Rigid foam high flame retardant phase change polyurethane material and preparation method thereof
By combining fatty acids with aerogel wall materials in a specific ratio, the problems of leakage and interfacial incompatibility of phase change materials were solved, and a rigid polyurethane foam material with good phase change heat storage performance and flame retardant properties was prepared, achieving efficient temperature regulation and control capabilities and thermal stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHIJIAZHUANG BANGDI POLYMER MATERIAL CO LTD
- Filing Date
- 2023-06-29
- Publication Date
- 2026-06-05
Smart Images
Figure CN116693798B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the preparation of a phase change foaming material, and more particularly to a rigid foam high flame retardant phase change polyurethane material and its preparation method. Background Technology
[0002] With energy issues becoming increasingly prominent, energy conservation and consumption reduction have become the central themes of building materials. Modifying rigid polyurethane foam with phase change materials (PCMs) possessing thermal storage capabilities to prepare composite materials with excellent temperature regulation and control is of great significance. PCMs typically require cross-linking or microencapsulation to address issues such as leakage, fatigue, and incompatibility with surrounding materials, thereby improving the service life of the composite material. Microencapsulated PCMs usually consist of a core material and a wall material. The effectiveness of the wall material's encapsulation of the core material directly affects the flowability, solubility, slow release, and permeability of the microcapsules, which in turn influence the pore structure, mechanical properties, and thermal conductivity of the rigid foam. Furthermore, the type of core material and wall material in the microencapsulated PCM also affects the phase change thermal storage performance of rigid polyurethane foam. Therefore, developing a rigid polyurethane foam material with good phase change thermal storage performance, a simple production process, and significantly improved energy efficiency has always been a key research focus in this field. Summary of the Invention
[0003] To address the above problems, this invention provides a rigid foam high flame retardant phase change polyurethane material and its preparation method.
[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0005] A rigid foam high flame retardant phase change polyurethane material, wherein the raw materials for making the rigid foam high flame retardant phase change polyurethane material include, by weight parts:
[0006] 60-65 parts polyether polyol, 10-15 parts calcium carbonate, 8-10 parts gel phase change material, 0.2-0.5 parts catalyst, 2-4 parts foaming agent, 1-1.5 parts foam stabilizer, 2-4 parts plasticizer, 5-7 parts chain extender, 3-5 parts ammonium polyphosphate, 1-3 parts antioxidant DNP, 1-3 parts ultraviolet absorber and 15-20 parts isocyanate;
[0007] The gel phase change material is made by using a mixture of fatty acids, namely myristic acid and octadecanoic acid, as the core material, and sodium silicate and tetraethyl silicate as the aerogel wall material. The hydrophobic end of the emulsifier is used to encapsulate the core material, and the hydrophilic end of the emulsifier is used to bond with the aerogel wall material.
[0008] Furthermore, the preparation process of the gel phase change material includes the following steps:
[0009] 11) Preparation of emulsions
[0010] Myristic acid and octadecanoic acid were mixed, heated, and ultrasonically mixed to obtain a mixed fatty acid;
[0011] After mixing hydrochloric acid aqueous solution with ethanol, an emulsifier is added to the resulting mixed solvent to dissolve it, the temperature is raised, and then mixed fatty acids are added and homogenized to obtain an emulsion.
[0012] 12) Preparation of gel phase change materials
[0013] After reacting the emulsion with sodium silicate aqueous solution and tetraethyl silicate dropwise, the pH value was adjusted, the mixture was cooled and allowed to stand, filtered, washed, and dried to obtain the gel phase change material.
[0014] Furthermore, in step 11), the temperature after heating is 50–55°C when preparing the mixed fatty acids;
[0015] When preparing the emulsion, the temperature after heating is 50-55℃, and the homogenization temperature is 50-55℃.
[0016] Furthermore, in step 11), the mixed solvent is a mixture of a 2 mol / L hydrochloric acid aqueous solution and ethanol with a volume ratio of 1:0.8-1.
[0017] Furthermore, in step 12), the temperature at which the sodium silicate aqueous solution and tetraethyl silicate are added is 50–55°C.
[0018] After the sodium silicate aqueous solution is added and before the tetraethyl silicate is added, the reaction should be maintained at 50-55℃ for 30-40 minutes.
[0019] After the addition of tetraethyl silicate is complete and before adjusting the pH value, the reaction should be maintained at 50-55℃ for 1-1.5 hours.
[0020] Furthermore, in step 12), the pH value is adjusted using ammonia water;
[0021] The adjusted pH value is 7.8–8.0;
[0022] After adjusting the pH value, the resulting system was mixed, cooled to room temperature, and kept at room temperature for 2–3 hours.
[0023] Furthermore, in step 12), the concentration of the sodium silicate aqueous solution is 20 wt%.
[0024] Furthermore, the weight ratio of myristic acid to octadecanoic acid in the mixed fatty acids is 1:3 to 3.5;
[0025] The weight ratio of the mixed fatty acids to sodium silicate and tetraethyl silicate is 1:0.8 to 1:1 to 1.5.
[0026] The weight ratio of the mixed fatty acids to the emulsifier is 1:0.45 to 0.6.
[0027] Furthermore, the emulsifier is made of dodecyl ammonium chloride and emulsifier OP-10 in a weight ratio of 3-4:1.5-2.
[0028] A method for preparing the above-mentioned rigid foam high flame retardant phase change polyurethane material, wherein the preparation method comprises mixing polyether polyol, calcium carbonate, the gel phase change material, catalyst, foaming agent, foam stabilizer, plasticizer, chain extender, ammonium polyphosphate, antioxidant DNP and ultraviolet absorber, then adding isocyanate, stirring rapidly, allowing it to foam freely, and curing to obtain the rigid foam high flame retardant phase change polyurethane material.
[0029] The beneficial effects of the rigid foam high flame retardant phase change polyurethane material and its preparation method of the present invention are as follows:
[0030] This invention uses two different fatty acids in a specific ratio to form a binary eutectic system, which broadens the phase change temperature range, improves cycle stability, effectively reduces the thermal conductivity of the prepared rigid foam high flame retardant phase change polyurethane material, reduces heat loss caused by heat transfer, and improves temperature regulation and control capabilities.
[0031] This invention employs a chemical precipitation method to prepare aerogel phase change materials. The hydrophobic end of an emulsifier encapsulates oil droplets formed from dispersed mixed fatty acids in the system, creating an ordered arrangement on the droplet surface. The hydrophilic end of the emulsifier extends into the system, forming a stable oil-in-water (O / W) emulsion. A sodium silicate aqueous solution and tetraethyl silicate are then slowly added dropwise to the emulsion. The hydrophilic end of the emulsifier binds to the sodium silicate first, and then dehydration condensation occurs after the introduction of ethoxy groups, resulting in a hierarchical porous structure that coats the core material. This increases the specific surface area and pore volume of the aerogel, while simultaneously enhancing the core material's coating capacity and adsorption capacity, thus providing excellent coating performance. This solves the problems of leakage, fatigue, and incompatibility with surrounding materials in phase change materials, thereby improving the performance of the prepared rigid foam high flame-retardant phase change polyurethane material.
[0032] This invention fills the macropores of aerogel with a mixed fatty acid, which is made by mixing two different fatty acids. The macropores of the aerogel have a rough core-shell structure, which enhances the loading capacity of the mixed fatty acid, broadens the phase transition temperature range, and improves the flowability, solubility, sustained release and permeability of the microcapsules.
[0033] This invention utilizes aerogel structures to coat mixed fatty acids as aerogel phase change materials for the preparation of polyurethane foam materials. It can also adjust the pore unit properties of the prepared rigid foam high flame retardant phase change polyurethane materials, thereby affecting their macroscopic properties.
[0034] The aerogel phase change material of this invention, in combination with ammonium polyphosphate, effectively improves the flame retardant properties of rigid foam high flame retardant phase change polyurethane material.
[0035] The process of this invention is simple, easy to operate, and suitable for industrial production. Attached Figure Description
[0036] Figures 1-2 These are the thermal stability test results of rigid foam high flame retardant phase change polyurethane materials YP1 and DYP1~DYP7 in Experimental Example 1 of this invention.
[0037] Figure 3 This is a diagram showing the heating process of rigid foam high flame retardant phase change polyurethane materials YP1 and DYP1~DYP3 in Experimental Example 1 of this invention.
[0038] Figure 4 yes Figure 3 A magnified view of the localized heating process;
[0039] Figure 5 This is a diagram showing the heating process of rigid foam high flame retardant phase change polyurethane materials YP1 and DYP4 to DYP7 in Experimental Example 1 of this invention.
[0040] Figure 6 yes Figure 5 A magnified view of the localized heating process;
[0041] Figure 7 This is a diagram showing the cooling process of rigid foam high flame retardant phase change polyurethane materials YP1 and DYP1~DYP3 in Experimental Example 1 of this invention.
[0042] Figure 8 yes Figure 7 A magnified view of the localized cooling process;
[0043] Figure 9 This is a diagram showing the cooling process of rigid foam high flame retardant phase change polyurethane materials YP1 and DYP4 to DYP7 in Experimental Example 1 of this invention.
[0044] Figure 10 yes Figure 9 A magnified view of the localized cooling process. Detailed Implementation
[0045] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0046] Example 1: A method for preparing a rigid foam high flame retardant phase change polyurethane material
[0047] This embodiment describes a method for preparing a rigid foam high flame retardant phase change polyurethane material, specifically including the following steps:
[0048] 1) Preparation of gel phase change materials
[0049] 11) Preparation of emulsions
[0050] Myristic acid and octadecanoic acid were mixed in a weight ratio of 1:3.3, heated in a water bath to 50-55°C (to 55°C in this example), and ultrasonically mixed to obtain mixed fatty acids.
[0051] A 2 mol / L hydrochloric acid aqueous solution with a volume ratio of 1:1 and ethanol are mixed to obtain a mixed solvent;
[0052] Take 100 mL of mixed solvent, add 3.5 g of dodecyl ammonium chloride and 2 g of emulsifier OP-10, stir at room temperature until dissolved, heat to 50-55℃ (in this example, the temperature is raised to 55℃), then add 10 g of mixed fatty acids, maintain at 50-55℃ for homogenization and emulsification for 30 min (in this example, the homogenization temperature is 55℃) to obtain an emulsion;
[0053] 12) Preparation of gel phase change materials
[0054] Maintaining a temperature of 50–55°C, 50 g of a 20 wt% sodium silicate aqueous solution (equivalent to 10 g of sodium silicate) was added dropwise to the emulsion. The first stirring reaction was carried out at 50–55°C for 30–40 min (in this embodiment, the temperature of the first stirring reaction was 55°C and the time was 30 min). Then, 10 g of tetraethyl silicate was added dropwise, and the second stirring reaction was carried out at 50–55°C for 1–1.5 h (in this embodiment, the temperature of the second stirring reaction was 55°C and the time was 1.5 h). Then, 10 wt% ammonia was added dropwise to adjust the pH value to 7.8–8.0 (in this embodiment, the pH value was adjusted to 7.8). After stirring evenly, the mixture was cooled to room temperature and allowed to stand at room temperature for 2–3 h (in this embodiment, it was allowed to stand for 2.5 h). The mixture was then filtered, and washed five times each with 20 mL of petroleum ether and 20 mL of deionized water. The mixture was then vacuum dried at 40°C for 24 h to obtain the gel phase change material, labeled as XB1.
[0055] 2) Preparation of rigid foam high flame retardant phase change polyurethane materials
[0056] At room temperature, 60g of polyether polyol (polypropylene glycol in this example), 13g of calcium carbonate, 9g of gel phase change material XB1, 0.3g of catalyst (1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine in this example), 3g of foaming agent (cyclopentane in this example), 1.2g of foam stabilizer (polyurethane rigid foam silicone oil AK-158), 3g of plasticizer (triphenyl phosphate in this example), 6g of chain extender (1,4-butanediol in this example), 4g of ammonium polyphosphate, 2g of antioxidant DNP and 2g of benzotriazole ultraviolet absorber (Fisorb 328 in this example) were stirred and mixed. Then, 20g of polymethylene polyphenyl isocyanate PM-400 was added and stirred rapidly for 5s. The mixture was poured into a mold for free foaming. After the foam had expanded and set, it was cured at room temperature to obtain a rigid foam high flame retardant phase change polyurethane material, labeled YP1.
[0057] Examples 2-5: Preparation methods of rigid foam high flame retardant phase change polyurethane materials
[0058] Examples 2-5 are methods for preparing rigid foam high flame retardant phase change polyurethane materials. Their steps are basically the same as in Example 1, differing only in the process parameters, as detailed in Table 1.
[0059] Table 1. Summary of process parameters in Examples 2-5
[0060]
[0061]
[0062] The process steps and parameters for other parts of Examples 2-5 are the same as those in Example 1.
[0063] Experiment Example 1: Comparative Experiment
[0064] Comparative Examples 1-7 are comparative experiments on the preparation methods of the rigid foam high flame retardant phase change polyurethane material in Example 1. The processes and raw material dosages are basically the same, with the only difference being:
[0065] In step 11) of Comparative Example 1, the weight ratio of myristic acid to octadecanoic acid in the mixed fatty acids was 1:1. The resulting gel phase change material was labeled DXB1. The rigid foam high flame retardant phase change polyurethane material prepared using gel phase change material DXB1 was labeled DYP1.
[0066] In step 11) of Comparative Example 2, the weight ratio of myristic acid to octadecanoic acid in the mixed fatty acids was 1:5. The resulting gel phase change material was labeled as DXB2. The rigid foam high flame retardant phase change polyurethane material prepared using the gel phase change material DXB2 was labeled as DYP2.
[0067] In step 11) of Comparative Example 3, the weight ratio of dodecyl ammonium chloride and emulsifier OP-10 in the emulsifier was 5:1. The resulting gel phase change material was labeled as DXB3. The rigid foam high flame retardant phase change polyurethane material prepared using gel phase change material DXB3 was labeled as DYP3.
[0068] In step 11) of Comparative Example 4, the weight ratio of dodecyl ammonium chloride and emulsifier OP-10 in the emulsifier was 1:1. The resulting gel phase change material was labeled as DXB4. The rigid foam high flame retardant phase change polyurethane material prepared using gel phase change material DXB4 was labeled as DYP4.
[0069] In step 12) of Comparative Example 5, the weight ratio of the mixed fatty acids added to sodium silicate and tetraethyl silicate was 1:0.5:0.5. The resulting gel phase change material was labeled as DXB5. The rigid foam high flame retardant phase change polyurethane material prepared using the gel phase change material DXB5 was labeled as DYP5.
[0070] In step 12) of Comparative Example 6, the weight ratio of the mixed fatty acids added to sodium silicate and tetraethyl silicate was 1:2:2. The resulting gel phase change material was labeled as DXB6. The rigid foam high flame retardant phase change polyurethane material prepared using the gel phase change material DXB6 was labeled as DYP6.
[0071] In step 11) of Comparative Example 7, the weight ratio of the mixed fatty acids to the emulsifier added was 1:0.2, wherein the emulsifier was made by combining dodecyl ammonium chloride and emulsifier OP-10 in a weight ratio of 3.5:2. The resulting gel phase change material was labeled as DXB7. The rigid foam high flame retardant phase change polyurethane material prepared using the gel phase change material DXB7 was labeled as DYP7.
[0072] The rigid foam high flame retardant phase change polyurethane materials YP1 and DYP1-DYP7 prepared in Example 1 and Comparative Examples 1-7 were used as samples for the following performance tests.
[0073] A. Thermogravimetric Analysis (TG): Thermogravimetric analysis was performed using a thermogravimetric analyzer. The test samples were tested under nitrogen atmosphere, with a temperature range of 30–800℃, a heating rate of 10℃ / min, and a hold time of 3 min. The results are shown in the figure. Figure 1 and Figure 2 .Depend on Figure 1 and Figure 2 It can be seen that the thermal stability of the rigid foam high flame retardant phase change polyurethane material YP1 prepared by the present invention is significantly higher than that of the rigid foam high flame retardant phase change polyurethane materials DYP1 to DYP7 prepared by comparative examples 1 to 7. This shows that the rigid foam high flame retardant phase change polyurethane material prepared by the present invention has good thermal stability.
[0074] B. Temperature Regulation Capability Test: A high-precision thermocouple multi-channel temperature tester was used to test the sample's temperature regulation capability. The sample was placed in a sample bottle, and the thermocouple sensor was inserted into the sample. The sample was then placed in an intelligent constant temperature bath, and the temperature was set to be heated from 0 to 100℃ at a rate of 0.65℃ / min. The heat absorption and temperature control capability of the sample during the heating process was tested. After holding the temperature for 1 hour, the temperature was set to be uniformly cooled to -20℃ at a rate of 0.3℃ / min. The heat release and temperature regulation capability of the sample during the cooling process was tested. The results are shown in […]. Figures 3 to 10 .Depend on Figures 3 to 10 It can be seen that the thermal insulation performance of the rigid foam high flame retardant phase change polyurethane material YP1 prepared by the present invention is significantly better than that of the rigid foam high flame retardant phase change polyurethane materials DYP1 to DYP7 prepared by comparative examples 1 to 7. It can effectively slow down the heating or cooling rate, indicating that the rigid foam high flame retardant phase change polyurethane material prepared by the present invention can effectively regulate the internal ambient temperature and reduce building energy consumption.
[0075] C. Thermal conductivity: The thermal conductivity of the samples was tested according to GB / T10294-2008.
[0076] D. Tensile properties: The tensile and compressive properties of the samples were tested according to GJB1585-93.
[0077] E. Combustion performance: The combustion performance of the samples was tested according to GB / T8333-2008.
[0078] The specific results for thermal conductivity, tensile properties, and combustion performance are shown in Table 2:
[0079] Table 2 Summary of Performance Test Results
[0080]
[0081] As can be seen from Table 2, the rigid foam high flame retardant phase change polyurethane material prepared using the formulation of the present invention has a very low thermal conductivity, good thermal insulation performance, excellent flame retardant performance, good tensile strength and fracture strength, and good stability and safety (see compressive strength parameters).
[0082] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
Claims
1. A rigid foam high flame retardant phase change polyurethane material, characterized in that, The raw materials for making the rigid foam high flame retardant phase change polyurethane material, by weight, include: 60-65 parts polyether polyol, 10-15 parts calcium carbonate, 8-10 parts gel phase change material, 0.2-0.5 parts catalyst, 2-4 parts foaming agent, 1-1.5 parts foam stabilizer, 2-4 parts plasticizer, 5-7 parts chain extender, 3-5 parts ammonium polyphosphate, 1-3 parts antioxidant DNP, 1-3 parts ultraviolet absorber and 15-20 parts isocyanate; The preparation process of the gel phase change material includes the following steps: 11) Preparation of emulsions Myristic acid and octadecanoic acid were mixed, heated, and ultrasonically mixed to obtain a mixed fatty acid; The weight ratio of myristic acid to octadecanoic acid in the mixed fatty acids is 1:3~3.5; After mixing hydrochloric acid aqueous solution with ethanol, an emulsifier is added to the resulting mixed solvent to dissolve it, the temperature is raised, and then mixed fatty acids are added and homogenized to obtain an emulsion. The weight ratio of the mixed fatty acids to the emulsifier is 1:0.45~0.6; The emulsifier is made of dodecyl ammonium chloride and emulsifier OP-10 in a weight ratio of 3~4:1.5~2; 12) Preparation of gel phase change materials After reacting the emulsion with sodium silicate aqueous solution and tetraethyl silicate dropwise, the pH value was adjusted, the mixture was cooled and allowed to stand, filtered, washed and dried to obtain the gel phase change material. The weight ratio of the mixed fatty acids to sodium silicate and tetraethyl silicate is 1:0.8~1:1~1.
5.
2. The rigid foam high flame-retardant phase change polyurethane material according to claim 1, characterized in that, In step 11), the temperature after heating is 50~55℃ when preparing the mixed fatty acids; When preparing the emulsion, the temperature after heating is 50~55℃, and the homogenization temperature is 50~55℃.
3. The rigid foam high flame-retardant phase change polyurethane material according to claim 1 or 2, characterized in that, In step 11), the mixed solvent is a mixture of a 2 mol / L hydrochloric acid aqueous solution and ethanol with a volume ratio of 1:0.8~1.
4. The rigid foam high flame-retardant phase change polyurethane material according to claim 1 or 2, characterized in that, In step 12), the temperature at which the sodium silicate aqueous solution and tetraethyl silicate are added is 50~55℃. After the sodium silicate aqueous solution is added dropwise and before the tetraethyl silicate is added dropwise, the reaction should be maintained at 50-55℃ for 30-40 minutes. After the addition of tetraethyl silicate is completed and before adjusting the pH value, the reaction should be maintained at 50-55℃ for 1-1.5 hours.
5. The rigid foam high flame-retardant phase change polyurethane material according to claim 1, characterized in that, In step 12), the pH value is adjusted using ammonia. The adjusted pH value is 7.8~8.0; After adjusting the pH value, the resulting system was mixed, cooled to room temperature, and kept at room temperature for 2-3 hours.
6. The rigid foam high flame-retardant phase change polyurethane material according to claim 1 or 2, characterized in that, In step 12), the concentration of the sodium silicate aqueous solution is 20 wt%.
7. The method for preparing the rigid foam high flame retardant phase change polyurethane material according to any one of claims 1-6, characterized in that, The preparation method involves mixing polyether polyol, calcium carbonate, the gel phase change material, catalyst, foaming agent, foam stabilizer, plasticizer, chain extender, ammonium polyphosphate, antioxidant DNP, and ultraviolet absorber, then adding isocyanate, stirring rapidly, allowing it to foam freely, and maturing to obtain the rigid foam high flame retardant phase change polyurethane material.