurethane material without separation, and can be used as a nucleating agent and a reinforcing agent when a polyurethane foam material is foamed, so that the structure and performance of the polyurethane foam are regulated and controlled.

Description

Technical Field

[0001] This application relates to the field of foam material preparation technology, and in particular to a polyol composition, a polyurethane foam material, and a method for preparing a polyurethane foam material. Background Technology

[0002] Polyurethane foam is a porous material formed by the chemical reaction of various components such as polyurethane prepolymer, foaming agent, and catalyst. Foamed plastics are one of the main types of synthetic polyurethane materials, characterized by their porosity, resulting in low relative density and high specific strength. Polyurethane foams include flexible foams and rigid foams. Flexible polyurethane foams are mainly used in furniture, bedding, and other household goods; rigid polyurethane foams are mainly used in refrigeration and freezing equipment and cold storage, insulation panels, wall insulation, pipe insulation, tank insulation, and single-component foam sealant.

[0003] Carbon dioxide can be used as a raw material to prepare green polymer materials. The resulting material has molecular chains that combine polyether and polycarbonate segments, with hydroxyl groups at the ends. It can be used as a polyol to prepare polyurethane materials, thus realizing the resource utilization of carbon dioxide.

[0004] Research on carbon dioxide-based polycarbonate polyols and corresponding polyurethane foam materials mainly focuses on the following areas: As can be seen from the above, the existing technology mainly focuses on the conversion rate and selectivity of polycarbonate polyols and their application in polyurethane, but does not pay attention to the influence of the catalyst components remaining in the polycarbonate polyols on the subsequent polyol and polyurethane material properties. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this application is to improve the thermal insulation performance of polyurethane foam materials.

[0006] Another objective of this application is to improve the mechanical properties of polyurethane foam materials.

[0007] To achieve the above objectives, this application adopts the following technical solution: This application discloses a polyol composition, which is prepared by using a polyhydroxy compound as an initiator and catalyzing an epoxide compound and carbon dioxide using a supported DMC catalyst, wherein the supported DMC catalyst includes a DMC catalyst supported on natural nanoclay.

[0008] In some embodiments of this application, the polyol composition comprises a polycarbonate polyol, the polycarbonate polyol having the structural formula represented by formula (1): Equation (1); In formula (1), R1 and R2 represent organic groups, m is 2, 3 or 4, and n≦10.

[0009] In some embodiments of this application, the supported DMC catalyst is prepared by mixing nano-clay dispersion, metal salt aqueous solution, metal cyanide salt aqueous solution and organic complex ligand; The nano-clay dispersion has a solid content of 0.5% to 2.0%, the metal salt aqueous solution has a concentration of 0.1% to 0.5%, the metal cyanide salt aqueous solution has a concentration of 0.12% to 0.6%, and the organic complex ligand has a concentration of 0.15% to 0.75%.

[0010] In some embodiments of this application, the nanoclay includes at least one of montmorillonite, attapulgite, illite, and sepiolite.

[0011] In some embodiments of this application, the metal salt includes at least one of inorganic zinc salt, organic zinc salt, inorganic ferrous salt, and inorganic nickel salt.

[0012] In some embodiments of this application, the inorganic zinc salt includes at least one of zinc sulfate, zinc oxalate, zinc nitrate, and zinc chloride.

[0013] In some embodiments of this application, the organic zinc salt includes zinc gluconate and / or zinc lactate.

[0014] In some embodiments of this application, the inorganic ferrous salt includes at least one of ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous carbonate, and ferrous oxalate.

[0015] In some embodiments of this application, the inorganic nickel salt includes at least one of nickel sulfate, nickel chloride, nickel nitrate, nickel carbonate, and oxalate.

[0016] In some embodiments of this application, the metal cyanide salt includes at least one of sodium hexacyanocobaltate, potassium hexacyanocobaltate, potassium hexacyanoferrate, calcium hexacyanocobaltate, and lithium hexacyanocobaltate.

[0017] In some embodiments of this application, the organic complex ligand comprises aliphatic ethers and / or aliphatic alcohols.

[0018] In some embodiments of this application, the organic complex ligand includes at least one selected from dimethoxyethane, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol.

[0019] In some embodiments of this application, the supported DMC catalyst is prepared by the following method: Add an aqueous solution of a metal salt, an aqueous solution of a metal cyanide salt, and an organic complex ligand to a nano-clay dispersion, mix thoroughly, and obtain a suspension. The above suspension was separated by centrifugation to obtain a crude supported DMC catalyst; The crude supported DMC catalyst was cleaned using organic complex ligands. The cleaned supported DMC catalyst was dried to obtain a refined supported DMC catalyst.

[0020] Another aspect of this application provides a polyurethane foam material, comprising component A and component B; component A comprises 70 to 100 parts by weight of the polyol composition as described in any of the preceding claims, 0.5 to 25 parts by weight of a blowing agent, and 0.05 to 10 parts by weight of an additive; component B comprises a polyisocyanate; the molar ratio of the hydroxyl groups in component A to the isocyanates in component B is 2:1 to 1:2.5.

[0021] In some embodiments of this application, the foaming agent includes at least one of water, cyclopentane, isopentane, and HFOs.

[0022] In some embodiments of this application, the additive includes at least one of a catalyst, a surfactant, and a flame retardant.

[0023] In some embodiments of this application, the polyisocyanate includes at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates.

[0024] Another aspect of this application provides a method for preparing a polyurethane foam material, used to prepare the polyurethane foam material as described in any of the preceding claims, the method comprising the following steps: Place the raw materials required for material A in a reaction vessel and mix thoroughly at room temperature; The above-mentioned mixed material A and material B are placed in a high-speed mixer and mixed evenly, and then quickly poured into a sealed mold for foaming and molding.

[0025] Beneficial effects: The polyol composition provided in this application is prepared by loading a DMC catalyst onto nano-clay as a catalyst. This supported catalyst can be directly used to prepare rigid polyurethane foam materials, serving as a nucleating agent and reinforcing agent for the foaming of rigid polyurethane foam materials.

[0026] The polyurethane foam material provided in this application includes component A and component B. Component A is prepared using the above-mentioned polyol composition. The supported catalyst in the polyol composition can act as a nucleating agent and reinforcing agent for the foaming of polyurethane foam material, so that the obtained rigid polyurethane foam has a closed-cell structure and excellent mechanical and thermal insulation properties, and can be used as a high-performance polyurethane thermal insulation foam material.

[0027] The method for preparing polyurethane foam material provided in another aspect of this application does not require the separation of catalysts from polyol compositions, and the process is simple and easy to implement. Attached Figure Description

[0028] Figure 1 Transmission electron microscope image of the MMT-Zn3[Co(CN)6]2 catalyst in Example 1 provided for this application.

[0029] Figure 2 Transmission electron microscope image of the ATP-Zn3[Fe(CN)6]2 catalyst in Example 2 provided for this application.

[0030] Figure 3 Transmission electron microscope image of the HNT-Fe3[Co(CN)6]2 catalyst in Example 3 provided for this application.

[0031] Figure 4 The 1H NMR spectra of the polycarbonate polyols in Examples 4, 5 and 6 provided for this application.

[0032] Figure 5 Scanning electron microscope image of MMT-PU Foam in Example 7 provided in this application.

[0033] Figure 6 Scanning electron microscope image of ATP-PU Foam in Example 8 provided for this application.

[0034] Figure 7 Scanning electron microscope image of HNT-PU Foam in Example 9 provided in this application. Detailed Implementation

[0035] This application provides a polyol composition, a polyurethane foam material, and a method for preparing the same. To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following detailed description is provided with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of this application and are not intended to limit the scope of this application.

[0036] In the description of this application, it should be understood that the terms "upper," "lower," "left," and "right," etc., indicating orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or a specific orientational structure and operation. Therefore, they should not be construed as limitations on this application. Furthermore, "first" and "second" are only for descriptive purposes and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, unless otherwise stated, "multiple" means two or more.

[0037] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0038] This application provides a polyurethane foam material. Exemplarily, the polyurethane foam material can be rigid polyurethane foam. This polyurethane foam material can be used as a high-performance thermal insulation material.

[0039] The raw materials for polyurethane foam material include component A and component B. Component A comprises 70-100 parts by weight of a polyol composition, 0.5-25 parts by weight of a blowing agent, and 0.05-10 parts by weight of an additive. Component B comprises a polyisocyanate. In this polyurethane foam material, the ratio of component A to component B is determined by the molar ratio of the content of active hydroxyl groups in component A to the content of active isocyanates in component B. Specifically, the molar ratio of hydroxyl groups in component A to isocyanates in component B is 2:1 to 1:2.5. Preferably, the molar ratio of hydroxyl groups in component A to isocyanates in component B is 1.5:1 to 1:1.5.

[0040] Preferably, material A comprises 90-100 parts by weight of a polyol composition. The polyol composition includes a polycarbonate polyol. This polyol composition is prepared using a polyhydroxy compound as an initiator via a supported DMC catalyst catalyzing an epoxide compound and carbon dioxide. The supported DMC catalyst includes a DMC catalyst supported on natural nanoclay.

[0041] Specifically, the structural formula of polycarbonate polyol is represented by formula (1): Equation (1); In formula (1), R1 and R2 represent organic groups, m is 2, 3 or 4, and n≦10.

[0042] In the above-mentioned polyol composition, the presence of nano-clay eliminates the need to separate the catalyst during subsequent preparation of polyurethane foam materials. The polyol composition can directly react with diisocyanates and / or polyisocyanates to convert into polyurethane materials, particularly rigid polyurethane materials. This polyol composition, catalyzed by nano-clay, enables efficient carbon dioxide conversion and allows for the control of polyurethane foam structure and properties. The polyurethane foam material prepared from this polyol composition containing a nano-clay-supported DMC catalyst exhibits closed-cell structure, high compressive strength, and low thermal conductivity, making it an ideal high-performance insulation material.

[0043] The supported DMC catalyst is prepared by mixing nano-clay dispersion, aqueous solution of metal salt, aqueous solution of metal cyanide salt and organic complex ligand; The nano-clay dispersion has a solid content of 0.5%–2.0%, a metal salt aqueous solution concentration of 0.1%–0.5%, a metal cyanide salt aqueous solution concentration of 0.12%–0.6%, and an organic complex ligand concentration of 0.15%–0.75%.

[0044] Nanoclays may include one or more of montmorillonite, attapulgite, illite, and sepiolite.

[0045] The aforementioned nanoclays possess unique layered or fibrous structures, enabling them to effectively support DMC catalysts and improve catalyst dispersibility and stability. In polyol compositions, nanoclays not only serve as catalyst supports but also interact with polyols, improving their performance and further enhancing the quality of polyurethane foam materials. Furthermore, the addition of nanoclays can, to some extent, regulate the microstructure of polyurethane foam materials, resulting in more uniform cell distribution and better mechanical properties.

[0046] Metal salts include one or more of the following: inorganic zinc salts, organic zinc salts, inorganic ferrous salts, and inorganic nickel salts.

[0047] Inorganic zinc salts include at least one of zinc sulfate, zinc oxalate, zinc nitrate, and zinc chloride. Organic zinc salts include zinc gluconate and / or zinc lactate. Inorganic ferrous salts include at least one of ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous carbonate, and ferrous oxalate. Inorganic nickel salts include at least one of nickel sulfate, nickel chloride, nickel nitrate, nickel carbonate, and nickel oxalate.

[0048] Metal cyanide salts include at least one of sodium hexacyanocobaltate, potassium hexacyanocobaltate, potassium hexacyanoferrate, calcium hexacyanocobaltate, and lithium hexacyanocobaltate.

[0049] In some embodiments, the organic complex ligand may include an aliphatic ether.

[0050] In other embodiments, the organic complex ligand may include an aliphatic alcohol.

[0051] In other embodiments, the organic complex ligand may include a combination of aliphatic ethers and aliphatic alcohols.

[0052] Specifically, the organic complex ligand can be selected from one or more of the following: dimethoxyethane, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol.

[0053] In some embodiments, the supported DMC catalyst can be prepared by the following steps: Step A001. Add an aqueous solution of metal salt and an aqueous solution of metal cyanide to the nano-clay dispersion, and then add one or more organic complex ligands to the mixed solution. Mix thoroughly to ensure complete reaction and obtain a suspension.

[0054] Step A002. The supported DMC catalyst is separated from the suspension obtained in step A001 using a centrifuge to obtain a crude supported DMC catalyst. The centrifugation speed is 2000-1000 rpm and the centrifugation time is 2-5 min.

[0055] Step A003. The crude supported DMC catalyst obtained in step A002 is washed with an aqueous solution of the organic complex ligand. The concentration of the organic complex ligand is 0.15–0.75%.

[0056] For example, the cleaning is performed 1 to 3 times, with each cleaning lasting 5 to 15 minutes, in order to fully remove impurities adhering to the surface of the crude supported DMC catalyst.

[0057] Step A004. After cleaning, the catalyst is dried by vacuum drying or forced air drying to obtain refined supported DMC catalyst. The drying temperature is 20-120℃, and the drying pressure is 0.1 mbar to atmospheric pressure (1013 mbar).

[0058] The drying time is determined according to the drying method and the specific conditions of the catalyst. Generally, the vacuum drying time is 8 to 15 hours and the forced air drying time is 8 to 15 hours to ensure that the catalyst is completely dried and to obtain a refined supported DMC catalyst with stable performance and high activity. This catalyst can be used in subsequent reactions such as the preparation of polyol compositions and polyurethane foam materials.

[0059] Preferably, material A contains 2 to 5 parts by weight of a foaming agent. The foaming agent may include water and / or a physical foaming agent. Specifically, the foaming agent may be selected from low-boiling-point liquids such as water, cyclopentane, isopentane, and HFOs (hydrofluoroolefins, such as trans-1-chloro-3,3,3-trifluoropropene).

[0060] By combining or using different foaming agents individually, the density, cell structure, and other properties of polyurethane foam materials can be adjusted according to actual needs. For example, when water is used as a foaming agent, it reacts with isocyanate during the reaction process to produce carbon dioxide gas, thereby achieving the foaming effect; while physical foaming agents such as cyclopentane, isopentane, and HFOs form cell structures through their own volatilization, thus preparing polyurethane foam materials with different properties.

[0061] Preferably, material A contains 0.2 to 4 parts by weight of additives.

[0062] Specifically, additives may include one or more of catalysts, surfactants, or flame retardants. The catalyst may be selected from dibutyltin dilaurate. The surfactant may be selected from VORASURF. TM DC series products. Flame retardants can be selected from ammonium polyphosphate, triphenyl phosphate, dimethyl methylphosphonate, etc.

[0063] The catalyst dibutyltin dilaurate can accelerate the reaction process and improve production efficiency; the surfactant VORASURF TM DC series products help improve the surface properties of foam materials, making them more uniform and delicate; flame retardants such as ammonium polyphosphate, triphenyl phosphate, and dimethyl methylphosphonate can significantly improve the flame retardant properties of foam materials and enhance their safety.

[0064] Polyisocyanates include at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates. Specifically, polyisocyanates may be selected from one or more combinations of toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), terephthalamide diisocyanate (XDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate (TMHDI), dicyclohexylmethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene polyphenyl polyisocyanate (PAPI), and poly(hexamethylene diisocyanate) (PolyHDI).

[0065] This application also provides a method for preparing a polyurethane foam material. The preparation process includes the preparation of a composite material and foaming molding.

[0066] Specifically, the preparation process includes the following steps: Step B001. Add the raw materials, polyol composition, foaming agent, and additives required for material A to the reaction vessel and mix thoroughly and evenly at room temperature. Material B requires no treatment and can be used directly. It is important to note that the preparation process of the combined material must strictly control the introduction of moisture and air.

[0067] During the mixing process, it is essential to ensure the reactor is well-sealed to prevent the entry of external moisture and air. The stirring speed and time also need to be precisely controlled according to the specific raw materials and process requirements to achieve a thorough and uniform mixture. Furthermore, after mixing is complete, the resulting mixture can be subjected to quality testing to ensure that its various performance indicators meet the requirements for subsequent foaming and molding.

[0068] B002. Accurately measure the amounts of material A and material B, place material B and the mixed material A in a high-speed mixer and mix evenly, then quickly pour into a sealed mold for foaming and molding. During the process, control the foaming temperature at 40-60℃ and the foaming time at 4-12 hours.

[0069] The rigid polyurethane foam material prepared using the above raw materials and methods has an apparent density of 35–120 kg / m³ according to the national standard GB / T 6343 / 2009. 3 .

[0070] This rigid polyurethane foam material has a closed-cell structure, and its closed-cell rate is ≥97% according to the national standard GB / T 10799-2008.

[0071] According to the national standard GB / T 8813-2020, the compressive strength of this rigid polyurethane foam material is 2.0 to 2.5 MPa.

[0072] According to the national standard GB / T 10294-2008, the thermal conductivity of this rigid polyurethane foam material is 0.026~0.038W / (m·K).

[0073] As described above, the polyurethane foam material disclosed in this application has a high closed-cell structure, resulting in high structural strength. It exhibits high compressive strength, providing strong support while remaining lightweight. This high compressive strength also endows the polyurethane foam with excellent resistance to deformation, making it less prone to cracking or failure, suitable for applications under long-term stress, and also usable as a cushioning material. Furthermore, this rigid polyurethane foam material has a low thermal conductivity, providing good insulation and making it suitable for use as a high-performance insulation material.

[0074] To better explain the technical solution of this application, the following specific embodiments will be used to further illustrate this application.

[0075] Example 1 Preparation of supported DMC catalysts using sheet-like montmorillonite support 0.5 g of flake montmorillonite was ultrasonically dispersed in 100 g of deionized water, followed by the addition of 0.1 g of zinc chloride and 0.12 g of lithium hexahydrocobalt oxide. After the zinc chloride and lithium hexahydrocobalt oxide were completely dissolved, 0.15 g of dimethoxyethane was added, and the mixture was stirred thoroughly at room temperature for 2 h. The mixture was then centrifuged at 2000 rpm for 5 min to collect the crude supported DMC. The crude supported DMC was washed three times with a 0.15% dimethoxyethane aqueous solution and then vacuum-dried at 50 °C and 0.1 mbar for 12 h to obtain the flake montmorillonite-supported DMC catalyst, named MMT-Zn3[Co(CN)6]2. The transmission electron microscope image of this flake montmorillonite-supported DMC catalyst is shown below. Figure 1 As shown.

[0076] Example 2 Supported DMC catalysts prepared using rod-shaped attapulgite as a support 1.0 g of rod-shaped attapulgite was ultrasonically dispersed in 100 g of deionized water, followed by the addition of 0.25 g of zinc sulfate and 0.3 g of potassium hexacyanoferrate. After the zinc sulfate and potassium hexacyanoferrate were completely dissolved, 0.4 g of isopropanol was added, and the mixture was stirred thoroughly at room temperature for 2 h. The mixture was then centrifuged at 2000 rpm for 5 min to collect the crude supported DMC catalyst. The crude supported DMC catalyst was washed three times with a 0.4% isopropanol aqueous solution, and then dried under forced-air drying at 120 °C and 1013 mbar for 12 h to obtain the rod-shaped attapulgite supported DMC catalyst, named ATP-Zn3[Fe(CN)6]2. The transmission electron microscope image of this rod-shaped attapulgite supported DMC catalyst is shown below. Figure 2 As shown.

[0077] Example 3 Supported DMC catalysts prepared using tubular halloysite as a support 2.0 g of tubular halloysite was ultrasonically dispersed in 100 g of deionized water, and 0.5 g of ferrous sulfate and 0.6 g of potassium hexahydrocobaltate were added. After the ferrous sulfate and potassium hexahydrocobaltate were completely dissolved, 0.75 g of tert-butanol was added, and the mixture was stirred thoroughly at room temperature for 2 h. The mixture was then centrifuged at 2000 rpm for 5 min to collect the crude supported DMC catalyst. The crude supported DMC catalyst was washed three times with a 0.75% tert-butanol aqueous solution, and then vacuum dried at 80 °C and 0.1 mbar for 12 h to obtain the tubular halloysite-supported DMC catalyst, named HNT-Fe3[Co(CN)6]2. The transmission electron microscope image of this tubular halloysite-supported DMC catalyst is shown below. Figure 3 As shown.

[0078] Example 4 MMT-Zn3[Co(CN)6]2 Catalyzed Preparation of Polycarbonate Polyols In a 1L stainless steel pressure reactor, 9.0g of glycerol, 60.0g of ethylene oxide, and 1.0g of sheet-like montmorillonite-supported DMC catalyst (MMT-Zn3[Co(CN)6]2) were pre-added under a nitrogen atmosphere and thoroughly mixed. 80.0g of carbon dioxide was introduced into the reactor, maintaining the pressure inside the reactor at 20–50 bar and the temperature at 120°C. The motor speed was maintained at 800 rpm, and the reaction was continued for 4–8 hours until the motor power stabilized. The product was then discharged, yielding a trifunctional polycarbonate polyol (OH value approximately 120 mg KOH / g), denoted as MMT-PC-OH3. The 1H NMR spectrum of MMT-PC-OH3 is shown below. Figure 4 As shown.

[0079] From the hydrogen NMR spectrum Figure 4 The spectrum clearly shows a characteristic peak of the carbonate segment (-O-CH2-CH2-O-CO-) at 4.2 ppm in MMT-PC-OH3, with a good peak shape and an integrated area consistent with the theoretical value, further confirming that the prepared MMT-PC-OH3 has the expected chemical structure. Furthermore, no obvious impurity peaks were observed in the spectrum, indicating that this preparation method has high product purity.

[0080] Example 5 Preparation of polycarbonate polyols using ATP-Zn3[Fe(CN)6]2 catalyst In a 1L stainless steel pressure reactor, 13.0g of trimethylolpropane, 60.0g of ethylene oxide, and 2.0g of rod-shaped attapulgite-supported DMC catalyst (ATP-Zn3[Fe(CN)6]2) were pre-added under a nitrogen atmosphere and thoroughly mixed. 80.0g of carbon dioxide was introduced into the reactor, maintaining the pressure inside the reactor at 20–50 bar and the temperature at 120°C. The motor speed was maintained at 800 rpm, and the reaction was continued for 4–8 hours until the motor power stabilized. The product was then discharged, yielding a trifunctional polycarbonate polyol (OH value approximately 120 mg KOH / g), denoted as ATP-PC-OH3. The 1H NMR spectrum of ATP-PC-OH3 is shown below. Figure 4 As shown.

[0081] From the hydrogen NMR spectrum Figure 4 The spectrum clearly shows a characteristic peak of the carbonate segment (-O-CH2-CH2-O-CO-) at 4.2 ppm in ATP-PC-OH3, with a good peak shape and an integrated area consistent with the theoretical value, further confirming that the prepared ATP-PC-OH3 has the expected chemical structure. Furthermore, no obvious impurity peaks were observed in the spectrum, indicating that this preparation method has high product purity.

[0082] Example 6 Preparation of polycarbonate polyols using HNT-Fe3[Co(CN)6]2 catalyst In a 1L stainless steel pressure reactor, 10.0g pentaerythritol, 60.0g ethylene oxide, and 4.0g tubular halloysite-supported DMC catalyst (HNT-Fe3[Co(CN)6]2) were pre-added under a nitrogen atmosphere and thoroughly mixed. 80.0g carbon dioxide was introduced into the reactor, maintaining the pressure inside the reactor at 20–50 bar and the temperature at 120°C. The motor speed was maintained at 800 rpm, and the reaction was continued for 4–8 hours until the motor power stabilized. The product was then discharged, yielding a tetrafunctional polycarbonate polyol (OH value approximately 120 mg KOH / g), denoted as HNT-PC-OH4. The 1H NMR spectrum of HNT-PC-OH4 is shown below. Figure 4 As shown.

[0083] From the hydrogen NMR spectrum Figure 4 The spectrum clearly shows a characteristic peak of carbonate segment (-O-CH2-CH2-O-CO-) at 4.2 ppm for HNT-PC-OH4, with a good peak shape and an integrated area consistent with the theoretical value, further confirming that the prepared HNT-PC-OH4 has the expected chemical structure. Furthermore, no obvious impurity peaks were observed in the spectrum, indicating that this preparation method has high product purity.

[0084] Example 7 Preparation of rigid polyurethane foam materials using MMT-PC-OH3 Take 100g of MMT-PC-OH3, add 2.0g of distilled water, 2.0g of silicone oil, 1.5g of triethanolamine, and 0.5g of dibutyltin dilaurate, and mix thoroughly. This mixture is designated as component A. Take 20g of toluene diisocyanate (TDI) as component B. Quickly mix component B and component A, and then pour the mixture into a stainless steel mold. Control the foaming temperature at 40℃ and foam for 12 hours to obtain rigid polyurethane foam material MMT-PU Foam. The scanning electron microscope image of the cell structure of this MMT-PU Foam is shown below. Figure 5 As shown.

[0085] Example 8 Preparation of rigid polyurethane foam materials using ATP-PC-OH3 Take 100g of ATP-PC-OH3, add 2.0g of distilled water, 1.0g of cyclopentane, 2.0g of silicone oil, 1.0g of triethylenediamine, and 0.5g of dibutyltin dilaurate, and mix thoroughly. This mixture is designated as component A. Take 30g of 4,4'-diphenylmethane diisocyanate (MDI) as component B. Quickly mix component B and component A, and then pour the mixture into a stainless steel mold. Control the foaming temperature at 50℃ and foam for 8 hours to obtain rigid polyurethane foam material ATP-PU Foam. The scanning electron microscope image of the cell structure of this ATP-PU Foam is shown below. Figure 6 As shown.

[0086] Example 9 Preparation of rigid polyurethane foam materials using HNT-PC-OH4 Take 100g of HNT-PC-OH4, add 2.0g of distilled water, 3.0g of isopentane, 2.0g of silicone oil, 0.5g of dimethylaminoethyl ether, and 0.5g of dibutyltin dilaurate, and mix thoroughly. This mixture is designated as component A. Take 40g of methylene polyphenyl polyisocyanate (PAPI) as component B. Quickly mix component B and component A, and then pour the mixture into a stainless steel mold. Control the foaming temperature at 60℃ and foam for 4 hours to obtain rigid polyurethane foam material HNT-PU Foam. The scanning electron microscope image of the cell structure of this ATP-PU Foam is shown below. Figure 7 As shown.

[0087] Comparative Example 1 DMC catalyst Add 0.1g of zinc chloride and 0.12g of lithium hexacyanocobalt oxide to 100g of deionized water. After the zinc chloride and lithium hexacyanocobalt oxide are completely dissolved, add 0.15g of dimethoxyethane. Stir thoroughly at room temperature for 2 hours, centrifuge at 2000rpm for 5 minutes, and collect the crude DMC catalyst. Wash the crude DMC catalyst three times with a 0.15% dimethoxyethane aqueous solution, and vacuum dry at 50℃ and 0.1mbar for 12 hours to obtain the DMC catalyst, named Zn3[Co(CN)6]2.

[0088] Comparative Example 2 Zn3[Co(CN)6]2 catalyst for the preparation of polycarbonate polyols In a 1L stainless steel pressure reactor, 9.0g of glycerol, 60.0g of ethylene oxide, and 0.2g of DMC catalyst (Zn3[Co(CN)6]2) were pre-added under a nitrogen atmosphere. The raw materials were thoroughly mixed, and 80.0g of carbon dioxide was introduced. The pressure inside the reactor was maintained at 20–50 bar, and the temperature inside the reactor was 120℃. The motor speed was maintained at 800 rpm, and the reaction was continued for 4–8 hours until the motor power stabilized. The product was discharged to obtain a trifunctional v polycarbonate polyol (OH value approximately 120 mg KOH / g), denoted as PC-OH3.

[0089] Comparative Example 3 PC-OH3 is used to prepare rigid polyurethane foam materials. Take 100g of PC-OH3, add 2.0g of distilled water, 1.0g of cyclopentane, 2.0g of silicone oil, 1.0g of triethylenediamine, and 0.5g of dibutyltin dilaurate, and mix thoroughly. This mixture is designated as component A. Take 30g of 4,4'-diphenylmethane diisocyanate (MDI) as component B. Quickly mix components A and B, then pour the mixture into a stainless steel mold. Control the foaming temperature at 50℃ and the foaming time at 8 hours to produce rigid polyurethane foam (PU Foam).

[0090] The macroscopic properties of the rigid polyurethane foam materials prepared in Examples 7, 8, 9 and Comparative Example 3 are shown in Table 1 below.

[0091] Table 1. Performance Comparison of Rigid Polyurethane Foam Materials

[0092] Generally, compressive strength increases with increasing surface density. However, closed-cell structures have greater mechanical strength than open-cell structures. Furthermore, according to... Figures 5 to 7 As shown in Table 1, the rigid polyurethane foam materials prepared in Examples 7, 8, and 9 have nano-clay filling in their pore structures, which can further enhance the structural strength of the rigid polyurethane foam. As shown in Table 1, although the surface density of Comparative Example 3 is significantly higher than that of Examples 8 and 9, the compressive strength of Comparative Example 3 is lower than that of Example 8 because its closed-cell ratio is lower.

[0093] Furthermore, since the rigid polyurethane foam materials prepared in Examples 7, 8 and 9 have a high closed-cell ratio, they can effectively suppress convective heat transfer, resulting in a thermal conductivity that is much lower than that of Comparative Example 3, making them suitable as high-quality insulation materials.

[0094] It is understood that those skilled in the art can make equivalent substitutions or changes based on the technical solution and concept of this application, and all such substitutions or changes should fall within the protection scope of the appended claims.

Claims

1. A polyol composition, characterized in that, The polyol composition is prepared by using a polyhydroxy compound as an initiator and catalyzing an epoxy compound and carbon dioxide using a supported DMC catalyst, wherein the supported DMC catalyst includes a DMC catalyst supported on natural nanoclay.

2. The polyol composition according to claim 1, characterized in that, The polyol composition includes a polycarbonate polyol, the polycarbonate polyol having the structural formula (1): Equation (1); In formula (1), R1 and R2 represent organic groups, m is 2, 3 or 4, and n≦10.

3. The polyol composition according to claim 1 or 2, characterized in that, The supported DMC catalyst is prepared by mixing nano-clay dispersion, metal salt aqueous solution, metal cyanide salt aqueous solution and organic complex ligand; The nano-clay dispersion has a solid content of 0.5% to 2.0%, the metal salt aqueous solution has a concentration of 0.1% to 0.5%, the metal cyanide salt aqueous solution has a concentration of 0.12% to 0.6%, and the organic complex ligand has a concentration of 0.15% to 0.75%.

4. The polyol composition according to claim 3, characterized in that, The nano-clay includes at least one of montmorillonite, attapulgite, illite, and sepiolite.

5. The polyol composition according to claim 3, characterized in that, The metal salt includes at least one of inorganic zinc salt, organic zinc salt, inorganic ferrous salt, and inorganic nickel salt.

6. The polyol composition according to claim 5, characterized in that, The inorganic zinc salt includes at least one of zinc sulfate, zinc oxalate, zinc nitrate, and zinc chloride.

7. The polyol composition according to claim 5, characterized in that, The organic zinc salts include zinc gluconate and / or zinc lactate.

8. The polyol composition according to claim 5, characterized in that, The inorganic ferrous salt includes at least one of ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous carbonate, and ferrous oxalate.

9. The polyol composition according to claim 5, characterized in that, The inorganic nickel salt includes at least one of nickel sulfate, nickel chloride, nickel nitrate, nickel carbonate, and oxalic acid.

10. The polyol composition according to claim 3, characterized in that, The metal cyanide salt includes at least one of sodium hexacyanocobaltate, potassium hexacyanocobaltate, potassium hexacyanoferrate, calcium hexacyanocobaltate, and lithium hexacyanocobaltate.

11. The polyol composition according to claim 3, characterized in that, The organic complex ligands include aliphatic ethers and / or aliphatic alcohols.

12. The polyol composition according to claim 3, characterized in that, The organic complex ligand includes at least one of dimethoxyethane, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol.

13. The polyol composition according to claim 3, characterized in that, The supported DMC catalyst was prepared by the following method: Add an aqueous solution of a metal salt, an aqueous solution of a metal cyanide salt, and an organic complex ligand to a nano-clay dispersion, mix thoroughly, and obtain a suspension. The above suspension was separated by centrifugation to obtain a crude supported DMC catalyst; The crude supported DMC catalyst was cleaned using organic complex ligands. The cleaned supported DMC catalyst was dried to obtain a refined supported DMC catalyst.

14. A polyurethane foam material, characterized in that, include: Material A and Material B; Material A comprises 70 to 100 parts by weight of the polyol composition as described in any one of claims 1 to 13, 0.5 to 25 parts by weight of a foaming agent, and 0.05 to 10 parts by weight of an additive; Material B comprises a polyisocyanate; The molar ratio of the hydroxyl group in Material A to the isocyanate group in Material B is 2:1 to 1:2.

5.

15. The polyurethane foam material according to claim 14, characterized in that, The foaming agent includes at least one of water, cyclopentane, isopentane, and HFOs.

16. The polyurethane foam material according to claim 14, characterized in that, The additives include at least one of catalysts, surfactants, and flame retardants.

17. The polyurethane foam material according to claim 14, characterized in that, The polyisocyanate includes at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates.

18. A method for preparing a polyurethane foam material, characterized in that, The method for preparing the polyurethane foam material according to any one of claims 14 to 17 comprises the following steps: Place the raw materials required for material A in a reaction vessel and mix thoroughly at room temperature; The above-mentioned mixed material A and material B are placed in a high-speed mixer and mixed evenly, and then quickly poured into a sealed mold for foaming and molding.

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