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, and the composition comprises a polyol component, a foaming agent, an auxiliary agent and an organic isocyanate, wherein the auxiliary agent comprises a catalyst, the polyol component comprises a bio-based fatty acid diethanolamide and a fossil-based polyol, the mass percentage of the bio-based fatty acid diethanolamide in the total mass of the polyol component is greater than 0% and not greater than 60%, the polyurethane foam material prepared based on the composition has good heat preservation performance, mechanical strength, low-temperature stability and aging resistance, and the polyurethane foam material can be applied to the refrigeration equipment.

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] Fossil-based polyols are one of the main raw materials used in the preparation of polyurethane foam materials. However, the production process of fossil-based polyols is highly polluting, and polyurethane foam materials based on fossil-based polyols are difficult to degrade after disposal, which is inconsistent with environmental protection trends. In related technologies, bio-based polyols (such as vegetable oil-based polyols) are used to partially replace fossil-based polyols in the preparation of polyurethane foam materials, but this has problems: bio-based polyols have lower reactivity, resulting in prolonged reaction time. If a large amount of additional catalyst is added to shorten the reaction time, it will not only increase costs but may also affect the aging resistance of polyurethane foam materials. 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 weight parts, 100 parts of a polyol component, 3 to 11 parts of a foaming agent, and 0.5 to 5 parts of an additive, the additive including a catalyst; the composition further comprising an organic isocyanate, 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 to 1.20); The polyol component includes bio-based fatty acid diethanolamide and fossil-based polyol, wherein the mass percentage of the bio-based fatty acid diethanolamide in the total mass of the polyol component is greater than 0% and not greater than 60%.

[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 compositions of this application can be used to prepare polyurethane foam materials. In the composition, bio-based fatty acid diethanolamide and fossil-based polyols are used as the polyol component. Since the bio-based fatty acid diethanolamide contains tertiary amine groups and hydroxyl groups, it possesses autocatalytic properties, capable of catalyzing the reaction between the polyol component, organic isocyanate, and blowing agent. This shortens the reaction time without requiring a large amount of catalyst, thus improving the aging resistance of the polyurethane foam material prepared based on the composition. By optimizing the ratio of the various components in the composition, bio-based fatty acid diethanolamide can efficiently replace fossil-based polyols, achieving a replacement ratio of up to 60%. Furthermore, the polyurethane foam material prepared based on the composition exhibits good thermal insulation properties, mechanical strength, and low-temperature stability.

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

[0011] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art 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. The hydroxyl value of the substance can be determined using Test Method (Polyether Polyols Part 3) as described in GB / T 12008.3-2009.

[0022] In existing refrigeration equipment, the preparation of polyurethane foam materials is highly dependent on fossil-based polyols, resulting in strong resource dependence, poor environmental performance, and difficulty in degradation after disposal. Replacing some fossil-based polyols with conventional bio-based polyols is limited in its substitution ratio (generally no more than 30%). Substitution ratios exceeding 30% lead to a significant increase in thermal conductivity and a decrease in insulation performance. Bio-based polyols have low reactivity, resulting in prolonged reaction times. Adding large amounts of catalysts to shorten reaction time not only increases costs but may also affect the aging resistance of the polyurethane foam material. Furthermore, some polyurethane foam materials prepared based on bio-based polyols exhibit uneven cell structure and excessively high open-cell ratios, leading to insufficient mechanical strength and potentially making them unable to withstand the assembly pressure and long-term structural stress of refrigeration equipment.

[0023] Based on this, embodiments of this application provide a composition comprising, by weight parts, 100 parts of a polyol component, 3-11 parts of a foaming agent, and 0.5-5 parts of an additive, including a catalyst. The composition also includes an organic isocyanate, wherein the ratio between the total moles of all active hydrogens in the composition and the moles of isocyanate groups in the organic isocyanate is 1:(1.05-1.20). The polyol component comprises bio-based fatty acid diethanolamide and fossil-based polyol, wherein the mass percentage of the bio-based fatty acid diethanolamide in the total mass of the polyol component is greater than 0% and not greater than 60%.

[0024] In the composition of this application embodiment, bio-based fatty acid diethanolamide and fossil-based polyol are used as polyol components. Since bio-based fatty acid diethanolamide contains tertiary amine groups and hydroxyl groups, it has self-catalytic properties and can catalyze the reaction between polyol components, organic isocyanates and foaming agents. Therefore, the reaction time can be shortened without adding more catalysts, which is beneficial to improving the aging resistance of polyurethane foam materials prepared based on the composition.

[0025] Furthermore, by optimizing the ratio of each component in the composition, bio-based fatty acid diethanolamide can be used to efficiently replace fossil-based polyols, with a replacement ratio of up to 60%. The polyurethane foam material prepared based on the composition also exhibits good thermal insulation properties, mechanical strength, and low-temperature stability.

[0026] In some embodiments of this application, the mass ratio between fossil-based polyols and bio-based fatty acid diethanolamides is (40-80):(20-60), for example, it can be 40:60, 50:50, 60:40, 70:30, 80:20, or any two of the aforementioned values ​​or a range thereof. This further increases the substitution ratio of bio-based fatty acid diethanolamides for fossil-based polyols, thereby further improving the environmental friendliness of the polyurethane foam material prepared based on the composition. For example, the biodegradability of the polyurethane foam material after disposal is increased by more than 40%, and the thermal insulation performance, mechanical properties, and aging resistance of the polyurethane foam material are further improved, achieving an initial thermal conductivity of the polyurethane foam material not exceeding 0.025 W / (m²). K), compressive strength not less than 130 KPa, closed-cell ratio not less than 93%, and thermal conductivity change rate not greater than 2.6% after 1000 h of aging.

[0027] In some embodiments of this application, the bio-based fatty acid diethanolamides include one or more of coconut oil fatty acid diethanolamide, palm oil fatty acid diethanolamide, soybean oil fatty acid diethanolamide, and castor oil fatty acid diethanolamide. These bio-based fatty acid diethanolamides all possess autocatalytic properties and are abundant in resources.

[0028] In some embodiments of this application, the raw materials for preparing bio-based fatty acid diethanolamide include industrial-grade bio-based fatty acid diethanolamide; in other words, the bio-based fatty acid diethanolamide is a purified product based on industrial-grade bio-based fatty acid diethanolamide. This allows for a further balance between increasing the proportion of bio-based fatty acid diethanolamide replacing fossil-based polyols and improving the performance of the polyurethane foam material prepared from the composition, avoiding problems such as uncontrolled cell structure and unbalanced reaction rates that occur when conventional bio-based polyols are used to replace fossil-based polyols.

[0029] In some embodiments of this application, the industrial-grade bio-based fatty acid diethanolamide has a hydroxyl value of 250-270 mg KOH / g and an amine value of 15-20 mg KOH / g, and the industrial-grade bio-based fatty acid diethanolamide has a moisture content of no more than 0.5 wt%, a free fatty acid content of no more than 2.0 wt%, and an ash content of no more than 0.3 wt%.

[0030] In some embodiments of this application, the bio-based fatty acid diethanolamide has a hydroxyl value of 280–320 mg KOH / g and an amine value of 12–18 mg KOH / g; the bio-based fatty acid diethanolamide has a moisture content of no more than 0.1 wt%, a free fatty acid content of no more than 0.3 wt%, and an ash content of no more than 0.05 wt%; and the bio-based fatty acid diethanolamide has a viscosity of 1800–2200 mPa at 25 °C. Thus, bio-based fatty acid diethanolamides have lower impurity content and their hydroxyl and amine values ​​are within a more suitable range, which can further improve the proportion of bio-based fatty acid diethanolamides replacing fossil-based polyols and the performance of polyurethane foam materials prepared based on the composition.

[0031] In some embodiments of this application, the fossil-based polyol has a hydroxyl value of 200–650 mg KOH / g and a viscosity of 500–8000 mPa at 25°C. This further improves the flow and filling properties of the composition. As an example, the fossil-based polyol has a hydroxyl value of 300–410 mg KOH / g and a viscosity of 2500–3000 mPa at 25 °C. s.

[0032] In some embodiments of this application, the initiator used to prepare the fossil-based polyol includes a polyhydroxy compound, wherein the polyhydroxy compound includes one or more selected from sucrose, sorbitol, mannitol, xylitol, pentaerythritol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and trimethylolpropane, and correspondingly, the fossil-based polyol is a polyether polyol. This further increases the crosslinking density of the polyurethane foam material prepared based on the composition, thereby further improving the compressive strength and dimensional stability of the polyurethane foam material.

[0033] In some embodiments of this application, the polyhydroxy compound includes one or more of sucrose, glycerol, sorbitol, diethylene glycol, and pentaerythritol, which can further improve the mechanical properties of the polyurethane foam material prepared based on the composition.

[0034] In some embodiments of this application, the polymeric monomers used to prepare fossil-based polyols include 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.

[0035] In some embodiments of this application, the polymer monomers used to prepare fossil-based polyols include one or more of ethylene oxide, propylene oxide, butane oxide, pentane oxide, and hexane oxide.

[0036] In some embodiments of this application, the mass ratio between the initiator and the polymerizing monomer used to prepare the fossil-based polyol is 1:(3-8), and the polymerizing monomer used to prepare the fossil-based polyol includes ethylene oxide and propylene oxide, with a mass ratio between ethylene oxide and propylene oxide of (1-4):(6-9).

[0037] In some embodiments of this application, the fossil-based polyols include one or more of polyether polyols H6437, H8635, YD8310, 4110, 330N, and sucrose-glycerol type polyether polyols.

[0038] The mass fraction of the foaming agent can be, for example, 3 parts, 5 parts, 8 parts, 11 parts, or any value or range between any two of the aforementioned values. In some embodiments of this application, the foaming agent includes one or more of water, hydrocarbon foaming agents, and 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, and the hydrohalogenated hydrocarbon foaming 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.

[0039] In some embodiments of this application, the foaming agent is water, and the mass fraction of the foaming agent is 3 to 4 parts, which improves environmental friendliness and saves the preparation cost of polyurethane foam materials.

[0040] In some other embodiments of this application, the foaming agent includes water and cyclopentane, with a mass ratio of water to cyclopentane of (1.5-3.0):(5.0-8.0), and the mass fraction of the foaming agent is 6.5-11 parts. This further improves the environmental friendliness and further reduces the thermal conductivity of the polyurethane foam material, thereby further improving the thermal insulation performance of the polyurethane foam material.

[0041] In some other embodiments of this application, the foaming agent includes water and 1,1,1,3,3-pentafluoropropane, with a mass ratio of water to 1,1,1,3,3-pentafluoropropane of (1.5 to 3.0): (3.0 to 5.0), and the mass fraction of the foaming agent is 4.5 to 8 parts. This further reduces the thermal conductivity of the polyurethane foam material while further improving the uniformity of the cell structure and the dimensional stability of the polyurethane foam material.

[0042] The mass fraction of the catalyst can be 0.5 to 1 part, for example, 0.5 parts, 0.7 parts, 0.9 parts, or any value or range between the aforementioned two values. In some embodiments of this application, the catalyst includes one or more of amine catalysts and metal catalysts. The amine catalysts include one or more of N-methyldicyclohexylamine, triethylenediamine, tetramethylhexanediamine, pentamethyldipropylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether, pentamethyldiethylenetriamine, N,N-dimethylbenzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, bis(2-dimethylaminoethyl) ether, and triethanolamine. The metal catalysts include one or more of dibutyltin dilaurate, stannous octanoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dichloro, and dibutyltin maleate.

[0043] To further improve the compatibility between the catalyst and other components in the composition, thereby further shortening the reaction time, in some embodiments of this application, the catalyst includes a first compound and a second compound, each independently selected from tertiary amine catalysts; or, one of the first and second compounds is selected from a tertiary amine catalyst, and the other is selected from the metal catalyst, with a mass ratio of (0.3–1.3):(0.2–0.5) between the first and second compounds. The tertiary amine catalyst includes, for example, one or more of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, triethylenediamine, and N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether, and the metal catalyst includes one or more of stannous octoate and dibutyltin dilaurate.

[0044] 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 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 to 1.20), for example, it can be 1:1.05, 1:1.10, 1:1.12, 1:1.15, 1:1.18, 1:1.20, or any value or range between the aforementioned two values. Active hydrogen refers to hydrogen atoms that react with isocyanate groups, including hydrogen in hydroxyl groups, hydrogen in amino groups (-NH2), hydrogen in imino groups (-NH-), hydrogen in water, etc.

[0045] In some embodiments of this application, the organic isocyanate includes one or more of diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (polymeric MDI), toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated polymethylene polyphenyl isocyanate. Organic isocyanates are commercially available.

[0046] In some embodiments of this application, the mass percentage of isocyanate groups in the organic isocyanate is 31-32%, which has moderate reactivity and is suitable for the crosslinking requirements of rigid polyurethane foam.

[0047] In some embodiments of this application, the additives further include silicone surfactants, with a mass ratio of catalyst to silicone surfactant of 100:(2.0–3.0), thereby further improving the cell uniformity of the resulting polyurethane foam material. Silicone surfactants include, for example, one or more of polyether-modified siloxanes, polyether-silicone copolymers, non-hydrolyzable polyether-polydimethylsiloxane copolymers, and polyepoxyalkylmethylsiloxane copolymers. Silicone surfactants are commercially available, and suitable examples may include one or more of VORASURF™ DC 5357, Dabco DC 193, Evonik TEGOSTAB B 8462, and Momentive Silquest L-6900.

[0048] It should be noted that the composition may also include other additives, such as flame retardants, antioxidants, fillers, etc. The flame retardant may be a phosphate ester flame retardant, such as one or more of triphenyl phosphate, tricresyl phosphate, triethyl phosphate, tri(2-chloroethyl) phosphate, and tri(2-chloropropyl) phosphate. The mass ratio between the polyol component and the flame retardant may be 100:(3-8).

[0049] This application also provides a polyurethane foam material, which is prepared using the composition described above.

[0050] In some embodiments of this application, the initial thermal conductivity of the polyurethane foam material is no greater than 0.0215 W / (m²). K), apparent core density not greater than 32.5 kg / m³ 3 The compressive strength is not less than 130 kPa and the closed-cell rate is not less than 92%. The initial decomposition temperature of the polyurethane foam material is not less than 220 ℃ and the mass loss rate at 300 ℃ is not greater than 5.2%. The change rate of thermal conductivity of the polyurethane foam material after 1000 h of aging is not greater than 3.1%.

[0051] 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.

[0052] In some embodiments of this application, the step of providing the composition includes: mixing a polyol component, an auxiliary agent, and a foaming agent according to a formulation ratio to obtain a premix; then, mixing the premix with an organic isocyanate to obtain the composition. The polyol component, auxiliary agent, and foaming agent can be mixed at 20–30 °C and a rotation speed of 400–600 r / min, and the mixing of the polyol component, auxiliary agent, and foaming agent can be carried out in a stirred tank. The premix and the organic isocyanate can be mixed at 20–30 °C and a rotation speed of 1500–2500 r / min for 15–20 s, resulting in a milky white system.

[0053] In some embodiments of this application, the preparation method of bio-based fatty acid diethanolamide in the polyol component includes the following steps: S1. Provide industrial-grade bio-based fatty acid diethanolamide, and perform solid-liquid separation on industrial-grade bio-based fatty acid diethanolamide to remove solid impurities with a particle size of not less than 180 µm to obtain liquid. S2. Dissolve the liquid in an organic solvent to obtain a mixture, mix the mixture with a first alkaline solution, the solvent of the first alkaline solution including water, allow it to stand and separate into layers, the upper layer being an organic phase and the lower layer being an aqueous phase, and collect the organic phase; S3. Wash the organic phase with a second alkaline solution, the solvent of which includes water. The washing operation is performed at least once until the pH of the aqueous phase obtained after washing is 7.0 to 7.5 and the conductivity is not greater than 20 μS / cm, thus obtaining a purified organic phase. S4. The purified organic phase is subjected to drying and desolventizing processes in sequence to obtain bio-based fatty acid diethanolamide.

[0054] In step S1, solid-liquid separation includes one or more of sedimentation and filtration. Sedimentation includes one or more of gravity sedimentation, centrifugal sedimentation, and electromagnetic sedimentation. Filtration includes one or more of atmospheric pressure filtration, pressure filtration, and vacuum filtration. Solid impurities include unreacted bio-based oil residues, catalysts, etc. As an example, the step of solid-liquid separation of industrial-grade bio-based fatty acid diethanolamide includes: filtering the industrial-grade bio-based fatty acid diethanolamide through an 80-mesh stainless steel screen under atmospheric pressure.

[0055] It should be noted that if the viscosity of the liquid at 25 °C is greater than 5000 mPa... If the viscosity is too low, the liquid can be heated to 35 °C to reduce its viscosity, thus facilitating subsequent dissolution. Furthermore, by detecting the hydroxyl value of the liquid and using potentiometric titration to determine the content of free fatty acids, the hydroxyl value can be controlled between 250 and 270 mPa. The content of s and free fatty acids should not exceed 2.0 wt% to reduce the number of subsequent washing operations.

[0056] In step S2, the endpoint of dissolving the liquid in the organic solvent is determined by the absence of any visible suspended matter. In some embodiments of this application, the organic solvent includes one or more of diethyl ether, ethanol, and isopropanol. These solvents have advantages such as low toxicity, matching solubility with the liquid, environmental friendliness, and ease of distillation recovery. The organic solvent can be an analytical grade reagent; and / or the volume ratio between the liquid and the organic solvent is 1:(2-4). As an example, the step of dissolving the liquid in the organic solvent to obtain a mixture includes: placing the liquid and the organic solvent in a reaction vessel equipped with a stirrer at a volume ratio of 1:(2-4), and mixing them at 20-30 °C and a rotation speed of 300-350 r / min.

[0057] In step S2, the purpose of mixing the mixture and the first alkaline solution is to remove insoluble carbonate impurities and residual fatty acids from the mixture. In some embodiments of this application, the alkali in the first alkaline solution includes one or more of alkali metal carbonates and alkali metal bicarbonates, such as sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. It should be noted that the first alkaline solution can be prepared 24 hours in advance. The water used to prepare the first alkaline solution can be deionized water (conductivity not greater than 10 μS / cm). Before use, the pH of the first alkaline solution can be calibrated to 8.0–8.5 using a precision pH meter to improve the removal rate of residual fatty acids. In some embodiments of this application, the mass percentage of alkali in the first alkaline solution is 3-7%, and the volume ratio between the mixed solution and the first alkaline solution is 1:(1-3).

[0058] In some embodiments of this application, the step of mixing the mixture and the first alkaline solution and allowing it to stand and separate includes: slowly adding the first alkaline solution to the mixture under the conditions of a stirring speed of 200-250 r / min and a temperature of 20-30 °C. The addition rate of the first alkaline solution should not exceed 10 L / min to avoid a sudden increase in local pH that could damage the structure of the bio-based fatty acid diethanolamide, until the volume ratio between the mixture and the first alkaline solution is 1:(1-3). Stirring is continued for 10-20 min, then stirring is stopped and the mixture is allowed to stand. It should be noted that step S2 can also be carried out in a reaction vessel. The lower aqueous phase is released through the separatory valve at the bottom of the reaction vessel and can be collected into a waste liquid tank. During the separation process, the interface changes are observed. When a turbid emulsion layer appears, the separation is paused, and the emulsion layer can be collected separately. Subsequently, an organic solvent can be added to the emulsion layer to extract and recover the bio-based fatty acid diethanolamide.

[0059] In some embodiments of this application, the alkali in the second alkaline solution independently includes one or more of alkali metal carbonates and alkali metal bicarbonates, such as sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate.

[0060] In some embodiments of this application, in each washing operation, the mass percentage of alkali in the second alkaline solution is 3-7%, and the volume ratio between the organic phase to be washed and the second alkaline solution is 1:(1-1.5).

[0061] In some embodiments of this application, each washing operation includes the following steps: adding a second alkaline solution to the organic phase to be washed, wherein the volume ratio of the organic phase to be washed to the second alkaline solution is 1:(1-1.5); stirring and mixing for 5-15 minutes at a stirring speed of 200-250 r / min and a temperature of 20-30 °C; allowing the mixture to stand and separate into layers; and collecting the upper organic phase. It should be noted that after each wash, 50 mL of the lower aqueous phase can be taken, and the pH and conductivity of the lower aqueous phase can be measured using a pH meter. As an example, the washing operation is repeated 5 times. If the pH is still higher than 7.5 after the 5th wash, the washing operation needs to be increased until the pH reaches the standard. If the conductivity exceeds the standard, anhydrous ethanol can be added during the last wash to promote salt dissolution, but the amount of ethanol should not exceed 1% of the volume of the organic phase to be washed to avoid affecting the effect of the subsequent desolvation process.

[0062] In some embodiments of this application, the step of sequentially drying the purified organic phase includes the following steps: adding a desiccant to the purified organic phase, wherein the mass ratio of the purified organic phase to the desiccant is 1:(0.03–0.06), drying for 1–3 hours, and then filtering to remove the desiccant. The desiccant may include, for example, one or more of anhydrous sodium sulfate and anhydrous magnesium sulfate. The drying process can also be carried out in a reactor equipped with a stirrer, and the drying process can be carried out under stirring conditions, with a stirring speed of 100–200 r / min. It should be noted that filtration can be carried out at a temperature not exceeding 25 °C to avoid solvent evaporation from the organic phase.

[0063] In some embodiments of this application, the solvent removal process includes the step of: performing vacuum distillation on the purified organic phase after the drying process to remove the solvent from the organic phase. The solvent removal process can be carried out in a rotary evaporator. As an example, the solvent removal process includes the steps of: lowering the temperature of the condenser in the rotary evaporator to 5 °C (by introducing a low-temperature cooling liquid circulation pump), calibrating the vacuum degree of the vacuum pump to -0.08±0.002 MPa, then placing the purified organic phase after the drying process into the evaporation flask of the rotary evaporator, with the liquid volume not exceeding 2 / 3 of the evaporation flask volume, setting the rotation speed to 60-80 r / min, the water bath temperature to 50±2 °C, and performing vacuum distillation. The volume of the distillate is recorded every 1 h, and the solvent removal endpoint is considered reached when the distillate rate is below 0.5 L / h. The distilled liquid is collected in a recovery tank after condensation.

[0064] In some embodiments of this application, after the desolventizing step, the preparation method of bio-based fatty acid diethanolamide further includes the step of: vacuum drying the purified organic phase after the desolventizing step until the moisture content of the organic phase is no more than 0.1 wt%. The vacuum drying step can be carried out in a vacuum drying oven. During the vacuum drying process, an inert gas can be introduced every 1 hour to purge and remove evaporated moisture. The inert gas can be nitrogen, the flow rate of the inert gas can be 3–7 L / min, and the purging time can be 20–40 s. After the vacuum drying process is completed, the temperature is lowered to below 40 ℃, and a 5 g sample is taken. The moisture content of the sample is detected using a Karl Fischer moisture analyzer, and the moisture content must meet the requirement of no more than 0.1 wt%.

[0065] To further improve the purity of bio-based fatty acid diethanolamide, in some embodiments of this application, after the vacuum drying step, the preparation method of bio-based fatty acid diethanolamide further includes the step of filtering the purified organic phase after vacuum drying using a filter membrane with a pore size of 0.22–0.45 μm.

[0066] It should be noted that purified bio-based fatty acid diethanolamide can be stored in a sealed PTFE iron drum at a temperature of 20–25 °C, avoiding direct sunlight.

[0067] In some embodiments of this application, the step of foaming the composition includes: injecting the composition into a mold, foaming and curing it at 20-35°C for 4-6 minutes, demolding it, then allowing it to stand and cure at 20-35°C for 18-24 hours, and then curing it at 35-45°C for 5-8 days.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] Example 1 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The composition comprises, by weight, 100 parts of a polyol component, 3 parts of a blowing agent, 136.36 parts of an organic isocyanate, 1 part of a catalyst, and 2.5 parts of a silicone surfactant.

[0072] The foaming agent was deionized water, and the organic isocyanate was polymethylene polyphenyl isocyanate (purchased from Dow, product model PAPI™ 27). The catalyst consisted of pentamethyldiethylenetriamine (Polycat® 5) and N,N-dimethylcyclohexylamine (Polycat® 8), with a mass ratio of pentamethyldiethylenetriamine to N,N-dimethylcyclohexylamine of 0.65:0.35. The silicone surfactant was polyether-modified polydimethylsiloxane (purchased from Dow, product model VORASURF™ DC 5357).

[0073] The 100-part polyol component consists of 20 parts coconut oil fatty acid diethanolamide and 80 parts fossil-based polyol, specifically polyether polyol H6437 (purchased from Nanjing Hongbaoli). The preparation method of the coconut oil fatty acid diethanolamide includes the following steps: S1.1 Take 100 kg of industrial-grade coconut oil fatty acid diethanolamide (purchased from Jinan Yuanyang Chemical Co., Ltd., brand name 6501), and mechanically filter the 100 kg of industrial-grade coconut oil fatty acid diethanolamide through an 80-mesh stainless steel sieve to remove solid impurities with a particle size of not less than 180 µm, obtaining a liquid. The viscosity of the liquid at 25 ℃ shall not exceed 5000 mPa. s; S1.2 Place the liquid and diethyl ether obtained in step S1.1 into a jacketed glass reactor (with a volume of not less than 1000L and equipped with a polytetrafluoroethylene stirring paddle), with a volume ratio of liquid to diethyl ether of 1:3, set the stirring speed to 320 r / min, and pass constant temperature water through the jacket to control the system temperature at 25±1 ℃. Stir for 30 min to obtain a mixture. S1.3 Under the conditions of a rotation speed of 220 r / min and a system temperature of 25±1 ℃, sodium bicarbonate solution (solvent is deionized water and sodium bicarbonate mass percentage is 5%) is slowly added to the mixture obtained in step S1.2. The feeding rate of sodium bicarbonate solution is 10 L / min until the volume ratio between the mixture and sodium bicarbonate solution is 1:2. Stirring is continued for 15 min and then stopped. The mixture is allowed to stand for 30 min. The system separates into layers, with the upper layer being the organic phase and the lower layer being the aqueous phase. The lower aqueous phase is slowly discharged through the separatory valve at the bottom of the reactor and collected into the waste liquid tank to obtain the organic phase. S1.4 Add an equal volume of sodium bicarbonate solution (deionized water as solvent and sodium bicarbonate mass percentage of 5%) to the organic phase obtained in step S1.3. Stir for 10 min at 220 r / min and let stand for 25 min. Discard the lower aqueous phase and collect the upper organic phase. Repeat the above washing operation several times (e.g., 5 times). After each washing, take 50 mL of the lower aqueous phase for pH and conductivity testing until the pH of the lower aqueous phase is 7.0-7.5 and the conductivity is not greater than 20 μS / cm, to obtain the purified organic phase. S1.5 Add anhydrous sodium sulfate to the purified organic phase obtained in step S1.4. The mass of anhydrous sodium sulfate is 5% of the mass of the purified organic phase. Dry the purified organic phase for 2 h under a stirring speed of 150 r / min. Filter the dried organic phase through a sand core funnel to remove anhydrous sodium sulfate. Collect the filtrate. During the filtration process, keep the system temperature no higher than 25 ℃ to avoid ether volatilization. S1.6. Reduce the temperature of the condenser in the rotary evaporator (model RE-52AA, equipped with a two-stage vacuum pump) to 5 ℃ (by introducing a low-temperature cooling liquid circulation pump). Calibrate the vacuum degree of the vacuum pump to -0.08±0.002 MPa. Then, place the filtrate collected in step S1.5 into the evaporation flask of the rotary evaporator, with the liquid volume not exceeding 2 / 3 of the evaporation flask volume. Set the rotation speed to 70 r / min and the water bath temperature to 50±2 ℃, and perform vacuum distillation. Record the volume of the distillate every 1 h. When the distillate rate is lower than 0.5 L / h, it is considered the end point of desolventization. The vacuum distillation time is 6 h to obtain the crude product after desolventization. S1.7 Place the crude product obtained in step S1.6 in a vacuum drying oven (with a volume of not less than 500 L and equipped with a nitrogen purging device), spread it to a thickness of not more than 5 cm, close the door of the vacuum drying oven, turn on the vacuum pump to evacuate to 0.1±0.01 MPa, and then heat it to 100 ℃ at a rate of 2 ℃ / min and keep it at that temperature for 5 h. During the holding process, purge with nitrogen once every 1 h (nitrogen flow rate 5 L / min and purging time 30 s). After dehydration is completed, cool it down to below 40 ℃, take a 5 g sample, and use a Karl Fischer moisture analyzer to detect the moisture content of the sample. The detection showed that the moisture content was not more than 0.1 wt%, and the dehydrated product was obtained. S1.8. The dehydrated product obtained in step S1.7 is filtered through a 0.45 μm organic phase filter membrane to obtain coconut oil fatty acid diethanolamide.

[0074] The tests showed that the hydroxyl value of coconut oil fatty acid diethanolamide was 292 mg KOH / g and the amine value was 15.2 mg KOH / g. The moisture content, free fatty acid content, and ash content of coconut oil fatty acid diethanolamide were no more than 0.05 wt%, no more than 0.18 wt%, and no more than 0.02 wt%. The viscosity of coconut oil fatty acid diethanolamide at 25 ℃ was 2020 mPa. s.

[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: S2.1 Add the polyol component, catalyst, silicone surfactant and foaming agent to a high-speed stirred tank according to the formulation ratio of the composition, and stir at 500 r / min for 5 min at 25 ℃ to obtain the premix; S2.2 Add organic isocyanate to the premix according to the formulation ratio of the composition, immediately increase the stirring speed to 2000 r / min, stir for 20 s, and obtain the composition; S2.3. The composition obtained in step S2.3 is rapidly injected into a refrigerator cabinet simulation mold (150 mm × 150 mm × 20 mm). It is allowed to foam freely at 25 °C. After foaming, it is cured in the mold for 5 min and then demolded. The demolded product is allowed to stand and cure at 25 °C for 24 h, and then transferred to a 40 °C constant temperature oven for 7 days to obtain polyurethane foam material.

[0076] Example 2 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The composition comprises, by weight, 100 parts of a polyol component, 3 parts of a blowing agent, 140.17 parts of an organic isocyanate, 0.77 parts of a catalyst, and 2.5 parts of a silicone surfactant.

[0077] The foaming agent was deionized water, the organic isocyanate was the same as that in Example 1, and the silicone surfactant was the same as that in Example 1. The catalyst consisted of pentamethyldiethylenetriamine (Polycat®5) and N,N-dimethylcyclohexylamine (Polycat®8), with a mass ratio of 0.45:0.32 between pentamethyldiethylenetriamine and N,N-dimethylcyclohexylamine. 100 parts of the polyol component consisted of 40 parts of coconut oil fatty acid diethanolamide (same as in Example 1) and 60 parts of fossil-based polyol (same as in Example 1).

[0078] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0079] Example 3 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The composition comprises, by weight, 100 parts of a polyol component, 3 parts of a blowing agent, 143.98 parts of an organic isocyanate, 0.55 parts of a catalyst, and 2.5 parts of a silicone surfactant.

[0080] The foaming agent was deionized water, the organic isocyanate was the same as that in Example 1, and the silicone surfactant was the same as that in Example 1. The catalyst consisted of pentamethyldiethylenetriamine (Polycat®5) and N,N-dimethylcyclohexylamine (Polycat®8), with a mass ratio of 0.31:0.24 between pentamethyldiethylenetriamine and N,N-dimethylcyclohexylamine. 100 parts of the polyol component consisted of 60 parts of coconut oil fatty acid diethanolamide (same as in Example 1) and 40 parts of fossil-based polyol (same as in Example 1).

[0081] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0082] Example 4 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 2, the difference in this embodiment is that "40 parts of coconut oil fatty acid diethanolamide" is replaced with "40 parts of palm oil fatty acid diethanolamide". Compared to the method for preparing coconut oil fatty acid diethanolamide in Example 1, the difference in the method for preparing palm oil fatty acid diethanolamide in this embodiment is that "100g of industrial-grade coconut oil fatty acid diethanolamide" in step S1.1 is replaced with "100g of industrial-grade palm oil fatty acid diethanolamide (purchased from Jinan Yuanyang Chemical Co., Ltd., brand name palm oil-based 6501)".

[0083] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0084] Example 5 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 2, the difference in this embodiment is that "40 parts of coconut oil fatty acid diethanolamide" is replaced with "40 parts of soybean oil fatty acid diethanolamide". Compared to the method for preparing coconut oil fatty acid diethanolamide in Example 1, the difference in the method for preparing soybean oil fatty acid diethanolamide in this embodiment is that "100g of industrial-grade coconut oil fatty acid diethanolamide" in step S1.1 is replaced with "100g of industrial-grade soybean oil fatty acid diethanolamide (purchased from Jinan Yuanyang Chemical Co., Ltd., brand name soybean oil-based 6501)".

[0085] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0086] 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 2 and the composition in this embodiment is that the fossil-based polyol is polyether polyol H8635 (purchased from Nanjing Hongbaoli).

[0087] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0088] 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 2 and the composition in this embodiment is that the fossil-based polyol is polyether polyol YD8310 (purchased from Hebei Yadong Chemical).

[0089] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0090] Example 8 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 2, the composition in this embodiment differs in that the catalyst consists of N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether (product model: Jeffcat® ZF-10) and stannous octoate (product model: Kosmos 29), with a mass ratio of N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether to stannous octoate of 0.45:0.32.

[0091] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0092] Example 9 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. Compared to the composition in Example 2, the composition in this embodiment differs in that the blowing agent comprises 8 parts by mass, and these 8 parts of blowing agent consist of 3 parts deionized water and 5 parts cyclopentane.

[0093] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0094] Example 10 This embodiment provides a composition, a polyurethane foam material, and a method for preparing the same. The difference between the composition in Example 2 and the composition in this embodiment is that "40 parts of coconut oil fatty acid diethanolamide" is replaced with "40 parts of industrial-grade coconut oil fatty acid diethanolamide (same as in Example 1)".

[0095] The polyurethane foam material was prepared using the composition of this embodiment. The polyurethane foam material of this embodiment was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0096] Comparative Example 1 This comparative example 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 comparative example is that 100 parts of the polyol component are 100 parts of polyether polyol H6437.

[0097] The polyurethane foam material was prepared using the composition of this comparative example. The polyurethane foam material of this comparative example was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[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 2, the composition in this comparative example differs in that "40 parts of coconut oil fatty acid diethanolamide" is replaced with "40 parts of bio-based polyol (purchased from BASF, product model BASF Sovermol 750)", and the mass fraction of the catalyst is 3 parts, wherein the 3 parts of catalyst consist of 1.95 parts of Polycat®5 and 1.05 parts of Polycat®8.

[0099] The polyurethane foam material was prepared using the composition of this comparative example. The polyurethane foam material of this comparative example was prepared using a method similar to that used for the polyurethane foam material in Example 1.

[0100] Performance testing The polyurethane foam materials in Examples 1 to 10, Comparative Examples 1 and 2 were subjected to performance tests. The performance test items included apparent core density, initial thermal conductivity, compressive strength, low-temperature dimensional stability, closed-cell ratio, thermal stability and aging resistance.

[0101] The apparent core density, initial thermal conductivity, compressive strength, low-temperature dimensional stability, and closed-cell ratio were tested according to the test methods described in standard GB / T26689-2024. For low-temperature dimensional stability, the maximum value among the absolute values ​​of the sample's length change rate, width change rate, and thickness change rate was used.

[0102] The thermal stability of polyurethane foam materials was tested using a thermogravimetric analyzer. The test method included the following steps: a 50 g (initial mass) sample of polyurethane foam material was placed in the sample container of the thermogravimetric analyzer, and the temperature was increased at a rate of 10 °C / min under a nitrogen atmosphere. The temperature-mass residual curve was recorded in real time. The temperature range was 45–800 °C. The initial decomposition temperature Td ( °C) was determined based on the temperature-mass residual curve, and the mass loss rate (W0, %) of the polyurethane foam material sample at 300 °C was calculated. The mass loss rate (W0, %) at 300 °C was calculated as follows: (W0, %) = 100% - (mass of polyurethane foam material sample at 300 °C / initial mass × 100%).

[0103] The testing method for aging resistance includes the following steps: placing polyurethane foam material samples at 70 ℃ and 90% relative humidity for 1000 h, and testing the initial thermal conductivity and compressive strength of the polyurethane foam material samples after aging using the testing method described in standard GB / T26689-2024. The change rate of initial thermal conductivity (K0, %) and the change rate of compressive strength (P0, %) are calculated, where the change rate of initial thermal conductivity (K0, %) = (initial thermal conductivity after aging - initial thermal conductivity before aging) / initial thermal conductivity before aging × 100%, and the change rate of compressive strength (P0, %) = (compressive strength after aging - compressive strength before aging) / compressive strength before aging × 100%.

[0104] In addition, the gel time (t, s) of the compositions in Examples 1 to 10 and the comparative examples was measured according to HG / T 4574. The 2014 standard was followed by the following steps: Under a standard environment with a temperature of 23±2 ℃ and a relative humidity of 50±5%, the composition was prepared according to the formula ratio, and then stirred rapidly and evenly at a constant speed of 2000 r / min while timing was performed simultaneously; the intermittent glass rod lifting method was used until the material could be pulled into a continuous filamentous gel, and the time taken was recorded as the foaming gel time. The arithmetic mean of three parallel tests was taken.

[0105] The test results are shown in Table 1 below: Table 1 Example 1 0.0198 32.5 200 -0.14 94 223.1 4.5 2.5 -2.9 40 Example 2 0.0202 32.0 180 -0.17 93 229.4 4.2 2.4 -2.6 35 Example 3 0.0208 31.0 150 -0.2 93 234.7 3.9 2.3 -2.5 30 Example 4 0.0204 31.8 170 -0.19 92 227.8 4.4 2.6 -2.8 37 Example 5 0.0205 31.5 165 -0.21 92 225.6 4.5 2.7 -2.9 38 Example 6 0.0203 32.5 190 -0.15 93 231.2 4.1 2.3 -2.4 34 Example 7 0.0201 31.7 175 -0.18 93 228.5 4.3 2.5 -2.7 36 Example 8 0.0202 32 178 -0.17 93 229.1 4.2 2.4 -2.6 34 Example 9 0.0196 30.5 160 -0.22 92 228.7 4.3 2.5 -2.7 36 Example 10 0.0215 31.2 130 -0.28 89 221.3 5.2 3.1 -3.5 42 Comparative Example 1 0.0195 33.0 220 -0.12 95 216.5 4.8 2.6 -3 45 Comparative Example 2 0.0232 34.2 120 -0.48 85 212.8 6.5 4.2 -5.8 52 As shown in Table 1, the initial thermal conductivity of the polyurethane foam materials in Examples 1 to 10 is 0.0196–0.0215 W / (m²). K), apparent core density is 30.5–32.5 kg / m³ 3 The compressive strength is 130–200 kPa, the low-temperature dimensional stability (low-temperature dimensional change rate) is -0.28–-0.14%, the closed-cell rate is 89–94%, the Td is 221.3–234.7 ℃, the W0 is 3.9–5.2%, the K0 is 2.3–3.1%, and the P0 is -3.5–-2.4%.

[0106] In Comparative Example 1, the polyol component used to prepare the polyurethane foam material was a fossil-based polyol. Compared with Comparative Example 1, the polyurethane foam materials in Examples 1 to 10 are more environmentally friendly while possessing good performance (meeting the standard requirements for rigid polyurethane foam plastics for refrigerators and freezers). They can improve the problems of high dependence on fossil-based polyols and difficulty in degradation after disposal, and are more in line with the green development trend of the refrigeration equipment industry.

[0107] Taking the polyurethane foam materials in Examples 1 to 3 as examples, the initial thermal conductivity of the polyurethane foam materials in Examples 1 to 3 increased slightly with the increase of the substitution ratio of bio-based fatty acid diethanolamide for fossil-based polyols. In Example 3, the substitution ratio of bio-based fatty acid diethanolamide for fossil-based polyols reached 60%, but the initial thermal conductivity of the polyurethane foam material in Example 3 was still not higher than 0.0208 W / (m). The polyurethane foam materials in Examples 1 to 3 meet the stringent insulation requirements of Level 1 energy efficiency refrigerators, and the change rate of thermal conductivity after aging is no greater than 2.6%, indicating long-term stable insulation performance. The compressive strength of the polyurethane foam materials in Examples 1 to 3 is above 150 kPa, and the absolute value of the change rate of compressive strength after aging is no greater than 2.9%, capable of withstanding the extrusion stress during the assembly of the refrigeration equipment and the structural load during long-term low-temperature use. The closed-cell rate of the polyurethane foam materials in Examples 1 to 3 is no less than 93%, effectively avoiding the decrease in mechanical strength and the deterioration of insulation performance caused by open cells. The Td of the polyurethane foam materials in Examples 1 to 3 increases to 234.7 °C with the increase of the substitution ratio of bio-based fatty acid diethanolamide for fossil-based polyols, and W0 is no greater than 4.5%, capable of withstanding the foaming temperature rise during the production process of refrigeration equipment (usually no greater than 120 °C) and temperature fluctuations during long-term use, with a service life comparable to that of the polyurethane foam material in Comparative Example 1 (no less than 15 years).

[0108] Compared to the polyurethane foam material in Comparative Example 2, the polyurethane foam materials in Examples 1 to 10 exhibit superior overall performance. The gel time of the compositions in Examples 1 to 10 is shorter than that of the composition in Comparative Example 2. This demonstrates that using a blend of bio-based fatty acid diethanolamide and fossil-based polyols as the polyol component, based on the presence of tertiary amine and hydroxyl groups in the bio-based fatty acid diethanolamide, results in a self-catalytic property. This property allows the bio-based fatty acid diethanolamide to catalyze the reaction between the polyol component, organic isocyanate, and blowing agent, thus shortening the reaction time without requiring a large amount of catalyst. This is beneficial for improving the aging resistance of the polyurethane foam material prepared based on the composition. By optimizing the ratio of the various components in the composition, a high-efficiency substitution of fossil-based polyols with bio-based fatty acid diethanolamide is achieved, with a substitution ratio reaching 60%. Furthermore, the polyurethane foam material prepared based on the composition possesses excellent thermal insulation properties, mechanical strength, and low-temperature stability.

[0109] In Comparative Example 2, polyurethane foam materials were prepared by partially replacing fossil-based polyols with conventional bio-based polyols. Due to the low reactivity of bio-based polyols, the reaction time was prolonged. Although the amount of catalyst was increased to control the reaction time, the thermal insulation and mechanical properties of the polyurethane foam materials decreased after aging.

[0110] 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 comprises, by weight, 100 parts of a polyol component, 3 to 11 parts of a foaming agent, and 0.5 to 5 parts of an additive, the additive including a catalyst; the composition also includes an organic isocyanate, wherein 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 to 1.20). The polyol component includes bio-based fatty acid diethanolamide and fossil-based polyol, wherein the mass percentage of the bio-based fatty acid diethanolamide in the total mass of the polyol component is greater than 0% and not greater than 60%.

2. The composition according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The mass ratio between the fossil-based polyol and the bio-based fatty acid diethanolamide is (40-80):(20-60); (2) The bio-based fatty acid diethanolamide includes one or more of coconut oil fatty acid diethanolamide, palm oil fatty acid diethanolamide, soybean oil fatty acid diethanolamide and castor oil fatty acid diethanolamide; (3) The raw materials for preparing the bio-based fatty acid diethanolamide include industrial-grade bio-based fatty acid diethanolamide; (4) The bio-based fatty acid diethanolamide has a hydroxyl value of 280–320 mg KOH / g and an amine value of 12–18 mg KOH / g, the bio-based fatty acid diethanolamide has a moisture content of no more than 0.1 wt%, a free fatty acid content of no more than 0.3 wt%, and an ash content of no more than 0.05 wt%, and the bio-based fatty acid diethanolamide has a viscosity of 1800–2200 mPa at 25 °C. s.

3. The composition according to claim 1, characterized in that, The fossil-based polyol has a hydroxyl value of 200–650 mg KOH / g and a viscosity of 500–8000 mPa at 25 °C. s; And / or, the initiator used to prepare the fossil-based polyol includes a polyhydroxy compound, wherein the polyhydroxy compound includes one or more of sucrose, sorbitol, mannitol, xylitol, pentaerythritol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and trimethylolpropane. And / or, the polymerizable monomers used to prepare the fossil-based polyols include 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.

4. The composition according to claim 3, characterized in that, The fossil-based polyol has a hydroxyl value of 300–410 mg KOH / g and a viscosity of 2500–3000 mPa at 25 °C. s; And / or, the polyhydroxy compound includes one or more of sucrose, glycerol, sorbitol, diethylene glycol, and pentaerythritol; And / or, the polymerizing monomers include one or more of ethylene oxide, propylene oxide, butane oxide, pentane oxide, and hexane oxide; And / or, the fossil-based polyols include one or more of polyether polyols H6437, H8635, YD8310, 4110, 330N, and sucrose-glycerol type polyether polyols.

5. The composition according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The foaming agent includes one or more of water, hydrocarbon foaming agents and 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, and the hydrohalogenated hydrocarbon foaming agent includes one or more of pentafluoropropane, pentafluorobutane, difluoroethane, tetrafluoroethane, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, hexafluoropropylene and hexafluorobutene; (2) The organic isocyanate includes one or more of diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated polymethylene polyphenyl isocyanate; (3) The functionality of the organic isocyanate is 2.7 to 2.9, and / or the mass percentage of isocyanate groups in the organic isocyanate is 28% to 33%, and / or the viscosity of the organic isocyanate at 25 °C is 180 to 250 mPa. s; (4) The catalyst comprises one or more of amine catalysts and metal catalysts, wherein the amine catalyst comprises one or more of N-methyldicyclohexylamine, triethylenediamine, tetramethylhexanediamine, pentamethyldipropylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N,N'-trimethyl-N'-hydroxyethyldiaminoethyl ether, pentamethyldiethylenetriamine, N,N-dimethylbenzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, bis(2-dimethylaminoethyl) ether, and triethanolamine; and the metal catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dichloro, and dibutyltin maleate. (5) The additives also include silicone surfactants, and the mass ratio between the polyol component and the silicone surfactant is 100:(2.0 to 3.0).

6. The composition according to claim 5, characterized in that, At least one of the following conditions must be met: (1) The foaming agent is water; or, the foaming agent comprises water and cyclopentane, wherein the mass ratio of water to cyclopentane is (1.5-3.0):(5.0-8.0); or, the foaming agent comprises water and 1,1,1,3,3-pentafluoropropane, wherein the mass ratio of water to 1,1,1,3,3-pentafluoropropane is (1.5-3.0):(3.0-5.0); (2) The catalyst comprises a first compound and a second compound, wherein the first compound and the second compound are each independently selected from tertiary amine catalysts; Alternatively, one of the first compound and the second compound is selected from a tertiary amine catalyst, and the other is selected from the metal catalyst, and the mass ratio between the first compound and the second compound is (0.3-1.3):(0.2-0.5); optionally, the tertiary amine catalyst includes one or more of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, triethylenediamine, and N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether, and the metal catalyst includes one or more of stannous octoate and dibutyltin dilaurate; (3) The silicone surfactant includes one or more of polyether modified siloxane, polyether-silicone oil copolymer, non-hydrolyzable polyether-polydimethylsiloxane copolymer and polyepoxyalkylmethylsiloxane copolymer.

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: mixing the polyol component, the auxiliary agent and the foaming agent in a formulation ratio to obtain a premix; and then mixing the premix and the organic isocyanate to obtain the composition; (2) The step of foaming the composition includes: injecting the composition into a mold, foaming and curing at 20-35°C for 4-6 minutes and then demolding, then standing and curing at 20-35°C for 18-24 hours, and then curing at 35-45°C for 5-8 days; (3) The preparation method of the bio-based fatty acid diethanolamide in the polyol component includes the following steps: An industrial-grade bio-based fatty acid diethanolamide is provided. The industrial-grade bio-based fatty acid diethanolamide is subjected to solid-liquid separation to remove solid impurities with a particle size of not less than 180 µm to obtain a liquid. The liquid is dissolved in an organic solvent to obtain a mixture, which is then mixed with a first alkaline solution, the solvent of which includes water. The mixture is allowed to stand and separate into layers, with an organic phase on top and an aqueous phase on the bottom. The organic phase is then collected. The organic phase is washed with a second alkaline solution, the solvent of which includes water, at least once, until the pH of the aqueous phase obtained after washing is 7.0–7.5 and the conductivity is not greater than 20 μS / cm, thereby obtaining a purified organic phase; and The purified organic phase is subjected to drying and desolventizing processes in sequence to obtain the bio-based fatty acid diethanolamide.

10. The method for preparing polyurethane foam material according to claim 9, characterized in that, The method for preparing the bio-based fatty acid diethanolamide also satisfies at least one of the following conditions: (1) In the step of dissolving the liquid in an organic solvent to obtain a mixture, the organic solvent includes one or more of diethyl ether, ethanol and isopropanol, and / or the volume ratio between the liquid and the organic solvent is 1:(2-4); (2) The alkali in the first alkaline solution and the alkali in the second alkaline solution each independently include one or more of alkali metal carbonates and alkali metal bicarbonates; optionally, the alkali in the first alkaline solution and the alkali in the second alkaline solution each independently include one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. (3) The mass percentage of alkali in the first alkaline solution is 3-7%, and the volume ratio between the mixed solution and the first alkaline solution is 1:(1-3); (4) In each of the washing operations, the mass percentage of alkali in the second alkaline solution is 3-7%, and the volume ratio between the organic phase and the second alkaline solution is 1:(1-1.5); (5) The step of drying the purified organic phase in sequence includes the following steps: adding a desiccant to the purified organic phase, wherein the mass ratio between the purified organic phase and the desiccant is 1:(0.03-0.06), drying for 1-3 h, and then filtering to remove the desiccant; optionally, the desiccant includes one or more of anhydrous sodium sulfate and anhydrous magnesium sulfate. (6) The solvent removal process includes the step of: performing vacuum distillation on the purified organic phase after the drying process; (7) After the desolventizing step, the method for preparing the bio-based fatty acid diethanolamide further includes the step of: vacuum drying the purified organic phase after the desolventizing step until the moisture content of the organic phase is not greater than 0.1 wt%; Optionally, after the vacuum drying step, the method for preparing the bio-based fatty acid diethanolamide further includes the step of: filtering the purified organic phase after the vacuum drying step using a filter membrane with a pore size of 0.22 to 0.45 μm.

11. 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 any one of claims 8 to 10.

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