Combination polyether, polyurethane composition, polyurethane foam, and refrigeration apparatus

Abstract

This application discloses a combined polyether, a polyurethane composition, a polyurethane foam, and a refrigeration device. The combined polyether comprises a polyether polyol and a filler, wherein the filler comprises an epoxy-based cage-like polysilsesquioxane; wherein at least one organic side chain attached to the silicon atom of the epoxy-based cage-like polysilsesquioxane contains an epoxy group, and at least one epoxy group is located at the end of the organic side chain. The combined polyether provided in this application, by adding an epoxy-based cage-like polysilsesquioxane as a filler, achieves molecular-level dispersion by forming covalent bonds with the hydroxyl groups of the polyether polyol and the -NCO groups of the isocyanate, due to the epoxy active groups contained in this filler. This prevents the thermally conductive filler from agglomerating and migrating. Furthermore, the cage-like structure of the epoxy-based cage-like polysilsesquioxane can effectively capture gas molecules inside the polyurethane foam, inhibiting gas heat conduction and significantly reducing the thermal conductivity of the polyurethane foam at low temperatures.

Description

Technical Field

[0001] This application relates to the field of polyurethane technology, and more particularly to a composite polyether, a polyurethane composition, a polyurethane foam, and a refrigeration device. Background Technology

[0002] In related technologies, polyether blends typically incorporate thermally conductive fillers such as nano-silica and hollow glass microspheres to reduce the thermal conductivity of polyurethane foam. However, the thermally conductive fillers have poor compatibility with the polyether system in the blend, and they are prone to agglomeration. This only slightly reduces the thermal conductivity at room temperature, and migration is likely to occur within the operating temperature range of -25°C to 5°C in refrigerators. Consequently, the thermal conductivity of the polyurethane foam tends to rise again, leading to a decrease in its insulation effect and failing to meet the requirements for high-efficiency insulation. Summary of the Invention

[0003] In view of this, this application provides a combination of polyethers, a polyurethane composition, a polyurethane foam, and a refrigeration device.

[0004] The embodiments of this application are implemented as follows: a combined polyether, the combined polyether comprising a polyether polyol and a filler, the filler comprising an epoxy-based cage-type polysilsesquioxane; Wherein, at least one organic side chain attached to the silicon atom of the epoxy-cage polysilsesquioxane contains an epoxy group, and at least one of the epoxy groups is located at the end position of the organic side chain.

[0005] Optionally, in some embodiments of this application, the epoxy value of the epoxy-based cage-type polysilsesquioxane is 0.30 eq / 100g to 0.40 eq / 100g.

[0006] Optionally, in some embodiments of this application, the epoxy-based cage-like polysilsesquioxane includes one or more of monoepoxy-terminated cage-like polysilsesquioxanes, diepoxy-terminated cage-like polysilsesquioxanes, and polyepoxy-terminated cage-like polysilsesquioxanes.

[0007] Optionally, in some embodiments of this application, the epoxy group includes one or more of glycidyl and glycidyl.

[0008] Optionally, in some embodiments of this application, the epoxy-based cage-type polysilsesquioxane includes one or more of glycidyl ether-based cage-type polysilsesquioxane, epoxypropyl cage-type polysilsesquioxane, and methylepoxypropyl cage-type polysilsesquioxane.

[0009] Optionally, in some embodiments of this application, the filler accounts for 0.5wt% to 1.2wt% of the total weight of the combined polyether; and the polyether polyol accounts for 60wt% to 75wt% of the total weight of the combined polyether.

[0010] Optionally, in some embodiments of this application, the filler accounts for 0.8wt% to 1.2wt% of the total weight of the combined polyether; and the polyether polyol accounts for 70wt% to 75wt% of the total weight of the combined polyether.

[0011] Optionally, in some embodiments of this application, the polyether polyol includes a first polyether polyol and a second polyether polyol, wherein the mass ratio of the first polyether polyol to the second polyether polyol is 3:1 to 3:2. Wherein, the hydroxyl value of the first polyether polyol is 400~450 mgKOH / g, and the hydroxyl value of the second polyether polyol is 350~400 mgKOH / g; The first polyether polyol and the second polyether polyol are each independently selected from one or more of sucrose polyether polyol, glycerol polyether polyol, sorbitol polyether polyol, propylene glycol polyether polyol, ethylene glycol polyether polyol, trimethylolpropane polyether polyol, and polyoxypropylene glycol.

[0012] Optionally, in some embodiments of this application, the combined polyether further includes an antioxidant, a foaming agent, a catalyst, a crosslinking agent, a foam stabilizer, and a third polyether polyol, wherein the hydroxyl value of the third polyether polyol is 320~380 mgKOH / g, and the antioxidant accounts for 0.3wt%~0.6wt% of the total weight of the combined polyether. The foaming agent accounts for 10wt% to 15wt% of the total weight of the combined polyether; The catalyst accounts for 0.8 wt% to 1.5 wt% of the total weight of the combined polyether; The crosslinking agent accounts for 1.5 wt% to 3.0 wt% of the total weight of the combined polyether; The foam stabilizer accounts for 1.0 wt% to 2.0 wt% of the total weight of the combined polyether; The third polyether polyol accounts for 5 wt% to 10 wt% of the total weight of the combined polyether.

[0013] Optionally, in some embodiments of this application, the third polyether polyol includes castor oil-based polyether polyol; The antioxidants include one or more of hindered phenolic antioxidants and phosphite antioxidants. The hindered phenolic antioxidants include 2,4-dimethyl-6-octylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-sec-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, n-octadecyl-β(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4... The antioxidant comprises one or more of the following: 4'-dihydroxybiphenol, 4,4'-thiobis(6-tert-butyl-o-cresol), p-butylphenol, p-isopropylphenol, p-(1,1,3,3-tetramethylbutyl)phenol, thymol, mixed m-cresol and p-cresol, and p-nonylphenol; the phosphite antioxidant comprises one or more of tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, optionally, the antioxidant comprises the hindered phenolic antioxidant and the phosphite antioxidant, wherein the mass ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 0.8:1 to 1:0.8.

[0014] Optionally, in some embodiments of this application, the blowing agent includes an alkane blowing agent, which includes one or more of cyclopentane, isopentane, n-pentane, and cyclohexane; and / or The catalyst comprises one or more of amine catalysts and organometallic compound catalysts. The amine catalyst comprises one or more of triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, dimethylethanolamine, N,N-dimethylbenzylamine, and 2,2'-dimorpholine diethyl ether. The organometallic compound catalyst comprises one or more of dibutyltin dilaurate, zinc octanoate, bismuth isooctanoate, tetrabutyl titanate, and lead naphthenate; and / or The crosslinking agent includes one or more of diethanolamine, diethylenetriamine, triethanolamine, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, 1,4-butanediol, ethylene glycol, and 1,6-butanediol; and / or The foam stabilizer is a polyether-modified silicone surfactant, which includes one or more of Momentive L-580 silicone oil, Dow Corning DC-193 silicone oil, Dow Corning DC-5043 silicone oil, and fluorinated polyglycerol ether-polydimethylsiloxane block copolymer.

[0015] Accordingly, embodiments of this application also provide a polyurethane composition comprising isocyanate and the aforementioned combined polyether.

[0016] Optionally, in some embodiments of this application, the isocyanate comprises polymeric diphenylmethane diisocyanate, wherein the functionality of the polymeric diphenylmethane diisocyanate is 2.7 to 2.9; and / or The mass ratio of the polyether to the isocyanate is 1:1.03 to 1:1.08.

[0017] Accordingly, this application also provides a polyurethane foam, which is obtained by foaming the polyurethane composition described above.

[0018] Optionally, in some embodiments of this application, the polyurethane foam has a thermal conductivity ≤0.018 W / (m·K) at -25°C.

[0019] Accordingly, this application also provides a refrigeration device, which includes an insulation layer made of the polyurethane foam described above.

[0020] The combined polyether provided in this application uses epoxy-based cage-type polysilsesquioxane as a filler. Since this filler contains epoxy active groups, it can form covalent bonds with the hydroxyl groups of the polyether polyol and the -NCO groups of the isocyanate, thereby achieving molecular-level dispersion. This avoids the aggregation and migration of thermally conductive fillers. Furthermore, the cage-like structure of the epoxy-based cage-type polysilsesquioxane can effectively capture gas molecules inside the polyurethane foam, inhibit gas heat conduction, and thus significantly reduce the thermal conductivity of the polyurethane foam at low temperatures. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a flowchart of a method for preparing polyurethane foam provided in an embodiment of this application. Detailed Implementation

[0023] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. 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. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0025] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the drawing directions in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0026] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0027] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0028] In this application, the term "on" forming another layer on a certain layer is a broad concept. It can mean that the formed other layer is adjacent to a certain layer, or it can mean that there are other spacer structures between the other layer and the certain layer. For example, when a second electrode is formed "on" a first charge carrier functional layer, the term "on" can mean that the formed second electrode is adjacent to the first charge carrier functional layer, or it can mean that there are other spacer structures between the second electrode and the first charge carrier functional layer, such as a light-emitting layer.

[0029] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; 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 referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0030] To address the issue of high low-temperature thermal conductivity in polyurethane foam prepared from polyether composites used for refrigerator insulation, current methods typically employ the physical addition of thermally conductive fillers such as nano-silica and hollow glass microspheres to reduce the thermal conductivity of the polyurethane foam. However, these fillers exhibit poor compatibility with the polyether system in the composite and are prone to agglomeration. They only slightly reduce the thermal conductivity at room temperature and tend to migrate within the refrigerator's operating temperature range of -25°C to 5°C, causing the thermal conductivity of the polyurethane foam to rebound and resulting in a decrease in its insulation effect, failing to meet the requirements for high-efficiency insulation.

[0031] Therefore, to address the technical issues of poor compatibility and easy agglomeration between thermally conductive fillers and the polyether system in the composite polyether, related technologies employ coupling agent-modified nano-silica as a thermally conductive filler. However, this not only increases costs, but the low-temperature thermal conductivity of polyurethane foam still cannot meet the high-efficiency insulation requirement of "thermal conductivity ≤0.018 W / (m·K) at -25℃".

[0032] The technical solution of this application is as follows: In a first aspect, this application provides a composite polyether comprising a polyether polyol and a filler, wherein the filler comprises an epoxy-coated cage polysilsesquioxane; wherein at least one organic side chain attached to the silicon atom of the epoxy-coated cage polysilsesquioxane contains an epoxy group, and at least one epoxy group is located at the end position of the organic side chain.

[0033] It should be noted that at least one organic side chain attached to the silicon atom of the epoxy-coated cage polysilsesquioxane contains an epoxy group, and at least one epoxy group is located at the end of the organic side chain. This indicates that the cage polysilsesquioxane (POS) specifically selected in this application is a reactive cage polysilsesquioxane, and the reactive cage polysilsesquioxane is an epoxy-terminated cage polysilsesquioxane, thereby the epoxy group can serve as a reactive group.

[0034] The epoxy-based cage-type polysilsesquioxane can be a monoepoxy-terminated cage-type polysilsesquioxane, a diepoxy-terminated cage-type polysilsesquioxane, or a polyepoxy-terminated cage-type polysilsesquioxane. To achieve low filler addition and effective thermal conductivity control, the epoxy-based cage-type polysilsesquioxane is preferably selected from diepoxy-terminated cage-type polysilsesquioxanes or polyepoxy-terminated cage-type polysilsesquioxanes.

[0035] Understandably, since the subsequent polyether combination needs to be foamed with isocyanate to form polyurethane foam, this embodiment uses epoxy-based cage-like polysilsesquioxane as a thermally conductive filler. This filler contains epoxy active groups that can covalently bond with the hydroxyl groups of the polyether polyol and the -NCO groups of the isocyanate, thereby reacting to form a dense, low-thermal-conductivity crosslinked network structure. This fixes the cage-like siloxane structure within the polyurethane molecular chain, achieving molecular-level dispersion and preventing the thermally conductive filler from agglomerating, thus ensuring the mechanical properties of the polyurethane foam. Furthermore, since the thermally conductive filler is covalently bonded to the polyether polyol using epoxy groups, an effective low-thermal-conductivity crosslinked network structure is generated, which can, to some extent, prevent excessive or insufficient crosslinking with the polyether polyol and isocyanate.

[0036] Using epoxy-terminated cage-like polysilsesquioxane as a thermally conductive filler can ensure the mechanical properties of polyurethane foam while achieving optimal low thermal conductivity. Specifically, the thermally conductive filler selected in this embodiment has a cage-like structure. This cage-like structure can trap gas molecules inside the polyurethane foam, inhibiting gas heat conduction, thereby reducing the low-temperature thermal conductivity of the polyurethane foam, improving the refrigerator's insulation effect, and reducing its energy consumption.

[0037] Furthermore, compared to physically adding thermally conductive fillers, this embodiment avoids the migration of thermally conductive fillers by adding reactive thermally conductive fillers, thereby solving the technical problem of the low-temperature thermal conductivity of polyurethane foam rebounding.

[0038] To significantly reduce its low-temperature thermal conductivity and thus significantly improve the refrigerator's insulation performance, the epoxy value of the epoxy-based cage-type polysilsesquioxane is further specified as 0.30 eq / 100g to 0.40 eq / 100g. The epoxy value is determined according to the national standard GB / T12007.1-1989, "Determination of Epoxy Value of Epoxy Resins," and can be, for example, 0.30 eq / 100g, 0.32 eq / 100g, 0.35 eq / 100g, 0.36 eq / 100g, 0.38 eq / 100g, 0.40 eq / 100g, or any range between two values. In one example, the epoxy-based cage-type polysilsesquioxane is an octaglycidyl ether-based cage-type polysilsesquioxane.

[0039] In this embodiment, the epoxy value within the above-mentioned range can effectively balance the reactivity and compatibility of the thermally conductive filler. This not only ensures efficient covalent bonding with the polyether polyol to avoid agglomeration, but also prevents a decrease in the mechanical properties of the foam due to excessive crosslinking. It should be noted that if the epoxy value of the epoxy-based cage-type polysilsesquioxane exceeds the above range, it can meet the insulation requirements, but it cannot achieve the requirement of "thermal conductivity ≤ 0.018 W / (m·K) at -25℃" for efficient insulation. If the epoxy value of the epoxy-based cage-type polysilsesquioxane is too low, for example, <0.30 eq / 100g, it will lead to insufficient crosslinking and poor dispersibility. If the epoxy value of the epoxy-based cage-type polysilsesquioxane is too high, for example, >0.40 eq / 100g, it will lead to excessive crosslinking and embrittlement of the resulting polyurethane foam.

[0040] This embodiment does not specifically limit the type of epoxy group. In some embodiments, the epoxy group includes one or more of glycidyl and glycidyl.

[0041] It should also be noted that if rigid cyclic epoxy groups (such as epoxy cyclohexyl ethyl) are selected, the large steric hindrance of the rigid cyclic epoxy may lead to low reactivity of the epoxy groups, which cannot fully covalently bond, resulting in poor dispersibility of the thermally conductive filler. Furthermore, the foam mechanical and thermal insulation properties of the polyurethane foam will decrease.

[0042] In some embodiments, epoxy-based cage-type polysilsesquioxanes include one or more of glycidyl ether-based cage-type polysilsesquioxanes, propyl oxide cage-type polysilsesquioxanes, and methyl propyl oxide cage-type polysilsesquioxanes.

[0043] The number of silicon atoms in the cage structure of epoxy-based cage-type polysilsesquioxane can be 6, 8, 10 or 12. In some embodiments, the number of silicon atoms in the epoxy-based cage-type polysilsesquioxane is 8.

[0044] Because the octamer cage structure has high symmetry, good stability, and uniform functional group distribution, in this embodiment, the epoxy-based cage-type polysilsesquioxane is selected from any one or more combinations of octamer epoxy-based cage-type polysilsesquioxanes. Preferably, the epoxy-based cage-type polysilsesquioxane is a methylepoxypropyl cage-type polysilsesquioxane with 8 silicon atoms.

[0045] In some embodiments, the filler accounts for 0.5wt% to 1.2wt% of the total weight of the polyether combination, for example, it can be 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, or any range between two values.

[0046] In this embodiment, by controlling the addition amount of epoxy-based cage-type polysilsesquioxane between 0.5wt% and 1.2wt%, optimal low-temperature thermal conductivity can be achieved while ensuring the mechanical properties of the polyurethane foam. If the addition amount is less than 0.5wt%, the thermally conductive filler will not be sufficiently dispersed and will not be able to effectively form covalent bonds with isocyanate, thus failing to form an effective cross-linked network, making it even more difficult to meet the requirements for the low-temperature thermal conductivity of the polyurethane foam. If the addition amount exceeds 1.2wt%, it will not only cause excessive cross-linking with isocyanate, thereby destroying the mechanical structure of the foam and leading to a decrease in the compressive strength of the polyurethane foam, but will also increase the cost to some extent.

[0047] Furthermore, the filler accounts for 0.8wt% to 1.2wt% of the total weight of the polyether blend.

[0048] In some embodiments, the polyether polyol accounts for 60wt% to 75wt% of the total weight of the combined polyether, for example, it can be 60wt%, 65wt%, 70wt%, 75wt%, or any range between two values. Within this range, the thermally conductive filler and the polyether polyol are sufficiently covalently linked to achieve molecular-level dispersion.

[0049] Furthermore, the polyether polyol accounts for 70wt% to 75wt% of the total weight of the combined polyether.

[0050] To ensure the hydroxyl value of the polyether system is balanced and its hydroxyl value range can match the reactivity and foam structure stability, in some embodiments, the polyether polyol includes a first polyether polyol and a second polyether polyol, and the mass ratio of the first polyether polyol to the second polyether polyol is 3:1 to 3:2.

[0051] The first polyether polyol and the second polyether polyol are each independently selected from one or more combinations of sucrose polyether polyol, glycerol polyether polyol, sorbitol polyether polyol, propylene glycol polyether polyol, ethylene glycol polyether polyol, trimethylolpropane polyether polyol, and polyoxypropylene glycol.

[0052] In some embodiments, the hydroxyl value of the first polyether polyol is 400~450 mgKOH / g, and the hydroxyl value of the second polyether polyol is 350~400 mgKOH / g.

[0053] In this embodiment, the hydroxyl value is determined according to the national standard GB / T 12008.3-2009 "Polyether Polyols Part 3: Determination of Hydroxyl Value". For example, the hydroxyl value of the first polyether polyol can be 400 mgKOH / g, 410 mgKOH / g, 420 mgKOH / g, 430 mgKOH / g, 440 mgKOH / g, 450 mgKOH / g, or any two of the aforementioned values. Within this range, the polyether polyol can balance reactivity and foam structure stability. The hydroxyl value of the second polyether polyol is 350 mgKOH / g, 360 mgKOH / g, 370 mgKOH / g, 380 mgKOH / g, 390 mgKOH / g, 400 mgKOH / g, or any two of the aforementioned values. Within this range, the polyether polyol can balance reactivity and foam structure stability.

[0054] Considering that the polyurethane foam generated by the polyether combination needs to be tightly bonded to the refrigerator liner and outer shell, and since the refrigerator liner is mostly made of aluminum foil or aluminum alloy, and the outer shell is mostly made of plastics such as acrylonitrile-butadiene-styrene copolymer (ABS) and polypropylene (PP), in order to improve the interfacial compatibility of the two substrates and enhance the storage stability of the refrigerator, in some embodiments, the polyether combination also includes a third polyether polyol, the hydroxyl value of which is 320~380 mgKOH / g.

[0055] In this embodiment, the hydroxyl value was determined according to the national standard GB / T 12008.3-2009 "Polyether Polyols - Part 3: Determination of Hydroxyl Value". For example, the hydroxyl value of castor oil-based polyether polyol can be 320 mgKOH / g, 330 mgKOH / g, 340 mgKOH / g, 350 mgKOH / g, 360 mgKOH / g, 370 mgKOH / g, 380 mgKOH / g, or any range between two of the aforementioned values. Within this range, not only can the reactivity of the polyether polyol with isocyanate be matched, but the adhesion and mechanical properties of the polyurethane foam can also be considered.

[0056] In some embodiments, the third polyether polyol includes castor oil-based polyether polyol.

[0057] In this embodiment, by introducing castor oil-based polyether polyol, on the one hand, the bio-based polyether molecule contains long-chain fatty acid groups, which have good lipophilic and metalophilic properties. This simultaneously improves the interfacial compatibility and interfacial adhesion between the combined polyether and metal substrates (such as aluminum inner liner) and plastic substrates (such as ABS outer shell), resulting in a bonding strength of ≥1.7 MPa between the polyurethane foam and the metal inner liner and plastic outer shell. This enhances the substrate bonding stability and avoids interfacial delamination and insulation gaps after alternating hot and cold temperatures, preventing further deterioration of the improved insulation effect due to these gaps. On the other hand, it also improves the compatibility of the components in the combined polyether (polyether polyol, filler, and conventional components such as catalysts, crosslinking agents, and foaming agents), thereby enhancing storage stability and increasing the storage stability of the combined polyether at 25°C to over 18 months. Furthermore, by using bio-based raw materials to replace part of the petroleum-based raw materials, this embodiment reduces dependence on fossil resources, making the combined polyether formulation provided in this embodiment more environmentally friendly.

[0058] In some embodiments, the third polyether polyol accounts for 5 wt% to 10 wt% of the total weight of the combined polyether, for example, it can be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or any range between two values. Within this range, the adhesiveness and mechanical properties of the polyurethane foam can be further balanced. It should also be noted that if the mass percentage of the third polyether polyol in the combined polyether exceeds 10 wt%, it will lead to a decrease in the mechanical properties of the polyurethane foam and increase the additional raw material cost.

[0059] Considering that the refrigerator insulation layer is in a constant alternating hot and cold environment, the polyether polyol molecular chains are prone to oxidative breakage. Therefore, in some embodiments, the combined polyether also includes an antioxidant.

[0060] Among them, antioxidants include one or more of hindered phenolic antioxidants and phosphite antioxidants. Hindered phenolic antioxidants include 2,4-dimethyl-6-octylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-sec-butylphenol, and 2,2'- One or more of the following: methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, n-octadecyl-β(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-dihydroxybiphenol, 4,4'-thiobis(6-tert-butyl-o-cresol), p-butylphenol, p-isopropylphenol, p-(1,1,3,3-tetramethylbutyl)phenol, thymol, mixed m-cresol and p-cresol, p-nonylphenol; and phosphite antioxidants including one or more of tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0061] Because antioxidants have limited anti-aging effects, polyurethane foam is prone to powdering and falling off after long-term use, resulting in loss of thermal insulation properties. Therefore, antioxidants further include hindered phenolic antioxidants and phosphite antioxidants, with a mass ratio of hindered phenolic antioxidants to phosphite antioxidants of 0.8:1 to 1:0.8.

[0062] The composite antioxidant provided in this embodiment can synergistically capture free radicals and decompose hydroperoxides to meet the anti-aging requirements of long-term alternating hot and cold environments. It effectively avoids the problems of powdering and shedding caused by long-term use of polyurethane foam, and solves the problem of easy migration of anti-aging agents during long-term use, leading to a continuous decline in foam performance. Specifically, the hindered phenolic anti-aging agent can efficiently capture free radicals generated by oxidation reactions, terminating the chain reaction. The phosphite anti-aging agent can decompose hydroperoxides generated during the oxidation of polyether molecular chains, preventing them from further initiating free radical reactions, greatly improving the anti-aging effect and significantly enhancing the long-term stability of polyurethane foam under alternating hot and cold environments. The polyurethane foam containing the composite antioxidant retains ≥90% of its tensile strength after 1000 hours of aging, extending the service life of refrigerator insulation layers to more than 15 years. Furthermore, the above-mentioned composite antioxidant can match the compatibility and reaction characteristics of each component (polyether polyol, filler, and conventional components such as catalysts, crosslinking agents, and foaming agents) to maximize the anti-aging effect.

[0063] It should be noted that, considering the anti-aging effect, the ratio of compound antioxidants needs to be precisely controlled to achieve a synergistic effect of free radical capture and hydroperoxide decomposition. If the mass ratio of hindered phenolic antioxidants to phosphite antioxidants is greater than 5:1, it will lead to an imbalance between hydroperoxide decomposition and free radical capture, resulting in a significant decrease in the anti-aging effect.

[0064] In some embodiments, the antioxidant accounts for 0.3wt% to 0.6wt% of the total weight of the combined polyether, for example, it can be 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, or any range between two values. Within this range, free radical capture and hydroperoxide decomposition can be synergistically achieved.

[0065] It is understood that the polyether composition also includes conventional components, and in some embodiments, the polyether composition also includes a foaming agent, a catalyst, a foam stabilizer, and a crosslinking agent.

[0066] In order to achieve environmentally friendly and fluorine-free production and meet the environmental protection requirements of the refrigerator industry, in some embodiments, the foaming agent includes alkane foaming agents, including one or more of cyclopentane, isopentane, n-pentane, and cyclohexane.

[0067] In some embodiments, the foaming agent accounts for 10 wt% to 15 wt% of the total weight of the polyether combination.

[0068] In some embodiments, the catalyst accounts for 0.8 wt% to 1.5 wt% of the total weight of the polyether combination.

[0069] The catalyst includes one or more of amine catalysts and organometallic compound catalysts. The amine catalysts include one or more of triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, dimethylethanolamine, N,N-dimethylbenzylamine, and 2,2'-dimorpholine diethyl ether. The organometallic compound catalysts include one or more of dibutyltin dilaurate, zinc octanoate, bismuth isooctanoate, tetrabutyl titanate, and lead naphthenate.

[0070] In some embodiments, the foam stabilizer accounts for 1.0 wt% to 2.0 wt% of the total weight of the polyether combination.

[0071] The foam stabilizer is a polyether-modified silicone surfactant, which includes one or more of Momentive L-580 silicone oil, Dow Corning DC-193 silicone oil, Dow Corning DC-5043 silicone oil, and fluorinated polyglycerol ether-polydimethylsiloxane block copolymer.

[0072] In some embodiments, the crosslinking agent accounts for 1.5 wt% to 3.0 wt% of the total weight of the combined polyether.

[0073] The crosslinking agent includes one or more of diethanolamine, diethylenetriamine, triethanolamine, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, 1,4-butanediol, ethylene glycol, and 1,6-butanediol.

[0074] Secondly, embodiments of this application provide a polyurethane composition comprising isocyanate and the above-described combined polyether.

[0075] In some embodiments, the mass ratio of the combined polyether to isocyanate is 1:1.03 to 1:1.08.

[0076] In some embodiments, the isocyanate includes polymeric diphenylmethane diisocyanate, the functionality of which is 2.7 to 2.9, and the functionality (f) = (NCO% × Mn) / (100 × 42.02); where NCO% is the mass fraction of isocyanate (%), Mn is the number-average molecular weight (g / mol), and 42.02 is the molar mass of the -NCO group (g / mol), which can be, for example, 2.7, 2.8, 2.9, or any range between two values. Within this range, the polymeric diphenylmethane diisocyanate contains multifunctional monomers, which is more suitable for the crosslinking density and foam properties required for the polyurethane foam in this embodiment.

[0077] It should also be noted that if the functionality of the polymeric diphenylmethane diisocyanate is 2.0, it will lead to a decrease in the mechanical properties and thermal insulation stability of the polyurethane foam.

[0078] Thirdly, embodiments of this application provide a polyurethane foam, which is obtained by foaming the aforementioned polyurethane composition.

[0079] Understandably, this application addresses the technical problems of existing polyurethane foam, such as high low-temperature thermal conductivity, easy aging and powdering after long-term use, and poor adhesion stability with the refrigerator liner / outer shell. It proposes a technical solution of "reactive thermally conductive filler - third polyether polyol interface compatibility enhancement - composite anti-aging synergy". This solution systematically optimizes the thermal conductivity stability and adhesion durability under the low-temperature working environment of refrigerators, significantly improving the insulation durability and service life of polyurethane foam at the normal operating temperature of refrigerators (-25℃). The resulting polyurethane foam has the characteristics of low-temperature thermal conductivity, long-term anti-aging, strong substrate adhesion, and high storage stability, which can fully meet the stringent requirements of high-end refrigerators for insulation materials.

[0080] In addition, by using reactive thermally conductive fillers, the thermal conductivity of polyurethane foam can be significantly increased at -25℃, which would otherwise be unable to meet the requirements for high-efficiency insulation, as is the case with physically added thermally conductive fillers.

[0081] In some embodiments, the thermal conductivity of the polyurethane foam is ≤0.018 W / (m·K) at -25°C.

[0082] In this embodiment, by using reactive thermally conductive fillers, the thermal conductivity of polyurethane foam is ≤0.018 W / (m·K) at -25℃, which can meet the requirements of high-efficiency insulation and make it suitable for various refrigeration and insulation equipment such as household refrigerators and cold chain refrigerators, with broad application prospects.

[0083] In addition, by adopting the technical solution of "third polyether polyol interface compatibility enhancement-composite anti-aging synergy", the tensile strength retention rate of polyurethane foam after 1000h aging test is ≥90%, the bonding strength with aluminum inner liner and ABS outer shell is ≥1.7 MPa, and the storage stability is ≥18 months (25℃).

[0084] Fourthly, this application provides a method for preparing polyurethane foam; please refer to [link to relevant documentation]. Figure 1 This includes the following steps: Step S10 provides polyether polyol, filler, castor oil-based polyether polyol, foaming agent, catalyst, foam stabilizer, crosslinking agent and antioxidant; Step S20: Mix the polyether polyol, filler, castor oil-based polyether polyol, foaming agent, catalyst, foam stabilizer, crosslinking agent and antioxidant to obtain a combined polyether; Step S30: Mix the polyether and isocyanate, and foam to obtain polyurethane foam.

[0085] The weight percentages of each component are as described above and will not be repeated here. Furthermore, the sum of the weight percentages of the polyether polyol, thermally conductive filler, third polyether polyol, foaming agent, catalyst, foam stabilizer, crosslinking agent, and antioxidant is 100 wt%.

[0086] The preparation method provided in this application is simple and widely applicable. Furthermore, the preparation process is compatible with existing production equipment, requires no additional equipment investment, and can be directly applied to existing refrigerator production lines. It is suitable for various refrigeration and insulation equipment such as household refrigerators and cold chain refrigerators, and has extremely high industrialization value.

[0087] In some embodiments, step S20 includes: Under normal temperature and nitrogen protection conditions, polyether polyol is added to the reactor and stirred at a speed of 200 r / min to 400 r / min. Filler, antioxidant and castor oil-based polyether polyol are added in sequence and stirred for 30 min to 40 min. Add catalyst, foam stabilizer and crosslinking agent, and continue stirring for 20 min to 30 min; Slowly add the foaming agent, stir for 15 min to 30 min, then degas under vacuum for 30 min to 40 min at a vacuum degree of -0.08 MPa to -0.05 MPa to obtain the composite polyether.

[0088] In some embodiments, step S30 includes: The polyether and isocyanate were mixed in a weight ratio of 1:1.03 to 1:1.08 and then stirred at a speed of 200 r / min to 400 r / min. After stirring evenly, the mixture is poured into a mold and foamed and cured for 45 min to 90 min at 20 ℃ to 30 ℃ and 40% to 60% humidity to obtain polyurethane foam.

[0089] In this embodiment, before the polyurethane foam is formed, the filler undergoes covalent bonding with the hydroxyl groups of the polyether polyol and the -NCO groups of the isocyanate, resulting in a dense, low-thermal-conductivity cross-linked network structure, achieving molecular-level dispersion. Therefore, after the polyurethane foam is formed, the molecularly dispersed filler further effectively suppresses gas convection and conduction, constructs a low-thermal-conductivity network, and thus significantly reduces the low-temperature thermal conductivity.

[0090] Fifthly, embodiments of this application also provide a refrigeration device, which includes an insulation layer made of the aforementioned polyurethane foam.

[0091] Since this refrigeration equipment adopts all the technical solutions of all the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be repeated here. The refrigeration equipment can be various refrigeration and insulation equipment such as household refrigerators and cold chain refrigerators.

[0092] The present application will be specifically described below through specific embodiments. These embodiments are only some embodiments of the present application and are not intended to limit the present application. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0093] Raw material preparation: Polyether polyols: sucrose polyether polyol (hydroxyl value 420 mg KOH / g) and glycerol polyether polyol (hydroxyl value 380 mg KOH / g) were purchased from Shandong Lanxing Dongda Chemical Co., Ltd. Filler: epoxy-terminated cage-like octapolysiloxane (epoxy value 0.35 eq / 100g), purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Antioxidants: 2,6-di-tert-butyl-4-methylphenol (hindered phenol) and tris(2,4-di-tert-butylphenyl) phosphite (phosphite), both purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Castor oil-based polyether polyol (hydroxyl value 350 mg KOH / g): purchased from Hubei Yuancheng Saichuang Technology Co., Ltd. Foaming agents: cyclopentane and isopentane, both industrial grade, purchased from Jiangsu Hengtong Petrochemical Co., Ltd. Catalysts: Triethylenediamine and dibutyltin dilaurate, purchased from Nanjing Weier Chemical Co., Ltd. Foam stabilizer: polyether-modified silicone surfactant (model L-580), purchased from Momentive Advanced Materials Group; Crosslinking agent: diethanolamine, industrial grade, purchased from Tianjin Damao Chemical Reagent Factory; Polymeric diphenylmethane diisocyanate: Model PM-200, purchased from Wanhua Chemical Group Co., Ltd.

[0094] Example 1 The polyether composition includes 70.0 wt% polyether polyol, 0.8 wt% filler, 0.4 wt% antioxidant, 8.0 wt% castor oil-based polyether polyol, 12.0 wt% blowing agent, 1.0 wt% catalyst, 1.5 wt% foam stabilizer, and 2.3 wt% crosslinking agent.

[0095] The antioxidants are 2,6-di-tert-butyl-4-methylphenol (hindered phenol) and tris(2,4-di-tert-butylphenyl) phosphite (phosphite) in a mass ratio of 1:1; the foaming agent is cyclopentane and isopentane in a mass ratio of 4:1; and the catalyst is triethylenediamine and dibutyltin dilaurate in a mass ratio of 2:1.

[0096] Under normal temperature and nitrogen protection conditions, polyether polyol was added to a reactor and stirred at 300 r / min. Filler, antioxidant, and castor oil-based polyether polyol were added sequentially and stirred for 30 min. Then, crosslinking agent, catalyst, and foam stabilizer were added and stirred for another 20 min. Finally, foaming agent was slowly added and stirred for 15 min. The mixture was then degassed under vacuum for 30 min (vacuum degree of -0.08 MPa) to obtain the composite polyether.

[0097] The combined polyether obtained above was mixed with polymeric diphenylmethane diisocyanate at a weight ratio of 1:1.05. After stirring evenly, the mixture was injected into a mold with dimensions of 300mm×300mm×50mm (simulating the heat preservation cavity of a refrigerator). The mixture was foamed and cured for 60 minutes at 25℃ and 50% humidity to obtain a polyurethane foam sample.

[0098] Example 2 The difference between this embodiment and Embodiment 1 is that the polyether formulation is different.

[0099] In this embodiment, the polyether composition includes 68.0 wt% polyether polyol, 1.2 wt% filler, 0.6 wt% antioxidant, 10.0 wt% castor oil-based polyether polyol, 13.0 wt% blowing agent, 1.2 wt% catalyst, 1.8 wt% foam stabilizer, and 2.2 wt% crosslinking agent.

[0100] Example 3 The difference between this embodiment and Embodiment 1 is that the polyether formulation is different.

[0101] In this embodiment, the polyether composition includes 72.0 wt% polyether polyol, 0.5 wt% filler, 0.3 wt% antioxidant, 5.0 wt% castor oil-based polyether polyol, 11.0 wt% blowing agent, 0.8 wt% catalyst, 1.2 wt% foam stabilizer, and 2.2 wt% crosslinking agent.

[0102] Example 4 The difference between this embodiment and Example 1 is that the weight percentage of castor oil-based polyether polyol is different; the castor oil-based polyether polyol is 6.0 wt%.

[0103] Example 5 The difference between this embodiment and Embodiment 1 is that the polyether formulation is different.

[0104] In this embodiment, the polyether composition includes 65.0 wt% polyether polyol, 1.0 wt% filler, 0.5 wt% antioxidant, 9.0 wt% castor oil-based polyether polyol, 14.0 wt% blowing agent, 1.3 wt% catalyst, 1.9 wt% foam stabilizer, and 2.3 wt% crosslinking agent.

[0105] Comparative Example 1 The difference between this comparative example and Example 1 is that the combined polyether formulation is different, with no filler (epoxy-terminated cage-like octapolysiloxane), no antioxidant, and no castor oil-based polyether polyol.

[0106] In this comparative example, the polyether composition includes 75.0 wt% polyether polyol, 15.0 wt% blowing agent, 1.0 wt% catalyst, 2.0 wt% foam stabilizer, and 2.0 wt% crosslinking agent.

[0107] Comparative Example 2 The difference between this comparative example and Example 1 is that the combined polyether formulation is different, and it is filler-free (epoxy-terminated cage-like octasiloxane), including antioxidants and castor oil-based polyether polyols.

[0108] In this comparative example, the polyether composition includes 70.0 wt% polyether polyol, 0.4 wt% antioxidant (containing only 2,6-di-tert-butyl-4-methylphenol, excluding phosphite antioxidants), 8.0 wt% castor oil-based polyether polyol, 12.0 wt% blowing agent, 1.0 wt% catalyst, 1.5 wt% foam stabilizer, and 2.3 wt% crosslinking agent.

[0109] Comparative Example 3 The difference between this comparative example and Example 1 is that the combined polyether formulation is different, and the weight percentage of the filler (epoxy-terminated cage-like octapolysiloxane) exceeds the range of 0.5~1.2wt%.

[0110] In this comparative example, the polyether composition includes 70.0 wt% polyether polyol, 1.5 wt% filler, 0.4 wt% antioxidant, 8.0 wt% castor oil-based polyether polyol, 12.0 wt% blowing agent, 1.0 wt% catalyst, 1.5 wt% foam stabilizer, and 2.3 wt% crosslinking agent.

[0111] The combined polyether components and weight percentages of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1 (Note: The sum of the weight percentages of each component is 100wt%).

[0112] Table 1. Polyether Components of Examples and Comparative Examples

[0113] Performance tests were conducted on Examples 1-5 and Comparative Examples 1-3, and the performance test results for each example and comparative example are shown in Table 2. The performance test items included: thermal conductivity at -25 ℃, tensile strength retention rate after 1000h aging, adhesion strength with aluminum inner liner at -25 ℃, adhesion strength with ABS outer shell at -25 ℃, storage stability time (25 ℃), and compressive strength.

[0114] The testing methods for each performance aspect are as follows: Thermal conductivity: The thermal conductivity of polyurethane foam at -25℃ was tested according to GB / T10295-2008 "Determination of steady-state thermal resistance and related properties of thermal insulation materials - protective hot plate method". Tensile strength retention rate after 1000h aging: According to GB / T 9641-2008 "Determination of tensile properties of rigid foamed plastics", the tensile strength of polyurethane foam was tested before and after 1000h aging. The retention rate = tensile strength after 1000h aging / tensile strength before aging × 100%; Bonding strength with aluminum liner at -25℃: According to GB / T 14517-2005, the bonding strength between polyurethane foam and aluminum substrate was tested at -25℃. Bond strength with ABS shell at -25℃: According to GB / T 14517-2005, the bond strength between polyurethane foam and ABS substrate was tested at -25℃. Storage stability time (25℃): The change in thermal conductivity of polyurethane foam at 25℃ is recorded every month. The thermal conductivity is measured in accordance with GB / T10295-2008 "Determination of Steady-State Thermal Resistance and Related Properties of Thermal Insulation Materials - Protective Hot Plate Method". The storage stability time is recorded when the change in thermal conductivity is greater than 1.1%. Compressive strength: The compressive strength of polyurethane foam was tested in accordance with GB / T10295-2008.

[0115] Table 2 Performance test results of the examples and comparative examples

[0116] Therefore, it can be seen that Examples 1-5 all added 0.5-1.2 wt% of reactive cage-like siloxane, and their thermal conductivity at -25℃ was ≤0.018 W / (m·K), which was significantly lower than that of Comparative Example 1 (0.025 W / (m·K)) and Comparative Example 2 (0.024 W / (m·K)) without the addition of this thermal conductivity modifier. This is because the reactive cage-like siloxane forms covalent bonds with polyether and isocyanate, achieving molecular-level dispersion. Its cage-like structure can effectively capture gas molecules inside the foam, inhibit gas heat conduction, and thus reduce the low-temperature thermal conductivity. Comparative Example 3 added 1.5 wt% of thermal conductivity modifier (0.5-1.2 wt% beyond the range specified in this application). Although its thermal conductivity (0.019 W / (m·K)) was slightly lower than that of the Examples, its compressive strength (0.25 MPa) was significantly lower than that of the Examples (0.33-0.38 MPa), indicating that excessive addition would destroy the mechanical structure of the foam, leading to a decrease in mechanical properties. Therefore, it can be seen that the addition amount of 0.5-1.2wt% specified in this application can achieve a balance between low thermal conductivity and mechanical properties, and the core innovation is significant.

[0117] In Examples 1-5, to maintain the synergistic effect of free radical capture and hydroperoxide decomposition, the antioxidant included a mixture of 2,6-di-tert-butyl-4-methylphenol and tris(2,4-di-tert-butylphenyl) phosphite in a weight ratio of 1:1. Using the hindered phenol-phosphite composite antioxidant, the tensile strength retention rate after 1000 hours of aging was ≥90 wt%, while the retention rates of Comparative Example 1 (without antioxidant) were only 65 wt% and 63 wt%, and the retention rate of Comparative Example 2 (single hindered phenol antioxidant) was 78 wt%. This indicates that the composite antioxidant can achieve a synergistic effect of free radical capture and hydroperoxide decomposition, and its anti-aging effect is far superior to that of the single antioxidant and antioxidant-free solutions. In Example 2, the retention rate of 0.6 wt% of the composite antioxidant reached 94 wt%, and in Example 5, the retention rate of 0.5 wt% reached 95 wt%. This shows that within the 0.3-0.6 wt% addition range specified in this application, the anti-aging effect increases with the addition amount and can meet the anti-aging requirements of long-term use of refrigerators.

[0118] Examples 1-5, which introduced 5-10 wt% castor oil-based polyether polyol, showed a bonding strength ≥1.7 MPa with the aluminum inner liner and ABS outer shell at -25°C, and a storage stability time ≥18 months. In contrast, Comparative Example 1, without castor oil-based polyether polyol, showed a bonding strength of only 0.9-1.2 MPa and a storage stability time of only 9-10 months. This is because the long-chain fatty acid groups in the castor oil-based polyether polyether molecule improve the interfacial compatibility between the combined polyether and the metal and plastic substrates, while also enhancing compatibility with other additives, thereby strengthening bonding and storage stability. In Example 2, with the addition of 10 wt% castor oil-based polyether polyol, the bonding strength reached 2.0-2.1 MPa, and the storage stability time reached 22 months.

[0119] In summary, Examples 1-5, through the synergistic effect of epoxy-terminated cage-like octapolysiloxane, antioxidants, and castor oil-based polyether polyols, achieved comprehensive advantages including low-temperature thermal conductivity, long-lasting anti-aging properties, strong substrate adhesion, and high storage stability. Examples 2 and 5 exhibited the best overall performance, fully meeting the stringent requirements of high-end refrigerators for insulation materials. Comparative Example 1, a conventional refrigerator insulation polyether formulation, showed the worst performance across all aspects; Comparative Example 2, lacking epoxy-terminated cage-like octapolysiloxane as a thermal conductivity modifier, also exhibited poor performance; Comparative Example 3, with an excessive amount of epoxy-terminated cage-like octapolysiloxane, failed to achieve a balance across all performance characteristics.

[0120] The technical solutions provided by 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 composite polyether, characterized in that, The combined polyether comprises a polyether polyol and a filler, wherein the filler comprises an epoxy-coated cage-type polysilsesquioxane; Wherein, at least one organic side chain attached to the silicon atom of the epoxy-cage polysilsesquioxane contains an epoxy group, and at least one of the epoxy groups is located at the end position of the organic side chain.

2. The composite polyether as described in claim 1, characterized in that, The epoxy value of the epoxy-based cage-type polysilsesquioxane is 0.30 eq / 100g to 0.40 eq / 100g.

3. The combined polyether as described in claim 1 or 2, characterized in that, The epoxy-based cage-type polysilsesquioxane includes one or more of monoepoxy-terminated cage-type polysilsesquioxanes, diepoxy-terminated cage-type polysilsesquioxanes, and polyepoxy-terminated cage-type polysilsesquioxanes.

4. The composite polyether as described in claim 1, characterized in that, The epoxy group includes one or more of glycidyl and glycidyl.

5. The combined polyether as described in claim 1 or 4, characterized in that, The epoxy-based cage-type polysilsesquioxane includes one or more of glycidyl ether-based cage-type polysilsesquioxane, propyl oxide cage-type polysilsesquioxane, and methyl propyl oxide cage-type polysilsesquioxane.

6. The composite polyether as described in claim 1, characterized in that, The filler comprises 0.5wt% to 1.2wt% of the total weight of the combined polyether; The polyether polyol accounts for 60wt% to 75wt% of the total weight of the combined polyether.

7. The composite polyether as described in claim 6, characterized in that, The filler accounts for 0.8wt% to 1.2wt% of the total weight of the combined polyether; The polyether polyol accounts for 70 wt% to 75 wt% of the total weight of the combined polyether.

8. The composite polyether as described in claim 1, characterized in that, The polyether polyol includes a first polyether polyol and a second polyether polyol, and the mass ratio of the first polyether polyol to the second polyether polyol is 3:1 to 3:

2. Wherein, the hydroxyl value of the first polyether polyol is 400~450 mgKOH / g, and the hydroxyl value of the second polyether polyol is 350~400 mgKOH / g; The first polyether polyol and the second polyether polyol are each independently selected from one or more of sucrose polyether polyol, glycerol polyether polyol, sorbitol polyether polyol, propylene glycol polyether polyol, ethylene glycol polyether polyol, trimethylolpropane polyether polyol, and polyoxypropylene glycol.

9. The composite polyether as described in claim 1, characterized in that, The combined polyether further includes antioxidants, foaming agents, catalysts, crosslinking agents, foam stabilizers, and a third polyether polyol, wherein the hydroxyl value of the third polyether polyol is 320~380 mgKOH / g. The antioxidant accounts for 0.3wt% to 0.6wt% of the total weight of the combined polyether; The foaming agent accounts for 10wt% to 15wt% of the total weight of the combined polyether; The catalyst accounts for 0.8 wt% to 1.5 wt% of the total weight of the combined polyether; The crosslinking agent accounts for 1.5 wt% to 3.0 wt% of the total weight of the combined polyether; The foam stabilizer accounts for 1.0 wt% to 2.0 wt% of the total weight of the combined polyether; The third polyether polyol accounts for 5 wt% to 10 wt% of the total weight of the combined polyether.

10. The composite polyether as described in claim 9, characterized in that, The third polyether polyol includes castor oil-based polyether polyol; The antioxidants include one or more of hindered phenolic antioxidants and phosphite antioxidants. The hindered phenolic antioxidants include 2,4-dimethyl-6-octylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-sec-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, n-octadecyl-β(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4... The antioxidant comprises one or more of the following: 4'-dihydroxybiphenol, 4,4'-thiobis(6-tert-butyl-o-cresol), p-butylphenol, p-isopropylphenol, p-(1,1,3,3-tetramethylbutyl)phenol, thymol, mixed m-cresol and p-cresol, and p-nonylphenol; the phosphite antioxidant comprises one or more of tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, optionally, the antioxidant comprises the hindered phenolic antioxidant and the phosphite antioxidant, wherein the mass ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 0.8:1 to 1:0.

8.

11. The composite polyether as described in claim 9, characterized in that, The foaming agent includes alkane-based foaming agents, which include one or more of cyclopentane, isopentane, n-pentane, and cyclohexane; and / or The catalyst comprises one or more of amine catalysts and organometallic compound catalysts. The amine catalyst comprises one or more of triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, dimethylethanolamine, N,N-dimethylbenzylamine, and 2,2'-dimorpholine diethyl ether. The organometallic compound catalyst comprises one or more of dibutyltin dilaurate, zinc octanoate, bismuth isooctanoate, tetrabutyl titanate, and lead naphthenate; and / or The crosslinking agent includes one or more of diethanolamine, diethylenetriamine, triethanolamine, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, 1,4-butanediol, ethylene glycol, and 1,6-butanediol; and / or The foam stabilizer is a polyether-modified silicone surfactant, which includes one or more of Momentive L-580 silicone oil, Dow Corning DC-193 silicone oil, Dow Corning DC-5043 silicone oil, and fluorinated polyglycerol ether-polydimethylsiloxane block copolymer.

12. A polyurethane composition, characterized in that, Includes isocyanates and the polyether combinations according to any one of claims 1 to 11.

13. The polyurethane composition of claim 12, characterized in that, The isocyanate includes polymeric diphenylmethane diisocyanate, wherein the functionality of the polymeric diphenylmethane diisocyanate is 2.7 to 2.9; and / or The mass ratio of the polyether to the isocyanate is 1:1.03 to 1:1.

08.

14. A polyurethane foam, characterized in that, The polyurethane foam is obtained by foaming the polyurethane composition according to claim 12 or 13.

15. The polyurethane foam according to claim 14, characterized in that, The polyurethane foam has a thermal conductivity of ≤0.018 W / (m·K) at -25℃.

16. A refrigeration device, characterized in that, The refrigeration equipment includes an insulation layer, which is made of polyurethane foam as described in claim 14 or 15.

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