Polyurethane cold storage plate composite material as well as preparation method and application thereof
By using a foaming agent composed of n-pentane and isopentane and a specific polyether polyol system, the problem of poor dimensional stability of polyurethane foam materials at low temperatures was solved, forming a uniform and delicate foam structure, which improved mechanical and thermal insulation properties.
Patent Information
- Application Number
- CN202511072575.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2025-05-27
- Filing Date
- 2025-08-01
- Publication Date
- 2025-11-11
AI Technical Summary
Existing polyurethane foam materials have poor dimensional stability at low temperatures and are prone to shrinkage and deformation, making it difficult to meet the requirements for low-temperature use. In addition, traditional foaming agents have problems such as uneven cell structure and insufficient mechanical properties.
Using n-pentane and isopentane in a specific ratio (6-7:3-4) as foaming agents, and combined with polyether polyols A and B with sucrose as the initiator, as well as low-viscosity, low-functionality polyether polyol C, a uniform and delicate foam structure is formed, which improves mechanical properties and low-temperature stability.
It achieves improved dimensional stability and mechanical properties of foam materials at low temperatures, with a stable foaming process, uniform cell size, and avoidance of shrinkage and deformation, thus meeting the requirements for low-temperature use.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of rigid polyurethane foam materials, specifically to a polyurethane cold storage panel composite material, its preparation method, and its applications. Background Technology
[0002] Rigid polyurethane foam is widely used in insulation applications such as cold storage, freezers, refrigerated trucks, and exterior wall insulation due to its excellent thermal insulation properties, light weight, high compressive strength, and simple foaming process. However, according to industry plans, the PU foam industry must complete the elimination of HCFCs across the entire industry by 2026.
[0003] Therefore, developing a novel foaming agent for polyurethane cold storage panels and its preparation method to replace HCFC-141b as a foaming agent has become a pressing technical problem for the industry. n-Pentane and isopentane, as polyurethane foaming agents, do not damage the ozone layer, have a low greenhouse effect, and meet environmental protection requirements. n-Pentane has a high boiling point and stable chemical properties, making it less prone to side reactions; however, when used alone, it results in low foam hardness and strength, and is prone to foam shrinkage. Isopentane, when used alone, has a fast foaming speed, but requires strict process parameters and is prone to problems such as excessively large cells and uneven foam density.
[0004] In addition, polyurethane foam materials prepared using n-pentane or isopentane as polyurethane blowing agents also have the problem of poor dimensional stability at low temperatures. This often leads to shrinkage and deformation of polyurethane foam materials when used at low temperatures, making it difficult to meet the requirements for use at low temperatures. Therefore, there is an urgent need for a polyurethane foam material with good low-temperature stability. Summary of the Invention
[0005] To address the problem that polyurethane foam materials using n-pentane or isopentane alone exhibit poor dimensional stability at low temperatures, are prone to shrinkage and deformation, and thus fail to meet the requirements for low-temperature applications, this invention provides a polyurethane cold storage panel composite material, its preparation method, and its uses. Primarily used for cold storage insulation, refrigerator insulation, and refrigerated truck insulation, it boasts advantages such as low thermal conductivity, good mechanical properties, and light weight. By using n- and isopentane in a specific ratio, the dimensional stability of the polyurethane foam material at low temperatures is improved, and the foaming process is stable with small cell size, resulting in a uniform and delicate foam structure with excellent mechanical and insulation properties.
[0006] The present invention first provides a polyurethane cold storage panel composite material, which, by weight, comprises the following components: 50-60 parts of polyether polyol A, 30-40 parts of polyether polyol B, 0-10 parts of polyether polyol C, 2-4 parts of foam stabilizer, 1-3 parts of composite catalyst, 20-30 parts of liquid flame retardant, 10-15 parts of foaming agent and 2-4 parts of water.
[0007] The foaming agent is a mixture of n-pentane and isopentane in a mass ratio of (6-7):(3-4). This ensures smooth foaming, resulting in uniform and fine foam bubbles with high mechanical strength, making the foam less prone to shrinkage and deformation at low temperatures.
[0008] In this system, polyether polyols A and B are both polyether polyols polymerized using sucrose as an initiator; optionally, polyether polyol C, which is a polyether polyol obtained using propylene glycol as an initiator, may also be added. This polyether polyol system uses polyether polyols A and B, both initiated with sucrose, to ensure that the rigid foam composition prepared using this combination has good strength. The addition of low-viscosity, low-functionality polyether polyol C enhances the toughness of the rigid foam composition while maintaining its compressive strength. Furthermore, the combination of these three components allows for better mixing with isopentane, ensuring a more uniform dispersion of the components in the composition.
[0009] Preferably, the polyether polyol A is a polyether polyol polymerized with sucrose as an initiator and propylene oxide as a monomer, with a viscosity of 2500-4500 cps at 25°C, a molecular weight of 400-600, a functionality of 4-5, and a hydroxyl value of 430-470 mgKOH / g. The polyether polyol B is a polyether polyol polymerized with sucrose as the initiator and propylene oxide as the monomer. Its viscosity at 25°C is 5000-8000 cps, its molecular weight is 600-700, its functionality is 4-5, and its hydroxyl value is 360-400 mgKOH / g.
[0010] The polyether polyol C is a polyether polyol polymerized with propylene glycol as the initiator and propylene oxide as the monomer. Its viscosity at 25°C is 100-150 cps, its molecular weight is 800-1000, its functionality is 2, and its hydroxyl value is 100-120 mgKOH / g.
[0011] In some embodiments of the present invention, RF-4113 of Jiahe Chemical Co., Ltd. is used as polyether polyol A, RF-8639x of Jiahe Chemical Co., Ltd. is used as polyether polyol B, and LE-210A of Shandong Longhua New Material Co., Ltd. is used as polyether polyol C.
[0012] Preferably, the foam stabilizer is a silicone surfactant, such as one or more of Evonik Specialty Chemicals' B-8545, B-8547, and B-84813, compounded in any proportion.
[0013] In some embodiments of the present invention, B-8547 is used as a foam stabilizer.
[0014] Preferably, the composite catalyst is an amine catalyst, which is one or more of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, tris(dimethylaminopropyl)hexahydrotriazine, N,N-dimethylbenzylamine, 2-hydroxy-N,N,N-trimethyl-1-propylaminocarbamate, and triethylenediamine; more preferably, it is a combination of N,N-dimethylcyclohexylamine, tris(dimethylaminopropyl)hexahydrotriazine, and N,N-dimethylbenzylamine.
[0015] Preferably, the liquid flame retardant is a phosphate ester flame retardant, more preferably tri(2-chloropropyl) phosphate.
[0016] The water used is preferably deionized water.
[0017] The present invention further provides a method for preparing the above-mentioned polyurethane cold storage panel composite material, wherein the components of the polyurethane cold storage panel composite material are mixed evenly to obtain the final product.
[0018] The present invention also provides a rigid polyurethane foam material, which is prepared from the above-mentioned polyurethane cold storage panel composite material.
[0019] More specifically, the preparation method of the above-mentioned rigid polyurethane foam material includes the following steps: 1) The polyurethane cold storage panel assembly is used as component B, and is stirred with component A at a speed of 3000 r / min for 8-10 seconds. Component A is isocyanate. Components B and A are individually temperature-controlled at 22-25°C before mixing; no temperature control is required during mixing, and mixing can be performed directly.
[0020] 2) Pour the material obtained in step 1) into the mold and let it solidify and take shape.
[0021] Preferably, component A is polyphenyl polymethylene polyisocyanate (PAPI); in some embodiments of the present invention, component A is purchased from BASF AG M20S.
[0022] Preferably, in step 1), the mass ratio of component B to component A is 1:(1.1-1.2).
[0023] Preferably, in step 2), the mold temperature during curing is 30-50℃ and the molding time is 30-40 min.
[0024] In step 1) above, the mixture after stirring components A and B will automatically foam. The foaming method and conditions are conventional methods and conditions in this field.
[0025] The present invention has achieved the following beneficial effects: The foaming agent of this invention is a compound of n-pentane and isopentane in a specific ratio (n-pentane: isopentane = 6-7: 3-4). Compared with using 141b, n-pentane, and isopentane as foaming agents, it maintains good thermal conductivity and compressive strength while exhibiting better low-temperature dimensional stability. This avoids shrinkage and deformation at low temperatures, better meeting the needs of low-temperature applications. The combination of n- and isopentane makes the foaming process smoother, the bubbles more uniform, and the mechanical properties higher, while also reducing shrinkage at low temperatures.
[0026] The polyether polyol system of this invention uses polyether polyol A and polyether polyol B, with sucrose as an initiator, to ensure that the rigid foam composition prepared using this combination has good strength. It is combined with low-viscosity, low-functionality polyether polyol C to enhance the toughness of the rigid foam composition while maintaining its compressive strength. Furthermore, the combination of these three components allows for better mixing with the blowing agent incorporating n-isopentane, ensuring more uniform dispersion of the components in the composition. Detailed Implementation
[0027] The technical solution of the present invention will be further described below with reference to specific embodiments. These embodiments are only used to illustrate the technical solution of the present invention in more detail and should not be construed as limiting the scope of protection of the present invention.
[0028] Some raw material information in the following embodiments is shown in Table 1: Table 1 Raw Material Information RF-4113 is a polyether polyol A, which is a polyether polyol polymerized with sucrose as the initiator and propylene oxide as the monomer. The molecular weight is 400-600, the hydroxyl value is 430-470 mgKOH / g, the functionality is 4.0-5.0, and the viscosity at 25℃ is 2500-4500 cps.
[0029] RF-8639x is a polyether polyol B, which is a polyether polyol polymerized with sucrose as the initiator and propylene oxide as the monomer. It has a molecular weight of 600-700, a hydroxyl value of 360-400 mgKOH / g, a functionality of 4.0-5.0, and a viscosity of 5000-8000 cps at 25℃.
[0030] The LE-210A is a polyether polyol C, which is a polyether polyol polymerized with propylene glycol as the initiator and propylene oxide as the monomer. The molecular weight is 800-1000, the hydroxyl value is 100-120 mgKOH / g, the functionality is 2.0, and the viscosity at 25℃ is 100-150 cps.
[0031] The M20S is a polyphenyl polymethylene polyisocyanate.
[0032] The composite catalyst was prepared by mixing N,N-dimethylcyclohexylamine, tris(dimethylaminopropyl)hexahydrotriazine, and N,N-dimethylbenzylamine in a mass ratio of 0.5:0.3:2.0.
[0033] The preparation steps for polyurethane cold storage panel composite materials are as follows: Weigh and mix the polyether polyol monomers, foam stabilizer, composite catalyst, liquid flame retardant, foaming agent and water according to the formula ratio to obtain polyurethane cold storage panel composite material.
[0034] The preparation steps of rigid polyurethane foam are as follows: 1) Take the polyurethane cold storage panel assembly as component B and M20S as component A. Mix component A and component B at 3000 r / min for 8-10 seconds according to the mass ratio of component B to component A of 1:1.1 to ensure that the two components are fully mixed and uniform. Before mixing and stirring, components B and A are individually heated to 22°C. 2) Pour the material obtained in step 1) into the mold and solidify it. The size of the foaming mold used in the solidification process is 25×25×5cm. The mold temperature is controlled at 40℃, the material density is 45kg / m³, and the molding time is 30min.
[0035] All parts in the following examples are by weight.
[0036] Example 1: Polyurethane cold storage panel composite material and polyurethane rigid foam material were prepared according to the following method.
[0037] Preparation of polyurethane cold storage panel assembly: Add 50 parts of polyether polyol RF-4113, 40 parts of polyether polyol RF-8639X, and 10 parts of polyether polyol LE-210A to a reaction vessel, then add 2.2 parts of composite catalyst, 25 parts of liquid flame retardant TCPP, 2.5 parts of foam stabilizer B-8547, 3 parts of water, and 12 parts of foaming agent (a mixture of n-pentane and isopentane in a weight ratio of 7:3). Stir until homogeneous to obtain the final product.
[0038] Preparation of rigid polyurethane foam materials: 1) The polyurethane cold storage panel composite material and M20S are respectively heated to 22°C. The composite material and M20S are mixed at a mass ratio of 1:1.1 in a high-speed stirrer at a speed of 3000r / min for 8-10 seconds to ensure that the two components are fully mixed and uniform. 2) Pour the material obtained in step 1) into the mold and let it solidify and take shape; 3) The size of the foaming mold used in the curing process is 25×25×5cm, the mold temperature is controlled at 40℃, the material density is 45kg / m³, and the molding time is 30min.
[0039] Example 2: Polyurethane cold storage panel composite material and polyurethane rigid foam material were prepared according to the following method.
[0040] Preparation of polyurethane cold storage panel assembly: Add 50 parts of polyether polyol RF-4113, 40 parts of polyether polyol RF-8639X, and 10 parts of polyether polyol LE-210A to a reaction vessel, then add 2.2 parts of composite catalyst, 25 parts of liquid flame retardant TCPP, 2.5 parts of foam stabilizer B-8547, 3 parts of water, and 12 parts of foaming agent (a mixture of n-pentane and isopentane in a weight ratio of 6:4). Stir until homogeneous to obtain the final product.
[0041] Using the obtained polyurethane cold storage panel composite material as raw material, polyurethane rigid foam material was prepared according to the same method as in Example 1.
[0042] Comparative Example 1: Polyurethane cold storage panel composite material and polyurethane rigid foam material were prepared according to the following method.
[0043] Preparation of polyurethane cold storage panel assembly: Add 50 parts of polyether polyol RF-4113, 40 parts of polyether polyol RF-8639X, and 10 parts of polyether polyol LE-210A to a reaction vessel, and then add 2.2 parts of composite catalyst, 25 parts of liquid flame retardant TCPP, 2.5 parts of foam stabilizer B-8547, 3 parts of water, and 12 parts of foaming agent n-pentane in sequence and stir until homogeneous.
[0044] Using the obtained polyurethane cold storage panel composite material as raw material, polyurethane rigid foam material was prepared according to the same method as in Example 1.
[0045] Comparative Example 2: Polyurethane cold storage panel composite material and polyurethane rigid foam material were prepared according to the following method.
[0046] Preparation of polyurethane cold storage panel assembly: Add 50 parts of polyether polyol RF-4113, 40 parts of polyether polyol RF-8639X, and 10 parts of polyether polyol LE-210A to a reaction vessel, and then add 2.2 parts of composite catalyst, 25 parts of liquid flame retardant TCPP, 2.5 parts of foam stabilizer B-8547, 3 parts of water, and 12 parts of foaming agent isopentane in sequence. Stir until homogeneous to obtain the final product.
[0047] Using the obtained polyurethane cold storage panel composite material as raw material, polyurethane rigid foam material was prepared according to the same method as in Example 1.
[0048] Comparative Example 3: Polyurethane cold storage panel composite material and polyurethane rigid foam material were prepared according to the following method.
[0049] Preparation of polyurethane cold storage panel assembly: Add 50 parts of polyether polyol RF-4113, 40 parts of polyether polyol RF-8639X, and 10 parts of polyether polyol LE-210A to a reaction vessel, and then add 2.2 parts of composite catalyst, 25 parts of liquid flame retardant TCPP, 2.5 parts of foam stabilizer B-8547, 3 parts of water, and 25 parts of foaming agent 141b (purchased from Changshu Sanai Fu Fluorochemical Co., Ltd.) and stir until homogeneous.
[0050] Using the obtained polyurethane cold storage panel composite material as raw material, polyurethane rigid foam material was prepared according to the same method as in Example 1.
[0051] The performance of the polyurethane rigid foam materials prepared in Examples 1 and 2 and Comparative Examples 1-3 were tested, and the results are shown in Table 2.
[0052] Table 2 Performance test results of polyurethane rigid foam materials in Examples 1, 2 and Comparative Examples 1-3 As shown in Table 2, compared with Examples 1 and 2 and Comparative Example 3, this invention not only uses less foaming agent, but also has a lower thermal conductivity, higher compressive strength and higher low-temperature dimensional stability.
[0053] As can be seen from the comparison of Examples 1 and 2 with Comparative Examples 1 and 2, when n-pentane and isopentane are compounded in a ratio of (6-7):(3-4) as a foaming agent, compared with using n-pentane or isopentane as a foaming agent, the compounded n-isopentane has good thermal conductivity and compressive strength, while the dimensional change rate at low temperature is significantly reduced, and it has better low-temperature stability.
[0054] The foaming effect varies slightly depending on the ratio of n-pentane to isopentane: a slightly higher proportion of n-pentane results in a slightly lower thermal conductivity and better insulation; a slightly higher proportion of isopentane results in slightly higher compressive strength and mechanical strength. The mixture of n-pentane and isopentane also exhibits a smaller dimensional change rate at low temperatures, effectively addressing the drawback of large dimensional change rates when using n-pentane or isopentane alone.
[0055] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any equivalent substitutions or modifications made by those skilled in the art within the spirit and principle of the present invention without any creative effort should be included within the protection scope of the present invention.
Claims
1. A polyurethane cold storage panel composite material, comprising, by weight, the following components: 50-60 parts polyether polyol A, 30-40 parts polyether polyol B, 0-10 parts polyether polyol C, 2-4 parts foam stabilizer, 1-3 parts composite catalyst, 20-30 parts liquid flame retardant, 10-15 parts foaming agent, and 2-4 parts water, characterized in that: The foaming agent is a mixture of n-pentane and isopentane in a mass ratio of 6-7:3-4.
2. The polyurethane cold storage panel assembly according to claim 1, characterized in that: Polyether polyol A and polyether polyol B are both polyether polyols obtained by polymerization using sucrose as an initiator; polyether polyol C is a polyether polyol obtained by polymerization using propylene glycol as an initiator.
3. The polyurethane cold storage panel assembly according to claim 2, characterized in that: The polyether polyol A is a polyether polyol polymerized with sucrose as the initiator and propylene oxide as the monomer. Its viscosity at 25°C is 2500-4500cps, its molecular weight is 400-600, its functionality is 4-5, and its hydroxyl value is 430-470mgKOH / g. The polyether polyol B is a polyether polyol polymerized with sucrose as the initiator and propylene oxide as the monomer. Its viscosity at 25°C is 5000-8000cps, its molecular weight is 600-700, its functionality is 4-5, and its hydroxyl value is 360-400mgKOH / g. The polyether polyol C is a polyether polyol polymerized with propylene glycol as the initiator and propylene oxide as the monomer. Its viscosity at 25°C is 100-150 cps, its molecular weight is 800-1000, its functionality is 2, and its hydroxyl value is 100-120 mgKOH / g.
4. The polyurethane cold storage panel assembly according to claim 3, characterized in that: RF-4113 from Jiahe Chemical Co., Ltd. was used as polyether polyol A, RF-8639x from Jiahe Chemical Co., Ltd. was used as polyether polyol B, and LE-210A from Shandong Longhua New Material Co., Ltd. was used as polyether polyol C.
5. The polyurethane cold storage panel assembly according to any one of claims 1-4, characterized in that: The foam stabilizer is one or more of Evonik Specialty Chemicals' B-8545, B-8547, and B-84813, in any proportion.
6. The polyurethane cold storage panel assembly according to any one of claims 1-4, characterized in that: The composite catalyst is an amine catalyst, which is one or more of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, tris(dimethylaminopropyl)hexahydrotriazine, N,N-dimethylbenzylamine, 2-hydroxy-N,N,N-trimethyl-1-propylaminocarbamate, and triethylenediamine; the liquid flame retardant is a phosphate ester flame retardant.
7. The polyurethane cold storage panel assembly according to claim 6, characterized in that: The composite catalyst is a combination of N,N-dimethylcyclohexylamine, tris(dimethylaminopropyl)hexahydrotriazine, and N,N-dimethylbenzylamine; the liquid flame retardant is tris(2-chloropropyl) phosphate or triethyl phosphate.
8. The method for preparing the polyurethane cold storage panel assembly as described in claim 1, characterized in that, The polyurethane cold storage panel assembly is obtained by mixing all components evenly.
9. A rigid polyurethane foam material, characterized in that: The polyurethane cold storage panel assembly described in claim 1 is prepared by the following steps: 1) The polyurethane cold storage panel assembly is used as component B, and is stirred with component A at a speed of 3000 r / min for 8-10 seconds. Component A is isocyanate. 2) Pour the material obtained in step 1) into the mold and let it solidify and take shape.
10. The rigid polyurethane foam material according to claim 9, characterized in that: Component A is polyphenyl polymethylene polyisocyanate; In step 1), the mass ratio of component B to component A is 1:1.1-1.2; In step 1), the temperature of components A and B is controlled within the range of 22-25℃ before stirring; In step 2), the curing process involves a mold temperature of 30-50°C and a molding time of 30-40 minutes.