A composition, polyurethane foam and method of making same and a refrigeration appliance

Abstract

The application provides a composition, a polyurethane foam material and a preparation method thereof and a refrigeration equipment, wherein the composition comprises 40-45% of a polyether component, 0.4-0.9% of a composite nucleating component, 10-16% of a foaming agent and 0.1-0.3% of a catalyst according to mass percentage, the composition further comprises an organic isocyanate and a first silane coupling agent, the ratio between the total number of moles of all active hydrogens in the composition and the number of moles of isocyanate groups in the organic isocyanate is 1:(1.05-1.20), and the mass of the first silane coupling agent is 0.15-0.25% of the mass of the composite nucleating component, wherein the composite nucleating component comprises a nucleating material, a two-dimensional material and an interface reinforcing material, and through the synergistic effect of the three, the cell uniformity and long-term stability of the prepared polyurethane foam material are improved.

Description

Technical Field

[0001] This application relates to the field of polyurethane foam technology, specifically to a composition, a polyurethane foam material, a method for preparing the same, and a refrigeration device. Background Technology

[0002] Polyurethane foam is a high-performance thermal insulation material widely used in refrigeration equipment, building energy conservation, furniture, transportation, packaging, and other fields. Polyurethane foam typically uses polyether and organic isocyanate as its core reactive components. These components undergo an addition polymerization reaction between hydroxyl and isocyanate groups. With the help of blowing agents and other additives, gas is generated within the system, forming a uniform cell structure. Finally, the foam is foamed and molded to obtain the polyurethane foam material.

[0003] In related technologies, polyurethane foam materials prepared by reacting conventional polyether components and organic isocyanates have problems such as uneven cell size and low closed-cell rate. Summary of the Invention

[0004] In view of the shortcomings of the prior art, this application provides a composition, a polyurethane foam material, a method for preparing the same, and a refrigeration device.

[0005] In a first aspect, this application provides a composition comprising, by mass percentage: 40-45% polyether component, 0.4-0.9% composite nucleating component, 10-16% blowing agent, and 0.1-0.3% catalyst; the composition further comprises an organic isocyanate and a first silane coupling agent, wherein the ratio between the total molar number of all active hydrogens in the composition and the molar number of isocyanate groups in the organic isocyanate is 1:(1.05-1.20), and the mass of the first silane coupling agent is 0.15-0.25% of the mass of the composite nucleating component; The composite nucleating component includes a nucleating material, a two-dimensional material, and an interface reinforcing material. The mass ratio of the nucleating material, the two-dimensional material, and the interface reinforcing material is (3-5):1:(0.5-1). The nucleating material includes one or more of nano-calcium carbonate, nano-talc, and nano-kaolin. The two-dimensional material includes one or more of graphene oxide, two-dimensional montmorillonite, and nano-mica sheets. The interface reinforcing material includes nanofillers modified with a second silane coupling agent. The nanofillers include one or more of nano-silica, nano-alumina, and nano-zinc oxide.

[0006] In a second aspect, this application provides a polyurethane foam material prepared using the composition described in the first aspect.

[0007] Thirdly, this application provides a method for preparing a polyurethane foam material, comprising the steps of: providing a composition as described in the first aspect, foaming the composition to obtain the polyurethane foam material.

[0008] Fourthly, this application provides a refrigeration device, which includes polyurethane foam material as described in the second aspect, or polyurethane foam material prepared by the method described in the third aspect.

[0009] This application provides a composition, a polyurethane foam material, a method for preparing the same, and a refrigeration device, which have the following technical effects: The composition of this application embodiment can be used to prepare polyurethane foam materials. In the composition, the composite polyether component includes three components: nucleating material, two-dimensional material, and interface reinforcing material. The nucleating material has high nucleation activity, the two-dimensional material has two-dimensional sheets, and the two-dimensional sheets have a barrier effect, thereby inhibiting the aggregation effect. The interface reinforcing material has the function of reinforcement and improving long-term stability. Through the synergistic effect of the three components of "nucleation-dispersion-reinforcement", the cell uniformity and long-term stability of the obtained polyurethane foam material are improved, which is beneficial to extending the service life of the polyurethane foam material.

[0010] The polyurethane foam material of this application embodiment can be applied to refrigeration equipment and has good thermal insulation performance and a long service life. Detailed Implementation

[0011] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0013] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. The various embodiments of this application may exist in a range format. It should be understood that the description in a range format is merely for convenience and simplicity and should not be construed as a rigid limitation on the scope of the invention. Therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0014] In this application, the terms first, second, third, etc. are used merely as identifiers and do not impose numerical requirements or establish an order.

[0015] The term "including" means "including but not limited to".

[0016] The term "and / or" is used to describe the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, or B exists alone. A and B can be singular or plural.

[0017] The term "multiple" refers to two or more.

[0018] The term "aliphatic chain hydrocarbon group" refers to an aliphatic straight-chain hydrocarbon group or an aliphatic branched hydrocarbon group. "C1-C10 aliphatic chain hydrocarbon group" can be a C10, C8, C5, C4, or C3 aliphatic chain hydrocarbon group. Examples of C1-C10 aliphatic chain hydrocarbon groups include C1-C10 alkyl groups, C1-C8 alkyl groups, C1-C4 alkyl groups, C1-C3 alkyl groups, C2-C10 alkenyl groups, C2-C4 alkenyl groups, C2-C10 alkynyl groups, or C2-C4 alkynyl groups. Suitable examples include methyl, ethyl, vinyl, ethynyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc.

[0019] The term "aliphatic chain hydrocarbon group" refers to a group with the general formula *-O-aliphatic chain hydrocarbon group, where * indicates a bonding site and O represents an oxygen atom. Suitable examples include, but are not limited to, methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), propoxy, or tert-butoxy (-OC(CH3)3 or -O t Bu).

[0020] The term "inert gas" refers to a class of gases that have stable chemical properties and do not readily react with other substances at room temperature and pressure. These include one or more of nitrogen, helium, neon, argon, krypton, and xenon.

[0021] In this application, the viscosity of the substance can be determined using Test Method A as described in standard ASTM D4878-23.

[0022] This application provides a composition comprising, by mass percentage: 40-45% polyether component, 0.4-0.9% composite nucleating component, 10-16% foaming agent, and 0.1-0.3% catalyst. The composition further comprises an organic isocyanate and a first silane coupling agent. The ratio between the total number of moles of all active hydrogens in the composition and the number of moles of isocyanate groups in the organic isocyanate is 1:(1.05-1.20), and the mass of the first silane coupling agent is 0.15-0.25% of the mass of the composite nucleating component. The composite nucleating component includes nucleating materials, two-dimensional materials, and interface reinforcing materials. The mass ratio of the nucleating materials, two-dimensional materials, and interface reinforcing materials is (3-5):1:(0.5-1). The nucleating materials include one or more of nano-calcium carbonate, nano-talc, and nano-kaolin. The two-dimensional materials include one or more of graphene oxide, two-dimensional montmorillonite, and nano-mica sheets. The interface reinforcing materials include nanofillers modified with a second silane coupling agent. The nanofillers include one or more of nano-silica, nano-alumina, and nano-zinc oxide.

[0023] The compositions of this application embodiment can be used to prepare polyurethane foam materials. In the composition, the composite nucleating component includes three components: a nucleating material, a two-dimensional material, and an interface reinforcing material. The nucleating material has high nucleation activity, the two-dimensional material has two-dimensional sheets, and the barrier effect of these two-dimensional sheets inhibits agglomeration. The interface reinforcing material has a reinforcing effect and improves long-term stability. Through the synergistic effect of "nucleation-dispersion-reinforcement" of the three components, the cell uniformity and long-term stability of the prepared polyurethane foam material are improved, which is beneficial to extending the service life of the polyurethane foam material, for example, controlling the five-year strength reduction rate of the polyurethane foam material to no more than 8%.

[0024] In the above composition, the nucleating material, the two-dimensional material, and the interface reinforcement material can be commercially available or prepared in-house. The mass ratio of the nucleating material, the two-dimensional material, and the interface reinforcement material can be, for example, 3:1:0.5, 3:1:0.7, 3:1:1, 3.5:1:0.7, 4:1:0.6, 4:1:0.8, 5:1:0.5, 5:1:1, or any two of the aforementioned values ​​or a range thereof. It should be noted that for the composite nucleating component, if the nucleating material is omitted, the improvement in the cell uniformity of the resulting polyurethane foam material is limited; if the two-dimensional material is omitted, the dispersion performance of the composition is poor; if the interface reinforcement material is omitted, the improvement in the dimensional stability and long-term performance stability of the resulting polyurethane foam material is limited. The percentage of the composite nucleating component by mass of the total composition can be 0.4–0.8%, 0.4–0.7%, 0.4–0.6%, or 0.4–0.5%.

[0025] In some embodiments of this application, the average particle size of the nucleating material is 10 to 30 nm, for example, it can be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm or any value or range between the two aforementioned values.

[0026] In some embodiments of this application, the thickness of a single layer of the two-dimensional material is no greater than 1.2 nm, for example, no greater than 1.1 nm, no greater than 1.0 nm, no greater than 0.9 nm, or no greater than 0.8 nm.

[0027] In some embodiments of this application, the average particle size of the nanofiller modified by the second silane coupling agent is 8 to 15 nm, for example, it can be 8 nm, 10 nm, 12 nm, 15 nm or any value or range between the two aforementioned values.

[0028] In some embodiments of this application, the first silane coupling agent and the second silane coupling agent independently comprise one or more of dimethyldichlorosilane, γ-aminopropyltriethoxysilane (KH-550), γ-glycidoxypropyltrimethoxysilane (KH-560), γ-methacryloyloxypropyltrimethoxysilane (KH-570), and 3-mercaptopropyltrimethoxysilane (KH-590).

[0029] In some embodiments of this application, the raw materials for preparing the nanofiller modified by the second silane coupling agent include the second silane coupling agent and the nanofiller. The mass ratio between the nanofiller and the second silane coupling agent is 1:(0.01 to 0.05), for example, it can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05 or any value or range between the aforementioned two values.

[0030] In some embodiments of this application, the preparation method of the nanofiller modified with the second silane coupling agent includes the following steps: dispersing the nanofiller in a liquid medium, wherein the mass ratio of the nanofiller to the liquid medium is 1:(5-10), ultrasonically dispersing for 15-20 min to obtain a mixture; then, under stirring conditions at 50-80 °C, adding the silane coupling agent dropwise to the mixture until the mass ratio of the nanofiller to the silane coupling agent is 1:(0.01-0.05), continuing stirring for 2-4 h to obtain a modified product; filtering the modified product, collecting the filtrate, and vacuum drying the filtrate to obtain the nanofiller modified with the second silane coupling agent. The liquid medium can be any solvent in which the nanofiller has good dispersibility, such as ethanol.

[0031] In the compositions of this application, the percentage of the mass of the first silane coupling agent to the mass of the composite nucleating component can be 0.15-0.23%, 0.15-0.20%, 0.15-0.18%, or 0.18-0.23%.

[0032] In some embodiments of this application, the first silane coupling agent includes silane coupling agent A and silane coupling agent B. Silane coupling agent A includes one or more of γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane, and silane coupling agent B includes one or more of γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. The mass ratio between silane coupling agent A and silane coupling agent B is 1:(0.8 to 1.2), for example, it can be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2 or any value or range between the aforementioned two values. In this process, silane coupling agent A is used to enhance the hydrophobicity of the composition, and silane coupling agent B is used to react with the hydroxyl groups on the surface of the nanofiller modified by the second silane coupling agent to enhance the interfacial bonding force between the composite nucleating component and the polyether component, thereby further improving the dispersion uniformity of the composite nucleating component. Therefore, the combined use of silane coupling agent A and silane coupling agent B is beneficial to further improve the dimensional stability and long-term performance stability of the prepared polyurethane foam material.

[0033] In the compositions of this application, the percentage of the mass of the polyether component to the total mass of the composition may be, for example, 40%, 41%, 42%, 43%, 44%, 45%, or any value or range between any two of the foregoing. The polyether component may be a single polyether, a composition of multiple polyethers, or a crosslinking reaction product of multiple polyethers. The polyether component may be prepared using conventional methods in the art or commercially available.

[0034] In some embodiments of this application, the hydroxyl value of the polyether component is 350–450 mgKOH / g, for example, it can be 350–430 mgKOH / g, 350–410 mgKOH / g, 350–400 mgKOH / g, or 350–380 mgKOH / g, and the viscosity of the polyether component at 25 °C is not greater than 2000 mPa·s, for example, not greater than 1800 mPa·s, not greater than 1500 mPa·s, not greater than 1200 mPa·s, not greater than 1000 mPa·s, not greater than 800 mPa·s, or not greater than 500 mPa·s. In this way, the flow properties of the composition can be further improved, and the crosslinking strength of the obtained polyurethane foam material can be further improved.

[0035] In some embodiments of this application, the polyether component includes a first polyether and a second polyether, wherein the first polyether includes WANOL. ® The crosslinking product of R2304 or polyether 330N and polyether 210, wherein the second polyether comprises hydroxyl-terminated polybutadiene, and the mass ratio of the first polyether to the second polyether is 1:(0.002~0.005), for example, it can be 1:0.002, 1:0.003, 1:0.004, 1:0.005 or any value or range between the aforementioned two values. Among them, WANOL ® R2304 is a product of Wanhua Chemical, and both polyether 330N and polyether 210 are commercially available. The presence of the second polyether further improves the interfacial compatibility between the polyether component and the composite nucleating component, and further enhances the closed-cell rate and anti-aging properties of the resulting polyurethane foam material. For example, the closed-cell rate of the resulting polyurethane foam material can be controlled to be no less than 99%, and the five-year strength reduction rate can be controlled to be no more than 8%. It also helps to further reduce the dimensional change rate of the resulting polyurethane foam material, for example, controlling the dimensional change rate to be no more than 0.3%. Understandably, omitting the second polyether would result in limited improvement in the anti-aging properties and closed-cell rate of the resulting polyurethane foam material.

[0036] In some embodiments of this application, the number-average molecular weight of the hydroxyl-terminated polybutadiene is 1000–2000, which allows for further control of the viscosity of the composition within a more suitable range, thereby further improving the flow properties of the composition. The hydroxyl-terminated polybutadiene is commercially available and custom-made.

[0037] In some embodiments of this application, the method for preparing the crosslinking reaction product of polyether 330N and polyether 210 includes the following steps: providing a second mixture comprising polyether 330N, polyether 210 and a crosslinking agent; heating the second mixture to 40-50 °C, adding a second amine catalyst and a silicone oil foam stabilizer to the second mixture, mixing and reacting to obtain the crosslinking reaction product of polyether 330N and polyether 210. The mass ratio of polyether 210 to polyether 330N is 1:(2-3), and the ratio of the total mass of polyether 330N and polyether 210, the mass of the crosslinking agent, the mass of the second amine catalyst, and the mass of the silicone oil foam stabilizer is (90-95):(2-5):(0.3-0.8):(1-3). The crosslinking agent includes one or more of glycerol, trimethylolpropane, pentaerythritol, diglycerol, and trimethylolethane. The second amine catalyst includes one or more of triethylenediamine, triethanolamine, diethylenetriamine, and diethanolamine. The silicone oil foam stabilizer includes silicone oil L-580, silicone oil L-620, and silicone oil B. 8715 and silicone oil Y One or more of 1036.

[0038] It should be noted that the first polyether can also be a polymer obtained by polymerization of an initiator and an epoxide in the presence of a catalyst. An initiator refers to a class of compounds containing active hydrogen groups, including one or more of polyhydroxy compounds and polyamino compounds known in the art. Polyhydroxy compounds include one or more of sucrose, sorbitol, mannitol, xylitol, pentaerythritol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylolpropane. Polyamino compounds include one or more of ethylenediamine, triethylamine, diethanolamine, triethanolamine, toluenediamine, phenylenediamine, and propylenediamine. Epoxides include, for example, compounds represented by the following general formula (I): (Ⅰ); In general formula (Ⅰ), each time R1 appears, it is independently selected from hydrogen, a C1-C10 aliphatic chain hydrocarbon group, a C1-C10 aliphatic chain hydroxyl group, or a combination of the aforementioned groups.

[0039] In some embodiments of this application, the epoxide includes one or more of ethylene oxide, propylene oxide, butane oxide, pentane oxide, and hexane oxide.

[0040] The first polyether can be commercially available and custom-made or prepared using conventional methods for preparing polyethers. Conventional methods for preparing polyethers include, for example, the following steps: placing an initiator and catalyst (e.g., potassium hydroxide, sodium hydroxide, etc.) in a reactor and dehydrating under vacuum at 100–120°C for 1–3 h to obtain a mixture; then, adding a monomer to the mixture and carrying out a polymerization reaction at 110–130°C and 0.2–0.6 MPa until the hydroxyl value reaches the desired target value to obtain the reaction product; neutralizing and desalting the reaction product, then subjecting it to vacuum treatment at 100–120°C (pressure -0.09 to -0.1 MPa) to remove volatile components, followed by cooling to 40–80°C, filtering to remove the filter residue, and obtaining the corresponding polyether. The step of neutralizing and desalting the reaction product may include the following steps: adding an acid, such as acetic acid, hydrochloric acid, or phosphoric acid, to the reaction product, with the acid mass being 0.1–0.5% of the total mass of the reaction product; carrying out a neutralization reaction at 60–70 °C for 10–60 min; and washing the neutralized product with water until neutral (pH 6.5–7.5). The step of washing the neutralized product with water to neutralize it includes: adding deionized water to the product obtained after the neutralization reaction, with a deionized water-to-product mass ratio of 1:1; stirring and mixing at 70–80 °C; then allowing it to stand and separate into layers; discarding the aqueous phase; and repeating the above operation several times until neutral. In the preparation of the polyether, the mass percentage of the catalyst relative to the total mass of the initiator, catalyst, and monomer is 0.1–0.3%.

[0041] In the compositions of this application embodiment, the percentage of the foaming agent by mass of the total mass of the composition may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, or any range or value between any two of the foregoing.

[0042] In some embodiments of this application, the blowing agent includes one or more of hydrocarbon blowing agents or hydrohalogenated hydrocarbon blowing agents, wherein the hydrocarbon blowing agent includes one or more of cyclopentane, isopentane, n-pentane, n-butane, isobutane, propane, hexane, and heptane, and the hydrohalogenated hydrocarbon blowing agent includes one or more of pentafluoropropane, pentafluorobutane, difluoroethane, tetrafluoroethane, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, hexafluoropropylene, and hexafluorobutene. Furthermore, hydrohalogenated hydrocarbon blowing agents include, for example, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,1-trifluoropropene, 3,3,3-trifluoropropene, 1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene, 1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobut-2-ene or their structural isomers, geometric isomers or stereoisomers, or combinations thereof.

[0043] In some embodiments of this application, the boiling point of the foaming agent is not higher than 45 °C and the global warming potential of the foaming agent is not greater than 25. For example, the boiling point of the foaming agent can be 32-42 °C. In this way, it can be matched with the working conditions of refrigerators and the environmental friendliness of the composition can be improved.

[0044] In some embodiments of this application, the foaming agent includes a hydrocarbon foaming agent, a hydrohalogenated hydrocarbon foaming agent, and a polysiloxane antipermeability agent, and the mass ratio of the hydrocarbon foaming agent, the hydrohalogenated hydrocarbon foaming agent, and the polysiloxane antipermeability agent is (25-35):(10-20):(1-3). Among them, the hydrocarbon foaming agent provides the core foaming power and accounts for the largest proportion; the hydrohalogenated hydrocarbon foaming agent serves as an auxiliary foaming agent, controlling the foaming rate and adapting to environmental protection standards; by adding the polysiloxane antipermeability agent, the airtightness and long-term stability of the obtained polyurethane foam material can be improved, which can improve the problem of short insulation life caused by easy penetration of the foaming agent, and the ten-year insulation performance degradation rate of the obtained polyurethane foam material can be controlled to no more than 3%, which is beneficial to improving the service life of the obtained polyurethane foam material.

[0045] In some embodiments of this application, the hydrocarbon blowing agent includes n-pentane, and the hydrohalogenated hydrocarbon blowing agent includes one or more of cis-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,1,1,3-tetrafluoropropylene, trans-1-chloro-3,3,3-trifluoropropylene, and cis-1,2,3,3,3-pentafluoropropylene. This further balances improved foaming efficiency, better suitability for refrigerator operating conditions, and greater environmental friendliness. The preparation method of the polysiloxane anti-permeability agent includes the following steps: providing a first mixture comprising hydrogen-containing silicone oil and allyl polyether, wherein the mass ratio of hydrogen-containing silicone oil to allyl polyether is 1:(2-3); heating the first mixture to 80-90 °C under an inert gas atmosphere, adding a platinum-containing catalyst to the first mixture, mixing and reacting for 3-4 h to obtain a reaction product; separating and purifying the reaction product to obtain the polysiloxane anti-permeability agent. The mass percentage of the platinum-containing catalyst in the total mass of the hydrogen-containing silicone oil, allyl polyether, and platinum-containing catalyst is 0.01 to 0.03%.

[0046] In some embodiments of this application, the hydrogen-containing silicone oil includes one or more of polymethylhydrosiloxane (CAS No. 63148-57-2) and methylphenyl silicone oil (CAS No. 63148-58-3). The viscosity of the hydrogen-containing silicone oil at 25 °C is, for example, 50–100 mPa·s.

[0047] In some embodiments of this application, the platinum-containing catalyst includes one or more of the following: a cassette catalyst, chloroplatinic acid, a platinum-vinylsiloxane complex, and a platinum-olefin complex. The platinum-containing catalyst may include, for example, a chloroplatinic acid solution, wherein the solvent of the chloroplatinic acid solution includes one or more of isopropanol, ethanol, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol methyl ether, toluene, and xylene, and the concentration of platinum in the chloroplatinic acid solution is 1000–5000 ppm.

[0048] In some embodiments of this application, the allyl polyether includes one or more of polyethylene glycol monoallyl ether (CAS No. 27274-31-3), polyethylene glycol polypropylene glycol allyl ether (CAS No. 9041-33-2), and allyl polyoxyethylene polyoxypropylene ether (CAS No. 68227-96-3). The number average molecular weight of the allyl polyether is, for example, 800 to 1200.

[0049] In some embodiments of this application, the step of separating and purifying the reaction product includes: treating the reaction product under a pressure of -0.09 to -0.1 MPa for 20 to 30 minutes to remove low-boiling substances.

[0050] In the compositions of this application embodiment, the percentage of the catalyst by mass of the total composition may be, for example, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or a range or value between any two of the foregoing.

[0051] In some embodiments of this application, the catalyst includes one or more of a first amine catalyst and an organotin catalyst. The first amine catalyst includes one or more of N-methyldicyclohexylamine, tetramethylhexanediamine, pentamethyldipropylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N-dimethylbenzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, bis(2-dimethylaminoethyl) ether, triethylenediamine, and triethanolamine. The organotin catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dichloro, and dibutyltin maleate. It should be noted that when the catalyst includes a first amine catalyst and an organotin catalyst, the mass ratio between the first amine catalyst and the organotin catalyst is 1:(0.8~1.2); when the catalyst is a first amine catalyst, the mass percentage of the catalyst in the total mass of the composition can be 0.15~0.3%; when the catalyst is an organotin catalyst, the mass percentage of the catalyst in the total mass of the composition can be 0.1~0.2%, which can be adjusted according to the actual foaming rate requirements.

[0052] In the compositions of this application, the organic isocyanate refers to an organic compound containing -NCO (isocyanate group) in its molecule. The ratio between the total molar number of active hydrogens in the composition and the molar number of isocyanate groups in the organic isocyanate is, for example, 1:(1.05 to 1.20), such as 1:1.05, 1:1.08, 1:1.10, 1:1.13, 1:1.16, 1:1.18, 1:1.20, or any value or range between the aforementioned two. Active hydrogen refers to hydrogen atoms that react with the isocyanate groups, including hydrogen in hydroxyl groups, hydrogen in amino groups (-NH2), hydrogen in imino groups (-NH-), hydrogen in water, etc. The mass percentage of isocyanate groups in the organic isocyanate is, for example, 28% to 32%, exhibiting moderate reactivity suitable for the crosslinking requirements of polyurethane foam.

[0053] In some embodiments of this application, the percentage of the organic isocyanate in the total mass of the composition is 41-48%, for example, it can be 42%, 44%, 46%, 48% or any value or range between the foregoing two values.

[0054] In some embodiments of this application, the organic isocyanate includes one or more of diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated polymethylene polyphenyl isocyanate.

[0055] In some embodiments of this application, the organic isocyanate includes MDI-50 and MDI-100, with a mass ratio of (6-8):(4-2) between MDI-50 and MDI-100, wherein MDI-100 represents 4,4'-diphenylmethane diisocyanate, and MDI-50 represents a mixture composed of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate (with a mass ratio of 1:1 between 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate). This allows for further adjustment of the reaction rate, enabling synergistic foaming and curing, thereby improving compatibility with the polyether component and the foaming agent, and further enhancing the overall performance of the resulting polyurethane foam material.

[0056] It should be noted that, in order to further improve the overall performance of the composition, the composition may also include functional additives, such as surfactants and flame retardants, such as organosilicon surfactants, and flame retardants such as triphenyl phosphate, tricresyl phosphate, triethyl phosphate, tri(2-chloroethyl) phosphate, and tri(2-chloropropyl) phosphate.

[0057] In some embodiments of this application, the composition includes a surfactant, wherein the surfactant accounts for 0.5 to 1% of the total mass of the composition.

[0058] In some embodiments of this application, the composition includes a flame retardant, the flame retardant accounting for 3 to 5% of the total mass of the composition.

[0059] This application also provides a polyurethane foam material, which is prepared using the composition described above.

[0060] In some embodiments of this application, the polyurethane foam material has a cell diameter of 32–60 nm, a coefficient of variation of 2.9–5.5, a closed-cell ratio of 97.5–99.5%, and an apparent core density of 16–22 kg / m³. 3 The initial thermal conductivity is 12.8–15.5 mW / m·K, the compressive strength is 135–155 KPa, the dimensional change rate is 0.2–0.45%, the five-year strength decrease rate is 5.2–10.0%, and the ten-year insulation attenuation rate is 1.8–4.5%.

[0061] This application also provides a method for preparing polyurethane foam material, which can be used to prepare polyurethane foam material as described above. The method uses the composition described above as the raw material and includes the steps of: providing the composition described above, foaming the composition to obtain polyurethane foam material.

[0062] In some embodiments of this application, providing the composition as described above includes the following steps: S1. Mix the composite nucleating component with the first silane coupling agent to obtain the composite nucleating component modified with the first silane coupling agent; S2. The composite nucleating component modified by the first silane coupling agent and the polyether component are mixed at 50-55 °C for 30-40 min to obtain a prepolymer system; S3. Mix the prepolymer system, foaming agent and organic isocyanate to obtain a composition.

[0063] In step S2, the composite nucleating component modified with the first silane coupling agent and the polyether component are dispersed at a low temperature of 50-55°C to ensure uniform dispersion of the composite nucleating component modified with the first silane coupling agent. The mixing in step S1, step S2, and step S3 can be carried out under stirring conditions.

[0064] In some embodiments of this application, the step of foaming the composition includes the following steps: injecting the composition into a mold, holding the mold at 60–61 °C for 10–20 min, then raising the temperature to 62–63 °C and holding for 10–20 min, then raising the temperature to 64–65 °C and holding for 10–20 min, followed by raising the temperature to 70–75 °C for curing and crosslinking for 20–30 min, and finally cooling and demolding. During the foaming stage, dynamic gradient heating of the composition can further improve the matching degree between the vaporization rate of the foaming agent and the cell expansion rate, reducing the problem of uneven cell structure caused by temperature differences inside and outside the mold, thereby further improving the phenomenon of cell collapse or over-expansion, which is beneficial to further improve the cell uniformity of the obtained polyurethane foam material; after dynamic gradient heating, the composition undergoes high-temperature crosslinking, thereby further improving the cell structure stability of the obtained polyurethane foam material, and further extending the insulation life of the obtained polyurethane foam material.

[0065] This application also provides a refrigeration device, which includes polyurethane foam material as described above, or polyurethane foam material prepared by the method described above. The refrigeration device can be a refrigerator, freezer, ultra-low temperature freezer, etc.

[0066] In some embodiments of this application, the refrigeration equipment includes a cabinet, which comprises a shell and a liner, the liner being disposed inside the shell, and an insulation layer being provided between the shell and the liner; and / or, the refrigeration equipment includes a door, which comprises a door panel and a door liner spaced apart, and an insulation layer being provided between the door panel and the door liner. The insulation layer is made of polyurethane foam material as described above, or polyurethane foam material prepared by the method described above, possessing good thermal insulation performance and a long service life, and meeting the industry demands for new energy-efficient, ultra-thin, and high-efficiency refrigerator production.

[0067] The technical solutions and effects of this application will be described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of this application and are not intended to limit this application.

[0068] Example 1 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The composition comprises, by mass percentage, 43% polyether component, 0.6% composite nucleating component, 0.0012% first silane coupling agent (this percentage is based on the total mass of the composition), 13% blowing agent, and 0.2% catalyst, with the balance being an organic isocyanate.

[0069] The polyether component includes a first polyether and a second polyether. The first polyether is a glycerol-based polyether polyol (purchased from Wanhua Chemical, model number WANOL). ® R2304), the second polyether is hydroxyl-terminated polybutadiene (number average molecular weight of 1500), and the mass ratio between the first polyether and the second polyether is 1:0.003.

[0070] The composite nucleating components include nano-calcium carbonate (CAS No. 471-34-1, customized average particle size of 20 nm), graphene oxide (purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., item number 100602 (XF002-2)), and modified silica, with a mass ratio of nano-calcium carbonate, graphene oxide, and modified silica of 4:1:0.8. The preparation method of modified silica includes the following steps: fumed silica (Evonik A200) and KH-560 are mixed and dispersed in anhydrous ethanol at a mass ratio of 1:0.03, stirred and reacted at 60 ℃ for 2 h, and then vacuum dried at 80 ℃ for 3 h to obtain modified silica.

[0071] The first silane coupling agent consists of KH-550 and KH-560, with a mass ratio of 1:1 between KH-550 and KH-560.

[0072] The foaming agent includes n-pentane, cis-1,1,1,4,4,4-hexafluoro-2-butene, and polysiloxane antipermeability agent, with a mass ratio of 30:15:2 between n-pentane, cis-1,1,1,4,4,4-hexafluoro-2-butene, and polysiloxane antipermeability agent. The preparation method of the polysiloxane anti-permeation agent includes the following steps: mixing and stirring hydrogen-containing silicone oil (Shin-Etsu KF-99) and allyl polyether (APEG-1000) with a mass ratio of 1:2.5 to obtain a first mixture; heating the first mixture to 80 °C under a nitrogen atmosphere, adding isopropanol chloroplatinate solution (with a platinum concentration of 1000 ppm) to the first mixture, wherein the mass of isopropanol chloroplatinate solution accounts for 0.03% of the total mass of hydrogen-containing silicone oil, allyl polyether, and isopropanol chloroplatinate solution, and reacting at a constant temperature for 4 h to obtain a reaction product; and treating the reaction product under a pressure of -0.095 MPa for 25 min to remove low-boiling substances to obtain the polysiloxane anti-permeation agent.

[0073] The catalyst is composed of pentamethyldiethylenetriamine and dibutyltin dilaurate, with a mass ratio of 1:1 between pentamethyldiethylenetriamine and dibutyltin dilaurate.

[0074] Organic isocyanates include MDI-50 and MDI-100, with a mass ratio of 7:3 between MDI-50 and MDI-100.

[0075] The polyurethane foam material is prepared using the composition of this embodiment. The preparation method of the polyurethane foam material includes the following steps: S1.1 Take each component according to the formulation ratio of the composition; S1.2. The composite nucleating component and the first silane coupling agent are mixed in a high-speed disperser and dispersed at 11000 r / min for 35 min to obtain the composite nucleating component modified by the first silane coupling agent; and the first polyether and hydroxyl-terminated polybutadiene are stirred and mixed at 50 °C and 800 r / min for 25 min to obtain the polyether component. S1.3. The composite nucleating component modified with the first silane coupling agent and the polyether component are placed in a constant temperature stirred reactor and stirred at 52 ℃ and 700 r / min for 35 min to obtain a prepolymer system. S1.4 Place the ultra-thin refrigerator insulation layer cavity (thickness 15 mm, width 5 mm) in the mold, then heat the ultra-thin refrigerator insulation layer cavity together with the mold to 60 ℃. Then, stir the prepolymer system, foaming agent and organic isocyanate at 2200 r / min for 12 s and pour it into the mold. Keep the mold at 60 ℃ for 10 min, then heat it to 62 ℃ and keep it for 10 min, then heat it to 65 ℃ and keep it for 15 min, then heat it to 72 ℃ for curing and crosslinking for 25 min. The heating rate is 1 ℃ / min. Finally, cool and demold.

[0076] Example 2 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that the mass ratio of nano-calcium carbonate, graphene oxide, and modified silica is 3:1:0.5.

[0077] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0078] Example 3 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that the mass ratio of nano-calcium carbonate, graphene oxide, and modified silica is 5:1:1.

[0079] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0080] Example 4 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that the first polyether is replaced with a crosslinking reaction product of polyether 330N and polyether 210.

[0081] The first polyether has a hydroxyl value of 370 mgKOH / g and a viscosity of 1800 mPa·s at 25 °C. The preparation method of the first polyether includes the following steps: mixing polyether 330N, polyether 210, and glycerol to obtain a second mixture; heating the second mixture to 45 °C, adding triethylenediamine and silicone foam stabilizer (L-580) to the second mixture, stirring and mixing until the target hydroxyl value and viscosity are reached, cooling to room temperature, and then separating and purifying to obtain the first polyether. The mass ratio of polyether 330N to polyether 210 is 1:2.5, and the ratio of the total mass of polyether 330N and polyether 210, the mass of glycerol, the mass of triethylenediamine, and the mass of silicone foam stabilizer is 93:3.5:0.5:3.

[0082] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0083] Example 5 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that the second polyether is omitted, meaning the polyether component is the first polyether.

[0084] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0085] Example 6 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that "0.6% of the composite nucleating component" is replaced with "0.4% of the composite nucleating component".

[0086] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0087] Example 7 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 1 and the composition in this embodiment is that "0.6% of the composite nucleating component" is replaced with "0.9% of the composite nucleating component".

[0088] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0089] Example 8 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 1, the composition in this embodiment differs in that the polysiloxane anti-permeability agent in the blowing agent is omitted; that is, the blowing agent consists of n-pentane and cis-1,1,1,4,4,4-hexafluoro-2-butene, with a mass ratio of cis-1,1,1,4,4,4-hexafluoro-2-butene to n-pentane of 6:4.

[0090] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0091] Example 9 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 1, the composition in this embodiment differs in that the mass ratio of n-pentane, cis-1,1,1,4,4,4-hexafluoro-2-butene, and the polysiloxane anti-permeability agent in the blowing agent is 28:18:1.

[0092] The polyurethane foam material in this embodiment is prepared using the composition of this embodiment. The polyurethane foam material of this embodiment is prepared using a method similar to that used in Example 1.

[0093] Example 10 This embodiment provides a polyurethane foam material and its preparation method. Compared with the preparation method of polyurethane foam material in Example 1, the difference in the preparation method of polyurethane foam material in this embodiment is that step S1.4 is replaced by "placing the ultra-thin refrigerator insulation layer cavity (thickness of 15 mm and width of 5 mm) in the mold, then heating the ultra-thin refrigerator insulation layer cavity together with the mold to 62 ℃, then stirring the prepolymer system, foaming agent and organic isocyanate at a speed of 2200 r / min for 12 s and then injecting it into the mold, keeping the mold at 62 ℃ for 35 min, then heating it to 72 ℃ for curing and crosslinking for 25 min, with a heating rate of 1 ℃ / min, and finally cooling and demolding".

[0094] Example 11 This embodiment provides a polyurethane foam material and its preparation method. Compared with the preparation method of polyurethane foam material in Example 1, the difference in the preparation method of polyurethane foam material in this embodiment is that "reheating to 65 ℃ and holding for 15 min" in step S1.4 is replaced with "reheating to 65 ℃ and holding for 10 min".

[0095] Example 12 This embodiment provides a polyurethane foam material and its preparation method. Compared with the preparation method of polyurethane foam material in Example 1, the difference in the preparation method of polyurethane foam material in this embodiment is that "reheating to 65 ℃ and holding for 15 min" in step S1.4 is replaced with "reheating to 65 ℃ and holding for 20 min".

[0096] Comparative Example 1 This comparative example provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 1, the composition in this comparative example differs in that: the second polyether is omitted, i.e., the polyether component is the first polyether; the composite nucleating component consists of nano-calcium carbonate (same as in Example 1) and graphene oxide (same as in Example 1), with a mass ratio of 4:1 between nano-calcium carbonate and graphene oxide; the polysiloxane anti-permeation agent in the blowing agent is omitted, i.e., the blowing agent consists of n-pentane and cis-1,1,1,4,4,4-hexafluoro-2-butene, with a mass ratio of 6:4 between cis-1,1,1,4,4,4-hexafluoro-2-butene and n-pentane.

[0097] Compared with the preparation method of polyurethane foam material in Example 1, the difference in the preparation method of polyurethane foam material in this comparative example is that step S1.4 is replaced by "placing the ultra-thin refrigerator insulation layer cavity (thickness of 15 mm and width of 5 mm) in the mold, then heating the ultra-thin refrigerator insulation layer cavity together with the mold to 62 ℃, then stirring the prepolymer system, foaming agent and organic isocyanate at a speed of 2200 r / min for 12 s and then injecting it into the mold, keeping the mold at 62 ℃ for 35 min, then heating it to 72 ℃ for curing and crosslinking for 25 min, with a heating rate of 1 ℃ / min, and finally cooling and demolding".

[0098] Comparative Example 2 This comparative example provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 1, the composition in this comparative example differs in that: the composite nucleating component consists of nano-calcium carbonate (same as in Example 1) and graphene oxide (same as in Example 1), with a mass ratio of 4:1 between nano-calcium carbonate and graphene oxide; the polysiloxane anti-permeation agent in the blowing agent is omitted, i.e., the blowing agent consists of n-pentane and cis-1,1,1,4,4,4-hexafluoro-2-butene, with a mass ratio of 6:4 between cis-1,1,1,4,4,4-hexafluoro-2-butene and n-pentane.

[0099] Compared with the preparation method of polyurethane foam material in Example 1, the difference in the preparation method of polyurethane foam material in this comparative example is that step S1.4 is replaced by "placing the ultra-thin refrigerator insulation layer cavity (thickness of 15 mm and width of 5 mm) in the mold, then heating the ultra-thin refrigerator insulation layer cavity together with the mold to 62 ℃, then stirring the prepolymer system, foaming agent and organic isocyanate at a speed of 2200 r / min for 12 s and then injecting it into the mold, keeping the mold at 62 ℃ for 35 min, then heating it to 72 ℃ for curing and crosslinking for 25 min, with a heating rate of 1 ℃ / min, and finally cooling and demolding".

[0100] Performance Test 1 The compositions in Examples 1 to 9, Comparative Examples 1 and 2 were subjected to performance testing to determine the appropriate refrigerator insulation layer thickness range for each composition. The testing method included the following steps: injecting the composition into refrigerator insulation layer cavity molds of different thicknesses; foaming the compositions in Examples 1 to 9 according to the polyurethane foam material preparation method in Example 1; and foaming the compositions in Comparative Examples 1 and 2 according to the polyurethane foam material preparation method in Comparative Example 1. The molding integrity, cell uniformity, and various performance indicators of each polyurethane foam material were tested to determine the appropriate thickness range. Specifically, for a refrigerator insulation layer cavity mold of a certain thickness, the resulting polyurethane foam material must meet the requirement that the apparent core density is not greater than 30 kg / m³. 3 The initial thermal conductivity is not higher than 20 mW / (m K), compressive strength not less than 135 kPa, and dimensional change rate not greater than 0.4%.

[0101] The test results are shown in Table 1 below: Table 1 serial number Compatible refrigerator insulation layer thickness range (mm) Example 1 10～18 Example 2 12～18 Example 3 10～18 Example 4 10～16 Example 5 14～18 Example 6 12～18 Example 7 10～16 Example 8 12～20 Example 9 10～18 Comparative Example 1 20～30 Comparative Example 2 18～25 As shown in Table 1, compared with the compositions in Comparative Examples 1 and 2, the compositions in Examples 1 to 9 are suitable for a wider range of refrigerator insulation layer thicknesses. Specifically, the compositions in Examples 1 to 9 are suitable for refrigerator insulation layer thicknesses as low as 10 mm, while the minimum thickness of the refrigerator insulation layer suitable for the compositions in Comparative Examples 1 and 2 is 18 mm.

[0102] This demonstrates that the compositions in Examples 1 to 9 possess good flow properties and excellent moldability in the cavity of ultra-thin refrigerator insulation layers. The compositions in Comparative Examples 1 and 2 exhibit poor flow properties and moldability, thus only suitable for thicker insulation layers.

[0103] Performance Test 2 The polyurethane foam materials in Examples 1 to 12, Comparative Examples 1 and 2 were subjected to performance tests. The performance test items included cell diameter, cell uniformity, apparent core density, initial thermal conductivity, compressive strength, dimensional change rate, five-year strength reduction rate, and ten-year insulation attenuation rate.

[0104] The apparent core density, initial thermal conductivity, compressive strength, and closed-cell ratio were tested according to the testing methods described in standard GB / T 26689-2024. The dimensional change rate was tested according to standard GB / T 8811-2008, measuring the dimensional change rate of polyurethane foam after being placed at 70 ℃ and 95% relative humidity for 48 h. The average cell size (cell diameter, nm) of the polyurethane foam was determined using scanning electron microscopy according to standard GB / T12811-2025. The cell uniformity was tested using the following steps: similar to the cell diameter test method, five fields of view were collected, and 500 cells were statistically analyzed. The average and standard deviation of the cell diameter of the 500 cells were calculated. The coefficient of variation (CV) for each polyurethane foam was calculated using the formula: CV(%) = standard deviation / average value × 100%. A smaller coefficient of variation indicates higher cell uniformity. The method for testing the five-year strength degradation rate includes the following steps: An accelerated aging test is conducted according to standard GB / T 9640-2008, simulating five years, to obtain the compressive strength of the aged polyurethane foam material. Then, the five-year strength degradation rate is calculated as follows: Five-year strength degradation rate (%) = (Initial compressive strength - Compressive strength after aging) / Initial compressive strength × 100%, where the initial compressive strength is the compressive strength tested earlier. The method for testing the ten-year thermal insulation degradation rate includes the following steps: An accelerated aging test is conducted according to standard GB / T 9640-2008, simulating ten years, to obtain the thermal conductivity of the aged polyurethane foam material. Then, the ten-year thermal insulation degradation rate is calculated as follows: Ten-year thermal insulation degradation rate (%) = (Temperature conductivity after aging - Initial thermal conductivity) / Initial thermal conductivity × 100%, where the initial thermal conductivity is the initial thermal conductivity obtained in the test earlier.

[0105] The test results are shown in Table 2 below: Table 2 serial number Pore ​​diameter (nm) CV(%) Closed-pore ratio (%) <![CDATA[Apparent core density (kg / m 3 )]]> Initial thermal conductivity mW / m·K Compressive strength (kPa) Dimensional deformation rate (%) Five-year intensity decline rate (%) Ten-year insulation degradation rate (%) Example 1 40 3.2 99.3 18 13.2 152 0.25 6.5 2.2 Example 2 45 3.8 99.0 19 14.0 148 0.3 7.8 2.8 Example 3 32 2.9 99.5 16 12.8 155 0.2 5.2 1.8 Example 4 42 3.5 99.2 17 13.0 150 0.23 6.0 2.0 Example 5 50 4.5 98.5 20 14.5 142 0.35 8.5 3.5 Example 6 48 4.0 98.8 19 13.8 145 0.32 7.2 2.6 Example 7 38 3.4 99.4 17 13.0 153 0.22 5.8 1.9 Example 8 55 5.0 98.0 21 15.0 138 0.40 9.2 4.0 Example 9 43 3.6 99.1 18 13.3 151 0.24 6.3 2.1 Example 10 60 5.5 97.5 22 15.5 135 0.45 10.0 4.5 Example 11 45 3.9 99.0 18 13.5 149 0.28 7.0 2.5 Example 12 41 3.3 99.2 17 13.1 151 0.21 5.9 1.9 Comparative Example 1 85 8.8 92.0 28 22.5 105 0.85 18.5 12.0 Comparative Example 2 75 7.5 94.5 25 19.0 118 0.70 15.0 9.5 As shown in Table 1, the polyurethane foam materials in Examples 1 to 12 exhibit better overall performance compared to those in Comparative Examples 1 and 2. Specifically, the polyurethane foam materials in Examples 1 to 12 have a cell diameter of 32–60 nm, a CV of 2.9–5.5, a closed-cell ratio of 97.5–99.5%, and an apparent core density of 16–22 kg / m³. 3 The initial thermal conductivity was 12.8–15.5 mW / m·K, the compressive strength was 135–155 kPa, the dimensional change rate was 0.2–0.45%, the five-year strength reduction rate was 5.2–10.0%, and the ten-year insulation attenuation rate was 1.8–4.5%. In Comparative Examples 1 and 2, the polyurethane foam materials had a cell diameter of not less than 75 nm, a CV of not less than 7.5%, a closed-cell rate of not more than 94.5%, and an apparent core density of not less than 25 kg / m³. 3 The initial thermal conductivity is not less than 19.0 mW / m·K, the compressive strength is not greater than 105 kPa, the dimensional change rate is not less than 0.70%, the five-year strength reduction rate is not less than 15.0%, and the ten-year insulation attenuation rate is not less than 9.5%.

[0106] Therefore, it can be seen that the polyurethane foam material prepared by using the composition of the embodiments of this application has improved the cell uniformity and long-term stability of the polyurethane foam material through the synergistic effect of the three components, namely, the nucleating component, the two-dimensional component, and the interface reinforcing component, which is beneficial to extending the service life of the polyurethane foam material. For example, the five-year strength reduction rate of the polyurethane foam material can be controlled to no more than 8%.

[0107] The polyurethane foam materials in Comparative Examples 1 and 2 exhibited poor overall performance due to the following reasons: First, the composite nucleating component did not include interfacial reinforcement materials, and the binary nucleation system suffers from poor long-term stability. Second, the blowing agent lacked a polysiloxane anti-permeability agent, resulting in easy permeation and a shorter insulation lifespan for the polyurethane foam, leading to a significantly increased ten-year insulation degradation rate. Third, the constant temperature insulation process during foaming resulted in cell collapse or over-expansion, causing a decrease in cell uniformity. Furthermore, in Comparative Example 1, the composition did not contain hydroxyl-terminated polybutadiene, resulting in a lower closed-cell ratio and significantly reduced anti-aging properties in the prepared polyurethane foam.

[0108] The embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A composition, characterized in that, The composition, calculated by mass percentage, comprises: 40–45% polyether component, 0.4–0.9% composite nucleating component, 10–16% foaming agent, and 0.1–0.3% catalyst; the composition further comprises an organic isocyanate and a first silane coupling agent, wherein the ratio of the total molar number of all active hydrogens in the composition to the molar number of isocyanate groups in the organic isocyanate is 1:(1.05–1.20), and the mass of the first silane coupling agent is 0.15–0.25% of the mass of the composite nucleating component; The composite nucleating component includes a nucleating material, a two-dimensional material, and an interface reinforcing material. The mass ratio of the nucleating material, the two-dimensional material, and the interface reinforcing material is (3-5):1:(0.5-1). The nucleating material includes one or more of nano-calcium carbonate, nano-talc, and nano-kaolin. The two-dimensional material includes one or more of graphene oxide, two-dimensional montmorillonite, and nano-mica sheets. The interface reinforcing material includes nanofillers modified with a second silane coupling agent. The nanofillers include one or more of nano-silica, nano-alumina, and nano-zinc oxide.

2. The composition according to claim 1, characterized in that, The first silane coupling agent and the second silane coupling agent each independently comprise one or more of dimethyldichlorosilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

3. The composition according to claim 2, characterized in that, At least one of the following conditions must be met: (1) The first silane coupling agent comprises silane coupling agent A and silane coupling agent B, wherein silane coupling agent A comprises one or more of γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane, and silane coupling agent B comprises one or more of γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, and the mass ratio between silane coupling agent A and silane coupling agent B is 1:(0.8~1.2); (2) The raw materials for preparing the nanofiller modified by the second silane coupling agent include the second silane coupling agent and the nanofiller, wherein the mass ratio between the nanofiller and the second silane coupling agent is 1:(0.01~0.05); (3) The average particle size of the nanofiller modified by the second silane coupling agent is 8-15 nm; (4) The average particle size of the nucleating material is 10–30 nm; (5) The thickness of a single layer of the two-dimensional material is not greater than 1.2 nm.

4. The composition according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The hydroxyl value of the polyether component is 350-450 mgKOH / g and the viscosity at 25 °C is not greater than 2000 mPa·s; (2) The foaming agent includes one or more of hydrocarbon foaming agents or hydrohalogenated hydrocarbon foaming agents, wherein the hydrocarbon foaming agent includes one or more of cyclopentane, isopentane, n-pentane, n-butane, isobutane, propane, hexane and heptane, the hydrohalogenated hydrocarbon foaming agent includes one or more of pentafluoropropane, pentafluorobutane, difluoroethane, tetrafluoroethane, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, hexafluoropropylene and hexafluorobutene, and / or the boiling point of the foaming agent is not higher than 45 °C and the global warming potential value of the foaming agent is not greater than 25; (3) The catalyst includes one or more of a first amine catalyst and an organotin catalyst, wherein the first amine catalyst includes one or more of N-methyldicyclohexylamine, tetramethylhexanediamine, pentamethyldipropylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N-dimethylbenzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, bis(2-dimethylaminoethyl) ether, triethylenediamine, and triethanolamine; and the organotin catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dichloro, and dibutyltin maleate. (4) The organic isocyanate includes one or more of diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated polymethylene polyphenyl isocyanate, and / or the mass percentage of isocyanate groups in the organic isocyanate is 28-32%; Optionally, the organic isocyanate includes MDI-50 and MDI-100, with a mass ratio of (6-8):(4-2) between MDI-50 and MDI-100.

5. The composition according to claim 1 or 4, characterized in that, At least one of the following conditions must be met: (1) The polyether component includes a first polyether and a second polyether, wherein the first polyether includes WANOL. ® The crosslinking reaction product of R2304 or polyether 330N and polyether 210, wherein the second polyether comprises hydroxyl-terminated polybutadiene, and the mass ratio between the first polyether and the second polyether is 1:(0.002-0.005); optionally, the number average molecular weight of the hydroxyl-terminated polybutadiene is 1000-2000, the hydroxyl value of the first polyether is 350-450 mgKOH / g, and the viscosity at 25 °C is not greater than 2000 mPa·s; (2) The foaming agent includes hydrocarbon foaming agent, hydrohalogenated hydrocarbon foaming agent and polysiloxane antipermeability agent, and the mass ratio between the hydrocarbon foaming agent, the hydrohalogenated hydrocarbon foaming agent and the polysiloxane antipermeability agent is (25~35):(10~20):(1~3); Optionally, the hydrocarbon blowing agent includes n-pentane; the hydrohalogenated hydrocarbon blowing agent includes one or more of cis-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,1,1,3-tetrafluoropropene, trans-1-chloro-3,3,3-trifluoropropene, and cis-1,2,3,3,3-pentafluoropropene. The preparation method of the polysiloxane anti-permeability agent includes the following steps: providing a first mixture comprising hydrogen-containing silicone oil and allyl polyether, wherein the mass ratio of the hydrogen-containing silicone oil to the allyl polyether is 1:(2-3); heating the first mixture to 80-90 °C under an inert gas atmosphere, adding a platinum-containing catalyst to the first mixture, mixing and reacting for 3-4 h to obtain a reaction product; separating and purifying the reaction product to obtain the polysiloxane anti-permeability agent; wherein the mass percentage of the platinum-containing catalyst to the total mass of the hydrogen-containing silicone oil, the allyl polyether, and the platinum-containing catalyst is 0.01-0.03%.

6. The composition according to claim 5, characterized in that, At least one of the following conditions must be met: (1) The method for preparing the crosslinking reaction product of polyether 330N and polyether 210 includes the following steps: providing a second mixture comprising polyether 330N, polyether 210 and a crosslinking agent; heating the second mixture to 40-50 °C, adding a second amine catalyst and a silicone oil foam stabilizer to the second mixture, mixing and reacting to obtain the crosslinking reaction product of polyether 330N and polyether 210; Optionally, the mass ratio of polyether 210 to polyether 330N is 1:(2-3), and the ratio of the total mass of polyether 330N and polyether 210, the mass of the crosslinking agent, the mass of the second amine catalyst, and the mass of the silicone oil foam stabilizer is (90-95):(2-5):(0.3-0.8):(1-3); the crosslinking agent includes one or more of glycerol, trimethylolpropane, pentaerythritol, diglycerol, and trimethylolethane; the second amine catalyst includes one or more of triethylenediamine, triethanolamine, diethylenetriamine, and diethanolamine; and the silicone oil foam stabilizer includes silicone oil L-580, silicone oil L-620, and silicone oil B. 8715 and silicone oil Y One or more of 1036; (2) The hydrogen-containing silicone oil includes one or more of polymethylhydrosiloxane and methylphenyl silicone oil, and / or the viscosity of the hydrogen-containing silicone oil at 25 °C is 50-100 mPa·s. (3) The platinum-containing catalyst includes one or more of the following: a cassiterite catalyst, chloroplatinic acid, a platinum-vinylsiloxane complex, and a platinum-olefin complex; optionally, the platinum-containing catalyst includes a chloroplatinic acid solution, wherein the solvent of the chloroplatinic acid solution includes one or more of the following: isopropanol, ethanol, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol methyl ether, toluene, and xylene, and the concentration of platinum in the chloroplatinic acid solution is 1000 to 5000 ppm; (4) The allyl polyether includes one or more of polyethylene glycol monoallyl ether, polyethylene glycol polypropylene glycol allyl ether and allyl polyoxyethylene polyoxypropylene ether, and / or the number average molecular weight of the allyl polyether is 800 to 1200. (5) The step of separating and purifying the reaction product includes: treating the reaction product under a pressure of -0.09 to -0.1 MPa for 20 to 30 minutes to remove low-boiling substances.

7. A polyurethane foam material, characterized in that, The polyurethane foam material is prepared using the composition described in any one of claims 1 to 6.

8. A method for preparing a polyurethane foam material, characterized in that, The method includes the steps of: providing a composition as described in any one of claims 1 to 6, foaming the composition to obtain the polyurethane foam material.

9. The method for preparing polyurethane foam material according to claim 8, characterized in that, At least one of the following conditions must be met: (1) The step of providing the composition includes the following steps: The composite nucleating component is mixed with the first silane coupling agent to obtain the composite nucleating component modified with the first silane coupling agent; The composite nucleating component modified with the first silane coupling agent and the polyether component are mixed at 50-55 °C for 30-40 min to obtain a prepolymer system; as well as The prepolymer system, the foaming agent, and the organic isocyanate are mixed to obtain a composition; (2) The step of foaming the composition includes the following steps: injecting the composition into a mold, keeping the mold at 60-61°C for 10-20 min, then raising the temperature to 62-63°C and keeping it at 64-65°C for 10-20 min, then raising the temperature to 70-75°C for curing and crosslinking for 20-30 min, and finally cooling and demolding.

10. A refrigeration device, characterized in that, The refrigeration equipment includes the polyurethane foam material as described in claim 7, or the polyurethane foam material prepared by the method described in claim 8 or 9. Optionally, the refrigeration equipment is a refrigerator, freezer, or ultra-low temperature freezer, and the insulation layer of the refrigeration equipment has a thickness of 10-20 mm, and the insulation layer is filled and molded from the polyurethane foam material.