Degradation method of polyurethane cold chain material and montmorillonite / polyurethane cold chain material

Abstract

The invention provides a degradation method of a polyurethane cold chain material and a montmorillonite / polyurethane cold chain material, and relates to the technical field of polyurethane materials. The degradation product polyol material is prepared from a component C and a component D according to a weight ratio of (1: 1)-(1: 10), wherein the component C comprises the following components in parts by weight: 0.1-10 parts of montmorillonite, 50-110 parts of a double-component alcoholysis agent and 5-30 parts of an auxiliary alcoholysis agent; and the component D is a polyurethane cold chain material. The montmorillonite is added in the degradation process of the waste polyurethane cold-chain material, so that the montmorillonite can be uniformly dispersed in a degradation product of the waste polyurethane cold-chain material, namely a recycled regenerated polyol material, the montmorillonite is promoted to toughen and reinforce the polyurethane cold-chain material in the re-preparation process of the polyurethane cold-chain material, and the effect can be better played.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane materials, in particular to a degradation method of polyurethane cold chain material and montmorillonite / polyurethane cold chain material. BACKGROUND

[0002] Polyurethane cold chain material is a new type of organic polymer material, which is a high-end cold chain material. Its products have various forms, including foamed plastic, elastomer, rubber, adhesive, fiber plastic, etc. Among them, polyurethane cold chain foam is the most widely used product of polyurethane cold chain material, accounting for more than 50% of the total amount of polyurethane products, and has occupied a stable market position in the field of cold chain material application. Polyurethane cold chain foam can be divided into three types according to its hardness: polyurethane soft foam, hard foam and semi-hard foam. Polyurethane soft foam is mainly used for cushions and handrails, polyurethane cold chain hard foam is mainly used for container refrigerators, gas storage tanks, underground gas storage, liquefied natural gas, pipelines, hydrates, compressed natural gas and other gas storage insulation and cold preservation fields, and polyurethane semi-hard foam is mainly used for making instrument panels, cushioning materials and automobile parts.

[0003] Polyurethane cold chain material has excellent cold preservation and waterproof functions, so it is widely used in various industries and fields, which has led to a serious increase in pollution of waste polyurethane cold chain material. The mass production and wide application of polyurethane cold chain material result in a large amount of polyurethane waste every year, including offcuts in production and various types of aging polyurethane cold chain material. These wastes are thermosetting polymer materials with cross-linked network structure, high cross-linking density, and high-density and high-energy carbon-nitrogen chemical bonds, which are difficult to depolymerize and cannot be simply remolded. They are not easily degraded in the natural environment, which not only brings enterprises the problem of solving waste polyurethane cold chain material pollution, but also seriously pollutes the environment. In China, the recoverable polyurethane cold chain foam waste can reach more than 2 million tons per year. Due to the defects of polyurethane cold chain waste recycling methods and utilization technology, a large amount of solid polyurethane cold chain waste material is discarded after simple treatment, or is buried or incinerated, which seriously damages the environment. Therefore, the treatment of waste polyurethane cold chain material has attracted widespread attention. The burial or incineration of solid waste plastic is prohibited, and energy saving and carbon reduction are advocated. Therefore, there is an urgent need for a method for reusing waste polyurethane cold chain material. SUMMARY

[0004] In view of the above analysis, the present application aims to provide a degradation method of polyurethane cold chain material and montmorillonite / polyurethane cold chain material, to solve at least one of the following problems: degradation and reuse of waste polyurethane cold chain material, reduction of environmental pollution, and improvement of the cold preservation performance of the prepared polyurethane cold chain material.

[0005] The purpose of the present application is mainly realized by the following technical solutions:

[0006] In a first aspect, the present application provides a degradation product polyol material, which is prepared by taking C component and D component as raw materials in a weight ratio of (1:1)-(1:10): the C component comprises the following components in weight fraction: montmorillonite: 0.1-10 parts, two-component alcoholysis agent: 50-110 parts, alcoholysis aid: 5-30 parts; the D component is a polyurethane cold chain material.

[0007] As a specific embodiment of the present application, the polyurethane cold chain material of the D component comprises one or more of polyurethane foam material, polyurethane composite board, polyurethane thermal insulation pipe, polyurethane heat conducting oil pipe, and polyurethane refrigerated truck compartment plate.

[0008] As a specific embodiment of the present application, the two-component alcoholysis agent in the C component comprises alcoholysis agent X and alcoholysis agent Y, wherein the weight ratio of the alcoholysis agent X to the alcoholysis agent Y is (10-90):(5-90).

[0009] As a specific embodiment of the present application, the alcoholysis agent X is selected from one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, pentanediol, butyne diol, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol, cyclohexanol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, decaglycol, prop-1,2-diol, prop-1,3-diol, but-1,3-diol, buten-1,4-diol, butyne-1,4-diol, pent-1,5-diol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 2-methylprop-1,3-diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, polypropylene glycol, dibutanediol, pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polybutanediol, and bis(hydroxymethyl)cyclohexane.

[0010] As a specific embodiment of the present application, the alcoholysis agent Y is selected from one or more of glycerol, trimethylolpropane, sorbitol, pentaerythritol, mannitol, erythritol, and lactitol.

[0011] As a specific embodiment of the present application, the alcoholysis aid is selected from one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-propanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, cyclohexylamine, tertiary amine, sodium hydroxide, potassium hydroxide, and titanium glycolate.

[0012] In a second aspect, the present application provides a method for degrading a polyurethane cold chain material, the degradation product of the method being the degradation product polyol material described above, the method comprising the following steps: S1: mixing montmorillonite, a two-component alcoholysis agent and an alcoholysis aid to obtain a mixed solution; S2: adding the polyurethane cold chain material which has been dried and crushed into a reaction kettle, and then adding the mixed solution obtained in step S1, and stirring under the condition of 130-220°C, and obtaining the degradation product polyol material after cooling to room temperature.

[0013] In a third aspect, the present application provides a montmorillonite / polyurethane cold chain material, which is prepared from a component A and a component B, wherein the weight ratio of the component A to the component B is (1:1)-(1:5): wherein the component A comprises the following components in parts by weight: degradation product polyol material: 1-50 parts, polyol: 0-40 parts, chain extension crosslinking agent: 1-15 parts, foaming agent: 4-35 parts, catalyst: 0.1-10 parts, and foam stabilizer: 0.1-10 parts; wherein the component B comprises isocyanate, and the degradation product polyol material in the component A is the degradation product polyol material described above or the degradation product polyol material prepared by the degradation method described above.

[0014] As a specific embodiment of the present application, the weight ratio of the component A to the component B is (1:1.5)-(1:2.5), and the component A comprises the following components in parts by weight: degradation product polyol material: 10-40 parts, polyol: 10-30 parts, chain extension crosslinking agent: 5-10 parts, foaming agent: 5-20 parts, catalyst: 1-5 parts, and foam stabilizer: 1-6 parts.

[0015] As a specific embodiment of the present application, the isocyanate in the component B is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, polyphenyl polymethylene polyisocyanate, and hexamethylene diisocyanate.

[0016] As a specific embodiment of the present application, the polyol in the component A is selected from one or more of polyether polyol or polyester polyol.

[0017] As a specific embodiment of the present application, the chain extension crosslinking agent is selected from one or more of glycerol, isosorbide, ethylene glycol, trimethylolpropane, 1,6-hexanediol, 4-cyclohexanediol, hydrogenated bisphenol A, 3,5-diamino-4-chlorobenzoic acid isobutyl ester, diethyl toluene diamine, 3,5-dimethylthio toluene diamine, sucrose, glucose, and 3,3-dichloro-4,4-diamino diphenyl methane.

[0018] As a specific embodiment of the present application, the blowing agent is selected from one or more of n-pentane, n-hexane, n-heptane, trichlorofluoromethane, monofluorodichloroethane, dichlorodifluoromethane, dichlorotetrafluoroethane, N,N-dinitrosopentamethylenetetramine, monochlorodifluoroethane, 1,1,1-trifluorodichloroethane, monochlorodifluoromethane, monofluorotrifluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,2-tetrafluoroethane, N,N-dimethyl-N,N-diphenylazomethine, azodicarbonamide, azobisisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazaminobenzene, water.

[0019] As a specific embodiment of the present application, the catalyst is selected from one or more of tris(dimethylaminopropyl)hexahydrotriazine, dimethylethanolamine, N,N,N',N",N"-pentamethyldiethylenetriamine, triethylenediamine, N,N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2,2'-dimorpholinodiethylether, N,N-dimethylbenzylamine, 3-propanolamine, N,N',N"-tetramethyl-1,6-hexanediamine, methyldiethanolamine, triethylamine, 1,2-dimethylimidazole, tetramethylethylenediamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, dimethylaminoethoxyethanol, N,N,N',N'-tetramethyl-1,3-propanamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, organotin, cyclohexylamine, propylbutane, triethanol diamine, triethanolamine, triethylamine, dibutyltin dilaurate, stannous octoate, potassium acetate, zinc acetate, calcium chloride, aluminum chloride, sodium hydroxide, or potassium hydroxide.

[0020] As a specific embodiment of the present application, the foam stabilizer is selected from one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, hexadecyl / octadecyl dimethyl tertiary amine, dodecyl / tetradecyl dimethyl tertiary amine, dimethylsiloxane, polydimethylsiloxane, or a modified product thereof.

[0021] In a fourth aspect, the present application provides a preparation method of a montmorillonite / polyurethane cold chain material, comprising the following steps: incubating a degradation product polyol material in an incubator at 40-50°C, stirring and mixing the degradation product polyol material with a polyol, a chain extender, a blowing agent, a catalyst, and a foam stabilizer to obtain component A, mixing and stirring component A with component B comprising isocyanate to obtain the montmorillonite / polyurethane cold chain material.

[0022] Advantages

[0023] (1) The present application degrades waste polyurethane cold chain materials to obtain a degradation product polyol material, which can be further used as a raw material for other chemical production, realizing the reuse of waste polyurethane cold chain materials and reducing environmental pollution.

[0024] (2) The present application degrades waste polyurethane cold chain materials using a two-component alcoholysis agent, and the obtained degradation product polyol material is applied to the downstream of the polyurethane cold chain material field to prepare new products. This not only solves the problems of harsh environment and high energy consumption in traditional material preparation, but also prepares products with low price and excellent performance, and can respond to the relevant policies of the state to protect the environment and achieve green environmental protection.

[0025] (3) The present application adds montmorillonite in the degradation process of waste polyurethane cold chain materials, so that it can be uniformly dispersed in the degradation product of waste polyurethane cold chain materials, i.e. recycled regenerated polyol material, to promote the toughening and strengthening of montmorillonite in the preparation process of polyurethane cold chain materials, and better play its role; the functional groups on the surface of montmorillonite, such as hydroxyl groups, form new links with the hydroxyl compounds containing benzene rings in the degradation product of waste polyurethane cold chain materials, i.e. the A component with hard segments (such as benzene rings) links montmorillonite, forming a new rigid structure, which further reacts with isocyanate, making isocyanate intercalate in the rigid structure linked by montmorillonite, which is beneficial to its secondary dispersion; in addition, montmorillonite is also embedded in the prepared polyurethane system to form a new cold chain material, which enhances and toughens the strength and rigidity of the polyurethane hard segment, supports the rigid structure of the polyurethane foam, makes the structure more stable, and makes the new cold chain material have better cold preservation effect.

[0026] (4) The method and material provided by the present application, montmorillonite is a solid powder, its addition will make the pore diameter of the prepared polyurethane cold chain material smaller, because the polyurethane foaming process needs to nucleate first and then grow, montmorillonite can act as a nucleating agent to promote the foaming of polyurethane, so the pore diameter becomes smaller and the number becomes more; in addition, the carbon atoms of montmorillonite form a two-dimensional honeycomb structure material in sp2 hybridization mode, which has a special monatomic layered structure, making it have excellent thermal and mechanical properties, the prepared polyurethane cold chain has a benzene ring rigid three-branching structure, the addition of montmorillonite can greatly improve the skeleton strength of the polyurethane cold chain material; montmorillonite is a sheet-like nanomaterial, its addition makes the structure of the cold chain material toughened and strengthened, improves the cold preservation performance, wear resistance, corrosion resistance and service life of the cold chain material, and increases the specific strength.

[0027] (5) The montmorillonite added in the degradation process of waste polyurethane cold chain materials of the present invention contains a large number of hydroxyl functional groups like the alcoholysis agent. Compared with the alcoholysis agent, the introduction of the montmorillonite structure brings a hard segment structure that can link the small molecule prepolymer of the alcoholysis agent. Montmorillonite is a rigid structure. The hard segment formed by the hard segment linking the small molecule alcohol prepolymer can form a system with good compatibility between the functional groups on the surface and the hydroxyl compounds of the small molecule alcohol, so that the small molecule alcohol is interspersed between the montmorillonites, which is beneficial to the dispersion of montmorillonite and the formation of a good compatibility and synergistic effect between montmorillonite and the alcoholysis agent. In this way, the montmorillonite and the alcoholysis agent are constructed into a uniformly dispersed degradation system, which has a synergistic promoting effect on the degradation of waste polyurethane cold chain materials and product enhancement.

[0028] (6) The present invention adds a dihydric alcoholysis agent during the degradation process of waste polyurethane cold chain materials, and promotes the formation of a cross-linked mesh layered structure of the re-prepared polyurethane by adding montmorillonite, so that the prepared polyurethane cold chain material has good tortuosity to gas, thereby improving the barrier property, greatly reducing the thermal conductivity of polyurethane, improving the cold insulation performance, and further improving the compressive strength of polyurethane. Among them, the alcoholysis agent X is a small molecule alcohol, does not contain an acrylate group, has a low molecular weight, and has better fluidity. The alcoholysis agent Y is a polyhydroxy compound, which is beneficial to the dispersibility and compatibility of montmorillonite with a large number of hydroxyl groups. The alcoholysis agent Y has a branched structure. The hydroxyl groups introduced on the branch can react with isocyanate during the foaming process to generate more carbamate groups. In addition, the alcoholysis agents X, Y, and montmorillonite synergistically promote the formation of more cross-linked mesh structures in the polyurethane molecules, thereby improving its compressive strength and cold insulation performance.

[0029] (7) The present invention degrades waste polyurethane cold chain materials by mixing montmorillonite with an alcoholysis agent to obtain a polyol material. The obtained polyol is evenly mixed with a chain extender, a foaming agent, a foam stabilizer, and a catalyst to form component A, and foamed with isocyanate. The toughness, compressive strength, and cold-keeping performance of the obtained montmorillonite / waste polyurethane cold chain material are greatly improved, and the cold-keeping performance is excellent. The thermal conductivity, apparent density, and water absorption rate are all higher than the national standards.

[0030] Therefore, the present invention has strong practicality for the comprehensive utilization of waste in the entire polyurethane industry, realizes the intelligent recycling and circular utilization of waste, conforms to the development of circular economy, and brings high benefits to the economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Thermogravimetric (TG) curves of the polyurethane cold chain materials prepared in the embodiments and comparative examples provided by the present invention.

[0032] Figure 2 This is an infrared characterization diagram of the degradation product polyol material of the examples and comparative examples provided by the present invention.

[0033] Figure 3 Microscope images of the cell structure of the polyurethane cold chain material prepared in the examples and comparative examples of the present application.

[0034] Figure 4 Infrared spectrum of the montmorillonite / polyurethane cold chain material provided in the present application. DETAILED DESCRIPTION

[0035] Hereinafter, the present application will be described in detail. Before proceeding, it should be understood that the terms used in the specification and the appended claims should not be construed as limiting to the general and dictionary meanings and should be construed as carrying the meaning and concepts that are consistent with the technical scope of the present application based on the principles of the inventor's intention to appropriately define the terms in order to describe the best explanation. Therefore, the description presented herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the present application and it should be understood that other equivalent ways or modifications can be derived from the application without departing from the spirit and scope of the present application.

[0036] The present application modifies the waste polyurethane cold chain material using montmorillonite nanomaterials. Montmorillonite has good thermal stability and other properties. The factors of thermal stability of montmorillonite mainly include the structure of montmorillonite itself, the density and uniformity of the interlayer column, and the interaction between the interlayer and the column. Montmorillonite has high thermal stability, and the crystal structure of montmorillonite collapses at 700℃. In addition, montmorillonite has chemical stability and does not react with strong bases, strong acids, strong oxidants and strong reducing agents. Montmorillonite is non-toxic, non-corrosive, non-irritating and does not cause secondary pollution, and can be used for nanomaterial modified polymers, soil conditioners and other applications.

[0037] In a first aspect, the present application provides a degradation product polyol material prepared from C component and D component as raw materials in a weight ratio of (1:1)-(1:10):

[0038] The C component includes the following components in parts by weight:

[0039] Montmorillonite: 0.1-10 parts,

[0040] Bicomponent alcoholysis agent: 50-110 parts,

[0041] Alcoholysis aid: 5-30 parts;

[0042] The D component is a waste polyurethane cold chain material.

[0043] It should be noted that the waste polyurethane cold chain material is degraded in the present application, and a polyol material is obtained as a degradation product, which can be further used as a raw material for other chemical production, realizing the reuse of the waste polyurethane cold chain material and reducing the pollution to the environment.

[0044] As a specific embodiment of the present application, the polyurethane cold chain material of the D component includes one or more of polyurethane foam material, polyurethane composite board, polyurethane insulation pipe, polyurethane heat conducting oil pipe, and polyurethane refrigerated truck compartment plate.

[0045] It should be noted that the polyurethane cold chain material of the present application is different from general polyurethane (PUR) material, and is a modified polyurethane material containing a polyisocyanurate ring in the molecular structure, which can be called polyisocyanurate material, and is abbreviated as PIR. PIR contains urethane groups and isocyanurate groups. Compared with the urethane bond in PUR, the unique six-membered isocyanurate ring structure of PIR makes it have a higher crosslinked network structure. In addition, the isocyanate used in polyisocyanurate is mainly aromatic polyisocyanate. The polyisocyanurate formed by aromatic isocyanate contains a large number of rigid benzene rings, and has high crosslinking density. Generally, it refers to a three-branched crosslinking structure and a polyurethane crosslinked network structure above. PIR belongs to waste high-crosslinking cold chain foam, has low thermal conductivity and high thermal stability, and is widely used in chemical industry, transportation, building board, aviation and other fields.

[0046] As a specific embodiment of the present application, the two-component alcoholysis agent in the C component includes alcoholysis agent X and alcoholysis agent Y, and the weight ratio of alcoholysis agent X to alcoholysis agent Y is (10-90):(5-90).

[0047] As a specific embodiment of the present application, the alcoholysis agent X can be selected from one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, pentylene glycol, butyne diol, GR-450A, GR-649, PEG-200, GR-8340A, GR-835G, GRA-6360, PEDA-1500, PEBA-2000, PEDA-2000, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, cyclohexanol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, decaglycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5-diol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, bis(hydroxymethyl)cyclohexane such as 1,4-(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, polypropylene glycol, dibutylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polybutylene glycol. It should be noted that the alcoholysis agent X is a small molecule alcohol, does not contain an acrylate group, has a low molecular weight, and has better flowability.

[0048] As a specific embodiment of the present application, the alcoholysis agent Y is selected from one or more of glycerol, trimethylolpropane, sorbitol, pentaerythritol, mannitol, erythritol, and lactitol. It should be noted that the alcoholysis agent Y is a polyhydroxy compound, which is beneficial to the dispersibility and compatibility of the montmorillonite with a large number of hydroxyl groups.

[0049] As a specific embodiment of the present application, the co-alcoholysis agent is selected from one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-propanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, cyclohexylamine, tertiary amine, sodium hydroxide, potassium hydroxide, and titanium glycolate.

[0050] As a specific embodiment of the present application, the weight ratio of the C component and the D component is (1:1)-(1:5), the weight fraction of the montmorillonite is 2-5 parts, the weight fraction of the two-component alcoholysis agent is 60-80 parts, and the weight fraction of the co-alcoholysis agent is 10-20 parts.

[0051] It should be noted that, in the degradation process of the waste polyurethane cold chain material, the montmorillonite is added, so that the montmorillonite can be uniformly dispersed in the waste polyurethane cold chain material degradation product, i.e. the above-mentioned degradation product polyol material, the functional groups on the surface of the montmorillonite form new links with the benzene ring-containing hydroxyl compounds in the waste polyurethane cold chain material degradation product, forming a new rigid structure, so that the performance of the degradation product polyol material is improved, and the montmorillonite and the alcoholysis agent have good compatibility and synergistic effect, so that the montmorillonite and the alcoholysis agent form a uniformly dispersed degradation system, which has a synergistic promoting effect on the degradation of the waste polyurethane cold chain material and the product enhancement.

[0052] In a second aspect, the present application provides a degradation method of a polyurethane cold chain material, comprising the following steps:

[0053] S1: mixing montmorillonite, two-component alcoholysis agent and alcoholysis aid, ultrasonic oscillation for 1-5h to mix uniformly, to obtain a mixed solution;

[0054] S2: adding the dried and crushed polyurethane cold chain material into a reaction kettle, then adding the mixed solution obtained in step S1, stirring at 130-220℃ for 1-5 hours, and obtaining a reusable degradation product polyol material after cooling to room temperature.

[0055] As a specific embodiment of the present application, in step S1, the montmorillonite is added in the degradation process of the waste polyurethane cold chain material, i.e. the montmorillonite is added to the alcoholysis agent and the alcoholysis aid for ultrasonic dispersion treatment.

[0056] As a specific embodiment of the present application, in step S2, the size of the crushed polyurethane cold chain material can be up to 10mm, and the method provided by the present application has low requirements on the crushing effect and saves cost.

[0057] As a specific embodiment of the present application, in step S2, the heating method is conventional heating, which does not require expensive equipment.

[0058] In a third aspect, the present application provides a montmorillonite / polyurethane cold chain material, which is prepared from A component and B component as raw materials, wherein the weight ratio of the A component to the B component is (1:1)-(1:5).

[0059] The A component comprises the following components by weight:

[0060]

[0061] The B component comprises isocyanate, and the degradation product polyol material of the A component is the degradation product polyol material described above.

[0062] It should be noted that the montmorillonite / polyurethane cold chain material provided by the present application is obtained by reacting the degradation product polyol material with isocyanate, taking montmorillonite as a hard segment, and inserting isocyanate into the rigid structure linked by montmorillonite, which is beneficial to the secondary dispersion of the isocyanate, and in addition, the montmorillonite is also embedded in the polyurethane system to form a new cold chain material, which enhances and toughens the strength and rigidity of the polyurethane hard segment, supports the more stable rigid structure of the polyurethane foam, and makes the new cold chain material have better cold preservation effect.

[0063] As a specific embodiment of the present application, the isocyanate of the B component is selected from one or more of diphenylmethane diisocyanate (MDI) (MDI-100LL, MDI-100HL, MR-200, M200, 44V20, M20S, 5005), toluene diisocyanate (TDI) (TDI80 / 20, TDI100), polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27, PAPI-135C), hexamethylene diisocyanate (HDI).

[0064] As a specific embodiment of the present application, the weight ratio of the A component to the B component can be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, etc. As preferred, the weight ratio of the A component to the B component is (1:1.5)-(1:2.5), and the A component includes the following components by weight: degradation product polyol material: 10-40 parts, polyol: 10-30 parts, chain extension crosslinking agent: 5-10 parts, foaming agent: 5-20 parts, catalyst: 1-5 parts, and foam stabilizer: 1-6 parts.

[0065] As a specific embodiment of the present application, the polyol in the A component can be a polyether polyol or a polyester polyol, and the polyether polyol can be polyether polyol 4110.

[0066] As a specific embodiment of the present application, the chain extension crosslinking agent in the A component is selected from one or more of glycerol, isosorbide, ethylene glycol, glycerol, trimethylolpropane, 1,6-hexanediol, 4-cyclohexanediol, hydrogenated bisphenol A, 3,5-diamino-4-chlorobenzoic acid isobutyl ester, diethyl toluene diamine, 3,5-dimethylthio toluene diamine, sucrose, glucose, 3,3-dichloro-4,4-diamino diphenyl methane.

[0067] As a specific embodiment of the present application, the blowing agent in the A component is selected from one or more of n-pentane, n-hexane, n-heptane, trichlorofluoromethane, monofluorodichloroethane, dichlorodifluoromethane, dichlorotetrafluoroethane, N,N-dinitrosopentamethylenetetramine (DPT), monochlorodifluoroethane, 1,1,1-trifluorodichloroethane, monochlorodifluoromethane, monofluorotrifluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,2-tetrafluoroethane, N,N-dimethyl-N,N-diphenyltartardiamide (NTA), azodicarbonamide (ADC), azobisisobutyronitrile, azodiisopropylxanthate, diethyl azodicarboxylate, diazaminobenzene, and water.

[0068] As a specific embodiment of the present application, the catalyst in the A component is selected from one or more of tris(dimethylaminopropyl)hexahydrotriazine, dimethylethanolamine, N,N,N',N",N"-pentamethyldiethylenetriamine, triethylenediamine, N,N-dimethylpiperazine, diethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2,2'-dimorpholinodiethylether, N,N-dimethylbenzylamine, N,N',N"-tetramethyl-1,6-hexanediamine, methyldiethanolamine, triethylamine, 1,2-dimethylimidazole, tetramethylethylenediamine, N,N-dimethylethanolamine, 3-propanolamine, N,N-diethylethanolamine, dimethylaminoethoxyethanol, N,N,N',N'-tetramethyl-1,3-propanamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, organotin, cyclohexylamine, propylbutane, triethanol diamine or a solution thereof, triethanolamine, triethylamine, dibutyltin dilaurate, stannous octoate, potassium acetate, zinc acetate, calcium chloride, aluminum chloride, sodium hydroxide, or potassium hydroxide.

[0069] As a specific embodiment of the present application, the foam stabilizer in the A component is selected from one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, cetylstearyl dimethyl tertiary amine, lauryl / myristyl dimethyl tertiary amine, dimethylsiloxane, polydimethylsiloxane, or a modified product thereof such as an alkylene oxide-modified polydimethylsiloxane.

[0070] In a fourth aspect, the present application provides a preparation method of a montmorillonite / polyurethane cold chain material, comprising the following steps:

[0071] The degradation product polyol material is kept in a thermostat at 40-50℃, the prepared degradation product polyol material is uniformly stirred and mixed with polyol, chain extender, foaming agent, catalyst and foam stabilizer to obtain component A, the stirring time is 10-25 min, isocyanate is used as component B, component A is mixed with component B and stirred, the stirring time is 10-25 s, and the montmorillonite / polyurethane cold chain material is obtained.

[0072] It should be noted that the montmorillonite is added in the degradation process of the waste polyurethane cold chain material, which greatly improves the rigid hard segment strength of the polyurethane degradation monomer, improves the crosslinking density of the monomer in the network structure of the waste polyurethane cold chain foaming material, and the reagent used is a non-toxic, harmless, safe and reliable small molecule alcohol substance, which is green and environmentally friendly. The preparation method described in the present application has simple processing technology and is easy to operate, and can be put into production. The prepared montmorillonite / polyurethane cold chain material has excellent cold preservation performance, greatly improved thermal conductivity, compressive strength, and apparent density and water absorption rate, which are all higher than the national standard. The preparation method described in the present application has no "three wastes" emission in the preparation process, is green and environmentally friendly, the recycling rate of the waste polyurethane cold chain foaming material is close to 100%, and the degradation product does not need subsequent treatment and can be directly used, which greatly reduces the cost of the polyurethane rigid cold chain product.

[0073] The present application will be further described below in conjunction with specific examples, but does not constitute any limitation on the present application.

[0074] Example 1

[0075] In a first aspect, a degradation product polyol material is prepared from components C and D with a weight ratio of 1:10 as raw materials:

[0076] The weight fractions of the components in component C are as follows:

[0077] Montmorillonite: 0.1 parts,

[0078] Butanediol (alcoholysis agent X): 50 parts,

[0079] Pentaerythritol (alcoholysis agent Y): 50 parts

[0080] Diethanolamine (co-alcoholysis agent): 5 parts;

[0081] Component D is waste polyurethane cold chain material.

[0082] In a second aspect, a degradation method of a polyurethane cold chain material includes the following steps: S1: mixing montmorillonite with butanediol, pentaerythritol and diethanolamine, ultrasonic oscillation for 2 h to obtain a mixed solution; S2: adding waste polyurethane cold chain material into a reaction kettle, then adding the mixed solution obtained in step S1, stirring at 190℃ for 2 hours, and cooling to room temperature to obtain a degradation product polyol material.

[0083] In a third aspect, a montmorillonite / polyurethane cold-chain material is prepared from a component A and a component B, wherein the weight ratio of the component A to the component B is 1:1.5; wherein the component B is a polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0084] wherein the component A comprises the following components in parts by weight:

[0085] degradation product polyol material: 50 parts,

[0086] glycerol (chain extension crosslinking agent): 10 parts,

[0087] monofluorodichloroethane (blowing agent): 5 parts,

[0088] N,N-dimethylethanolamine (catalyst): 0.3 parts,

[0089] silicone oil CGY-5 (foam stabilizer): 0.1 parts.

[0090] In a fourth aspect, a method for preparing a montmorillonite / polyurethane cold-chain material comprises the following steps: uniformly stirring a degradation product polyol material with glycerol, monofluorodichloroethane, N,N-dimethylethanolamine, and silicone oil CGY-5, and then stirring the mixture with PAPI-27 for 15 seconds to make it foam, and cooling to obtain the montmorillonite / polyurethane cold-chain material.

[0091] Example 2

[0092] In a first aspect, a degradation product polyol material is prepared from a component C and a component D at a weight ratio of 1:1:

[0093] The weight parts of each component in the component C are as follows:

[0094] montmorillonite: 5 parts,

[0095] 1,3-butanediol (alcoholysis agent X): 60 parts,

[0096] pentaerythritol (alcoholysis agent Y): 30 parts

[0097] 3-propanolamine (co-alcoholysis agent): 7 parts;

[0098] The component D is a waste polyurethane cold-chain material.

[0099] In a second aspect, a method for degrading a polyurethane cold-chain material comprises the following steps: S1: mixing montmorillonite with 1,3-butanediol, pentaerythritol, and 3-propanolamine, and ultrasonically oscillating for 2 hours to obtain a mixed solution; S2: adding a waste polyurethane cold-chain material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 180°C for 1.5 hours, and cooling to room temperature to obtain a degradation product polyol material.

[0100] In a third aspect, a montmorillonite / polyurethane cold-chain material is prepared from a component A and a component B, wherein the weight ratio of the component A to the component B is 1:2; wherein the component B is a polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0101] The component A comprises the following components in parts by weight:

[0102] Degradation product polyol material: 40 parts,

[0103] Polyester polyol: 10 parts,

[0104] 1,6-hexanediol (chain extender): 2 parts,

[0105] Chlorodifluoroethane (blowing agent): 5 parts,

[0106] N,N-diethylethanolamine (catalyst): 1 part,

[0107] Silicone oil CGY-5 (foam stabilizer): 1 part.

[0108] In a fourth aspect, a method for preparing a montmorillonite / polyurethane cold-chain material comprises the following steps: uniformly stirring a degradation product polyol material with a polyester polyol, 1,6-hexanediol, chlorodifluoroethane, N,N-diethylethanolamine, and silicone oil CGY-5, and then stirring with PAPI-27 for 17 s to make it foam, and cooling to obtain the montmorillonite / polyurethane cold-chain material.

[0109] Example 3

[0110] In a first aspect, a degradation product polyol material is prepared from a component C and a component D at a weight ratio of 1:3:

[0111] The weight parts of each component in the component C are as follows:

[0112] Montmorillonite: 5 parts,

[0113] Triethylene glycol (alcoholysis agent X): 70 parts,

[0114] Pentaerythritol (alcoholysis agent Y): 35 parts

[0115] Monoethanolamine (co-alcoholysis agent): 7 parts;

[0116] The component D is a waste polyurethane cold-chain material.

[0117] The second aspect is a degradation method of a polyurethane cold chain material, comprising the following steps: S1: mixing montmorillonite with triethylene glycol, pentaerythritol and monoethanolamine, and preparing a mixed solution after ultrasonic oscillation for 2h; S2: adding waste polyurethane cold chain material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 195℃ for 1h, and obtaining a degradation product polyol material after cooling to room temperature.

[0118] The third aspect is a montmorillonite / polyurethane cold chain material prepared from A component and B component as raw materials, wherein the weight ratio of the A component to the B component is 1:2.1; wherein the B component is polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0119] The A component comprises the following components in parts by weight:

[0120] The degradation product polyol material: 30 parts,

[0121] The polyester polyol: 5 parts,

[0122] The isosorbide (chain extension crosslinking agent): 3 parts,

[0123] The monofluorodichloroethane (blowing agent): 5 parts,

[0124] The 3-propanolamine (catalyst): 2 parts,

[0125] The silicone oil L-600 (foam stabilizer): 2 parts.

[0126] The fourth aspect is a preparation method of a montmorillonite / polyurethane cold chain material, comprising the following steps: uniformly stirring the degradation product polyol material, the polyester polyol, the isosorbide, the monofluorodichloroethane, the 3-propanolamine and the silicone oil L-600, and then stirring the PAPI-27 for 19s to make it foam, and cooling to obtain the montmorillonite / polyurethane cold chain material.

[0127] Example 4

[0128] The first aspect is a degradation product polyol material prepared from the C component and the D component as raw materials with a weight ratio of 1:2:

[0129] The weight parts of each component in the C component are as follows:

[0130] The montmorillonite: 2 parts,

[0131] The diethylene glycol (alcoholysis agent X): 80 parts,

[0132] The pentaerythritol (alcoholysis agent Y): 15 parts

[0133] The mono-isopropanolamine (alcoholysis aid): 7 parts;

[0134] The D component is waste polyurethane cold chain material.

[0135] In a second aspect, a method for degrading polyurethane cold chain material includes the following steps: S1: mixing montmorillonite with diethylene glycol, pentaerythritol and monoisopropanolamine, and preparing a mixed solution after ultrasonic oscillation for 2 hours; S2: adding waste polyurethane cold chain material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 185℃ for 3 hours, and obtaining a degradation product polyol material after cooling to room temperature.

[0136] In a third aspect, a montmorillonite / polyurethane cold chain material is prepared from a component A and a component B, wherein the weight ratio of the component A to the component B is 1:2.2; wherein the component B is a polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0137] The component A includes the following components in parts by weight:

[0138] The degradation product polyol material: 20 parts,

[0139] Polyether polyol 4110: 20 parts,

[0140] Glycerol (chain extender): 3 parts,

[0141] 1,1,1-trifluorodichloroethane (blowing agent): 11 parts,

[0142] Propyl butane (catalyst): 2 parts,

[0143] Silicone oil L-600 (foam stabilizer): 3 parts.

[0144] In a fourth aspect, a method for preparing a montmorillonite / polyurethane cold chain material includes the following steps: uniformly stirring a degradation product polyol material with polyether polyol 4110, glycerol, 1,1,1-trifluorodichloroethane, propyl butane, and silicone oil L-600, and then stirring with PAPI-27 for 21 seconds to make it foam, and cooling to obtain the montmorillonite / polyurethane cold chain material.

[0145] Example 5

[0146] In a first aspect, a degradation product polyol material is prepared from a component C and a component D with a weight ratio of 1:5:

[0147] The weight parts of each component in the component C are as follows:

[0148] Montmorillonite: 2 parts,

[0149] Triethylene glycol (alcoholysis agent X): 90 parts,

[0150] Pentaerythritol (alcoholysis agent Y): 10 parts,

[0151] Titanium glycol (auxiliary alcoholysis agent): 14 parts;

[0152] D component is waste polyurethane cold chain material.

[0153] The second aspect is a degradation method of polyurethane cold chain material, comprising the following steps: S1: mixing montmorillonite with triethylene glycol, pentaerythritol and titanium glycolate, and preparing a mixed solution after ultrasonic oscillation for 3h; S2: adding waste polyurethane cold chain foaming material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 200℃ for 1h, and obtaining a degradation product polyol material after cooling to room temperature.

[0154] The third aspect is a montmorillonite / polyurethane cold chain material prepared from A component and B component as raw materials, wherein the weight ratio of the A component to the B component is 1:2.3; wherein the B component is diphenyl methane diisocyanate,

[0155] The A component comprises the following components in parts by weight:

[0156] The degradation product polyol material: 15 parts,

[0157] Polyether polyol 4110: 25 parts,

[0158] Glycerol (chain extender): 5 parts,

[0159] N,N-azobisisobutyronitrile (foaming agent): 4 parts,

[0160] Cyclohexylamine (catalyst): 5 parts,

[0161] Silicone oil L-600 (foam stabilizer): 4 parts.

[0162] The fourth aspect is a preparation method of montmorillonite / polyurethane cold chain material, comprising the following steps: uniformly stirring the degradation product polyol material with polyether polyol 4110, glycerol, cyclohexylamine, N,N-azobisisobutyronitrile (AZDN), and silicone oil L-600, and then stirring the mixture with diphenyl methane diisocyanate for 20s to make it foam, and cooling to obtain the montmorillonite / polyurethane cold chain material.

[0163] Example 6

[0164] The first aspect is a degradation product polyol material prepared from C component and D component as raw materials in a weight ratio of 1:7:

[0165] The weight parts of each component in the C component are as follows:

[0166] Montmorillonite: 10 parts,

[0167] Butynediol (alcoholysis agent X): 95 parts,

[0168] Sorbitol (alcoholysis agent Y): 5 parts

[0169] N,N-dimethyl ethanolamine (co- alcoholysis agent): 6 parts;

[0170] The D component is a waste polyurethane cold chain material.

[0171] In a second aspect, a degradation method of a polyurethane cold chain material includes the following steps: S1: mixing montmorillonite with butyne diol, sorbitol and N,N-dimethyl ethanolamine, and preparing a mixed solution after ultrasonic oscillation for 4 hours; S2: adding a waste polyurethane cold chain foaming material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 210°C for 3.5 hours, and obtaining a degradation product polyol material after cooling to room temperature.

[0172] In a third aspect, a montmorillonite / polyurethane cold chain material is prepared from the A component and the B component as raw materials, wherein the weight ratio of the A component to the B component is 1:5; wherein the B component is toluene diisocyanate,

[0173] The A component includes the following components in parts by weight:

[0174] The degradation product polyol material: 10 parts,

[0175] The polyether polyol 4110: 30 parts,

[0176] 4-cyclohexanediol (chain extender): 5 parts,

[0177] 1,1,1-trifluorodichloroethane (blowing agent): 14 parts,

[0178] Cyclohexylamine (catalyst): 4 parts,

[0179] Silicone oil L-600 (foam stabilizer): 5 parts.

[0180] In a fourth aspect, a preparation method of a montmorillonite / polyurethane cold chain material includes the following steps: uniformly stirring the degradation product polyol material, the polyether polyol 4110, 4-cyclohexanediol, 1,1,1-trifluorodichloroethane, cyclohexylamine and silicone oil L-600, and then stirring the toluene diisocyanate for 18s to make it foam, and cooling to obtain the montmorillonite / polyurethane cold chain material.

[0181] Example 7

[0182] In a first aspect, a degradation product polyol material is prepared from the C component and the D component as raw materials in a weight ratio of 1:8:

[0183] The weight parts of each component in the C component are as follows:

[0184] Montmorillonite: 5 parts,

[0185] 1,2-cyclohexanediol (alcoholysis agent X): 10 parts,

[0186] Pentaerythritol (alcoholysis agent Y): 90 parts

[0187] N,N-dimethylethanolamine (co-alcoholysis agent): 30 parts;

[0188] The D component is a waste polyurethane cold chain material.

[0189] In a second aspect, a degradation method of a polyurethane cold chain material includes the following steps: S1: mixing montmorillonite, 1,2-cyclohexanediol, pentaerythritol and N,N-dimethylethanolamine, and preparing a mixed solution after ultrasonic oscillation for 4 hours; S2: adding a waste polyurethane cold chain foaming material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 200°C for 4 hours, and obtaining a degradation product polyol material after cooling to room temperature.

[0190] In a third aspect, a montmorillonite / polyurethane cold chain material is prepared from the A component and the B component as raw materials, wherein the weight ratio of the A component to the B component is 1:1.2; wherein the B component is a polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0191] The A component includes the following components in parts by weight:

[0192] Degradation product polyol material: 5 parts,

[0193] Polyether polyol 4110: 35 parts,

[0194] Hydrogenated bisphenol A (chain extension crosslinking agent): 2 parts,

[0195] n-Heptane (foaming agent): 15 parts,

[0196] Methyldiethanolamine (catalyst): 10 parts,

[0197] Silicone oil L-600 (foam stabilizer): 9 parts.

[0198] In a fourth aspect, a preparation method of a montmorillonite / polyurethane cold chain material includes the following steps: uniformly stirring the degradation product polyol material, polyether polyol 4110, hydrogenated bisphenol A, n-heptane, methyldiethanolamine and silicone oil L-600, and then stirring the mixture with PAPI-27 for 20 seconds to make it foam, and cooling to obtain the montmorillonite / polyurethane cold chain material.

[0199] Example 8

[0200] In a first aspect, a degradation product polyol material is prepared from the C component and the D component as raw materials in a weight ratio of 1:1.2:

[0201] The weight parts of each component in the C component are as follows:

[0202] Montmorillonite: 5 parts,

[0203] Dipropylene glycol (alcoholysis agent X): 20 parts,

[0204] Pentaerythritol (alcoholysis agent Y): 90 parts

[0205] N,N-diethyl ethanolamine (co-alcoholysis agent): 10 parts;

[0206] The D component is a waste polyurethane cold chain material.

[0207] In a second aspect, a degradation method of a polyurethane cold chain material includes the following steps: S1: mixing montmorillonite with dipropylene glycol, pentaerythritol and N,N-diethyl ethanolamine, and preparing a mixed solution after ultrasonic oscillation for 4 hours; S2: adding a waste polyurethane cold chain foaming material into a reaction kettle, and then adding the mixed solution obtained in step S1, stirring at 220°C for 4 hours, and obtaining a degradation product polyol material after cooling to room temperature.

[0208] In a third aspect, a montmorillonite / polyurethane cold chain material is prepared from the A component and the B component as raw materials, wherein the weight ratio of the A component to the B component is 1:1.1; wherein the B component is a polyphenyl polymethylene polyisocyanate (PAPI) (PAPI-27),

[0209] The A component includes the following components in parts by weight:

[0210] Degradation product polyol material: 1 part,

[0211] Polyether polyol 4110: 40 parts,

[0212] Dimethylthiuram toluene diamine (chain extension crosslinking agent): 2 parts,

[0213] Dichlorotetrafluoroethane (foaming agent): 15 parts,

[0214] Dibutyltin dilaurate (catalyst): 2 parts,

[0215] Silicone oil L-600 (foam stabilizer): 10 parts.

[0216] In a fourth aspect, a preparation method of a montmorillonite / polyurethane cold chain material includes the following steps: uniformly stirring the degradation product polyol material, polyether polyol 4110, dimethylthiuram toluene diamine, dichlorotetrafluoroethane, dibutyltin dilaurate and silicone oil L-600, and then stirring the mixture with PAPI-27 for 23 seconds to make it foam, and cooling to obtain a rigid polyurethane cold chain material.

[0217] Comparative Examples 1-8

[0218] Comparative Example 1-8 respectively corresponds to Example 1-8, the specific process of Comparative Example 1-8 is only different from the above-mentioned Example 1-8 in that no montmorillonite is added in the degradation process of step 1, and other process conditions are unchanged.

[0219] Comparative Example 9

[0220] Comparative Example 9 is basically the same as Example 1, and the specific process of Comparative Example 9 is only different from Example 1 in that no alcoholysis agent X is added in the degradation process, and other process conditions are unchanged.

[0221] Comparative Example 10

[0222] Comparative Example 10 is basically the same as Example 1, and the specific process of Comparative Example 10 is only different from Example 1 in that no montmorillonite is added in the degradation process, and montmorillonite is added in the foaming process of the prepared polyurethane cold chain material, and other process conditions are unchanged.

[0223] Comparative Example 11

[0224] Comparative Example 11 is basically the same as Example 1, and the specific process of Comparative Example 11 is only different from Example 1 in that no alcoholysis agent Y is added in the degradation process of step 1, and other process conditions are unchanged.

[0225] Experimental Example 1

[0226] (1) The performance of the degradation product polyol material obtained by the example and comparative example of the present application is detected, and the performance of the degradation product polyol obtained by the conventional method of the prior art for degrading the waste polyurethane cold chain material is compared.

[0227] The performance indicators of the degradation product polyol are shown in Table 1 below.

[0228] Table 1. Performance indicators of the degradation product polyol material

[0229]

[0230] As can be seen from the data in Table 1, Comparative Example 1 is compared with Example 1, because no montmorillonite is added in the degradation process, the hydroxyl value is reduced, the polyurethane hard segment represented by the montmorillonite is less, and the viscosity is reduced; Comparative Example 9 is compared with Example 1, because no alcoholysis agent X is added in the degradation process, the hydroxyl value of the degradation product is reduced, the viscosity system is increased, which has an adverse effect on the foaming performance, and the product performance is reduced; Comparative Example 10 is compared with Example 1, montmorillonite is added in the subsequent foaming process, and no synergistic effect is formed with the alcoholysis agent, which results in an increase in viscosity and a decrease in hydroxyl value; Comparative Example 11 is compared with Example 1, because no alcoholysis agent Y is added in the degradation process, the hydroxyl value of the degradation product is reduced, and the viscosity is reduced.

[0231] (2) The degradation product polyol material obtained in the present application example 1 and the comparative example 1 was tested and analyzed by using an IR-960 infrared spectrometer, and was pressed into a test piece by using a tablet press under a pressure of 5 MPa, was ground into a powder in a corundum mortar, and was mixed with KBr according to a certain proportion to prepare a sample. The scanning range was 4000-500 cm -1 . The infrared test results are shown in Figure 2 .

[0232] Figure 2 The infrared spectra of the waste polyurethane cold chain material degradation product polyol material obtained in the present application example 1 and the comparative example 1 are shown in the figure. Both of them have an absorption peak of -OH near 3392 cm -1 , a stretching vibration peak of -C-H near 1620 cm -1 , and a vibration absorption peak of C-O-C at 1067 cm -1 , which show the structure of the polyol. The montmorillonite contains a large amount of hydroxyl groups, and the intensity of the hydroxyl peak in the degradation product increases after the montmorillonite is added. There is a characteristic absorption peak of -NCO at 2279 cm -1 , and the peak intensity decreases after the montmorillonite is added, which shows that the hydroxyl groups and the isocyanate groups remaining in the degradation product react and are connected as a whole through a chemical bond.

[0233] The montmorillonite added in the degradation process of the waste polyurethane cold chain material contains a large amount of hydroxyl functional groups like the alcoholysis agent, and compared with the alcoholysis agent, the introduction of the structure of the montmorillonite brings a hard segment which can make the small molecules of the alcoholysis agent penetrate into the interlayer. The montmorillonite has a nano-restricted space structure of the hard segment lamella constituted by benzene rings, which can be expanded by the small molecules, and the functional groups on the surface of the montmorillonite form a system with good compatibility with the hydroxyl compounds of the small molecule alcohol, so that the small molecule alcohol is inserted between the montmorillonite, which can preliminarily expand the interlayer spacing of the montmorillonite and make the small molecule alcohol penetrate into the lamellar structure, which is beneficial to the dispersion of the montmorillonite. The structure is beneficial to the good compatibility and synergistic effect between the montmorillonite and the alcoholysis agent. In this way, the montmorillonite and the alcoholysis agent are constructed into a uniformly dispersed degradation system, which has a synergistic promoting effect on the degradation of the waste polyurethane cold chain material and the product enhancement.

[0234] Experimental example 2

[0235] (1) In order to prove the technical effect of the present application, the performance of the polyurethane cold chain material prepared in the present application example and the comparative example was detected, and was compared with the performance of the commercially available polyurethane cold chain material. The results are shown in Table 2.

[0236] Table 2. Comparison of performance indexes of polyurethane cold chain materials

[0237]

[0238] As shown in the data in Table 2, the re-prepared polyurethane cold chain material provided by the application has high density, high compressive strength, low water absorption and low thermal conductivity, and the performance is better than that of the comparative examples.

[0239] The application adds the montmorillonite in the reaction system, the montmorillonite is a solid powder, and the addition of the montmorillonite can make the polyurethane cell diameter smaller. Since the polyurethane foaming process needs to be nucleated and then grown, the montmorillonite can act as a nucleating agent and promote the foaming of the polyurethane, so that the cell diameter is smaller and the number is more. In addition, the montmorillonite has a special two-dimensional lamellar structure, which makes it have excellent thermal and mechanical properties, and the addition of the montmorillonite can greatly improve the skeleton strength of the polyurethane cold chain foaming material. The polyurethane cold chain foaming material obtained by the method of the application has excellent cold insulation performance, the closed cell rate is about 90%, and the thermal conductivity, compressive strength, apparent density and water absorption are all higher than the national standard. The material is saved, and significant economic benefits are obtained. After the addition of the montmorillonite, the structure of the cold chain material is toughened and strengthened, the cold insulation performance, wear resistance, corrosion resistance and service life of the cold chain material are improved, the specific strength is increased, the toughness, compressive strength and cold insulation performance of the montmorillonite / polyurethane cold chain material obtained are greatly improved, and the cold insulation performance is excellent.

[0240] (2) Figure 1 The thermogravimetric (TG) curves of the re-prepared polyurethane cold chain material of the examples and the comparative examples provided by the application are shown in the following figures. Figure 1 As can be seen from the figures, the thermal weight loss of the polyurethane cold chain materials prepared by adding different contents of montmorillonite in example 1, example 4 and comparative example 10 can be divided into three stages. The first stage is 100-300℃, the free water and bound water in the waste polyurethane cold chain material volatilize to cause the weight loss of the foam, the second stage is 300-410℃, this stage is the rupture of the isocyanate hard segment in the polyurethane chain, and the third stage is 410-600℃, this stage is the rupture of the polyether soft segment in the polyurethane chain end. The waste polyurethane cold chain material prepared in example 1 and example 4 has a large weight loss temperature of about 250℃, and stops decomposing at about 410℃. The waste polyurethane cold chain material prepared in example 1 has a weight loss temperature of about 343℃, and it can be seen that the weight loss speed of the material in example 1 is slower than that of the other three samples, which shows that the chemical bond energy of the prepared polyurethane cold chain material is larger, and the thermal stability is better. Therefore, the addition of the montmorillonite can improve the thermal stability of the polyurethane cold chain foaming material, thereby enhancing its strain capacity to environmental changes.

[0241] The montmorillonite has a lattice network structure of benzene ring, and the functional groups on the surface of the montmorillonite form new links with the benzene ring-containing hydroxyl compounds in the degradation products of the waste polyurethane cold chain material, that is, the white material with hard segments (for example, benzene ring) is inserted between the montmorillonite, and the new structure formed is reacted with isocyanate to expand the interlayer spacing of the montmorillonite, so that the isocyanate is inserted in the interlayer structure, which is beneficial to secondary dispersion. In addition, the montmorillonite is also embedded in the polyurethane system to form a rigid and enhanced cold chain material.

[0242] (3) The surface morphology and morphological structure of the polyurethane cold chain material finally obtained in Example 1 and Comparative Example 1 were characterized by using an optical microscope. A1 microscope of Zeiss Company was used for testing. The sample was cut into a 1 mm thin piece and placed on a glass slide for observation. The structure image of the montmorillonite / waste polyurethane cold chain material is shown in Figure 3 .

[0243] Figure 3 In the figure, (a) is Comparative Example 1 (without adding montmorillonite), and (b) is the cell structure of the polyurethane cold chain material finally obtained in Example 1 observed under a microscope. As can be seen from the figure, after adding the montmorillonite in figure b, the cell structure is more compact, the surface is smoother, the degree of closure is high, the structure is more tough, the spacing between the cell walls is reduced, and the gas can be better closed to achieve the effect of heat insulation and cold preservation.

[0244] (4) The chemical structure of the polyurethane cold chain material finally obtained in Examples 1-4 was tested and analyzed by using an IR-960 infrared spectrometer before and after modification. The sample was pressed into a test piece by using a tablet press at a pressure of 5 MPa, and was ground into a powder in an agate mortar. KBr was added according to a certain proportion, and was mixed and prepared. The infrared test results are shown in Figure 4 .

[0245] Figure 4 is the infrared spectrum of the montmorillonite / waste polyurethane cold chain foaming material. The absorption peak of -OH is at 3392 cm -1 , the stretching vibration peak of C=O is at 1712 cm -1 , the absorption peak of -NH is at 1520 cm -1 , and the vibration absorption peak of C-O-C is at 1067 cm -1 . No new functional group is generated, which indicates that the addition of the montmorillonite does not affect the overall structure of the material, and therefore the substance is a polyurethane cold chain foaming material.

[0246] Any numerical values recited herein include all values from the lower value and up to the upper value. Values that are recited herein also include values that are "framed" by the recited values. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 25%, 30%, and 35% are expressly enumerated. All integer values are used "open ended" such that "50%" really means "50% to 50%". The same principle applies to ranges recited as being "between" two values. Discrete, non-integer values can be assumed within the stated ranges. These are only a few of the specific examples that are given. In the application, all possible combinations of numerical values between the lowest value and the highest value enumerated, are to be considered to be expressly stated in this application.

[0247] It should be noted that the foregoing examples have been provided merely for the purpose of explanation and are in no way to be construed as limiting of the present application. While the application has been described with reference to exemplary embodiments, it is understood that the words that have been used herein are words of description, and that they are being used under the descriptive and explanatory privilege intended to aid in the understanding of the application. Modifications can be made to the application in light of the teachings herein, and other steps can be added or deleted thereof without departing from the intended scope of the application. Although the application has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can effect a wide variety of modifications to the preferred embodiments of the application without departing from the scope of the intended application. While the preferred embodiments of the application have been made this description is illustrative and not restrictive. Various modifications can become apparent to those skilled in the art, and the present application is to be limited only by the scope of the appended claims.

Claims

1. A degradation product polyol material characterized in that, The C component and the D component are used as raw materials in a weight ratio of (1:1)-(1:10) to prepare: The C component includes the following components in parts by weight: Montmorillonite: 0.1-10 parts, Two-component alcoholysis agent: 50-110 parts, Co-alcoholysis agent: 5-30 parts; The D component is a polyurethane cold chain material.

2. The degradation product polyol material of claim 1, wherein, The polyurethane cold chain material of the D component includes one or more of polyurethane foam, polyurethane composite board, polyurethane insulation pipe, polyurethane heat conducting oil pipe, and polyurethane refrigerated truck compartment plate.

3. The degradation product polyol material of claim 1 or 2, wherein, The two-component alcoholysis agent in the C component includes alcoholysis agent X and alcoholysis agent Y, wherein the weight ratio of the alcoholysis agent X to the alcoholysis agent Y is (10-90):(5-90).

4. The degradation product polyol material of any one of claims 1-3, wherein, The alcoholysis agent X is selected from one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, pentylene glycol, butyne diol, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol, cyclohexanol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, decaglycol, propylene-1,2-diol, propylene-1,3-diol, butylene-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5-diol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 2-methylpropane-1,3-diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, polypropylene glycol, dibutylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polybutylene glycol, and bis(hydroxymethyl)cyclohexane. The alcoholysis agent Y is selected from one or more of glycerol, trimethylolpropane, sorbitol, pentaerythritol, mannitol, erythritol, and lactitol, and / or The co-alcoholysis agent is selected from one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 3-propanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, cyclohexylamine, tertiary amine, sodium hydroxide, potassium hydroxide, and titanium glycolate.

5. A method for degrading a polyurethane cold chain material, the degradation product of the method being a degradation product polyol material according to any one of claims 1 to 4, characterized in that, The method includes the following steps: S1: mixing montmorillonite, two-component alcoholysis agent, and co-alcoholysis agent to obtain a mixed solution; S2: adding polyurethane cold chain material that has been dried and crushed into a reaction kettle, then adding the mixed solution obtained in step S1, stirring at 130-220°C, and obtaining the degradation product polyol material after cooling to room temperature.

6. A montmorillonite / polyurethane cold chain material characterized in that, The A component and the B component are used as raw materials, wherein the weight ratio of the A component to the B component is (1:1)-(1:5); The A component includes the following components in parts by weight: Degradation product polyol material: 1-50 parts, Polyhydric alcohol: 0-40 parts, Chain extension crosslinking agent: 1-15 parts, Foaming agent: 4-35 parts, Catalyst: 0.1-10 parts, Foam stabilizer: 0.1-10 parts; wherein the B component comprises isocyanate, the degradation product polyol material in the A component is the degradation product polyol material of any one of claims 1-4 or the degradation product polyol material made by the degradation process of claim 5.

7. The material of claim 6, wherein The weight ratio of the A component to the B component is (1:1.5)-(1:2.5), the A component comprises the following components in parts by weight: degradation product polyol material: 10-40 parts, polyol: 10-30 parts, chain extender crosslinker: 5-10 parts, blowing agent: 5-20 parts, catalyst: 1-5 parts, foam stabilizer: 1-6 parts.

8. The material according to claim 6 or 7, characterized in that The isocyanate in the B component is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, polyphenyl polymethylene polyisocyanate, hexamethylene diisocyanate.

9. The material according to any one of claims 6-8, characterized in that, The polyol in the A component is selected from one or more of a polyether polyol or a polyester polyol; and / or The chain extender crosslinker is selected from one or more of glycerol, isosorbide, ethylene glycol, trimethylolpropane, 1,6-hexanediol, 4-cyclohexanediol, hydrogenated bisphenol A, 3,5-diamino-4-chlorobenzoic acid isobutyl ester, diethyl toluene diamine, 3,5-dimethylthio toluene diamine, sucrose, glucose, 3,3-dichloro-4,4-diaminodiphenyl methane; and / or The blowing agent is selected from one or more of n-pentane, n-hexane, n-heptane, trichlorofluoromethane, monofluorodichloroethane, dichlorodifluoromethane, dichlorotetrafluoroethane, N,N-dinitrosopentamethylenetetramine, monochlorodifluoroethane, 1,1,1-trifluorodichloroethane, monochlorodifluoromethane, monofluorotrifluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,2-tetrafluoroethane, N,N-dimethyl-N,N-diphenylazinimidate, azodicarboxamide, azobisisobutyronitrile, azodiisopropyl carbonate, azodicarbonic acid diethyl ester, diazaminobenzene, water; and / or The catalyst is selected from one or more of tris(dimethylaminopropyl)hexahydrotriazine, dimethylethanolamine, N,N,N',N",N"-pentamethyldiethylenetriamine, triethylenediamine, N,N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2,2'-dimorpholinodiethylether, N,N-dimethylbenzylamine, 3-propanolamine, N,N',N"-tetramethyl-1,6-hexanediamine, methyldiethanolamine, triethylamine, 1,2-dimethylimidazole, tetramethylethylenediamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, dimethylaminoethoxyethanol, N,N,N',N'-tetramethyl-1,3-propanamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, organotin, cyclohexylamine, propylbutane, triethanol diamine, triethanolamine, triethylamine, dibutyltin dilaurate, stannous octoate, potassium acetate, zinc acetate, calcium chloride, aluminum chloride, sodium hydroxide, or potassium hydroxide; and / or The foam stabilizer is selected from one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154, silicone oil SC-155, silicone oil SD-601, C12 tertiary amine, cetyl / stearyl dimethyl tertiary amine, lauryl / myristyl dimethyl tertiary amine, dimethyl silicone, polydimethylsiloxane, or modifications thereof.

10. A method of preparing the montmorillonite / polyurethane cold chain material according to any one of claims 6-9, comprising the steps of: The degradation product polyol material is incubated in an incubator at 40-50°C, the degradation product polyol material is mixed with polyol, chain extending crosslinking agent, foaming agent, catalyst, foam stabilizer to obtain component A, component A is mixed with component B comprising isocyanate and stirred to obtain the montmorillonite / polyurethane cold chain material.

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