A polyisocyanurate low-temperature insulation material

Abstract

This invention relates to a polyisocyanurate low-temperature insulation material. Based on existing technology, this invention utilizes a MOF (metal-organic framework) material as a CO2 carrier to prepare a novel foaming agent. When applied to polyisocyanurate low-temperature insulation materials and combined with traditional foaming agents, superior technical effects are achieved.

Description

Technical Field

[0001] This invention relates to the field of polyisocyanurate technology, and particularly to a polyisocyanurate low-temperature thermal insulation material. Background Technology

[0002] With the global energy structure transformation, the demand for high-efficiency thermal insulation materials continues to grow in areas such as building energy conservation, liquefied natural gas (LNG) storage and transportation, and cold chain logistics. Polyisocyanurate (PIR) foam, as an upgraded version of polyurethane (PUR) foam, significantly improves the material's temperature resistance, flame retardancy, and dimensional stability by increasing the isocyanate index to form a large number of isocyanurate rings with higher thermal stability in the molecular chain.

[0003] Polyisocyanate (PIR) foam has a low thermal conductivity, far lower than traditional inorganic insulation materials (such as rock wool, which has a thermal conductivity of 0.040 W / (m·K)), and a density of only 30~60 kg / m³. It combines lightweight and high strength, making it widely used in cryogenic insulation and a core insulation material for cryogenic storage and transportation systems. Current technology achieves foaming performance by reacting water with isocyanate to generate CO2. Water as a foaming agent source is low-cost, environmentally friendly, and has a simple process. However, the reaction between water and isocyanate is exothermic, which accelerates the reaction rate of the isocyanate system, leading to uneven foaming and reduced strength.

[0004] Metal-organic frameworks (MOFs) are a rapidly developing new type of material in recent years. They are porous crystalline materials formed by the self-assembly of metal ions / clusters and organic ligands through coordination bonds. They possess characteristics such as large specific surface area, low density, and functional modifiability. They show broad application prospects in catalysis, drug delivery systems, and other fields. Based on existing technologies, this invention utilizes MOFs as CO2 carriers to prepare a novel blowing agent. This agent is then applied to polyisocyanurate low-temperature insulation materials and, when combined with traditional blowing agents, achieves superior technical results. Summary of the Invention

[0005] This invention provides a polyisocyanurate low-temperature insulation material, which is composed of the following components: Component A: 60-80 parts of aromatic polyester polyol 20-40 parts of glycerol polyether polyol 110-30 parts of foaming agent 25-10 parts of foaming agent 3-9 parts catalyst 1-3 parts foam stabilizer 5-10 parts flame retardant Component B: 250-280 parts of polyisocyanate; Furthermore, the aromatic polyester polyol is obtained by condensation of one or more of phthalic anhydride, terephthalic acid, and adipic acid with one or more of ethylene glycol, propylene glycol, glycerol, butanediol, diethylene glycol, and trimethylolpropane. Furthermore, the aromatic polyester polyol has a functionality of 2 to 2.2 and a hydroxyl value of 300 to 330 mgKOH / g; Furthermore, the aromatic polyester polyol is selected from PS-3152 of Nanjing Jinling Stepan. Furthermore, the glycerol polyether polyol has a functionality of 3 and a hydroxyl value of 150~300 mgKOH / g; Furthermore, the glycerol polyether polyol is selected from MN-500 of Dongda Chemical. Furthermore, the foaming agent 2 is selected from one or more combinations of cyclopentane, n-pentane, and isopentane.

[0006] Furthermore, the foaming agent 2 is selected from cyclopentane; Furthermore, the catalyst is selected from one or more of potassium formate, potassium acetate, potassium octanoate, and potassium isooctanoate; Furthermore, the foam stabilizer is selected from silicone foam stabilizers; Furthermore, the silicone foam stabilizer is selected from Momentive L6900; Furthermore, the flame retardant is selected from phosphate ester flame retardants; Furthermore, the flame retardant is selected from one or more combinations of TPP, TCPP, and TDCPP; Furthermore, the polyisocyanate is selected from polymethylene polyphenyl polyisocyanates. The polymethylene polyphenyl polyisocyanate has a viscosity of 200-600 mPa·s; an NCO content of 30-32%; and a functionality of 2.5-3.0. Furthermore, the polymethylene polyphenyl polyisocyanate is selected from Wanhua Chemical's PM200; Furthermore, the foaming agent 1 is selected from UiO-66-NH2 / CO2 composite foaming agent; Furthermore, the preparation process of the UiO-66-NH2 / CO2 composite foaming agent is as follows: Step 1 (Preparation of UiO-66-NH2): Zirconium chloride (ZrCl4) was dissolved in 20-30 ml of N,N-dimethylformamide (DMF) and stirred to form solution A. 2-Aminoterephthalic acid (NH2BDC) was dissolved in 20-30 ml of N,N-dimethylformamide (DMF) and stirred to form solution B. Solution A and solution B were mixed, and 2-8 ml of glacial acetic acid was added and stirred to form solution C. Solution C was transferred to a stainless steel reactor with a polytetrafluoroethylene liner and reacted at 80℃~120℃ for 12~24 h. After natural cooling, centrifugation, washing, and drying, UiO-66-NH2 was obtained.

[0007] Step 2: Immerse the UiO-66-NH2 obtained in Step 1 in methanol, replacing the methanol every 24 hours for 72 hours, and then vacuum dry it at 60~90℃ for 6~8 hours to obtain activated UiO-66-NH2; Step 3: Load the activated UiO-66-NH2 into a high-pressure reactor, introduce CO2 into the reactor, heat to 50-60℃, slowly pressurize to 12-15MPa and maintain for 10-12h, then slowly depressurize to obtain UiO-66-NH2 / CO2 composite foaming agent.

[0008] Furthermore, in step one, the mass ratio of zirconium chloride to 2-aminoterephthalic acid is 1.2~1.5:1.

[0009] Furthermore, in step three, the pressurization rate of the slow pressurization is <1 MPa / min, and the depressurization rate of the slow depressurization is <0.5 MPa / min.

[0010] Furthermore, the preparation process of the polyisocyanurate low-temperature thermal insulation material includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 500~1000 rpm, the stirring time is 3~5 min, and the stirring temperature is 10~15℃; Step 2: Add the polyisocyanate of component B to the mixture obtained in Step 1, stir at a speed of 1000~3000 rpm for 3~5 min, and then pour it into a steel mold preheated to 40℃~60℃ within 20~30 s for foaming reaction. The foaming reaction time is 2~5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an oven at 60-100℃ and heat for 2-5 hours to obtain polyisocyanurate low-temperature insulation material.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention first prepares metal-organic framework structure UiO-66-NH2, which is a porous nanoparticle with a large specific surface area and adsorption characteristics. Using it as a carrier of CO2 foaming agent can improve the stability of CO2 foaming agent. The CO2 density in the micropores of MOF is close to that of liquid, which is far greater than the solubility of gas phase foaming agent in polyol. This can improve the pore density and avoid the exothermic reaction of water and isocyanate in traditional foaming agent to release CO2, which leads to the reaction rate of isocyanurate system accelerated, uneven foaming, and reduced strength.

[0012] (2) UiO-66-NH2 has active amino groups, which can react with polyisocyanates to graft the MOF metal-organic framework structure into the polyisocyanurate structure, thereby improving the mechanical properties of polyisocyanurate low-temperature insulation materials. Moreover, since UiO-66-NH2 has good flame retardancy, it can also further improve the flame retardancy of polyisocyanurate low-temperature insulation materials. Detailed Implementation

[0013] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0014] Preparation Example 1 Preparation of UiO-66-NH2 / CO2 composite foaming agent: Step 1 (Preparation of UiO-66-NH2): Dissolve 1.3g of zirconium chloride in 20ml of DMF and stir to form solution A; dissolve 1g of 2-aminoterephthalic acid in 20ml of DMF and stir to form solution B; mix solution A and solution B, add 3ml of glacial acetic acid, and stir to form solution C. Transfer solution C to a stainless steel reactor with a polytetrafluoroethylene liner and react at 90℃ for 14h. After natural cooling, centrifugation, washing, and drying, UiO-66-NH2 is obtained.

[0015] Step 2: Immerse the UiO-66-NH2 obtained in Step 1 in methanol, replacing the methanol every 24 hours for 72 hours, and then vacuum dry it at 80℃ for 6 hours to obtain activated UiO-66-NH2. Step 3: The activated UiO-66-NH2 is loaded into a high-pressure reactor, CO2 is introduced into the reactor, the temperature is raised to 55°C, and the pressure is slowly increased to 13MPa at a rate of 0.5MPa / min and maintained for 12h. Then, the pressure is slowly released at a rate of 0.1MPa / min to obtain UiO-66-NH2 / CO2 composite foaming agent A.

[0016] Preparation Example 2 Preparation of UiO-66-NH2 / CO2 composite foaming agent: Step 1 (Preparation of UiO-66-NH2): 1.4 g of zirconium chloride was dissolved in 30 ml of DMF and stirred to form solution A; 1 g of 2-aminoterephthalic acid was dissolved in 30 ml of DMF and stirred to form solution B; solution A and solution B were mixed, and 4 ml of glacial acetic acid was added and stirred to form solution C. Solution C was transferred to a stainless steel reactor with a polytetrafluoroethylene liner and reacted at 80 °C for 15 h. After natural cooling, centrifugation, washing, and drying, UiO-66-NH2 was obtained.

[0017] Step 2: Immerse the UiO-66-NH2 obtained in Step 1 in methanol, replacing the methanol every 24 hours for 72 hours, and then vacuum dry it at 80℃ for 6 hours to obtain activated UiO-66-NH2. Step 3: The activated UiO-66-NH2 is loaded into a high-pressure reactor, CO2 is introduced into the reactor, the temperature is raised to 60°C, the pressure is slowly increased to 15MPa at a rate of 0.5MPa / min and maintained for 12h, and then the pressure is slowly released at a rate of 0.1MPa / min to obtain UiO-66-NH2 / CO2 composite foaming agent B.

[0018] Comparative Preparation Example 1 Preparation of UiO-66 / CO2 composite foaming agent: Step 1 (Preparation of UiO-66): Dissolve 1.3g of zirconium chloride in 20ml of DMF and stir to form solution A; dissolve 1g of terephthalic acid in 20ml of DMF and stir to form solution B; mix solution A and solution B, add 3ml of glacial acetic acid, and stir to form solution C. Transfer solution C to a stainless steel reactor with a polytetrafluoroethylene liner and react at 90℃ for 14h. After natural cooling, centrifugation, washing, and drying, UiO-66 is obtained.

[0019] Step 2: Immerse the UiO-66 obtained in Step 1 in methanol, replacing the methanol every 24 hours for 72 hours, and then vacuum dry it at 80℃ for 6 hours to obtain activated UiO-66. Step 3: The activated UiO-66 is loaded into a high-pressure reactor, CO2 is introduced into the reactor, the temperature is raised to 55°C, and the pressure is slowly increased to 13MPa at a rate of 0.5MPa / min and maintained for 12h. Then, the pressure is slowly released at a rate of 0.1MPa / min to obtain UiO-66 / CO2 composite foaming agent C.

[0020] Example 1 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings UiO-66-NH2 / CO2 composite foaming agent A 15 parts 8 parts of cyclopentane 6 parts potassium acetate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0021] Example 2 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings UiO-66-NH2 / CO2 composite foaming agent B 15 parts 8 parts of cyclopentane 6 parts potassium acetate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0022] Example 3 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings UiO-66-NH2 / CO2 composite foaming agent B 15 parts 8 parts of cyclopentane 4 parts potassium acetate 2 parts potassium isooctanoate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0023] Example 4 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 70 copies MN-500 30 servings UiO-66-NH2 / CO2 composite foaming agent B 20 parts 8 parts of cyclopentane 4 parts potassium acetate 2 parts potassium isooctanoate Momentive L6900 (3 copies) TCPP 6 copies; Component B: PM200 265 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0024] Comparative Example 1 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings UiO-66 / CO2 composite foaming agent C 15 parts 8 parts of cyclopentane 6 parts potassium acetate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0025] Comparative Example 2 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings UiO-66-NH2 (Preparation Example 1) 15 parts 8 parts of cyclopentane 6 parts potassium acetate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0026] Comparative Example 3 The composition of polyisocyanurate low-temperature insulation material is as follows: Component A: PS-3152 60 copies MN-500 40 servings 23 parts of cyclopentane 6 parts potassium acetate Momentive L6900 (2 copies) TCPP 6 copies; Component B: PM200 260 copies; The preparation process of polyisocyanurate low-temperature insulation materials includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 800 rpm, the stirring time is 4 min, and the stirring temperature is 12℃. Step 2: Add PM200 of component B to the mixture obtained in Step 1, stir at 3000 rpm for 3 min, and then pour into a steel mold preheated to 50°C within 20 s for foaming reaction. The foaming reaction time is 5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an 80℃ oven and heat for 3 hours to obtain polyisocyanurate low-temperature insulation material.

[0027] Performance testing 1. Molded core density: Tested according to GB / T6343-2009; 2. Compressive strength: Tested according to GB / T8813-2020; 3. Thermal conductivity: determined according to GB / T10294-2008 using the plate heat flow meter method; 4. Limiting oxygen index: Tested according to GB / T2406.2-2009; 5. Low temperature dimensional stability (-30℃ / 24h): Tested according to GB / T8811-2019.

[0028] Table 1. Performance test results of polyisocyanurate low-temperature insulation materials obtained from each embodiment and comparative example. ; As shown in Table 1, the polyisocyanurate low-temperature insulation material prepared using the present invention has a lower density and exhibits comprehensive performance advantages in compressive strength, thermal insulation, flame retardancy, and low-temperature dimensional stability. Furthermore, compared to Example 1, Comparative Example 1 used UiO-66 (without active amino groups) instead of UiO-66-NH2 to prepare the blowing agent, resulting in a decrease in the compressive strength, thermal insulation, flame retardancy, and low-temperature dimensional stability of the obtained polyisocyanurate low-temperature insulation material. Compared to Example 1, Comparative Example 2 used UiO-66-NH2 obtained in Preparation Example 1 instead of the UiO-66-NH2 / CO2 composite blowing agent A obtained in Example 1. Although the compressive strength was improved, the molded core density was higher, resulting in poor thermal insulation performance, and reduced flame retardancy and low-temperature dimensional stability. Compared to Example 1, Comparative Example 3 used cyclopentane instead of the UiO-66-NH2 / CO2 composite blowing agent A obtained in Example 1. Although the density was lower, the thermal insulation, compressive strength, flame retardancy, and low-temperature dimensional stability all decreased.

[0029] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the defined scope, they should all fall within the protection scope of the present invention.

Claims

1. A polyisocyanurate low-temperature thermal insulation material, characterized in that, The polyisocyanurate low-temperature insulation material is composed of the following components: Component A: 60-80 parts of aromatic polyester polyol 20-40 parts of glycerol polyether polyol Foaming agent 1 10-30 parts Foaming agent 2 5-10 parts 3-9 parts catalyst 1-3 parts foam stabilizer 5-10 parts flame retardant Component B: 250-280 parts of polyisocyanate.

2. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The aromatic polyester polyol has a functionality of 2 to 2.2 and a hydroxyl value of 300 to 330 mgKOH / g.

3. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The glycerol polyether polyol has a functionality of 3 and a hydroxyl value of 150~300 mgKOH / g.

4. The polyisocyanurate low-temperature insulation material as described in claim 2, characterized in that, The foaming agent 1 is selected from UiO-66-NH2 / CO2 composite foaming agent.

5. The polyisocyanurate low-temperature insulation material as described in claim 4, characterized in that, The foaming agent 2 is selected from one or more of cyclopentane, n-pentane, and isopentane.

6. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The catalyst is selected from one or more of potassium formate, potassium acetate, potassium octanoate, and potassium isooctanoate.

7. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The foam stabilizer is selected from silicone foam stabilizers, and the flame retardant is selected from phosphate ester flame retardants.

8. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The polyisocyanate is selected from polymethylene polyphenyl polyisocyanate, and the viscosity of the polymethylene polyphenyl polyisocyanate is 200~600 mPa·s; the NCO content is 30~32%; and the functionality is 2.5~3.

0.

9. The polyisocyanurate low-temperature insulation material as described in claim 4, characterized in that, The preparation process of the UiO-66-NH2 / CO2 composite foaming agent is as follows: Step 1: Zirconium chloride was dissolved in 20-30 ml of N,N-dimethylformamide and stirred to form solution A; 2-aminoterephthalic acid was dissolved in 20-30 ml of N,N-dimethylformamide and stirred to form solution B; solution A and solution B were mixed, and 2-8 ml of glacial acetic acid was added and stirred to form solution C; solution C was transferred to a stainless steel reactor with a polytetrafluoroethylene liner and reacted at 80℃~120℃ for 12~24 h; after natural cooling, centrifugation, washing, and drying, UiO-66-NH2 was obtained. Step 2: Immerse the UiO-66-NH2 obtained in Step 1 in methanol, replacing the methanol every 24 hours for 72 hours, and then vacuum dry it at 60~90℃ for 6~8 hours to obtain activated UiO-66-NH2; Step 3: Load the activated UiO-66-NH2 into a high-pressure reactor, introduce CO2 into the reactor, heat to 50-60℃, slowly pressurize to 12-15MPa and maintain for 10-12h, then slowly depressurize to obtain UiO-66-NH2 / CO2 composite foaming agent.

10. The polyisocyanurate low-temperature insulation material as described in claim 1, characterized in that, The preparation process of the polyisocyanurate low-temperature insulation material includes the following steps: Step 1: Mix all components of component A thoroughly to obtain a mixture; the stirring speed is 500~1000 rpm, the stirring time is 3~5 min, and the stirring temperature is 10~15℃; Step 2: Add the polyisocyanate of component B to the mixture obtained in Step 1, stir at a speed of 1000~3000 rpm for 3~5 min, and then pour it into a steel mold preheated to 40℃~60℃ within 20~30 s for foaming reaction. The foaming reaction time is 2~5 min to obtain the foamed product. Step 3: Place the foamed product obtained in Step 2 into an oven at 60-100℃ and heat for 2-5 hours to obtain polyisocyanurate low-temperature insulation material.