High-strength high-temperature-resistant polyurethane foam composite material as well as preparation method and application thereof

Abstract

The invention relates to the field of polymer supports, in particular to a high-strength and high-temperature-resistant polyurethane foam composite material and a preparation method and application thereof.The high-strength and high-temperature-resistant polyurethane foam composite material is composed of a component A and a component B. The component A is prepared from, by mass, 10-15 parts of epoxy modified polyester polyol; 30 to 40 parts of polyester polyol A; 35 to 40 parts of polyester polyol B; 15 to 20 parts of a chain extender A; 2-3 parts of a chain extender B; 0.5 to 1 part of a double metal cyanide catalyst; 0.3 to 0.8 part of a foam stabilizer; 0.3 to 0.6 part of a water foaming agent; the component B is prepared from the following raw materials in parts by mass: 25 to 30 parts of polymerized diphenylmethane diisocyanate; and 70 to 75 parts of polyester polyol A. Carbon dioxide naturally generated in the polyurethane foaming process is converted into a component beneficial to the material performance, and the problem that in a traditional technology, carbon dioxide escapes, and consequently the foam structure is uneven is solved.

Description

Technical Field

[0001] The present invention relates to the field of polymer supports, and in particular to a high-strength, high-temperature-resistant polyurethane foam composite material and a preparation method and application thereof. Background Art

[0002] In the preparation process of traditional polyurethane foam materials, when water is used as a blowing agent, the hydrolysis of polymerized diphenylmethane diisocyanate produces carbon dioxide, which helps foaming. However, due to the low solubility, fast diffusion rate and uneven distribution of carbon dioxide in the reaction system, it is easy to cause uncontrolled gas escape during the foaming process, forming a defective structure with large differences in cell size and uneven cell wall thickness. This unevenness not only reduces the mechanical strength and dimensional stability of the foam, but also causes cell collapse or deformation due to local stress concentration during high-temperature molding, resulting in a significant decrease in key properties such as the material's heat resistance and compression resilience, seriously restricting its application under high-temperature and high-pressure conditions. The existing technology has not yet effectively solved the controllability and structural homogenization problems of carbon dioxide foaming systems. CN 108084394 B relates to a lightweight, high-open-porosity, high-hardness shape-memory rigid polyurethane foam plastic composition and its preparation method. It is obtained by reacting a prepolymer component and a polyol component. The preparation method is simple, and the resulting product has high hardness and low density, is safe and environmentally friendly, and has good process performance. However, it does not propose the control of carbon dioxide, especially the problem of uneven foam caused by carbon dioxide generated in the reaction system. Summary of the Invention

[0003] In order to make up for the above shortcomings, the present invention provides a high-strength and high-temperature resistant polyurethane foam combination material and its preparation method and application, which converts the carbon dioxide naturally generated during the polyurethane foaming process into components that are beneficial to the material properties, solving the problem of uneven foam structure caused by carbon dioxide escape in traditional processes.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A high-strength, high-temperature-resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:0.8-1.2, wherein:

[0006] Component A includes, by mass:

[0007] 10-15 parts of epoxy-modified polyester polyol;

[0008] 30-40 parts of polyester polyol A;

[0009] 35-40 parts of polyester polyol B;

[0010] Chain extender A 15-20 parts;

[0011] Chain extender B 2-3 parts;

[0012] 0.5-1 part of double metal cyanide catalyst;

[0013] Foam stabilizer 0.3-0.8 parts;

[0014] 0.3-0.6 parts of water foaming agent;

[0015] Component B includes, by mass:

[0016] 25-30 parts of polymeric diphenylmethane diisocyanate;

[0017] 70-75 parts of polyester polyol A;

[0018] The epoxy-modified polyester polyol is an aliphatic polyester polyol having a hydroxyl value of 80-100 mgKOH / g and an epoxy value of 0.3-0.5 mol / kg.

[0019] Preferably, the polyester polyol A is an aliphatic polyester polyol having a molecular weight of 1800-2200 and a hydroxyl value of 53-59 mgKOH / g; and the polyester polyol B is an aliphatic polyester polyol having a molecular weight of 800-1200 and a hydroxyl value of 106-118 mgKOH / g.

[0020] Preferably, the chain extender A is 3,3'-dichloro-4,4'-diaminodiphenylmethane; and the chain extender B is hydroquinone dihydroxyethyl ether.

[0021] Preferably, the double metal cyanide catalyst is zinc cobalt cyanide or zinc ferrocyanide; and the foam stabilizer is a silicone-polyether copolymer with a flash point of ≥80°C.

[0022] Preferably, the water foaming agent is distilled water or deionized water.

[0023] This solution also proposes a method for preparing the above-mentioned high-strength and high-temperature resistant polyurethane foam composite material, comprising the following steps:

[0024] (1) Mix and stir the raw materials in component A at 50-60°C for 20-30 minutes to form a homogeneous mixture;

[0025] (2) Component B is heated to 40-50°C, mixed with component A in proportion, and injected into the mold. It is then pre-reacted at 60-80°C for 10-20 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to form cyclic carbonate. The temperature is further raised to 160-180°C for foaming and curing for 30-60 minutes to form a polyurethane foam with a closed-cell rate of ≥85%.

[0026] Preferably, after the cyclic carbonate is generated in step (2), vacuum degassing is applied with a vacuum degree of -0.08 to -0.1 MPa and a degassing time of 5-10 min.

[0027] The high-strength and high-temperature resistant polyurethane foam composite material proposed in this scheme is used in high-end ultra-light sports equipment brackets. The long-term use temperature is ≥150°C, the tensile strength is ≥10 MPa, and the tear strength is ≥6 kgf / mm.

[0028] The core innovation of this patent lies in converting the carbon dioxide naturally generated during the polyurethane foaming process into a component that benefits the material's performance. This solves the problem of uneven foam structure caused by carbon dioxide escape in traditional processes. In traditional methods, the carbon dioxide generated by the reaction of isocyanate and water escapes rapidly, forming cells of varying sizes and reducing the material's strength. This solution introduces epoxy groups into polyester polyols and uses a specific catalyst to preferentially react with the carbon dioxide to form a cyclic compound (cyclic carbonate). This compound can further react with the polyurethane raw materials to form a more stable cross-linked structure. This process chemically fixes the carbon dioxide within the material, preventing it from escaping as a gas. This avoids the defect of coarse cells while increasing the material's flexibility.

[0029] Another innovation lies in the selection of catalysts and process control. Traditional catalysts accelerate the generation and escape of carbon dioxide, but the bimetallic catalyst used in this solution is specifically optimized for the reaction between epoxy groups and carbon dioxide, ensuring that carbon dioxide is captured and participates in the chemical reaction at the initial stage of foaming. The process uses staged temperature control: first, the carbon dioxide and epoxy groups are allowed to fully react at 60-80°C, then the residual gas is removed through vacuum degassing, and finally the material is cured at high temperature. This method not only ensures the effective utilization of carbon dioxide, but also further refines the pores through the vacuum step, making the foam structure more uniform.

[0030] In terms of actual results, this technology has increased the utilization rate of carbon dioxide from less than 50% to more than 80%, reduced the bubble diameter to 1 / 5 of the traditional process, and significantly improved the distribution uniformity. The tensile strength of the material has increased by nearly 70%, and the deformation rate has been reduced to less than 3% during long-term use at a high temperature of 150°C. Compared with solutions that require the addition of additional chemical foaming agents or exogenous carbon dioxide, this technology directly utilizes the naturally generated carbon dioxide in the system without the need for complex equipment or additional costs, thus improving performance while simplifying the production process. This series of improvements breaks through the application limitations of traditional water-foamed polyurethane materials in high-temperature and high-load scenarios, and provides innovative solutions for the lightweight needs of sports equipment, industrial brackets and other fields.

[0031] The present invention has the following beneficial effects:

[0032] 1. Converting the carbon dioxide naturally generated during the polyurethane foaming process into components that are beneficial to the material's performance, solving the problem of uneven foam structure caused by carbon dioxide escape in traditional processes;

[0033] 2. The bimetallic catalyst used is specifically optimized for the reaction between epoxy groups and carbon dioxide, ensuring that the carbon dioxide is captured and participates in the chemical reaction at the initial stage of foaming. The process uses staged temperature control: first, the carbon dioxide and epoxy groups are fully reacted at 60-80°C, then residual gases are removed through vacuum degassing, and finally, the material is cured at high temperature. This method not only ensures the effective utilization of carbon dioxide, but also further refines the cell structure through the vacuum step, making the foam structure more uniform. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0035] In this embodiment and comparative example, the epoxy-modified polyester polyol used was prepared by the following method:

[0036] By weight, 100 parts of dried polyester polyol A were heated to 80° C., 30 parts of toluene, 15 parts of glycidyl ether and 0.5 parts of triphenylphosphine were added, and the temperature was slowly raised to 120° C. under nitrogen conditions, and the reaction was carried out at a constant temperature for 3 hours. Samples were taken every 30 minutes to detect the epoxy value. The reaction was stopped when the epoxy value dropped from the initial 0.55 mol / kg to 0.4 mol / kg. The temperature was lowered to 60° C., 0.1 parts of antioxidant BHT were added, and the mixture was stirred for 30 minutes. Subsequently, the mixture was distilled under reduced pressure at 80° C. and -0.1 MPa for 1 hour to remove toluene and unreacted glycidyl ether. The mixture was filtered through a 0.45 μm polytetrafluoroethylene filter membrane to obtain an aliphatic polyester polyol with a hydroxyl value of 90 mgKOH / g and an epoxy value of 0.4 mol / kg.

[0037] Example 1

[0038] A high-strength, high-temperature resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:1, wherein:

[0039] Component A includes, by mass:

[0040] 13 parts of epoxy-modified polyester polyol;

[0041] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0042] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0043] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0044] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0045] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0046] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0047] 0.5 parts of distilled water;

[0048] Component B includes, by mass:

[0049] 28 parts of polymeric diphenylmethane diisocyanate;

[0050] 72 parts of polyester polyol A;

[0051] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0052] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0053] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0054] Example 2

[0055] A high-strength, high-temperature resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:1, wherein:

[0056] Component A includes, by mass:

[0057] 13 parts of epoxy-modified polyester polyol;

[0058] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0059] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0060] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0061] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0062] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0063] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0064] 0.5 parts of distilled water;

[0065] Component B includes, by mass:

[0066] 28 parts of polymeric diphenylmethane diisocyanate;

[0067] 72 parts of polyester polyol A;

[0068] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0069] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0070] (2) Component B is heated to 45°C, mixed with component A in proportion, and then injected into the mold. Pre-react at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The temperature is further raised to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0071] Example 3

[0072] A high-strength, high-temperature resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:1.2, wherein:

[0073] Component A includes, by mass:

[0074] 15 parts of epoxy-modified polyester polyol;

[0075] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 1900 and a hydroxyl value of 55 mgKOH / g;

[0076] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1100 and a hydroxyl value of 110 mgKOH / g;

[0077] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0078] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0079] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0080] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0081] 0.5 parts of distilled water;

[0082] Component B includes, by mass:

[0083] 30 parts of polymeric diphenylmethane diisocyanate;

[0084] 75 parts of polyester polyol A;

[0085] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0086] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0087] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0088] Comparative Example 1

[0089] The difference from Example 1 is that epoxy-modified polyester polyol is not added:

[0090] A high-strength, high-temperature resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:1, wherein:

[0091] Component A includes, by mass:

[0092] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0093] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0094] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0095] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0096] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0097] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0098] 0.5 parts of distilled water;

[0099] Component B includes, by mass:

[0100] 28 parts of polymeric diphenylmethane diisocyanate;

[0101] 72 parts of polyester polyol A;

[0102] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0103] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0104] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0105] Comparative Example 2

[0106] The difference from Example 1 is that the mass ratio of component A to component B is 1:0.5

[0107] A high-strength, high-temperature resistant polyurethane foam composite material, consisting of component A and component B in a mass ratio of 1:0.5, wherein:

[0108] Component A includes, by mass:

[0109] 13 parts of epoxy-modified polyester polyol;

[0110] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0111] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0112] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0113] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0114] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0115] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0116] 0.5 parts of distilled water;

[0117] Component B includes, by mass:

[0118] 28 parts of polymeric diphenylmethane diisocyanate;

[0119] 72 parts of polyester polyol A;

[0120] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0121] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0122] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0123] Comparative Example 3

[0124] The difference from Example 1 is that the mass ratio of component A to component B is 1:1.5:

[0125] A high-strength, high-temperature resistant polyurethane foam composite material, consisting of component A and component B in a mass ratio of 1:1.5, wherein:

[0126] Component A includes, by mass:

[0127] 13 parts of epoxy-modified polyester polyol;

[0128] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0129] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0130] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0131] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0132] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0133] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0134] 0.5 parts of distilled water;

[0135] Component B includes, by mass:

[0136] 28 parts of polymeric diphenylmethane diisocyanate;

[0137] 72 parts of polyester polyol A;

[0138] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0139] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0140] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0141] Comparative Example 4

[0142] The difference from Example 1 is that the catalyst is triethylenediamine:

[0143] A high-strength, high-temperature-resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:0.8-1.2, wherein:

[0144] Component A includes, by mass:

[0145] 13 parts of epoxy-modified polyester polyol;

[0146] 35 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol with a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0147] 38 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0148] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0149] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0150] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0151] 0.8 parts of triethylenediamine catalyst;

[0152] 0.5 parts of distilled water;

[0153] Component B includes, by mass:

[0154] 28 parts of polymeric diphenylmethane diisocyanate;

[0155] 72 parts of polyester polyol A;

[0156] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0157] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0158] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0159] Comparative Example 5

[0160] The difference from Example 1 is that only polyol A is used:

[0161] A high-strength, high-temperature-resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:0.8-1.2, wherein:

[0162] Component A includes, by mass:

[0163] 13 parts of epoxy-modified polyester polyol;

[0164] 73 parts of polyester polyol A; polyester polyol A is an aliphatic polyester polyol having a molecular weight of 2000 and a hydroxyl value of 55 mgKOH / g;

[0165] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0166] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0167] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0168] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0169] 0.5 parts of distilled water;

[0170] Component B includes, by mass:

[0171] 28 parts of polymeric diphenylmethane diisocyanate;

[0172] 72 parts of polyester polyol A;

[0173] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0174] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0175] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to obtain a high-strength, high-temperature resistant polyurethane foam composite material.

[0176] Comparative Example 6

[0177] The difference from Example 1 is that only polyester polyol B is used:

[0178] A high-strength, high-temperature-resistant polyurethane foam composite material, comprising component A and component B in a mass ratio of 1:0.8-1.2, wherein:

[0179] Component A includes, by mass:

[0180] 13 parts of epoxy-modified polyester polyol;

[0181] 73 parts of polyester polyol B; polyester polyol B is an aliphatic polyester polyol having a molecular weight of 1000 and a hydroxyl value of 110 mgKOH / g;

[0182] Chain extender A is 18 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0183] Chain extender B is 2.5 parts of hydroquinone dihydroxyethyl ether;

[0184] The double metal cyanide catalyst is 0.8 parts of zinc cobalt cyanide;

[0185] The foam stabilizer is 0.5 parts of silicone-polyether copolymer;

[0186] 0.5 parts of distilled water;

[0187] Component B includes, by mass:

[0188] 28 parts of polymeric diphenylmethane diisocyanate;

[0189] 72 parts of polyester polyol B;

[0190] The method for preparing the high-strength, high-temperature-resistant polyurethane foam composite material comprises the following steps:

[0191] (1) Mix and stir the raw materials in component A at 55°C for 25 minutes to form a homogeneous mixture;

[0192] (2) Component B was heated to 45°C, mixed with component A in proportion, and then injected into the mold. The mixture was pre-reacted at 70°C for 15 minutes to allow the epoxy-modified polyester polyol to react with carbon dioxide to generate cyclic carbonate. The vacuum degree was -0.09 MPa, and the degassing time was 8 minutes. The mixture was further heated to 170°C for foaming and curing for 50 minutes to form a high-strength, high-temperature resistant polyurethane foam composite material with a closed-cell rate of 92%.

[0193] Performance testing:

[0194] 1. Closed porosity: refer to ASTM D6226;

[0195] 2. Mechanical properties: Refer to ASTM D1621 including tensile strength and elongation at break; ASTM D624 including tear strength, etc.

[0196] 3. High temperature resistance: 150°C, 1MPa load, deformation rate under load conditions of 1000h; the temperature required to detect 5% weight loss.

[0197] The test results are shown in Table 1.

[0198] Table 1

[0199] Test items Closed cell rate (%) Tensile strength (MPa) Tear strength (kN / m) Elongation at break (%) 150℃ thermal deformation rate (%) 5% weight loss temperature (℃) Example 1 92.5 10.8 7.2 260 2.8 315 Example 2 90.3 9.5 6.5 240 3.5 305 Example 3 91.8 10.2 6.9 250 3 310 Comparative Example 1 68.2 5.6 3.1 120 9.5 280 Comparative Example 2 75.6 6.3 3.8 150 7.8 290 Comparative Example 3 63.4 4.8 2.7 100 12.3 275 Comparative Example 4 71.5 6 3.5 130 8.2 285 Comparative Example 5 69.8 5.2 2.9 110 10.1 278 Comparative Example 6 66.7 4.5 2.4 90 13.6 270

[0200] Examples 1-3 have significant improvements compared to Comparative Examples 1-6, which is mainly due to the uniformity of the size of the foam and the strengthening of the foam by the epoxy-modified polyester polyol.

[0201] Compared to Example 1, Comparative Example 1 omitted the addition of an epoxy-modified polyol, resulting in a lower closed-cell ratio. The carbon dioxide generated by the reaction of isocyanate and water could not be chemically captured, allowing a large amount of gas to escape and form coarse cells. Furthermore, the lack of a cyclic carbonate chain extender resulted in a crosslinked network composed solely of the rigid chain extender, significantly increasing the material's brittleness and decreasing its temperature resistance.

[0202] In Comparative Example 2, compared to Example 1, the mass ratio of Component A to Component B was 1:0.5. Excessive polyol resulted in insufficient crosslinking density and incomplete curing. The cell wall thickness decreased, the material structure became loose, and the mechanical properties deteriorated overall.

[0203] In Comparative Example 3, compared to Example 1, the mass ratio of Component A:Component B was 1:1.5. Excessive isocyanate resulted in an excessively fast primary reaction rate, preventing the epoxy groups from fully capturing carbon dioxide, and the gases coalesced into large bubbles before curing. Excessive isocyanate residue also triggered a late hydrolysis side reaction, reducing the thermal stability of the material.

[0204] Compared to Example 1, in Comparative Example 4, triethylenediamine was used as the catalyst. Triethylenediamine accelerated the reaction between isocyanate and water, causing the carbon dioxide generation rate to exceed the chemical capture capacity of the epoxy groups, leading to a large amount of gas escape and forming cell defects. Furthermore, triethylenediamine catalyzed the side reaction to form allophanates, which compromised the network integrity.

[0205] Compared with Example 1, Comparative Example 5 uses only polyester polyol A and lacks low molecular weight polyester polyol B (hydroxyl value 110 mgKOH / g). The system has insufficient crosslinking density and low molecular chain entanglement, resulting in a simultaneous decrease in mechanical properties and thermal stability.

[0206] Compared to Example 1, Comparative Example 6 uses only polyester polyol B. The absence of high-molecular-weight polyester polyol A results in a loss of flexibility. The high crosslink density may lead to embrittled cell walls, allowing carbon dioxide to escape through cracks. Excessive rigidity also triggers stress concentration, accelerating creep deformation at high temperatures.

[0207] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high-strength, high-temperature-resistant polyurethane foam composite material, characterized in that: It is composed of component A and component B in a mass ratio of 1:0.8-1.2, wherein: Component A includes, by mass: 10-15 parts of epoxy-modified polyester polyol; 30-40 parts of polyester polyol A; 35-40 parts of polyester polyol B; Chain extender A 15-20 parts; Chain extender B 2-3 parts; 0.5-1 part of double metal cyanide catalyst; Foam stabilizer 0.3-0.8 parts; 0.3-0.6 parts of water foaming agent; Component B includes, by mass: 25-30 parts of polymeric diphenylmethane diisocyanate; 70-75 parts of polyester polyol A; The epoxy-modified polyester polyol is an aliphatic polyester polyol having a hydroxyl value of 80-100 mgKOH / g and an epoxy value of 0.3-0.5 mol / kg.

2. The high-strength and high-temperature resistant polyurethane foam composition according to claim 1, characterized in that: The polyester polyol A is an aliphatic polyester polyol with a molecular weight of 1800-2200 and a hydroxyl value of 53-59 mgKOH / g; the polyester polyol B is an aliphatic polyester polyol with a molecular weight of 800-1200 and a hydroxyl value of 106-118 mgKOH / g.

3. The high-strength and high-temperature-resistant polyurethane foam composition according to claim 1, characterized in that: The chain extender A is 3,3'-dichloro-4,4'-diaminodiphenylmethane; and the chain extender B is hydroquinone dihydroxyethyl ether.

4. The high-strength and high-temperature-resistant polyurethane foam composition according to claim 1, characterized in that: The double metal cyanide catalyst is zinc cobalt cyanide or zinc ferrocyanide; and the foam stabilizer is a silicone-polyether copolymer.

5. The high-strength and high-temperature-resistant polyurethane foam composition according to claim 1, wherein: The water foaming agent is distilled water or deionized water.

6. A method for preparing the high-strength, high-temperature-resistant polyurethane foam composition according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Mix and stir the raw materials in component A at 50-60°C for 20-30 minutes to form a homogeneous mixture; (2) Component B is heated to 40-50°C, mixed with component A in proportion and injected into the mold, followed by pre-reaction at 60-80°C for 10-20 minutes, and further heated to 160-180°C for foaming and curing for 30-60 minutes to form a polyurethane foam with a closed-cell rate of ≥85%.

7. The method for preparing the high-strength and high-temperature resistant polyurethane foam composition according to claim 6, characterized in that: After the cyclic carbonate is generated in step (2), vacuum degassing is applied with a vacuum degree of -0.08 to -0.1 MPa and a degassing time of 5-10 minutes.

8. A high-strength, high-temperature-resistant polyurethane foam composite material as claimed in any one of claims 1 to 5, used in high-end ultra-light sports equipment brackets.