A composition, a method of producing a foamed material, a foamed material, and a refrigeration apparatus

Abstract

The application provides a composition, a foamed material preparation method, a foamed material and a refrigeration device. The composition comprises, by weight, 100 parts of a polyol, 45-55 parts of an isocyanate, 6 parts of a foaming agent and 2.9-4.4 parts of an auxiliary agent. The polyol comprises one or more of a cellulose-based polyol and a hemicellulose-based polyol. The polyol can replace a petrochemical-based polyol, and a foamed material with uniform cell structures can be prepared, which meets the requirements of environmental protection and mechanical properties.

Description

Technical Field

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

[0002] To address environmental concerns, bio-based polyols are being introduced to replace some petrochemical-based polyols. However, current bio-based substitution rates are low, with most technologies only achieving 30-60% partial substitution, still relying heavily on petrochemical raw materials and failing to achieve true environmental friendliness and low carbon emissions. Furthermore, the poor molecular structure regularity of bio-based materials results in insufficient mechanical properties in the prepared foams, limiting their application in load-bearing and thermal insulation applications. Summary of the Invention

[0003] The embodiments of this application provide a composition, a method for preparing a foaming material, a foaming material, and a refrigeration device, which can improve the technical problem that existing polyurethane materials are unable to meet the requirements of environmental protection and compression resistance.

[0004] In a first aspect, embodiments of this application provide a composition comprising, by weight, 100 parts of a polyol, 45-55 parts of an isocyanate, 6 parts of a foaming agent, and 2.9-4.4 parts of an additive. The polyols include one or more of cellulose-based polyols and hemicellulose-based polyols.

[0005] Secondly, embodiments of this application provide a method for preparing a foamed material, wherein the foamed material is prepared using the composition described above, and the preparation method includes the following steps: The polyol, the auxiliary agent, the isocyanate, and the foaming agent are taken according to the specified ratio; the polyol, the auxiliary agent, the isocyanate, and the foaming agent are mixed to obtain a composition; and, The composition is foamed and molded to obtain the foamed material; Mix 100 parts of polyol and 2.9 to 4.4 parts of additives, add 45 to 55 parts of isocyanate and 6 parts of foaming agent, mix, and foam to obtain foamed material; Optionally, the mixing step specifically includes: mixing the polyol and the additive at a speed of 800~1500 r / min, and adding the isocyanate and the foaming agent at a speed of 1000~1500 r / min.

[0006] Thirdly, embodiments of this application provide a foaming material prepared by foaming the composition as described above, or by preparing the foaming material using the method described above.

[0007] Fourthly, embodiments of this application provide a refrigeration device, including a housing and an insulation layer disposed within the housing, the insulation layer comprising the foaming material as described above.

[0008] The beneficial effects of the embodiments of this application are as follows: In the embodiments of this application, by selecting cellulose-based polyols and / or hemicellulose-based polyols as polyols, not only can petrochemical-based polyols in related technologies be completely replaced, but also foamed materials with uniform cell structure can be obtained by utilizing the complete molecular chains and high hydroxyl density of cellulose-based polyols and / or hemicellulose-based polyols, while meeting the requirements of environmental protection and mechanical properties. Detailed Implementation

[0009] 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.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] In this application, petrochemical-based polyols refer to polyols synthesized from petrochemical products (propylene, ethylene, benzene, formaldehyde, etc.) as raw materials.

[0014] In this application, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0015] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted.

[0016] The term "amino" refers to a group whose structure is considered as -NH2.

[0017] The term C2-C10 aliphatic hydrocarbons refers to aliphatic straight-chain hydrocarbons or aliphatic branched-chain hydrocarbons. The number of carbon atoms in a hydrocarbon compound can be, for example, 2 to 10, 2 to 8, 2 to 6, or 2 to 4, with examples being 2, 4, 6, 8, 10, or any two of the aforementioned values.

[0018] The technical solution of this application is as follows: In a first aspect, this application provides a composition comprising, by weight, 100 parts of a polyol, 45-55 parts of an isocyanate, 6 parts of a blowing agent, and 2.9-4.4 parts of an additive. The polyols include one or more of cellulose-based polyols and hemicellulose-based polyols.

[0019] It should be noted that cellulose-based polyols refer to compounds obtained from the alcoholysis of cellulose. Hemicellulose-based polyols refer to compounds obtained from the alcoholysis of hemicellulose.

[0020] Understandably, in related technologies, only a portion of petrochemical-based polyols can be replaced by bio-based polyols, making it impossible to achieve true environmental protection and low carbon emissions; furthermore, the hydroxyl groups of some bio-based materials have poor uniformity, resulting in insufficient mechanical properties of the prepared foam.

[0021] In this embodiment, by adding cellulose-based polyols and / or hemicellulose-based polyols to the composition, their regular molecular chains and high hydroxyl density enhance the reactivity with isocyanates, thereby improving the crosslinking density, cell uniformity, thermal insulation performance, and compressive strength of the resulting foamed material. Furthermore, the molecular chains of cellulose-based and hemicellulose-based polyols exhibit good biodegradability, enabling environmentally friendly closed-loop utilization of the material. This solves the problems of low bio-based material substitution rates and reliance on petrochemical raw materials in related technologies. In addition, related technologies also use lignin-based polyols to replace petrochemical-based polyols. Lignin-based polyols have stronger molecular chains, which not only easily increase the brittleness of the foamed material but also easily lead to a decrease in degradation rate and thermal insulation performance, and have lower reactivity with isocyanates. If all polyols in the polyurethane foaming system are petrochemical-based, compared to using all bio-based polyols in this embodiment, the resulting foamed material has poorer toughness, a higher carbon footprint, lower raw material costs, and lower biodegradability.

[0022] When using cellulose-based polyols or hemicellulose-based polyols alone, the mixture containing cellulose-based polyols and hemicellulose-based polyols obtained in other examples by reacting straw, alkali, aliphatic alcohols and phosphoric acid catalyst can be separated and used separately. The separation method can be a method disclosed in the art; or cellulose-based polyols and hemicellulose-based polyols that are directly available in the art can be used.

[0023] Using both cellulose-based and hemicellulose-based polyols simultaneously results in foamed materials that are less brittle and less prone to breakage compared to using cellulose-based polyols alone; and foamed materials that are stronger than those that use hemicellulose-based polyols alone.

[0024] In some examples, the number of parts of isocyanate may also be selected from the following values ​​or any range between any two of the following values: 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55. The number of parts of adjuvant may also be selected from the following values ​​or any range between any two of the following values: 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4.

[0025] In some embodiments, the polyol comprises the cellulose-based polyol and the hemicellulose-based polyol, wherein the mass ratio between the cellulose-based polyol and the hemicellulose-based polyol is (6~7):(3~4); And / or, the cellulose-based polyol and the hemicellulose-based polyol are prepared by reacting straw, alkali, aliphatic alcohols and a phosphoric acid catalyst; the aliphatic alcohols include C2-C10 aliphatic hydrocarbons substituted with at least two hydroxyl groups; And / or, the adjuvant includes a cross-linking agent, which includes a polysaccharide.

[0026] It should be noted that polysaccharides are polymeric high-molecular-weight carbohydrates formed by the glycosidic bonds formed by the dehydration condensation of multiple monosaccharide molecules. Polysaccharides have one or more of the following: aliphatic cyclic hydrocarbon groups with 5-6 ring atoms substituted by at least one substituent, and aliphatic heterocyclic hydrocarbon groups with 5-6 ring atoms substituted by at least one substituent. The substituents include one or more of hydroxyl and amino groups, and the heteroatoms in the heterocyclic hydrocarbon groups include oxygen atoms.

[0027] It is understandable that when a polyol contains both cellulose-based and hemicellulose-based polyols, controlling the ratio of the two within the above range will result in a foamed material with better overall performance.

[0028] Alkali breaks the chemical bonds between lignin and cellulose in straw, thereby disrupting the crystalline structure of hemicellulose and exposed cellulose. Cellulose and hemicellulose are degraded into polyhydroxyl oligools through alcoholysis with C2-C10 aliphatic hydrocarbons substituted with at least two hydroxyl groups and a phosphoric acid catalyst under heating. It is important to note that straw contains relatively little lignin, and the alcoholysis primarily forms small molecules with phenolic hydroxyl groups, contributing little to the reaction between polyols and isocyanates.

[0029] By incorporating the aforementioned polysaccharides into the additives, the substituents on the polysaccharide cyclic structure undergo a thorough cross-linking reaction with polyols and isocyanates, constructing a dense three-dimensional cross-linked network in the foam material and enhancing the bonding strength of the molecular chains. Based on the substitution of petrochemical-based polyols with cellulose-based and hemicellulose-based polyols, the mechanical properties of bio-based foams are improved, expanding their applications in thermal insulation and load-bearing. Compared to other inorganic fillers that easily degrade the thermal insulation performance of foams, such as calcium carbonate and glass fiber, chitosan, as a biodegradable material, significantly improves the degradation performance of foams while ensuring their thermal insulation properties, and also exhibits better compatibility with other materials.

[0030] In some examples, under the condition that the mass ratio of the cellulose-based polyol to the hemicellulose-based polyol is (6~7):(3~4), the value of the cellulose-based polyol within the above mass ratio range can also be the following values ​​or any range between any two of the following values: 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7. The value of the hemicellulose-based polyol within the above mass ratio range can also be the following values ​​or any range between any two of the following values: 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.7, 3.7, 3.8, 3.9, 4.

[0031] In some embodiments, the straw is selected from one or more of corn straw, wheat straw, rice straw, barley straw, and sorghum straw; And / or, the base is selected from one or more of sodium hydroxide and potassium hydroxide; And / or, the C2-C10 aliphatic hydrocarbon compound substituted with at least two hydroxyl groups is selected from one or more of ethylene glycol (CAS: 107-21-1), 1,2-propanediol (CAS: 57-55-6), 1,3-propanediol (CAS: 504-63-2), glycerol (CAS: 56-81-5), trimethylolpropane (CAS: 77-99-6), pentaerythritol (CAS: 115-77-5), sorbitol (CAS: 50-70-4), and mannitol (CAS: 69-65-3); And / or, the phosphoric acid catalyst is selected from one or more of phosphoric acid, pyrophosphoric acid (CAS: 2466-09-3), monoethyl phosphate (CAS: 1623-14-9), diethyl phosphate (CAS: 48042-47-3), and dibutyl phosphate (CAS: 1623-15-0); And / or, the mass ratio of the straw, the alkali, the aliphatic alcohol compound, and the phosphoric acid catalyst is (1~1.5):(0.8~2.7):1:(0.005~0.015); And / or, the crosslinking agent is selected from one or more of chitosan (CAS: 9012-76-4), pectin (CAS: 9000-69-5), sodium alginate (CAS: 9005-38-3), chitosan polysaccharide (CAS: 1398-61-4), heparin (CAS: 9005-49-6), hyaluronic acid (CAS: 9004-61-9), and chitosan oligosaccharide (CAS: 148411-57-8).

[0032] It is understood that by selecting the materials provided in this embodiment, straw is fully converted into bio-based polyols to better react with isocyanates.

[0033] The aforementioned straws can all be used to obtain cellulose-based polyols and hemicellulose-based polyols, reducing the requirements for raw material types and the cost of raw materials. The crosslinking agent is selected from the above materials. Utilizing the abundant amino and hydroxyl groups in these materials, a crosslinking reaction can occur with the hydroxyl groups on the polyols and the isocyanate groups of the isocyanates, forming a dense three-dimensional crosslinked network, significantly improving the compressive strength of the foam. The straw and polysaccharides provided in this embodiment are widely available, inexpensive, and have a simple preparation process, making them easy to industrialize and possessing good economic benefits and market application prospects.

[0034] Provided that the mass ratio of the straw, the alkali, the aliphatic alcohol compound, and the phosphoric acid catalyst is (1~1.5):(0.8~2.7):1:(0.005~0.015), the value of the straw within the above mass ratio range can also be the following values ​​or any two of the following values: 1, 1.1, 1.2, 1.3, 1.4, 1.5; the value of the alkali within the above mass ratio range can also be the following values ​​or any two of the following values: 0.8, 0. 9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7; The values ​​of phosphoric acid catalyst within the above mass ratio range can also be the following values ​​or any range between the following two values: 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015.

[0035] In some examples, the ratio of straw to alkali may also be the following ratios or a range between any two of the following ratios: 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8.

[0036] In some embodiments, the isocyanate comprises a bio-based isocyanate; optionally, the bio-based isocyanate is selected from lysine diisocyanate (CAS: 45172-15-4), 4,4'-diphenylmethane diisocyanate (CAS: 101-68-8), 1,5 One or more of the following: glutaraldehyde diisocyanate (source: Covestro Desmodur® eco73).

[0037] It should be noted that bio-based isocyanates are isocyanates containing isocyanate groups synthesized using renewable biomass (such as vegetable oils, amino acids, sugars, lignin, fermented amines, etc., but not limited to these) as raw materials, replacing the petroleum-based route.

[0038] Understandably, compared to traditional petrochemical-based isocyanates (such as MDI and TDI), bio-based isocyanates have better biocompatibility, further reducing the use of petrochemical raw materials, improving biodegradability, and being more compatible with other bio-based materials without affecting the performance of foamed materials.

[0039] In some embodiments, the additive includes 1-2 parts of the crosslinking agent, 0.4 parts of the catalyst, and 1.5-2 parts of the modified surfactant, wherein the modified surfactant is prepared by a bio-based polyether modified silane coupling agent; Optionally, the bio-based polyether is selected from one or more of soybean oil-derived polyether (CAS: 68122-67-8) and castor oil-based polyether (CAS: 61791-12-6); Optionally, the silane coupling agent is selected from one or more of KH-590 (CAS: 4420-74-0), KH-560 (CAS: 2530-83-8), and KH-550 (CAS: 919-30-2); Optionally, the catalyst includes an organobismuth catalyst and an amine catalyst; the organobismuth catalyst is selected from bismuth isooctanoate (CAS: 67874). 71 9) Bismuth neodecanoate (CAS: 34364) 26 6) Bismuth naphthenate (CAS: 85736) 59 One or more of the following (0), wherein the amine catalyst is selected from one or more of triethylenediamine (CAS: 280-57-9), dimethylcyclohexylamine (CAS: 98-94-2), N,N-dimethylbenzylamine (CAS: 103-83-3), 2,2'-dimorpholine diethyl ether (CAS: 6425-33-8), pentamethyldiethylenetriamine (CAS: 3030-47-5), and 1,4-diazabicyclo[2.2.2]octane (CAS: 280-57-9).

[0040] It should be noted that the modified surfactant is a polyether segment modified silane modified surfactant derived from renewable biomass (such as vegetable oils, starch fermentation products, etc., but not limited to these).

[0041] Bio-based polyethers are polyether polyols synthesized from renewable raw materials (vegetable oils, sugars, straw, lignin, bio-based propylene oxide), to distinguish them from petroleum-based polyethers.

[0042] It is understandable that using bio-based polyether-modified silane coupling agents improves the compatibility between bio-based materials and other materials.

[0043] Organic bismuth catalysts can precisely balance foaming and gelation rates, optimize cell structure, and improve foam stability and environmental friendliness. Selecting from the materials provided in this embodiment can better ensure compatibility and synergy with other materials.

[0044] In conjunction with other embodiments, this application bio-based polyols, isocyanates, modified surfactants, and crosslinking agents, while still ensuring good compatibility between the components of the composition. Without sacrificing other properties of the foaming material, it increases the bio-based content and composting degradation rate in the foaming material, achieving improvements in environmental protection, high strength, and heat insulation, and greatly reducing the use of petrochemical-based raw materials.

[0045] In some examples, the number of parts of the crosslinking agent may also be selected from the following values ​​or any range between any two of the following values: 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2. The number of parts of the modified surfactant may also be selected from the following values ​​or any range between any two of the following values: 1.5, 1.6, 1.7, 1.8, 1.9, 2.

[0046] In some embodiments, the modified surfactant may also be selected directly from one or more of Evonik Tego® Foamex 805 Bio, Momentive Niax® Silicone L-616 Bio, Mistex BD-8805 / BD-8810, and Mitsukoshi Chemical SY-6193 Bio.

[0047] It is understood that the materials selected from the above are those with high compatibility with other bio-based materials for foaming. Alternatively, the modified surfactant can be prepared using the methods provided in other embodiments.

[0048] In some embodiments, the GWP of the blowing agent is ≤15; optionally, the blowing agent is selected from one or more of isopentane (GWP=11), cyclopentane (GWP=15), HFO-1234yf (GWP=4, CAS:754-12-1), trans-HFO-1234ze (GWP=1, CAS:1645-83-6), and cis-HFO-1234ze (GWP=1, CAS:29118-24-9).

[0049] Understandably, while achieving foaming and ensuring good compatibility with other components, selecting a foaming agent with a GWP (Global Warming Potential) of 15 or below to replace traditional high-GWP foaming agents reduces the environmental impact of foaming agents. Specifically, the materials provided in this embodiment can be selected for better compatibility with other bio-based materials, resulting in a lower carbon footprint and being more low-carbon than petroleum-based raw materials.

[0050] In some examples, both isopentane and cyclopentane are bio-based raw materials; the bio-based raw materials for the foaming agent include, but are not limited to, corn stalks, wheat stalks, rice stalks, cotton stalks, soybean oil, rapeseed oil, palm oil, etc. The aforementioned bio-based raw materials can be used to prepare the foaming agent using techniques known in the art.

[0051] Secondly, embodiments of this application provide a method for preparing a foamed material, wherein the foamed material is prepared using the composition described above, and the preparation method includes the following steps: The polyol, the auxiliary agent, the isocyanate, and the foaming agent are taken according to the specified ratio; the polyol, the auxiliary agent, the isocyanate, and the foaming agent are mixed to obtain a composition; and, The composition is foamed and molded to obtain the foamed material; Mix 100 parts of polyol and 2.9 to 4.4 parts of additives, add 45 to 55 parts of isocyanate and 6 parts of foaming agent, mix, and foam to obtain foamed material; Optionally, the mixing step specifically includes: mixing the polyol and the additive at a speed of 800~1500 r / min, and adding the isocyanate and the foaming agent at a speed of 1000~1500 r / min.

[0052] It is understandable that polyols and additives are stirred at high speed to improve the dispersion of various components and avoid cell defects and reduced strength caused by uneven local concentrations in some combinations.

[0053] Adding isocyanate and foaming agent and stirring at high speed can generate stronger shear force, which can break the large bubbles formed by the foaming agent into tiny bubbles; it can also promote the uniform mixing of other components with the foaming agent, avoid bubble agglomeration, control the pores to remain in a small diameter range and be evenly distributed, and improve the thermal insulation performance of the foamed material.

[0054] In some examples, the stirring speed when mixing the 100 parts of polyol and the 2.9 to 4.4 parts of additives can also be the following values ​​or a range between any two of the following values: 800 r / min, 900 r / min, 1000 r / min, 1100 r / min, 1200 r / min, 1300 r / min, 1400 r / min, 1500 r / min. The stirring speed when mixing the 45 to 55 parts of isocyanate and the 6 parts of foaming agent can also be the following values ​​or a range between any two of the following values: 1000 r / min, 1100 r / min, 1200 r / min, 1300 r / min, 1400 r / min, 1500 r / min.

[0055] In some examples, the foaming temperature is 25~35℃. The foaming temperature can also be the following values ​​or any range between any two of the following values: 25℃, 26℃, 27℃, 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃, 35℃.

[0056] In some embodiments, the method for preparing polyols includes the following steps: The straw is mixed with alkali, and then a C2-C10 aliphatic hydrocarbon compound substituted with at least two hydroxyl groups and a phosphoric acid catalyst are added. The mixture is heated to obtain the polyol.

[0057] Understandably, alkali breaks the chemical bonds between lignin and cellulose in straw, thereby disrupting the crystalline structure of hemicellulose and exposed cellulose. Cellulose and hemicellulose are degraded into polyhydroxyl small-molecule oligools through alcoholysis with a phosphoric acid catalyst under heating, utilizing C2-C10 aliphatic hydrocarbons substituted with at least two hydroxyl groups. It is important to note that straw contains relatively little lignin, and after alcoholysis, it primarily forms small-molecule compounds with phenolic hydroxyl groups, contributing little to the reaction between polyols and isocyanates.

[0058] In some examples, the preparation method of polyols specifically includes the following steps: The straw is mixed with the alkali, and then the aliphatic alcohol compound and the phosphoric acid catalyst are added and heated to obtain the polyol. The heating temperature is 120~150℃.

[0059] It is understood that the heating range provided in this embodiment fully converts straw into bio-based polyols, thereby enabling better reaction with isocyanates.

[0060] In some examples, the heating temperature may also be the following values ​​or a range between any two of the following values: 120°C, 130°C, 140°C, 150°C.

[0061] In some specific examples, the preparation method of polyols includes the following steps: Crush straw and collect straw powder of 80-120 mesh. Add 10-15% sodium hydroxide aqueous solution for alkali treatment for 2-4 hours. The mass ratio of straw powder to sodium hydroxide aqueous solution is 1:(8-12). After filtration and washing until neutral, add C2-C10 aliphatic hydrocarbons substituted with at least two hydroxyl groups and phosphoric acid catalyst. Perform alcoholysis reaction at 120-150℃ for 3-5 hours. After cooling, filter to obtain polyol.

[0062] The mesh size of straw powder can also be the following values ​​or any range between the following two values: 80, 90, 100, 110, 120.

[0063] In some embodiments, the preparation method of the bio-based polyether modified silane coupling agent includes the following steps: A bio-based polyether, a silane coupling agent, and an organotin catalyst are mixed and heated to obtain the bio-based polyether-modified silane coupling agent. Wherein, the mass ratio of the bio-based polyether, the silane coupling agent, and the organotin catalyst is 100:(30~50):(0.1~0.5); and / or, the heating temperature is 70~90℃; and / or, the organotin catalyst is selected from one or more of dibutyltin dilaurate (CAS:77-58-7), dioctyltin dilaurate (CAS:3648-18-8), and stannous isooctanoate (CAS:301-08-6).

[0064] It is understandable that the de-alcoholization condensation of the siloxane alkyl group of the silane coupling agent with the hydroxyl group on the bio-based polyether is catalyzed by the organotin catalyst, thereby improving the compatibility of the bio-based polyether with other bio-based materials and stabilizing the cell structure.

[0065] In some examples, provided that the mass ratio of the bio-based polyether, the silane coupling agent, and the organotin catalyst is 100:(30~50):(0.1~0.5), the value of the silane coupling agent within the above mass ratio range can also be the following values ​​or any range between the following two values: 30, 35, 40, 45, 50. The value of the organotin catalyst within the above mass ratio range can also be the following values ​​or any range between the following two values: 0.1, 0.2, 0.3, 0.4, 0.5.

[0066] In some examples, the reaction time in the preparation method of the bio-based polyether modified silane coupling agent is 3-6 hours.

[0067] Thirdly, embodiments of this application provide a foaming material, which is obtained by foaming the composition as described above, or by preparing the foaming material as described above.

[0068] It is understandable that the foamed materials obtained by using the above-mentioned composition or preparation method have a high degree of cross-linking, good cell uniformity, good thermal insulation performance, strong compressive strength, and can also meet the environmental protection requirements of easy degradation.

[0069] In some embodiments, the foamed material obtained by using the stirring speed in the above preparation method can control the pore size to 50~100μm, thereby improving the thermal insulation performance of the foamed material.

[0070] Fourthly, embodiments of this application provide a refrigeration device, including a housing and an insulation layer disposed within the housing, the insulation layer comprising the foaming material as described above.

[0071] It is understandable that the use of the aforementioned foaming materials in the insulation layer of refrigeration equipment not only ensures the insulation performance but also meets the environmental protection and low-carbon requirements of refrigeration equipment, and allows refrigeration equipment to be applied in the field of load-bearing insulation, thus expanding its application scope.

[0072] The technical solutions and effects of this application will be described in detail below through specific preparation examples, embodiments and comparative examples. The following preparation examples and embodiments are only some of the preparation examples and embodiments of this application, and are not intended to limit this application in any specific way.

[0073] Preparation Example 1 Corn stalks were crushed and stalk powder in the range of 80-120 mesh was collected. A 12% sodium hydroxide aqueous solution was added for alkali treatment for 3 hours. The mass ratio of stalk powder to sodium hydroxide aqueous solution was 1:10. After filtration and washing until neutral, glycerol and pyrophosphate were added and reacted at 135℃ for 4 hours. After cooling to 25℃, the mixture was filtered to obtain a polyol containing cellulose-based polyol and hemicellulose-based polyol in a mass ratio of 2:1. The mass ratio of straw powder, glycerol and pyrophosphate is 1:1:0.005.

[0074] The polyol containing cellulose-based polyol and hemicellulose-based polyol in a mass ratio of 2:1 was added to isopropanol, stirred and dissolved, then allowed to stand, centrifuged, the precipitate was collected and vacuum dried to obtain cellulose-based polyol, and the supernatant was rotary evaporated to remove the solvent to obtain hemicellulose-based polyol.

[0075] Preparation Example 2 This application provides a modified surfactant and its preparation method, the preparation method including the following steps: 100g of epoxidized soybean oil (CAS: 8013-07-8) was dehydrated under vacuum at 105℃ for 2h, and then cooled to 80℃. 150mL of toluene was added, stirred and dissolved, and the mixture was protected with N2. 0.5g of ZnCl2 was added and stirred until dissolved. Then, 42.3g of KH-590 (CAS: 4420-74-0) was slowly added dropwise while the temperature was raised to 80℃ and the reaction was stirred under N2 for 4-6h. The mixture was then cooled to 25℃. Subsequently, 300mL of ethyl acetate was added for dilution, and the mixture was washed with 5% NaHCO3 aqueous solution until neutral. The mixture was then washed twice with water. The resulting organic phase was dried with anhydrous MgSO4 and filtered. The solvent was removed by distillation at 80℃ and 0.09MPa to obtain the modified surfactant.

[0076] Preparation Example 3 This application provides a lignin-based polyol and a method for its preparation. The preparation method includes the following steps: Lignin was pulverized and dried at 80°C for 2 hours. Lignin powder in the range of 80-120 mesh was collected and then mixed with glycerol at a mass ratio of 1:1.5. Phosphoric acid was added, and the mixture was stirred at 160°C under normal pressure for 3 hours. After cooling to 25°C, the mixture was filtered to obtain lignin polyether polyol. The mass ratio of lignin powder, glycerol, and phosphoric acid was 1:1:0.008.

[0077] Example 1 This application provides a foaming material and a method for preparing the same. The preparation method includes the following steps: S1. The polyol obtained in Preparation Example 1 was preheated to 45°C, the chitosan was pulverized and the powder with a mesh size greater than or equal to 200 mesh was collected. Then, 100 parts of polyol, 1 part of chitosan, 0.4 parts of bismuth isooctanoate and 1.5 parts of modified surfactant (from Preparation Example 2) were mixed and stirred at 1300 r / min for 12 min. S2. Add 45 parts of lysine diisocyanate and 6 parts of cyclopentane, and continue stirring for 20-30 seconds; pour into a mold, stir at 1300 r / min for 25 seconds, then foam at 30℃ for 4 minutes; cure in an oven at 45℃ for 18 hours to obtain the foamed material.

[0078] Example 2 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace 1 part chitosan in step S1 with 1.5 parts chitosan.

[0079] Example 3 This application provides a foaming material and its preparation method, which differs from Example 1 in that: Replace 1 part chitosan with 2 parts chitosan in step S1.

[0080] Example 4 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the 6 parts of cyclopentane in step S2 with HFC-365mfc (CAS:406-58-6).

[0081] Example 5 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the 1300 r / min rotation speed in step S1 with a 500 r / min rotation speed; Replace the 1300 r / min rotation speed in step S2 with a 500 r / min rotation speed.

[0082] Example 6 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the rotational speed of 1300 r / min in step S1 with a rotational speed of 1000 r / min; Replace the 1300 r / min rotation speed in step S2 with a 1000 r / min rotation speed.

[0083] Example 7 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the 1300 r / min rotation speed in step S1 with a 1500 r / min rotation speed; Replace the 1300 r / min rotation speed in step S2 with a 1500 r / min rotation speed.

[0084] Example 8 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the chitosan in step S1 with sodium alginate (CAS: 9005-38-3).

[0085] Example 9 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the lysine diisocyanate in step S2 with 4,4'-diphenylmethane diisocyanate.

[0086] Example 10 This application provides a foaming material and its preparation method, which differs from Example 2 in that: One portion of chitosan in step S1 is omitted.

[0087] Example 11 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the polyol in step S1 with a cellulose-based polyol.

[0088] Example 12 This application provides a foaming material and its preparation method, which differs from Example 2 in that: Replace the polyol in step S1 with a hemicellulose-based polyol.

[0089] Comparative Example 1 This application provides a foaming material and its preparation method as a comparative example, which differs from Example 2 in that: Replace the polyol obtained in Preparation Example 1 in step S1 with the lignin-based polyol obtained in Preparation Example 3.

[0090] Comparative Example 2 This application provides a foaming material and its preparation method as a comparative example, which differs from Example 2 in that: In step S1, replace 100 parts of the polyol obtained in Preparation Example 1 with 60 parts of the polyol obtained in Preparation Example 1 and 40 parts of Dow Voranol 360. Replace 45 parts of lysine diisocyanate in step S2 with 45 parts of pentamethylene diisocyanate (CAS: 28976-61-0).

[0091] Performance testing The foamed materials obtained in Examples 1 to 12 and Comparative Examples 1 to 2 were tested using the following methods, and the test results are shown in Table 1: Bio-based content: determined by radiocarbon dating in accordance with ASTM D6866-22 standard.

[0092] Compostable degradation rate: According to GB / T20197-2006 "Definition, classification, marking and degradation performance requirements of degradable plastics", the degradation rate was determined after 6 months of cultivation under composting conditions of 58±2℃ and 55±5%.

[0093] Compressive strength: According to GB / T8813-2022 "Determination of compressive properties of rigid foamed plastics", the maximum stress that the foamed material can withstand during the compression process is tested. The compression speed during the test is 2 mm / min, and the average value of the maximum stress of 5 parallel samples is calculated.

[0094] Average thermal conductivity: According to GB / T10294-2008 "Determination of steady-state thermal resistance and related properties of thermal insulation materials - protective hot plate method", the test temperature is 25℃.

[0095] GWP: Also known as Global Warming Potential, it is calculated based on the type and amount of foaming agent added, according to the method of the IPCC Sixth Assessment Report.

[0096] Cell diameter: Using scanning electron microscopy (SEM), the diameter of 50 cells was randomly measured on a flat cross-section of the foamed material and the average value was calculated.

[0097] Table 1:

[0098] As shown in Table 1: Compared to Comparative Examples 1 and 2, Examples 1 to 12 exhibit higher bio-based content and a higher 6-month compostable degradation rate in the foamed materials, indicating that the bio-based materials used in these examples contribute significantly to the degradation efficiency of the foamed materials. Examples 1 to 9 show higher compressive strength compared to Example 10, primarily because the use of a crosslinking agent increases the crosslinking density of the foamed materials made from bio-based materials, achieving compressive strength that is even higher than that of foamed materials made from a combination of petroleum-based and bio-based materials.

[0099] Compared with other examples and comparative examples, Example 5 has a higher thermal conductivity and a larger cell diameter, indicating that the rotational speed of the compositions in other examples and comparative examples during the mixing and foaming processes can improve the dispersion of each component, reduce the cell size, and thus reduce the thermal conductivity of the foamed material.

[0100] The embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A composition, characterized in that, It includes, by weight, 100 parts of polyol, 45-55 parts of isocyanate, 6 parts of foaming agent, and 2.9-4.4 parts of additives; The polyols include one or more of cellulose-based polyols and hemicellulose-based polyols.

2. The composition according to claim 1, characterized in that, The polyols include the cellulose-based polyols and the hemicellulose-based polyols, and the mass ratio between the cellulose-based polyols and the hemicellulose-based polyols is (6~7):(3~4); And / or, the cellulose-based polyol and the hemicellulose-based polyol are prepared by reacting straw, alkali, aliphatic alcohols and a phosphoric acid catalyst; the aliphatic alcohols include C2-C10 aliphatic hydrocarbons substituted with at least two hydroxyl groups; And / or, the adjuvant includes a cross-linking agent, which includes a polysaccharide.

3. The composition according to claim 2, characterized in that, The straw is selected from one or more of the following: corn straw, wheat straw, rice straw, barley straw, and sorghum straw. And / or, the base is selected from one or more of sodium hydroxide and potassium hydroxide; And / or, the aliphatic alcohol compound is selected from one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and mannitol; And / or, the phosphoric acid catalyst is selected from one or more of phosphoric acid, pyrophosphate, monoethyl phosphate, diethyl phosphate, and dibutyl phosphate; And / or, the mass ratio of the straw, the alkali, the aliphatic alcohol compound, and the phosphoric acid catalyst is (1~1.5):(0.8~2.7):1:(0.005~0.015); And / or, the crosslinking agent is selected from one or more of chitosan, pectin, sodium alginate, chitosan polysaccharide, heparin, hyaluronic acid, and chitosan oligosaccharide.

4. The composition according to any one of claims 1 to 3, characterized in that, The isocyanate includes a bio-based isocyanate; optionally, the bio-based isocyanate is selected from lysine diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5'-... One or more of glutaric diisocyanates.

5. The composition according to claim 4, characterized in that, The additives include 1-2 parts of the crosslinking agent, 0.4 parts of the catalyst, and 1.5-2 parts of the modified surfactant; The modified surfactant was prepared using a bio-based polyether-modified silane coupling agent; Optionally, the bio-based polyether is selected from one or more of soybean oil-derived polyether and castor oil-based polyether; Optionally, the silane coupling agent is selected from one or more of KH-590, KH-560, and KH-550; Optionally, the catalyst includes an organobismuth catalyst and an amine catalyst; the organobismuth catalyst is selected from one or more of bismuth isooctanoate, bismuth neodecanoate, and bismuth naphthenate, and the amine catalyst is selected from one or more of triethylenediamine, dimethylcyclohexylamine, N,N-dimethylbenzylamine, 2,2'-dimorpholine diethyl ether, pentamethyldiethylenetriamine, and 1,4-diazabicyclo[2.2.2]octane; Alternatively, the modified surfactant is selected from one or more of Evonik Tego® Foamex 805 Bio, Momentive Niax® Silicon L-616 Bio, Mistex BD-8805 / BD-8810, and Mitsukoshi Chemical SY-6193 Bio; And / or, the GWP of the foaming agent is ≤15; optionally, the foaming agent is selected from one or more of isopentane, cyclopentane, HFO-1234yf, cis-HFO-1234ze, and trans-HFO-1234ze.

6. A method for preparing a foamed material, characterized in that, The foamed material is prepared by using the composition according to any one of claims 1 to 5, wherein the preparation method includes the following steps: The polyol, the auxiliary agent, the isocyanate, and the foaming agent are taken according to the specified ratio, and the polyol, the auxiliary agent, the isocyanate, and the foaming agent are mixed to obtain a composition; as well as, The composition is foamed and molded to obtain the foamed material; Mix 100 parts of polyol and 2.9 to 4.4 parts of additives, add 45 to 55 parts of isocyanate and 6 parts of foaming agent, mix, and foam to obtain foamed material; Optionally, the mixing step specifically includes: mixing the polyol and the additive at a speed of 800~1500 r / min, and adding the isocyanate and the foaming agent at a speed of 1000~1500 r / min.

7. The method for preparing the foamed material according to claim 6, characterized in that, The preparation method of the polyol includes the following steps: The straw is mixed with the alkali, and then the aliphatic alcohol compound and the phosphoric acid catalyst are added and heated to obtain the polyol. The heating temperature is 120~150℃.

8. The method for preparing the foamed material according to claim 6, characterized in that, The preparation method of the bio-based polyether modified silane coupling agent includes the following steps: A bio-based polyether, a silane coupling agent, and an organotin catalyst are mixed and heated to obtain the bio-based polyether-modified silane coupling agent. Wherein, the mass ratio of the bio-based polyether, the silane coupling agent, and the organotin catalyst is 100:(30~50):(0.1~0.5); and / or, the heating temperature is 70~90℃; and / or, the organotin catalyst is selected from one or more of dibutyltin dilaurate (CAS:77-58-7), dioctyltin dilaurate (CAS:3648-18-8), and stannous isooctanoate (CAS:301-08-6).

9. A foaming material, characterized in that, It is prepared by foaming the composition according to any one of claims 1 to 5, or by the method for preparing foamed materials according to any one of claims 6 to 8.

10. A refrigeration device, characterized in that, It includes a housing and an insulation layer disposed within the housing, the insulation layer comprising the foaming material as described in claim 9.

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