Foaming material and refrigeration equipment

Abstract

The invention provides a foaming material and refrigeration equipment. The foaming material is prepared by foaming a composition, the composition is prepared from the following components in parts by weight: 5 to 40 parts of polyester polyol, 48 to 88 parts of composite polyether polyol, 7 to 12 parts of a modified material, 10 to 55 parts of a foaming agent, 120 to 180 parts of isocyanate, 0.3 to 6 parts of water and an auxiliary agent, wherein the modified material comprises one or more of a copolymer as shown in a formula (I) and a copolymer as shown in a formula (II). The chain segment flowability of the modified material at low temperature is improved, low-temperature embrittlement shrinkage is avoided, the low-temperature dimensional stability of the foaming material is improved, and the inner container made of the foaming material is not prone to low-temperature embrittlement stripping.

Description

Technical Field

[0001] This application relates to the field of rigid polyurethane foam technology, specifically to a foaming material and a refrigeration device. Background Technology

[0002] While some rigid polyurethane foam materials currently address environmental protection and basic insulation issues, they are prone to embrittlement and shrinkage at low temperatures (≤-10℃). For example, after the annual defrosting cycle, the inner liner of a refrigerator door is prone to peeling off from the foam, leading to a decrease in insulation performance. Summary of the Invention

[0003] The embodiments of this application provide a foaming material and a refrigeration device that can improve the technical problem of the inner liner delaminating from the foaming material at low temperatures.

[0004] In a first aspect, embodiments of this application provide a foamed material, which is prepared by foaming a composition; The composition comprises, by weight, 5-40 parts polyester polyol, 48-88 parts composite polyether polyol, 7-12 parts modifier, 10-55 parts foaming agent, 120-180 parts isocyanate, 0.3-6 parts water, and additives. The modified material includes one or more copolymers as shown in formula (I) and copolymers as shown in formula (II); ; ; Wherein, R1 and R3 are respectively selected from unsubstituted or substituted with at least one substituent C1-C30 aliphatic alkylene groups, unsubstituted or substituted with at least one substituent C1-C30 aliphatic alkylene oxy groups, unsubstituted or substituted with at least one substituent aryl groups having 6 to 30 ring atoms, unsubstituted or substituted with at least one substituent aryl groups having 5 to 30 ring atoms, or combinations of these groups; each time the substituent appears, it is independently selected from deuterium, -NR z R m The R2 and R4 are selected from unsubstituted or substituted C1 to C30 aliphatic hydrocarbon groups. The R z and the R m The aliphatic chain hydrocarbon group (H, D, C1-C30), aliphatic chain hydroxyl group (C1-C30), aliphatic cyclic hydrocarbon group (3 to 30 ring atoms), aliphatic heterocyclic hydrocarbon group (3 to 30 ring atoms), aryl group (6 to 30 ring atoms), or heteroaryl group (5 to 30 ring atoms) are selected independently from H, D, C1-C30 ... a, b, c, and d are all integers greater than 0.

[0005] Secondly, embodiments of this application provide a refrigeration device, including the foaming material as described above.

[0006] The beneficial effects of the embodiments of this application are as follows: by introducing flexible segments into the modified material to reduce the entanglement and rigidity of the molecular chains, low-temperature embrittlement and shrinkage are avoided, and the low-temperature dimensional stability of the foam material is improved, so that the foam material and the inner liner are not easily embrittled and separated at low temperatures. Detailed Implementation

[0007] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in 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 implementation methods described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0008] 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; 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 an order.

[0009] 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.

[0010] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one," "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.

[0011] 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.

[0012] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted.

[0013] The term "aliphatic lactone ring" refers to a compound of an alicyclic family with -COO- rings attached to the inner ring.

[0014] The term "aliphatic chain hydrocarbon group" refers to aliphatic straight-chain hydrocarbon group or aliphatic branched hydrocarbon group. "Aliphatic chain hydrocarbon group of C1 to C30" can be, for example, aliphatic chain hydrocarbon group of C1 to C25, aliphatic chain hydrocarbon group of C1 to C20, aliphatic chain hydrocarbon group of C1 to C18, aliphatic chain hydrocarbon group of C1 to C15, aliphatic chain hydrocarbon group of C1 to C12, aliphatic chain hydrocarbon group of C1 to C10, aliphatic chain hydrocarbon group of C1 to C8, and aliphatic chain hydrocarbon group of C1 to C6. The number of carbon atoms in the chain hydrocarbon group can be, for example, 1 to 25, 1 to 20, 1 to 18, 1 to 15, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 3, with examples being 1, 3, 6, 8, 10, 15, 20, 25, 30, or any value between any two of the aforementioned values. For example, it can be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, or C10 alkyl. Suitable examples of "chain hydrocarbon group" include, but are not limited to, methyl, ethyl, vinyl, ethynyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, n-nonyl, n-decyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl 2-Octodecyl, n-Undecyl, n-Dodecyl, 2-Ethyldodecyl, 2-Butyldodecyl, 2-Hexyldodecyl, 2-Octodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadedecyl, n-Hexadecyl, 2-Ethylhexadecyl, 2-Butylhexadecyl, 2-Hexylhexadecyl, 2-Octodecyl, n-Heptadedecyl, n-Octadedecyl, n-Nondecyl, n-Eicosyl, 2-Ethyleicosyl, 2-Butyleicosyl, 2-Hexyleicosyl, 2-Octodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, n-Iconodecyl, or n-Trianedecyl.

[0015] The term "aliphatic alkylene group" refers to an aliphatic straight-chain hydrocarbon group or an aliphatic branched hydrocarbon group in which a hydrogen atom is substituted.

[0016] The term "aliphatic hydrocarbon oxy group" refers to a group with the general formula *-O-aliphatic 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), tert-butoxy (-OC(CH3)3 or -OtBu), and n-hexyloxy (-O-C6H). 13 ), n-Decaalkoxy (-OC) 10 H 21 ), or n-dodecyloxy (-OC) 12 H 25 ).

[0017] The term "aliphatic alkylene group" refers to a group with the general formula *-O-aliphatic alkylene group, where * represents the linking site and O represents the oxygen atom.

[0018] In this application, "ring atom number" refers to the number of atoms in the ring itself of a compound formed by atomic bonds, such as monocyclic compounds, fused-ring compounds, cross-linked compounds, carbocyclic compounds, and heterocyclic compounds. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, a benzene ring has 6 ring atoms, a naphthalene ring has 10 ring atoms, and a thiophene group has 5 ring atoms.

[0019] The term "aliphatic cyclic hydrocarbon group" refers to an aliphatic cyclic hydrocarbon group. The number of ring atoms in an "aliphatic cyclic hydrocarbon group with 3 to 30 ring atoms" can be, for example, 3 to 28, 3 to 24, 3 to 20, 5 to 10, 3 to 14, 3 to 10, 3 to 8, 3 to 6, or 3 to 5, with examples being 3, 5, 6, 8, 10, 14, 20, 24, 28, 30, or any value between any two of the aforementioned values.

[0020] The term "aliphatic heterocyclic hydrocarbon group" refers to an aliphatic cyclic hydrocarbon group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom can be one or more of N, O, S, Si, and P atoms, and the number of heteroatoms in the aliphatic heterocyclic hydrocarbon group is independently between 1 and 20. The number of ring atoms in "aliphatic heterocyclic hydrocarbon group with 3 to 30 ring atoms" can be, for example, 3 to 28, 3 to 24, 3 to 20, 5 to 10, 3 to 14, 3 to 10, 3 to 8, 3 to 6, or 3 to 5, with examples being 3, 5, 6, 8, 10, 14, 20, 24, 28, 30, or values ​​between any two of the aforementioned values.

[0021] The term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl, and in the case of a polycyclic ring, at least one of the rings is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6-40 ring atoms" means an aryl containing 6-40 ring atoms, preferably a substituted or unsubstituted aryl having 6-30 ring atoms, more preferably a substituted or unsubstituted aryl having 6-18 ring atoms, particularly preferably a substituted or unsubstituted aryl having 6-14 ring atoms, and optionally further substituted. Suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives. It is understandable that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., non-H atoms with a molar ratio of less than 10%, such as C, N, or O atoms). Specific examples such as acenaphthene, fluorene, 9,9-diarylfluorene, triarylamines, and diaryl ether systems should also be included in the definition of aryl groups.

[0022] The term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, "substituted or unsubstituted heteroaryl with 5-40 ring atoms" refers to a heteroaryl with 5-40 ring atoms, preferably a substituted or unsubstituted heteroaryl with 6-30 ring atoms, more preferably a substituted or unsubstituted heteroaryl with 6-18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl with 6-14 ring atoms. The heteroaryl group may optionally be further substituted, and suitable examples include, but are not limited to, thiophene, furanyl, pyrrole, imidazolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, and pyrimidine. Triazinyl, acridineyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiopheneyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienopyrrolyl, furanolyl, furanolyl, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridineyl, primidyl, quinazolinoneyl, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0023] The term "aryl" refers to a group derived from an aromatic ring compound by removing two hydrogen atoms, such as... .

[0024] The term "hybrid aryl" refers to a group derived from a heteroaryl ring compound by removing two hydrogen atoms, such as... .

[0025] The technical solution of this application is as follows: In a first aspect, embodiments of this application provide a foaming material, which is obtained by foaming a composition; The composition comprises, by weight, 5-40 parts polyester polyol, 48-88 parts composite polyether polyol, 7-12 parts modifier, 10-55 parts foaming agent, 120-180 parts isocyanate, 0.3-6 parts water, and additives. The modified material includes one or more copolymers as shown in formula (I) and copolymers as shown in formula (II); ; ; Wherein, R1 and R3 are respectively selected from unsubstituted or substituted by at least one substituent C1-C30 aliphatic alkylene groups, unsubstituted or substituted by at least one substituent C1-C30 aliphatic alkylene oxygen groups, unsubstituted or substituted by at least one substituent aryl groups having 6 to 30 ring atoms, unsubstituted or substituted by at least one substituent aryl groups having 5 to 30 ring atoms, or combinations of these groups; each time the substituent appears, it is independently selected from deuterium, -NR z R m The R2 and R4 are selected from unsubstituted or substituted C1 to C30 aliphatic hydrocarbon groups. The R z and the R m The aliphatic chain hydrocarbon group (H, D, C1-C30), aliphatic chain hydroxyl group (C1-C30), aliphatic cyclic hydrocarbon group (3 to 30 ring atoms), aliphatic heterocyclic hydrocarbon group (3 to 30 ring atoms), aryl group (6 to 30 ring atoms), or heteroaryl group (5 to 30 ring atoms) are selected independently from H, D, C1-C30 ... a, b, c, and d are all integers greater than 0.

[0026] It should be noted that in this embodiment, the amount of water is 0.3 to 6 parts, and the amount of additives is not limited here. It can be adjusted according to the actual addition situation in other embodiments.

[0027] It is understandable that the copolymer shown in Formula (I) has -O-R2-CO- blocks, and the copolymer shown in Formula (II) has -O-R4-CO- blocks. This introduces flexible segments into the modified material to reduce the entanglement and rigidity of the molecular chains, thereby lowering the glass transition temperature. At the same time, it improves the segment flowability of the modified material at low temperatures, avoids low-temperature embrittlement and shrinkage, improves the low-temperature dimensional stability of the foamed material, and makes it less likely for the foamed material to embrittle and peel off from the inner liner of the refrigeration equipment at low temperatures.

[0028] In some embodiments, the copolymer of formula (I) is formed by copolymerization of a first polymer and an unsubstituted or substituted aliphatic lactone ring having a ring number of 3 to 30 atoms, wherein the first polymer has a structure as shown in formula (III). ; Wherein, R5 is selected from unsubstituted or substituted C1-C20 aliphatic alkylene groups, unsubstituted or substituted C1-C20 aliphatic alkylene groups, or combinations of these groups; n1 is 3-200. The copolymer shown in formula (II) is formed by copolymerization of a second polymer and an unsubstituted or substituted aliphatic lactone ring having a ring number of 3 to 30 atoms, wherein the second polymer has the structure shown in formula (IV). ; Wherein, R6 is selected from unsubstituted or substituted C1-C20 aliphatic alkylene groups, unsubstituted or substituted C1-C20 aliphatic alkylene oxygen groups, unsubstituted or substituted aryl groups having 6 to 20 ring atoms, or combinations of these groups; and n2 is 10 to 3000.

[0029] It is understood that the aliphatic lactone ring provided in this embodiment is introduced in a block form onto the main chain of the first or second polymer through ring-opening, without affecting the molding process and other properties of the foamed material. The first polymer has a polyether structure, and the second polymer has a polyester structure. Different functions can be introduced into the modified material by further designing the molecular structure of the first or second polymer.

[0030] In some embodiments, the first polymer is selected from one or more of glycerol polyether, pentaerythritol polyether, trimethylolpropane polyether, castor oil polyether, o-toluene diamine polyether, and polyethylene glycol monomethyl ether; The second polymer is selected from one or more of polylactic acid, polybutylene succinate, polyglycolic acid, polybutylene adipate, and phthalic anhydride polyester polyol; The aliphatic lactone ring is selected from one or more of δ-valerolactone, lactide, glycolide, and ε-caprolactone.

[0031] It should be noted that glycerol polyether refers to a polymer obtained by ring-opening polymerization of glycerol with an epoxide as a starting agent, with a degree of polymerization of 4 to 100. For example, polyoxyethylene glycerol ether has the CAS number 31694-55-0.

[0032] Pentaerythritol polyethers are polymers obtained by ring-opening polymerization of pentaerythritol with epoxides, with a degree of polymerization ranging from 4 to 100. For example, pentaerythritol polyoxyethylene ether has the CAS number 9005-68-7.

[0033] Trimethylolpropane polyether is a polymer obtained by ring-opening polymerization of trimethylolpropane with an epoxide as an initiator, with a degree of polymerization of 6 to 120. For example, trimethylolpropane polyoxypropylene ether has the CAS number 37205-86-2.

[0034] Castor oil polyether is a polymer obtained by ring-opening polymerization of castor oil with an epoxide. For example, castor oil polyoxyethylene ether has the CAS number 61791-12-6.

[0035] o-Toluenediamine polyether refers to a polymer obtained by ring-opening polymerization of o-toluenediamine with an epoxide as an initiator, with a degree of polymerization of 4 to 40. For example, toluenediamine polyoxypropylene ether has the CAS number 9046-10-0.

[0036] Polyethylene glycol monomethyl ether (PEG) is a polymer obtained by ring-opening polymerization of methanol with an epoxide as an initiator, with a degree of polymerization ranging from 3 to 200. For example, PEG monomethyl ether has the CAS number 9004-74-4.

[0037] The structural formula of polylactic acid is -[OCH(CH3)CO]- n The degree of polymerization n is 100~3000; polylactic acid and ε-caprolactone yield polylactic acid-caprolactone copolymer, CAS number 68937-10-4.

[0038] The structural formula of polybutylene succinate is -[O(CH2)4OCO(CH2)2CO]- n The degree of polymerization n is 200~500; The structural formula of polyglycolic acid is -[OCH2CO]- n The degree of polymerization n is 625~2500.

[0039] The structural formula of polybutylene adipate is -[O(CH2)4OCO(CH2)4CO]- n The degree of polymerization, n, is 10~25.

[0040] Phthalic anhydride polyester polyols are produced by the polycondensation reaction of phthalic anhydride (phthalic anhydride) and polyol. For example, it is produced by the polycondensation reaction of phthalic anhydride and ethylene glycol.

[0041] δ-valproic acid lactone has a CAS number of 542-28-9, DL-lactide has a CAS number of 95-96-5, L-lactide has a CAS number of 4511-42-6, glycolide has a CAS number of 502-97-6, and ε-caprolactone has a CAS number of 502-44-3.

[0042] It is understandable that the aforementioned aliphatic lactone rings can all be opened and copolymerized with the first polymer or the second polymer to form modified materials.

[0043] In some examples, repeating units obtained after opening the aliphatic lactone ring account for 40-60 wt% of the modified material.

[0044] In some embodiments, the adjuvant includes 0.1 to 2 parts of a composite antibacterial agent, wherein the composite antibacterial agent includes a silane coupling agent and an inorganic nano-antibacterial agent linked by oxygen atoms.

[0045] Understandably, the alkoxy groups on the silane coupling agent hydrolyze to generate silanol groups (Si-OH), which then dehydrate and condense with the hydroxyl groups on the surface of the inorganic nano-antibacterial agent to form stable ether bonds. This grafts the epoxy groups from the silane coupling agent onto the surface of the inorganic nano-antibacterial agent. This process retains the epoxy groups of the silane coupling agent, allowing them to react with the hydroxyl groups of the polyol in the composition, while also improving the compatibility between the inorganic nano-antibacterial agent and the polyol in the composition, reducing cell defects in the foaming material, and improving the cell quality. Simultaneously, the inorganic nano-antibacterial agent also provides long-lasting antibacterial effects.

[0046] In some embodiments, the silane coupling agent is selected from one or more of KH550, KH560, and A-171.

[0047] In some embodiments, the inorganic nano-antibacterial agent is selected from one or more of the following combinations: nano-silver and zinc oxide, nano-silver and titanium dioxide, zinc oxide and modified montmorillonite, nano-copper and graphene oxide (CAS No. 73919-53-6); optionally, the inorganic nano-antibacterial agent is selected from nano-silver and zinc oxide in a mass ratio of 1:(2~5).

[0048] In some embodiments, the modified montmorillonite includes montmorillonite and one or more of quaternary ammonium cations and inorganic antibacterial ions intercalated in the montmorillonite.

[0049] It should be noted that quaternary ammonium cations and inorganic antibacterial ions intercalate by exchanging inorganic cations between montmorillonite layers, endowing montmorillonite with hydrophobicity and antibacterial properties, and improving its compatibility with polymers, thus obtaining modified montmorillonite. Furthermore, the hydroxyl groups on the surface of this modified montmorillonite can also undergo dehydration condensation with the silanol groups generated by the hydrolysis of alkoxy groups on the silane coupling agent, forming silane ether bonds.

[0050] When inorganic nano-antibacterial agents use one or more of nano-silver and zinc oxide, or nano-silver and titanium dioxide, the metal atoms of the above-mentioned elements and compounds can be linked to silicon atoms on the silanol groups generated by the hydrolysis of alkoxy groups on the silane coupling agent through oxygen atoms, thereby improving the compatibility between inorganic nano-antibacterial agents and other materials.

[0051] When inorganic nano-antibacterial agents use nano-copper and graphene oxide, the surface hydroxyl groups of graphene oxide and nano-copper can both be attached to silicon atoms on the silanol groups generated by the hydrolysis of alkoxy groups on the silane coupling agent.

[0052] Understandably, by selecting from the above combinations, nano-silver and nano-copper can achieve rapid antibacterial effects by disrupting bacterial cell membranes, while zinc oxide and titanium dioxide can achieve long-lasting antibacterial effects by slowly releasing their metal ions. When the inorganic nano-antibacterial agent is selected from nano-silver and zinc oxide in a mass ratio of 1:(2~5), the aggregation problem when using nano-silver alone for antibacterial purposes can be improved, the fluctuation of the antibacterial rate can be reduced, and the problem of slow onset of action when using zinc oxide alone for antibacterial purposes can also be solved.

[0053] In some specific examples, the particle size of nano-silver is 20~50nm, and the particle size of nano-zinc oxide is 30~80nm.

[0054] Understandably, by controlling the particle size of nano-silver and nano-zinc oxide within the aforementioned range, they can be better filled into the foam cells, thereby improving the impact resistance of the foamed material.

[0055] The particle size of nano-silver can also be any of the following values ​​or any range between two values: 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm. The particle size of nano-zinc oxide can also be any of the following values ​​or any range between two values: 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm.

[0056] In some embodiments, the quaternary ammonium cation is selected from one or more of hexadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, and bis(octadecyldimethylammonium) ion, and the inorganic antibacterial ion is selected from one or more of silver ion, zinc ion, and copper ion.

[0057] It is understandable that by selecting from the aforementioned ions, intercalation modification of montmorillonite can be achieved, resulting in modified montmorillonite with antibacterial properties. The method for intercalation modification of montmorillonite employs conventional methods disclosed in the art.

[0058] In some examples, hexadecyltrimethylammonium ion is a cation in hexadecyltrimethylammonium bromide (CAS: 57-09-0), octadecyldimethylbenzylammonium ion is a cation in octadecyldimethylbenzylammonium chloride (CAS: 122-19-0), and bis(octadecyldimethylammonium) ion is a cation in bis(octadecyldimethylammonium) chloride (CAS: 3401-74-9).

[0059] Silver ions come from silver nitrate, zinc ions come from zinc nitrate, and copper ions come from copper sulfate.

[0060] In some embodiments, the adjuvant further includes 0.2 to 1.5 parts of a composite anti-aging agent, wherein the composite anti-aging agent comprises a hindered phenolic antioxidant and an ultraviolet absorber in a mass ratio of (2 to 4):1.

[0061] It should be noted that hindered phenolic antioxidants are materials that capture free radicals generated during the thermal oxidation of polymers, terminate the oxidation chain reaction, and thus delay polymer degradation.

[0062] Ultraviolet absorbers are materials that selectively absorb ultraviolet light (wavelength 290~400nm) from sunlight and convert the absorbed light energy into heat energy or harmless low-energy radiation, thus preventing ultraviolet light from exciting polymer molecules to produce free radicals and preventing photoaging of materials.

[0063] Understandably, using both hindered phenolic antioxidants and UV absorbers simultaneously can comprehensively address the causes of aging in refrigeration equipment and improve the long-term performance stability of foaming materials.

[0064] In some embodiments, the hindered phenolic antioxidant is selected from one or more of Irganox 1098 and Irganox 1010; The ultraviolet absorber is selected from one or more of Tinuvin 326 and Tinuvin 328; Understandably, by selecting materials within the aforementioned range, the foamed material retains high thermal conductivity and compressive strength even after aging. Specifically, the composite anti-aging agent comprises Irganox 1098 and Tinuvin 326 in a mass ratio of 3:1.

[0065] In some embodiments, the blowing agent includes one or more of hydrofluoroolefin (HFO) blowing agents and alkane blowing agents.

[0066] It should be noted that both hydrofluoroolefin blowing agents and alkane blowing agents are physical blowing agents. It is understandable that the aforementioned foaming agents have advantages such as low ozone depletion potential (ODP) and low global warming potential (GWP).

[0067] In some embodiments, the blowing agent comprises 20-50 wt% of the hydrofluoroolefin blowing agent and 50-80 wt% of the alkane blowing agent; Optionally, the hydrofluoroolefin blowing agent is selected from one or more of HFO-1234yf, HFO-1234ze(E), and trans-1,1,1,3-tetrafluoropropylene; Optionally, the alkane-based foaming agent is selected from one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclobutane, and cyclopentane.

[0068] Understandably, the aforementioned foaming agent can better cooperate with other materials for foaming.

[0069] In some embodiments, the blowing agent includes 20-60 wt% cyclopentane, 20-50 wt% trans-1,1,1,3-tetrafluoropropylene (GBA), and 10-30 wt% isobutane (R600a).

[0070] Understandably, by employing multiple types of foaming agents to meet the requirements of Ozone Depletion Potential (ODP) = 0 and Global Warming Potential (GWP) < 10, the surface bubble level can be improved and the overfill rate reduced, thus achieving both environmental protection and low cost. Furthermore, using isobutane instead of propane (R290) can reduce the risk of foaming agent escape and, in synergy with composite anti-aging agents, enhance the long-term performance stability of the foam.

[0071] In some examples, the mass fraction of cyclopentane can also be selected from any of the following values ​​or a range between any two values: 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%. The mass fraction of GBA can also be selected from any of the following values ​​or a range between any two values: 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%. The mass fraction of R600a can also be selected from any of the following values ​​or a range between any two values: 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%.

[0072] In some embodiments, the polyester polyol is selected from one or more of the following: adipic acid-ethylene glycol polyester polyol, adipic acid-propylene glycol polyester polyol, polycaprolactone polyol, sebacic acid-ethylene glycol polyester polyol, terephthalic acid polyester polyol, and phthalic anhydride polyester polyol; and / or, The composite polyether polyol is selected from one or more of glycerol polyether, sucrose polyether, o-tolyl diamine polyether, pentaerythritol polyether, trimethylolpropane polyether, sorbitol polyether, ethylenediamine polyether, propylene glycol polyether, and ethylene glycol-propylene glycol copolymer polyether.

[0073] It is understandable that by using a variety of polyester polyols and polyether polyols, the different properties of foaming materials can be controlled, while also allowing for better foaming in combination with other materials.

[0074] In some embodiments, the additive further includes 1 to 12 parts of a composite catalyst, wherein the composite catalyst comprises a foaming catalyst, a gelling catalyst, and a trimerizing catalyst in a mass ratio of (0.5 to 1):(1 to 3):(0.5 to 1.5).

[0075] It should be noted that a foaming catalyst refers to a catalyst that accelerates the reaction between water and isocyanate to generate CO2 gas, driving the system to foam and form. A gel catalyst refers to a catalyst that accelerates the addition reaction between polyol polyether and isocyanate to form a polyurethane urea crosslinked network. A trimerizing catalyst refers to a catalyst that catalyzes the self-polymerization reaction of isocyanate to form a heat-resistant polyisocyanurate (PIR) ring structure.

[0076] It is understandable that foaming catalysts, gel catalysts, and trimerizing catalysts are used to promote the synthesis of foamed materials. At the same time, free radical scavenging antioxidants are added to capture the peroxide free radicals and alkoxy free radicals generated by the oxidation of the foamed materials under the action of heat, light, and oxygen, so as to avoid the occurrence of chain degradation.

[0077] The number of parts of the composite catalyst can be the following values ​​or any range between any two of the following values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.

[0078] In some examples, when the mass ratio of the gel catalyst to the trimerizing catalyst satisfies (1~3):(0.5~1.5), the foaming catalyst can be any of the following values ​​or any range between any two of the following values: 0.5, 0.6, 0.7, 0.8, 0.9, 1. When the mass ratio of the foaming catalyst to the trimerizing catalyst satisfies (0.5~1):(0.5~1.5), the gel catalyst can be any of the following values ​​or any range between any two of the following values: 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3. When the mass ratio of the foaming catalyst to the gel catalyst satisfies (0.5~1):(1~3), the trimerizing catalyst can be any of the following values ​​or any range between any two of the following values: 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5.

[0079] In some embodiments, the foaming catalyst is selected from one or more of pentamethyldiethylenetriamine (abbreviated as PC-5, CAS:3030-47-5), triethylenediamine (abbreviated as DABCO, CAS:280-57-9), bis(dimethylaminoethyl) ether (A-1) (CAS:3033-62-3), and N,N-dimethylethanolamine (CAS:108-01-0); The gel catalyst is selected from one or more of N,N-dimethylcyclohexylamine (CAS: 98-94-2), 1,4-diazabicyclo[2.2.2]octane (abbreviated as DABCO33-LV, CAS: 280-57-9), N,N-diethylcyclohexylamine (CAS: 91-65-6), and trimethylaminoethylpiperazine (CAS: 104-19-8); The trimer catalyst is selected from one or more of potassium formate (CAS: 590-29-4), potassium acetate (CAS: 127-08-2), bismuth isooctanoate (CAS: 67874-71-9), and DABCOTMR-30 (CAS: 33329-35-0).

[0080] In some embodiments, the additive further includes 0.5 to 8 parts of a surfactant, the surfactant including one or more of silicone oil B84806, silicone oil AK8830, Momentive TSA730, Evonik B8871, Dow Corning DC193, and Wacker B8631.

[0081] It is understandable that by selecting the above-mentioned surfactants, the cell structure can be controlled, foam performance optimized, and the stability of the foaming process ensured.

[0082] The number of surfactants can also be any of the following values ​​or any range between two values: 0.5, 1, 2, 3, 4, 5, 6, 7, 8.

[0083] In some embodiments, the composite polyether polyol comprises 30-55 parts sucrose polyether, 12-22 parts o-toluene diamine polyether, and 6-11 parts glycerol polyether.

[0084] It should be noted that sucrose polyether refers to a polymer material prepared by ring-opening polymerization of sucrose as the core initiator and an epoxy compound under the action of a catalyst.

[0085] o-Toluenediamine polyether is a polymer material prepared by ring-opening polymerization of o-toluenediamine as the core initiator and an epoxy compound under the action of a catalyst.

[0086] Glyceryl polyether is a polymer material obtained by ring-opening polymerization of glycerol as the core initiator and epoxy compound under the action of a catalyst.

[0087] Epoxides are a class of organic compounds whose molecular structure contains a three-membered epoxy ring (a ring structure consisting of one oxygen atom and two adjacent carbon atoms); for example, propylene oxide (PO) and ethylene oxide (EO).

[0088] It is understandable that by using the above-mentioned polyether polyols, a dense three-dimensional network structure can be formed by reacting with isocyanates, thereby endowing the foamed material with compressive strength, dimensional stability and heat resistance.

[0089] The number of parts of sucrose polyether can be the following values ​​or any two of the following ranges: 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55.

[0090] The number of o-toluene diamine polyethers can be the following values ​​or any range between any two of the following values: 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22.

[0091] The number of parts of glycerol polyether can be the following values ​​or any range between the following two values: 6, 7, 8, 9, 10, 11.

[0092] In some embodiments, the NCO content of the isocyanate is 29-32%; and / or, The isocyanate is selected from at least one of Wanhua PM-200 and Wanhua PM-4010.

[0093] The CAS number for Wanhua PM400 is 9016-87-9. The CAS number for Wanhua PM-4010 is 9016-87-9.

[0094] In some embodiments, the adjuvants include 0.1 to 2 parts of a compound antibacterial agent, 0.2 to 1.5 parts of a compound anti-aging agent, 1 to 12 parts of a compound catalyst, and 0.5 to 8 parts of a surfactant.

[0095] It is understandable that the above-mentioned additives are selected to better catalyze the synthesis of foam materials.

[0096] Secondly, embodiments of this application provide a method for preparing a foamed material, comprising the following steps: Mix 5-40 parts of polyester polyol, 48-88 parts of composite polyether polyol, 7-12 parts of modifier, 0.3-6 parts of water, 0.1-2 parts of composite antibacterial agent, 0.2-1.5 parts of composite anti-aging agent, 1-12 parts of composite catalyst, and 0.5-8 parts of surfactant. Stir at 500-800 rpm for 15-20 minutes at 20-25°C. Then add 10-55 parts of foaming agent and continue stirring for 5-8 minutes. Cool to 8-10°C to obtain the premix. The premixed material is mixed with 120-180 parts of isocyanate and foamed under high pressure at a nozzle pressure of 120-140 kPa and a temperature of 16-18℃. The mixture is then injected into a mold at 45-50℃, cured for 10-15 minutes, and then demolded to obtain the foamed material.

[0097] In some embodiments, prior to obtaining the premix, the following steps are also included: A first polymer in a mass ratio of 1:1 is mixed with an unsubstituted aliphatic lactone ring, or a ring with 3 to 30 ring atoms substituted by at least one substituent, and then a titanium-based catalyst is added. The mixture is reacted at 80–85 °C under a vacuum of 0.1 MPa for 3–4 h to obtain the modified material; or, A second polymer in a mass ratio of 1:1 and an unsubstituted or at least substituted aliphatic lactone ring with 3 to 30 ring atoms were mixed and then added to a titanium-based catalyst. The mixture was reacted at 80–85 °C and 0.1 MPa vacuum for 3–4 h to obtain the modified material.

[0098] It should be noted that the above-mentioned unsubstituted or substituted aliphatic lactone rings with a ring number of 3 to 30 are referred to the examples in other embodiments, and the first polymer and the second polymer are both referred to the examples in other embodiments.

[0099] Understandably, the above-mentioned titanium-based catalyst promotes the ring-opening of aliphatic lactone rings. The carbon-oxygen single bond in the -COO- of the aliphatic lactone ring breaks to achieve ring opening, and then undergoes transesterification reaction with the terminal hydroxyl groups on the first or second polymer, thereby attaching to the molecular chain of the polymer to form a block structure.

[0100] In some embodiments, the titanium catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, and diisopropoxytitanium diacetylacetone.

[0101] In some specific examples, the copolymer structure obtained by reacting glycerol polyether with ε-caprolactone under the catalysis of tetrabutyl titanate is: HO-(-O-CH2CH2-). p -O-(-CH2CH2CH2CH2CH2-CO-) q -H, where p and q represent the number of times the repeating unit appears, and both are integers greater than 0.

[0102] In some embodiments, prior to obtaining the premix, the following steps are also included: A first solution containing the silane coupling agent and a first solvent is mixed with a second dispersion containing the inorganic nano antibacterial agent and a second solvent, and heated to react and obtain a composite antibacterial agent. The first solvent includes one or more of water and alcohol compounds.

[0103] It should be noted that alcohols refer to solvents containing hydroxyl groups in their molecules.

[0104] It is understandable that the alkoxy group in the above-mentioned silane coupling agent hydrolyzes in water or alcohol medium to generate silanol group (Si-OH), which then dehydrates and condenses with the hydroxyl group on the surface of the inorganic nano antibacterial agent to form a stable ether bond.

[0105] In some examples, the alcohol compound is selected from one or more of ethanol, isopropanol, and n-butanol.

[0106] The second solvent is selected from one or more of deionized water and distilled water.

[0107] In some examples, the heating temperature is 80~120°C. The inorganic nano-antibacterial agent is selected from nano-silver and zinc oxide in a mass ratio of 1:(2~5).

[0108] Thirdly, embodiments of this application provide a refrigeration device, including the foamed material as described above, or the foamed material prepared by the method described above.

[0109] In some examples, the refrigeration equipment includes a housing, the housing comprising a shell and a liner, the liner being disposed inside the shell, and the insulation layer being provided between the shell and the liner; and / or, The refrigeration equipment includes a door body, which includes a door panel and a door liner spaced apart, and the insulation layer is provided between the door panel and the door liner.

[0110] Preparation Example 1 This preparation example provides a modified material and its preparation method, the preparation method including the following steps: Glyceryl polyether and polycaprolactone (number average molecular weight 2000, hereinafter referred to as PCL) were mixed in a mass ratio of 1:1 and tetrabutyl titanate was added. The mixture was reacted at 85°C and 0.1 MPa vacuum for 4 hours. After cooling, a modified polyether with a hydroxyl value of 200 mg KOH / g and a PCL content of 50% was obtained.

[0111] Preparation Example 2 This preparation example provides a composite antibacterial agent and its preparation method, which includes the following steps: S1. Add 1g of 40nm silver nanoparticles and 3g of 60nm ZnO nanoparticles to 150mL of anhydrous ethanol to obtain a dispersion.

[0112] In a separate beaker, add 0.1g of KH-550 and 0.4ml of deionized water, and add 0.1~0.2mL of glacial acetic acid to adjust the pH to 4~5. Stir at 25℃ to form a transparent hydrolysate.

[0113] S2. Add the hydrolysate to the dispersion, heat to 80℃, and stir at 500 rpm for 4 hours under a nitrogen atmosphere. After the reaction is complete, centrifuge at 2000 rpm for 10 minutes, and wash 3-5 times alternately with anhydrous ethanol / deionized water to remove free silane and byproducts. Finally, dry under vacuum at 100℃ for 12 hours, and grind to obtain a KH550 silane coupling agent modified nano-silver / zinc oxide mixture, i.e., a composite antibacterial agent.

[0114] Example 1 This application provides a foaming material and a method for preparing the same. The preparation method includes the following steps: S1. Mix 30 parts sucrose polyether, 12 parts o-tolyldiamine polyether, 6 parts glycerol polyether, 12 parts modified polyether, 40 parts phthalic anhydride polyester polyol, 2 parts composite antibacterial agent, 1.5 parts composite anti-aging agent, 8 parts silicone oil B84806, 12 parts composite catalyst and 6 parts water, and stir at 25°C and 600 rpm for 20 min to obtain the mixture. The composite anti-aging agent comprises Irganox1098 and Tinuvin326 in a mass ratio of 3:1. The composite catalyst comprises pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, and potassium formate in a mass ratio of 0.8:2:1.

[0115] S2. Add 55 parts of composite foaming agent to the mixture, continue stirring for 6 minutes, and cool to 9°C to obtain the premix. The composite foaming agent includes 60wt% cyclopentane, 20wt% GBA, and 20wt% R600a.

[0116] S3. Mix the premixed material with 180 parts of PM-200 (NCO index: 1.4), inject it into a 50°C mold under a nozzle pressure of 130 kPa and a temperature of 17°C, and demold after curing for 15 minutes to obtain the foamed material.

[0117] Example 2 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace step S1 with: mixing 40 parts sucrose polyether, 15 parts o-toluene diamine polyether, 7.5 parts glycerol polyether, 12.5 parts modified polyether, 25 parts phthalic anhydride polyester polyol, 1.2 parts composite antibacterial agent, 1.2 parts composite anti-aging agent, 6 parts silicone oil B84806, 10 parts composite catalyst and 4.5 parts water, and stirring at 25°C and 600 rpm for 20 minutes to obtain the mixture.

[0118] Replace the 55 parts of composite foaming agent in step S2 with 45 parts of composite foaming agent, which includes cyclopentane, GBA and R600a in a mass ratio of 50:30:20.

[0119] Replace the 180 PM-200 samples (NCO index: 1.4) in step S3 with 165 PM-200 samples (NCO index: 1.3).

[0120] Example 3 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace step S1 with: mix 45 parts sucrose polyether, 18 parts o-toluene diamine polyether, 8.5 parts glycerol polyether, 13 parts modified polyether, 15 parts phthalic anhydride polyester polyol, 1 part composite antibacterial agent, 1 part composite anti-aging agent, 4 parts silicone oil B84806, 8 parts composite catalyst and 3 parts water, and stir at 25°C and 600 rpm for 20 minutes to obtain the mixture.

[0121] Replace the 55 parts of composite foaming agent in step S2 with 35 parts of composite foaming agent, which includes cyclopentane, GBA and R600a in a mass ratio of 40:40:20.

[0122] Replace the 180 PM-200 samples (NCO index: 1.4) in step S3 with 150 PM-200 samples (NCO index: 1.2).

[0123] Example 4 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace step S1 with: mix 50 parts sucrose polyether, 20 parts o-toluene diamine polyether, 10 parts glycerol polyether, 10 parts modified polyether, 10 parts phthalic anhydride polyester polyol, 0.5 parts composite antibacterial agent, 0.6 parts composite anti-aging agent, 2 parts silicone oil B84806, 5 parts composite catalyst and 1.5 parts water, and stir at 25°C and 600 rpm for 20 minutes to obtain the mixture.

[0124] Replace the 55 parts of composite foaming agent in step S2 with 20 parts of composite foaming agent, which includes cyclopentane, GBA and R600a in a mass ratio of 30:50:20.

[0125] Replace the 180 PM-200 samples (NCO index: 1.4) in step S3 with 135 PM-200 samples (NCO index: 1.1).

[0126] Example 5 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace step S1 with: mix 55 parts sucrose polyether, 22 parts o-toluene diamine polyether, 11 parts glycerol polyether, 7 parts modified polyether, 5 parts phthalic anhydride polyester polyol, 0.1 parts composite antibacterial agent, 0.2 parts composite anti-aging agent, 0.5 parts silicone oil B84806, 1 part composite catalyst and 0.3 parts water, and stir at 25°C and 600 rpm for 20 minutes to obtain the mixture.

[0127] Replace the 55 parts of composite foaming agent in step S2 with 10 parts of composite foaming agent, which includes cyclopentane, GBA and R600a in a mass ratio of 20:50:30.

[0128] Replace the 180 PM-200 samples (NCO index: 1.4) in step S3 with 120 PM-200 samples (NCO index: 1.0).

[0129] Example 6 This application provides a foaming material and its preparation method, which differs from Example 3 in that: The compound antibacterial agent includes 30nm nano-silver.

[0130] Example 7 This application provides a foaming material and its preparation method, which differs from Example 3 in that: The composite foaming agent includes 75 wt% cyclopentane, 23 wt% GBA and 2 wt% propane.

[0131] Example 8 This application provides a foaming material and its preparation method, which differs from Example 3 in that: No compound anti-aging agents are added.

[0132] Comparative Example 1 This application provides a foaming material and a method for preparing the same. The preparation method includes the following steps: S1. Mix 45 parts sucrose polyether, 18 parts o-toluene diamine polyether, 8.5 parts glycerol polyether, 15 parts phthalic anhydride polyester polyol, 4 parts silicone oil B84806, 8 parts composite catalyst and 3 parts water, and stir at 25°C and 600 rpm for 20 min to obtain the mixture.

[0133] S2. Add 35 parts of cyclopentane to the mixture, continue stirring for 6 minutes, and cool to 9°C to obtain the premix.

[0134] S3. Mix the premixed material with 150 parts of PM-200 (NCO index: 1.4), inject it into a 50°C mold under a nozzle pressure of 130 kPa and a temperature of 17°C, and demold after curing for 15 minutes to obtain the foamed material.

[0135] Comparative Example 2 This application provides a foaming material and its preparation method, which differs from Example 3 in that: The 13 parts of modified polyether in step S1 are replaced with 13 parts of glycerol polyether; therefore, the mixture obtained in step S1 contains a total of 21.5 parts of glycerol polyether.

[0136] Material information:

[0137] Performance testing The foamed materials prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were tested using the following methods: Foam core density: Refer to GB / T6343-2009, drainage method.

[0138] Low temperature shrinkage rate: After being placed at -20℃ for 12 hours, it is placed at 5℃ for 12 hours. This treatment is considered as one cycle. The cycle is repeated 100 times. The shrinkage rate in the length direction is tested according to GB / T8811-2008.

[0139] Antibacterial rate: According to GB / T31402-2015, Escherichia coli (ATCC25922) and Staphylococcus aureus (ATCC6538) were tested.

[0140] Changes in thermal conductivity after aging: At 70℃ and RH80%, the product was placed for 120 days (corresponding to 10 years of actual use), with an accelerated aging coefficient of 30:1; subsequently, the thermal conductivity before and after aging was tested in accordance with GB / T10295-2008.

[0141] Compression strength retention rate: After being placed at 70℃ and RH80% for 120 days (corresponding to 10 years of actual use), the accelerated aging coefficient is 30:1; then the compression strength is tested according to GB / T10295-2008, and the retention rate is calculated as: strength after aging / initial strength × 100%.

[0142] Surface bubble level: Laneige mold test, mold size: 5cm×20cm×200cm; the bubble level is divided into three grades: I, II and III.

[0143] Overfill rate: Laneige mold test, mold size: 5cm×20cm×200cm; Overfill rate = specified injection volume / exact filling volume × 100%.

[0144] The test results are shown in Tables 1 and 2.

[0145] Table 1:

[0146] Table 2:

[0147] From Table 1 and Table 2, we can see that: The foamed materials prepared in Examples 1 to 8 exhibited lower low-temperature shrinkage rates and smaller changes in thermal conductivity after aging compared to the foamed material prepared in Comparative Example 1. This is primarily due to the use of modified polyether, in which polycaprolactone can be grafted onto the polymer, buffering low-temperature stress through its flexible molecular chains and significantly improving dimensional stability. Furthermore, compared to the comparative example, the above examples showed significant improvements in antibacterial effects and compressive strength retention.

[0148] The foamed materials prepared in Examples 1 to 5, as well as Examples 7 and 8, exhibit better antibacterial effects compared to Example 6 due to the use of a composite antibacterial agent. Furthermore, Examples 1 to 5, compared to Example 6, also reduce cell defects and achieve a higher level of surface bubble formation.

[0149] 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 foaming material, characterized in that, The foaming process is carried out using a composition comprising, by weight, 5-40 parts polyester polyol, 48-88 parts composite polyether polyol, 7-12 parts modifier, 10-55 parts foaming agent, 120-180 parts isocyanate, 0.3-6 parts water, and additives. The modified material includes one or more copolymers as shown in formula (I) and copolymers as shown in formula (II); ； ； Wherein, R1 and R3 are respectively selected from unsubstituted or substituted by at least one substituent C1-C30 aliphatic alkylene groups, unsubstituted or substituted by at least one substituent C1-C30 aliphatic alkylene oxygen groups, unsubstituted or substituted by at least one substituent aryl groups having 6 to 30 ring atoms, unsubstituted or substituted by at least one substituent aryl groups having 5 to 30 ring atoms, or combinations of these groups; each time the substituent appears, it is independently selected from deuterium, -NR z R m The R2 and R4 are selected from unsubstituted or substituted C1 to C30 aliphatic hydrocarbon groups. The R z and the R m The aliphatic chain hydrocarbon group selected independently from H, D, C1 to C30, aliphatic chain hydrocarbon oxygen group selected from C1 to C30, aliphatic cyclic hydrocarbon group with 3 to 30 ring atoms, aliphatic heterocyclic hydrocarbon group with 3 to 30 ring atoms, aryl group with 6 to 30 ring atoms, or heteroaryl group with 5 to 30 ring atoms. a, b, c, and d are all integers greater than 0.

2. The foamed material according to claim 1, characterized in that, The copolymer shown in formula (I) is formed by copolymerization of a first polymer and an unsubstituted or substituted aliphatic lactone ring having a ring number of 3 to 30 atoms, wherein the first polymer has the structure shown in formula (III). ； Wherein, R5 is selected from unsubstituted or substituted C1-C20 aliphatic alkylene groups, unsubstituted or substituted C1-C20 aliphatic alkylene groups, or combinations of these groups; n1 is 3-200. The copolymer shown in formula (II) is formed by copolymerization of a second polymer and an unsubstituted or substituted aliphatic lactone ring having a ring number of 3 to 30 atoms, wherein the second polymer has the structure shown in formula (IV). ； Wherein, R6 is selected from unsubstituted or substituted C1-C20 aliphatic alkylene groups, unsubstituted or substituted C1-C20 aliphatic alkylene oxygen groups, unsubstituted or substituted aryl groups having 6 to 20 ring atoms, or combinations of these groups; and n2 is 10 to 3000.

3. The foaming material according to claim 2, characterized in that, The first polymer is selected from one or more of glycerol polyether, pentaerythritol polyether, trimethylolpropane polyether, castor oil polyether, o-toluene diamine polyether, and polyethylene glycol monomethyl ether; The second polymer is selected from one or more of polylactic acid, polybutylene succinate, polyglycolic acid, polybutylene adipate, and phthalic anhydride polyester polyol; The aliphatic lactone ring is selected from one or more of δ-valerolactone, lactide, glycolide, and ε-caprolactone.

4. The foamed material according to claim 1, characterized in that, The adjuvant includes 0.1 to 2 parts of a composite antibacterial agent, which includes a silane coupling agent linked by oxygen atoms and an inorganic nano-antibacterial agent.

5. The foamed material according to claim 4, characterized in that, The silane coupling agent is selected from one or more of KH550, KH560, and A-171; The inorganic nano-antibacterial agent is selected from one or more of the following combinations: nano-silver and zinc oxide, nano-silver and titanium dioxide, zinc oxide and modified montmorillonite, nano-copper and graphene oxide; optionally, the inorganic nano-antibacterial agent is selected from nano-silver and zinc oxide in a mass ratio of 1:(2~5); The modified montmorillonite includes montmorillonite and one or more of the following: quaternary ammonium cations and inorganic antibacterial ions intercalated in the montmorillonite.

6. The foamed material according to claim 5, characterized in that, The quaternary ammonium cation is selected from one or more of hexadecyltrimethylammonium ion, octadecyldimethylbenzylammonium ion, and bis(octadecyldimethylammonium) ion, and the inorganic antibacterial ion is selected from one or more of silver ion, zinc ion, and copper ion.

7. The foamed material according to claim 1 or 4, characterized in that, The additives include 0.2 to 1.5 parts of a compound anti-aging agent, which comprises a hindered phenolic antioxidant and an ultraviolet absorber in a mass ratio of (2 to 4):

1.

8. The foamed material according to claim 7, characterized in that, The hindered phenolic antioxidant is selected from one or more of Irganox1098 and Irganox1010; The ultraviolet absorber is selected from one or more of Tinuvin 326 and Tinuvin 328.

9. The foamed material according to claim 7, characterized in that, The foaming agent includes one or more of hydrofluoroolefin foaming agents and alkane foaming agents.

10. The foamed material according to claim 9, characterized in that, The foaming agent comprises 20-50 wt% of the hydrofluoroolefin foaming agent and 50-80 wt% of the alkane foaming agent; Optionally, the hydrofluoroolefin blowing agent is selected from one or more of HFO-1234yf, HFO-1234ze(E), and trans-1,1,1,3-tetrafluoropropylene; Optionally, the alkane-based foaming agent is selected from one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclobutane, and cyclopentane.

11. The foamed material according to claim 9, characterized in that, The polyester polyol is selected from one or more of the following: adipic acid-ethylene glycol polyester polyol, adipic acid-propylene glycol polyester polyol, polycaprolactone (PCL) polyol, sebacic acid-ethylene glycol polyester polyol, terephthalic acid polyester polyol, and phthalic anhydride polyester polyol; and / or, The composite polyether polyol is selected from one or more of glycerol polyether, sucrose polyether, o-tolyl diamine polyether, pentaerythritol polyether, trimethylolpropane polyether, sorbitol polyether, ethylenediamine polyether, propylene glycol polyether, and ethylene glycol-propylene glycol copolymer polyether.

12. A refrigeration device, characterized in that, Includes the foaming material as described in any one of claims 1 to 11.

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