CN111793473B - Preparation method of shape stable phase change material - Google Patents
Preparation method of shape stable phase change material Download PDFInfo
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- CN111793473B CN111793473B CN202010711334.5A CN202010711334A CN111793473B CN 111793473 B CN111793473 B CN 111793473B CN 202010711334 A CN202010711334 A CN 202010711334A CN 111793473 B CN111793473 B CN 111793473B
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- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种低密度、高相变焓值的形状稳定相变储热（蓄冷）材料，解决了相变材料使用过程中的易泄露和不耐形变的缺点。本发明分为两部分：一方面对现有胶凝材料进行重新设计，采用低成本的自身模板法，以热固性高分子材料作为胶凝材料，制备高负载量的形状稳定相变材料，从而实现相变材料具有较大的相变焓值；另一方面，采用具有“栅格”且耐迁移的复合包装材料装载上述相变材料，进一步提高相变材料体系的耐迁移和抗形变特性，从而整体上实现相变储热（蓄冷）材料的轻量化和高相变焓值。The invention discloses a shape-stable phase-change heat storage (cold storage) material with low density and high phase-change enthalpy value, which solves the defects of easy leakage and deformation resistance during the use of the phase-change material. The present invention is divided into two parts: on the one hand, the existing cementitious material is redesigned, and a low-cost self-template method is adopted, and a thermosetting polymer material is used as the cementing material to prepare a shape-stable phase change material with a high load, thereby realizing The phase change material has a large phase change enthalpy; on the other hand, the above-mentioned phase change material is loaded with a "grid" and migration-resistant composite packaging material, which further improves the migration resistance and deformation resistance of the phase change material system. On the whole, the lightweight and high phase change enthalpy value of phase change heat storage (cold storage) materials are realized.
Description
Technical Field
The invention belongs to the field of phase change heat storage (cold accumulation), and particularly relates to a flexible phase change heat storage (cold accumulation) material which is resistant to migration and deformation and prepared by gelation of a phase change heat storage (cold accumulation) material.
Background
In phase change heat storage (cold storage) material applications, in order to meet the requirements of different application fields, a variety of phase change materials have been found to meet the temperature requirements of different application fields. For example, the phase-change material applied to the field of low-temperature preservation comprises inorganic salt solution with the phase-change temperature of-30-24 ℃, paraffin, polyethylene glycol (PEG), organic alcohol and the like; the paint is applied to air-conditioning energy conservation and building constant temperature environments, and contains inorganic salt hydrate, paraffin, PEG, organic acid and the like. These phase change heat storage (cold storage) materials have solid-liquid transition before and after phase change, and therefore these phase change materials are collectively called solid-liquid phase change materials. Solid-liquid phase change materials which are not subjected to any coating (loading) and gelation modification are liquid above the phase transition temperature, and in order to prevent the solid-liquid phase change materials from leaking in the using process, the following three types of methods are mainly adopted at present: the solid-liquid phase-change material is packaged by a plastic container or bag, the shape-stable phase-change material is prepared by physical adsorption or capacity increasing of the solid-liquid phase-change material, and the solid-liquid phase-change material with reactivity, such as PEG, is converted into the solid-solid phase-change material by polyurethane synthesis through chemical reaction. However, the current methods such as packaging the phase change material in the plastic container have the disadvantages of extra weight of the container, increased transportation cost, poor recycling of the container, high use cost, and the like. Flexible polyethylene plastic bags are widely used to package inorganic phase change cold storage agents such as ice bags; although the problem of plastic containers is solved, when the polyethylene flexible package is applied to encapsulation of solid-liquid phase change materials such as paraffin, organic alcohol and the like, the polyethylene and other flexible package materials have poor barrier property, organic phase change material molecules always permeate outwards in the storage and use processes, and transportation objects are easily polluted. In severe cases, the penetrated organic micromolecular phase change material can also generate fire and other hidden dangers under the electrostatic action. In addition, the existing flexible polyethylene packaging bag has poor deformation resistance, particularly after a large amount of phase-change materials are loaded and sealed, the problem that a large amount of liquid is gathered at the lower end and only a small amount of phase-change materials are arranged at the upper end easily occurs due to the influence of gravity, the uniform distribution of the phase-change materials is not facilitated, the problem of nonuniform temperature distribution and the like is caused, and partial medicinal products are caused to lose efficacy. The problem of leakage of the solid-liquid phase change material can be solved by adopting an adsorbent such as a porous material or a high specific surface powder material to adsorb the solid-liquid phase change material, but the traditional cheap porous material such as expanded graphite, silicon dioxide, wood powder and the like has low load capacity (generally only 100-200%) on the solid-liquid phase change material, so that the enthalpy value of the shape-stable phase change material prepared by the method is low. In recent years, in order to increase the loading capacity of the solid-liquid phase change material and realize a high phase change enthalpy value, inorganic aerogel materials such as mesoporous carbon materials and graphene prepared by a sacrificial template method, an ice template-freeze drying method and the like are reported in succession, and the inorganic aerogel material has a very high loading capacity (more than 1000%) of the solid-liquid phase change material and a phase change enthalpy value almost equivalent to that of the solid-liquid phase change material. However, the materials have the disadvantages of high manufacturing cost, incapability of realizing industrialized application and the like. In fact, when the load of the solid-liquid phase-change material in the shape-stable phase-change material exceeds 900%, the phase change enthalpy value of the solid-liquid phase-change material is almost consistent with that of the original solid-liquid phase-change material, the load is continuously increased, the lifting space of the phase change enthalpy value is not large, and the solid-liquid phase-change material is obviously leaked just like water in sponge after the material is extruded due to the excessive load. Although the solid-solid phase change material can well solve the leakage of the solid-liquid phase change material, the solid-liquid phase change material also has the problems of low phase change enthalpy value and the like, which are mainly caused by the fact that the solid-liquid phase change material is grafted to a molecular chain and is influenced by a crosslinking system, and the crystallization of a phase change molecular chain segment is hindered and is incomplete.
Therefore, the development of a packaged shape-stable phase-change material system with high load (more than 400%), excellent barrier property and deformation resistance has important significance for phase-change heat storage (cold accumulation) systems, particularly for cold chain transportation of pharmaceuticals, fruits, seafood and the like at present.
Disclosure of Invention
Aiming at the defects and shortcomings of the existing phase change material, the invention provides a method for constructing a shape-stable phase change material with high solid-liquid phase change material load capacity by adopting a solid-liquid phase change material self-template method, and a phase change heat storage (cold accumulation) material system is constructed by adopting a multi-layer composite flexible packaging material with a grid structure to package the shape-stable phase change material. According to the method, solid-liquid phase-change material molecules crystallize like spherical, flaky or needle crystals in the crystallization process of the organic solid-liquid phase-change material to form a rejection effect on other molecules, so that a high-molecular coating material is effectively concentrated among the crystals, and a network-shaped cross-linked high-molecular structure is further formed through a cross-linking reaction, so that the shape-stable phase-change material with high solid-liquid phase-change material loading capacity (or coating rate) is realized; meanwhile, in order to enable the phase-change heat storage (cold accumulation) system to have the deformation resistance, the material is packaged in a flexible blocking packaging material with a grid structure to form the phase-change heat storage (cold accumulation) system with high phase-change enthalpy value, migration resistance and deformation resistance.
The invention adopts the self-crystallization of the solid-liquid phase-change material as a template to control and synthesize a macromolecular crosslinking network, thereby further preparing the shape-stable phase-change material. The specific implementation method comprises the following steps: firstly, uniformly mixing a thermosetting high polymer material prepolymer or a crosslinkable high polymer material with an organic or inorganic phase change material, then adding a corresponding crosslinking agent, and fully and uniformly mixing for later use. Then loading the mixed solution into a composite packaging material which is provided with grids and is migration-resistant, sealing and then placing the composite packaging material below the phase change temperature of the phase change material at 0-20 ℃ and keeping the temperature for 12-30h, so that the thermosetting polymer material prepolymer or the crosslinkable polymer material and the corresponding crosslinking agent are "excluded" from the crystals by the crystallization of the phase change material, and concentration enrichment of the prepolymer or the crosslinkable polymer material and the corresponding crosslinking agent is formed outside the crystals, thus being beneficial to forming a polymer gel network between the phase change material crystals, and being beneficial to reducing the dosage of the gel material, namely improving the loading capacity of the phase change material and the phase change enthalpy value of the shape-stable phase change material. And finally, placing the system at 40-120 ℃, and enabling the prepolymer or the crosslinkable high polymer material to fully react with a corresponding crosslinking agent to form a gel network and coat the phase-change material, so that the phase-change material with high load capacity, high phase-change enthalpy and stable shape can be obtained.
Aiming at the problems, the invention provides a preparation method of a shape-stable phase-change material, which comprises the following steps:
firstly, uniformly mixing SBS or SEBS, a peroxide crosslinking agent and a phase-change material, then placing the mixture at a temperature lower than the phase-change temperature of the phase-change material to crystallize the phase-change material, and keeping the temperature for 12-30h during the temperature period to enrich the SBS or SEBS and the peroxide crosslinking agent outside the phase-change material crystals and form concentration enrichment;
and finally, placing the system at 60-120 ℃ for reaction, so that a gel network formed by the reaction of SBS or SEBS and a peroxide crosslinking agent is formed among phase change material crystals, and the formed gel network is formed, thereby preparing the shape-stable phase change material.
The ratio of styrene to butadiene in the SBS or SEBS material is 60:40-90:10, the viscosity of 25% wt toluene solution is more than or equal to 1000cp, and the molecular structure is linear or star structure.
The peroxide crosslinking agent comprises one or more of hydrogen peroxide, benzoyl peroxide, dicumyl peroxide and di-tert-butyl dicumyl peroxide.
The phase-change material is paraffin, organic alcohol, organic acid, ester of higher fatty acid and alcohol, and their composition.
In the phase-change material, the paraffin with the phase-change temperature of 0-140 ℃ is selected as the paraffin, and the esterification products of organic alcohol, organic acid, higher fatty acid and alcohol are capric acid, lauric acid, myristic acid, palmitic acid, dodecanol, tetradecanol, cetyl alcohol, propyl palmitate, isopropyl stearate and butyl stearate.
The mass ratio of the SBS or the SEBS to the peroxide cross-linking agent to the phase-change material is 100:0.1-1.0: 300-1000.
Compared with the prior art, the invention has the following advantages and prominent effects: the high polymer material cross-linked network is formed by a self-template method, so that the dosage of a gel material can be effectively reduced, and the load capacity (or coating rate) of a solid-liquid phase-change material is improved, thereby improving the phase change enthalpy value of the shape-stable phase-change material. By the method, the technical process of preparing the porous material by a sacrificial template method or an ice template method can be effectively avoided, and the preparation process of the shape-stable phase-change material is simplified. Compared with the method, the method has the advantages of low energy consumption, low cost, large-scale production and the like, and is beneficial to large-scale application and popularization of the technology. The flexible composite packaging with the grid structure can realize the light weight and low cost of the phase change heat storage (cold accumulation) material, and has wide application prospect in cold chain transportation of foods and pharmaceuticals.
Detailed Description
Example 1
The preparation method of the shape-stable phase-change material system taking solid-liquid phase-change materials such as phase-change paraffin, organic alcohol, organic acid and the like as coating objects comprises the following steps:
firstly, 1000g of SBS (10 wt% toluene solution with viscosity of 1000cp and B/S of 60/40), 1000g of SEBS (star-shaped structure, ba ling petrochemical-604 and B/S of 67/33), 40g of dicumyl peroxide, Sasol phase change paraffin RT-2 and dodecanol solid-liquid phase change material are uniformly mixed according to the mass ratio of 1:1, 12000g of the mixture is taken, then the mixture is placed at the phase change temperature lower than that of the phase change material to crystallize the phase change material, and the phase change material is kept for 24 hours during the temperature period (the phase change temperature is 5 ℃), so that SBS, SEBS and peroxide crosslinking agent are enriched outside the phase change material crystals to form concentration enrichment, and a gel network which is beneficial to the reaction of SBS, SEBS and the peroxide crosslinking agent at the later stage is formed among the phase change agent crystals, thereby being beneficial to reducing the dosage of the gel material.
And finally, placing the system at 120 ℃ to ensure that SBS and SEBS fully react with the peroxide crosslinking agent to form a gel network, thereby preparing the phase-change paraffin and organic alcohol shape-stable phase-change material. And extruding the jelly-like gel, pouring the jelly-like gel between flexible composite packaging materials, and sealing by heat seal to solidify the phase-change gel material between grids of the flexible composite packaging materials to finally form a phase-change heat storage (cold accumulation) system with migration resistance and deformation resistance.
Example 2
The preparation process is the same as example 1, wherein SEBS (503T lineal of ba lingpetrochemical, 67/33 for B/S) 2000g, a crosslinking agent bis-tert-butylperoxy diisopropylbenzene 30g, and solid-liquid phase change materials comprising Shanghai Joule phase change wax (type 2T8) and tetradecanol are uniformly mixed according to the mass ratio of 1:1, and 10150g is taken. The detailed formulation is shown in table 1.
Example 3
The preparation process is the same as example 1, wherein 2000g of SEBS (ba Ling petrochemical 688 star type, B/S is 87/13), 35g of crosslinking agent bis-tert-butylperoxy diisopropylbenzene, and 10175g of Sasol phase change paraffin RT-27 and lauric acid are uniformly mixed according to the mass ratio of 1: 1. The detailed formulation is shown in table 1.
Example 4
The preparation process is the same as example 1, wherein SEBS (the brining petrochemical 561 line type + star type, B/S is 66/34)2000g, a crosslinking agent bis-tert-butylperoxydiisopropylbenzene 20g, solid-liquid phase change materials are Shanghai Joule phase change waxes T5 and 2T8, and the materials are uniformly mixed according to the mass ratio of 1:1 to obtain 10100 g. The detailed formulation is shown in table 1.
Example 5
The preparation process is the same as example 1, wherein SEBS (the brining petrochemical 561 line type + star type, B/S is 66/34)2000g, the crosslinking agent bis-tert-butylperoxydiisopropylbenzene 20g, the solid-liquid phase change material is Shanghai Joule phase change wax T20, propyl palmitate and butyl stearate are uniformly mixed according to the mass ratio of 1:1:1, and 10100g is taken. The detailed formulation is shown in table 1.
Example 6
The example is the same as the gel material of the example 5, wherein the solid-liquid phase change materials are Shanghai Joule transformation wax T20, propyl palmitate and butyl stearate, the solid-liquid phase change waxes are uniformly mixed according to the mass ratio of 1:1:1, 5000g is taken, the load capacity of the solid-liquid phase change materials is reduced, and the enthalpy value and other performance differences of the prepared shape-stable phase change materials are compared. The detailed formulation is shown in table 1.
And (3) comparison test: formulation according to example 1: 1000g of SBS (10 wt% toluene solution with viscosity of 1000cp and B/S of 60/40), 1000g of SEBS (star structure, ba ling petrochemical-604 and B/S of 67/33), 40g of dicumyl peroxide, Sasol phase change paraffin RT-2 and dodecanol solid-liquid phase change material are uniformly mixed according to the mass ratio of 1:1, 12000g is taken and uniformly mixed to obtain MIX 2. In order to contrast the present invention, which uses the phase change material itself as a template to prepare a shape stable phase change material, the comparative test does not cool MIX2 below the phase transition temperature of the solid-liquid phase change material to crystallize it, which is different from that of example 1: directly encapsulating the MIX2 in a flexible composite packaging material, placing the flexible composite packaging material in an oven at 120 ℃, and keeping the temperature for 2 hours to ensure that SBS and SEBS fully react with a peroxide crosslinking agent. And after the solid-liquid phase change material is fully reacted, performing leakage test evaluation on the performance of the solid-liquid phase change material coated by the solid-liquid phase change material.
The phase change heat storage (cold storage) material systems prepared in the above examples 1 to 5 were subjected to energy storage performance tests, and subjected to 200-cycle aging tests, and migration and leakage conditions thereof were observed, and the results are shown in table 1.
TABLE 1 formulation and Properties of shape-Stable phase Change Material
Claims (3)
1. The preparation method of the shape-stable phase-change material is characterized by comprising the following steps of:
(1) uniformly mixing SBS and/or SEBS, a peroxide cross-linking agent and a phase-change material, then placing the mixture at a temperature lower than the phase-change temperature of the phase-change material by 5 ℃, and keeping the temperature for 24 hours, so that the phase-change material is crystallized, the phase-change material is one or more of paraffin, organic alcohol, organic acid, ester compounds of higher fatty acid and alcohol, so that SBS and/or SEBS and the peroxide cross-linking agent are enriched outside the phase-change material crystal and form concentration enrichment, the ratio of styrene to butadiene in the SBS or SEBS material is 60:40-90:10, the viscosity of 25% wt toluene solution is more than or equal to 1000cp, the molecular structure is a linear or star structure, and the mass ratio of SBS or SEBS, the peroxide cross-linking agent and the phase-change material is 100:0.1-1.0:300- > 1000;
(2) and (3) placing the system at 60-120 ℃ for reaction, so that a gel network formed by the reaction of SBS or SEBS and a peroxide crosslinking agent is formed among phase-change material crystals, and the formed gel network is formed, thereby preparing the shape-stable phase-change material.
2. The method of claim 1, wherein the peroxide cross-linking agent comprises one or more of hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, and di-t-butylperoxy dicumyl peroxide.
3. The method according to claim 1, wherein the ester of organic alcohol, organic acid, higher fatty acid and alcohol comprises one or more of capric acid, lauric acid, myristic acid, palmitic acid, dodecanol, tetradecanol, cetyl alcohol, propyl palmitate, isopropyl stearate, and butyl stearate.
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| CN114569322A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Cooling nursing bag with soft texture and long cooling time |
| CN112489553A (en) * | 2020-12-08 | 2021-03-12 | 上海海洋大学 | Cold chain logistics intelligent indicating label |
| CN114854375A (en) * | 2022-05-25 | 2022-08-05 | 安徽禾基科技有限公司 | A composite phase change material for energy release in winter and energy storage in summer, production method and application thereof |
| EP4735554A1 (en) * | 2023-06-27 | 2026-05-06 | Pluss Advanced Technologies Limited | A process for making temperature regulating polymeric retrofits through form stabilization |
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| CN1258577C (en) * | 2004-07-09 | 2006-06-07 | 清华大学 | High heat conductive fixed phase change heat storage material suitable for large scale industrial production |
| ES2379637T3 (en) * | 2004-12-09 | 2012-04-30 | E. I. Du Pont De Nemours And Company | Compositions of phase change materials (MCF) for thermal management |
| CN101423749B (en) * | 2007-11-01 | 2011-06-01 | 中国人民解放军军事医学科学院野战输血研究所 | Fixed shape phase-change material based on tetradecane and method for producing the same |
| CN106520076A (en) * | 2016-10-28 | 2017-03-22 | 松冷（武汉）科技有限公司 | Novel solid phase change cold storage agent for cold chain transportation at temperature of 2-8 DEG C and preparing method and application of novel solid phase change cold storage agent |
| CN110713728B (en) * | 2019-10-08 | 2024-02-09 | 郑州轻工业学院 | Preparation method of paraffin-SEBS thermoplastic elastomer composite phase change material |
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