Hard polyurethane foam material for high-temperature-resistant pipeline and preparation method thereof

Abstract

The invention belongs to the technical field of polyurethane, and particularly relates to a rigid polyurethane foam material for a high-temperature-resistant pipeline and a preparation method of the rigid polyurethane foam material. The polyurethane foam is prepared from a component A and a component B according to the mass ratio of 100: (130-150), and the component A comprises the following raw materials in percentage by mass: 7-36% of polyether polyol A; 13 to 35 percent of polyether polyol B; 13 to 37% of polyether polyol C; 3-8% of a catalyst; 3-14% of an auxiliary agent; 0.3%-4.2% of a dispersing agent; 1.3 to 2.5 percent of foam stabilizer; 6-15% of a pentane foaming agent; and the component B is polymethylene polyphenyl isocyanate. Through specific polyether compounding, nano zirconium dioxide and the dispersing agent are added, and the ratio of the component A to the component B is optimized, so that the high temperature resistance, the compression strength and the dimensional stability of the polyurethane foam are greatly improved, and the polyurethane foam is suitable for preparing a pipeline thermal insulation material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of polyurethane, and particularly relates to a hard polyurethane foam material for high-temperature-resistant pipelines and a preparation method thereof. BACKGROUND

[0002] The hard polyurethane foaming pipeline is a building material taking polyol and isocyanate as two-component raw materials, and is mainly applied to the fields of building waterproofing and pipeline corrosion prevention and insulation. The material can be quickly formed through a site spraying process, has the remarkable characteristics of high closed cell rate, good insulation effect and wide application range, and is particularly suitable for petroleum and chemical hot oil conveying pipelines, steam tracing pipelines and smelting plant high-temperature fluid conveying systems.

[0003] The temperature resistance range of conventional hard polyurethane insulation materials is usually between-50 DEG C and 120 DEG C, however, in specific scenarios of high-temperature medium conveying such as petroleum and chemical industry, the medium temperature in the pipeline can break through 150 DEG C or even higher. If the high-temperature resistance of the insulation material is insufficient, the insulation layer is prone to softening, decomposition and even burning in the long-term high-temperature working environment, which not only leads to the failure of the insulation function, but also can cause safety accidents.

[0004] Therefore, it has important practical significance and application value to develop a high-performance polyurethane insulation material suitable for high-temperature scenarios. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a hard polyurethane foam material for high-temperature-resistant pipelines, which greatly improves the high-temperature resistance, compressive strength and dimensional stability of the polyurethane foam by specific polyether compounding, adding nano zirconium dioxide and dispersant, and optimizing the ratio of component A and component B, and is suitable for the preparation of pipeline insulation materials.

[0006] Another purpose of the present application is to provide a preparation method of the hard polyurethane foam material for high-temperature-resistant pipelines.

[0007] The technical solutions adopted by the present application are as follows: The hard polyurethane foam material for high-temperature-resistant pipelines is made of component A and component B in a mass ratio of 100: (130-150), wherein the component A comprises the following raw materials in mass percentage: Polyether polyol A: 7-36%; Polyether polyol B: 13-35%; Polyether polyol C: 13-37%; Catalyst: 3-8%; Auxiliary agent: 3-14%; Dispersant: 0.3-4.2%; Foam stabilizer: 1.3-2.5%; Pentane blowing agent: 6-15%; The B component is a polymethylene polyphenyl isocyanate; The initiator of the polyether polyol A includes sucrose, the functionality is 6-8, and the hydroxyl value is 500-600 mgKOH / g; The initiator of the polyether polyol B includes pentaerythritol, the functionality is 4-8, and the hydroxyl value is 500-600 mgKOH / g; The initiator of the polyether polyol C includes o-toluidine, the functionality is 3-4, and the hydroxyl value is 500-600 mgKOH / g.

[0008] The polyether polyol A is prepared by using sucrose as a single initiator or using sucrose and trimethylolpropane as a composite initiator, and then performing ring-opening polymerization reaction with propylene oxide under the action of a potassium hydroxide catalyst, and then performing neutralization with phosphoric acid, and then performing adsorption, dehydration and filtration.

[0009] The polyether polyol B is prepared by using pentaerythritol as a single initiator or using pentaerythritol and sucrose as a composite initiator, and then performing ring-opening polymerization reaction with propylene oxide under the action of a potassium hydroxide catalyst, and then performing neutralization with phosphoric acid, and then performing adsorption, dehydration and filtration.

[0010] The polyether polyol C is prepared by using o-toluidine as a single initiator or using o-toluidine and triethanolamine as a composite initiator, and then performing ring-opening polymerization reaction with propylene oxide under the action of a potassium hydroxide catalyst, and then performing neutralization with phosphoric acid, and then performing adsorption, dehydration and filtration.

[0011] The catalyst is a mixture of pentamethyldiethylenetriamine (PC-5), N,N-dimethylcyclohexylamine (PC-8) and tris(dimethylaminopropyl)hexahydrotriazine (PC-41), and the mass ratio of the mixture is (1-2):(1-6):(1-3).

[0012] The auxiliary agent is nano zirconium dioxide, and the particle size is 20-50 nm.

[0013] The dispersing agent is sodium polyacrylate.

[0014] The foam stabilizer is a polyether-modified organosilicon surfactant, and preferably TEGOSTAB B 8407, TEGOSTAB B 8460 or TEGOSTAB B84823 of Wacker Special Chemicals (Shanghai) Co., Ltd.

[0015] The pentane blowing agent is one or more of cyclopentane, isopentane or n-pentane.

[0016] The preparation method of the rigid polyurethane foam material for high-temperature resistant pipelines comprises the following steps: Polyether polyol A, polyether polyol B, polyether polyol C, foam stabilizer, catalyst, auxiliary, dispersant, pentane foaming agent are mixed in turn, and stirred at room temperature for 1-2h to obtain A component (combined polyether); when used, A component is mixed with B component according to weight ratio, foaming and curing, and then high-temperature-resistant rigid polyurethane foam material for pipeline is obtained.

[0017] Compared with the prior art, the beneficial effects of the present application are as follows: (1) The present application introduces high-temperature-resistant nano-zirconium dioxide material into the combined polyether system, which significantly improves the compressive strength and dimensional stability of the rigid polyurethane foam product in a long-term high-temperature environment, effectively solves the problem of easy failure of thermal insulation materials under high-temperature working conditions, and is particularly suitable for high-temperature pipeline insulation field; (2) The nano-zirconium dioxide particle size selected in the present application is small, and has good nano-level dispersion compatibility with the combined polyether; at the same time, by adding an appropriate amount of sodium polyacrylate dispersant, the dispersion effect of nano-zirconium dioxide in the combined polyether is further strengthened, and the storage stability of the combined polyether is greatly improved, effectively avoiding the agglomeration or precipitation of nano-zirconium dioxide; (3) The hydroxyl value of the polyether polyol selected in the present application is above 500mgKOH / g, compared with the conventional rigid foam polyether 300-500mgKOH / g hydroxyl value range, the molecular weight is lower, so that the hard segment content in the product polyurethane is higher, which helps to improve the high-temperature resistance of the material; among them, the sucrose polyether polyol selects the super high functionality (6-8) product, the pentaerythritol polyether polyol has excellent dimensional stability and lower viscosity due to its regular molecular structure, which can balance the overall viscosity of the system, and the o-toluidine polyether polyol can also enhance the high-temperature resistance of the product due to the benzene ring in its molecular structure. Through the special selection and optimization of the compounding ratio of the above three kinds of polyether polyols, the comprehensive high-temperature resistance of the product is further improved; (4) The present application adopts the scheme of high excess of B component poly-methylene polyphenyl isocyanate, which can promote the system to form a polyurea structure with excellent thermal stability and heat resistance; at the same time, by accurately adjusting the ratio of A and B components, the high-temperature resistance of the product is further optimized, ensuring its long-term stable operation under high-temperature working conditions. DETAILED DESCRIPTION

[0018] The present application will be further described below in conjunction with the examples, but it does not limit the implementation of the present application.

[0019] The raw materials used in the examples and comparative examples are all conventional commercially available raw materials unless otherwise specified, and the process methods used in the examples and comparative examples are all conventional methods in the art unless otherwise specified.

[0020] Some of the raw materials used in the examples and comparative examples are described as follows: Nano-zirconium dioxide, particle size 35±15 nm.

[0021] INOVOL R8243 (functionality 4, hydroxyl value 430 mgKOH / g), purchased from Shandong YINOWEI New Material Co., Ltd.

[0022] INOVOL R6205 (functionality 4, hydroxyl value 380 mgKOH / g), purchased from Shandong YINOWEI New Material Co., Ltd.

[0023] INOVOL R305 (functionality 3, hydroxyl value 340 mgKOH / g), purchased from Shandong YINOWEI New Material Co., Ltd.

[0024] Polyether polyol A1 is prepared by ring-opening polymerization of propylene oxide with sucrose as a single initiator under the action of potassium hydroxide catalyst, and the reaction product is prepared after neutralization with phosphoric acid, adsorption, dehydration and filtration, with a functionality of 8 and a hydroxyl value of 600 mgKOH / g, and the ring-opening polymerization reaction temperature is 110℃.

[0025] Polyether polyol A2 is prepared by ring-opening polymerization of propylene oxide with sucrose and trimethylolpropane as a composite initiator under the action of potassium hydroxide catalyst, and the reaction product is prepared after neutralization with phosphoric acid, adsorption, dehydration and filtration, with a functionality of 7.5 and a hydroxyl value of 500 mgKOH / g, and the ring-opening polymerization reaction temperature is 110℃.

[0026] Polyether polyol B1 is prepared by ring-opening polymerization of propylene oxide with pentaerythritol as a single initiator under the action of potassium hydroxide catalyst, and the reaction product is prepared after neutralization with phosphoric acid, adsorption, dehydration and filtration, with a functionality of 4 and a hydroxyl value of 600 mgKOH / g, and the ring-opening polymerization reaction temperature is 120℃.

[0027] Polyether polyol B2 is prepared by ring-opening polymerization of propylene oxide with pentaerythritol and sucrose as a composite initiator under the action of potassium hydroxide catalyst, and the reaction product is prepared after neutralization with phosphoric acid, adsorption, dehydration and filtration, with a functionality of 6 and a hydroxyl value of 500 mgKOH / g, and the ring-opening polymerization reaction temperature is 120℃.

[0028] Polyether polyol C1 is prepared by ring-opening polymerization of propylene oxide with o-toluidine as a single initiator under the action of potassium hydroxide catalyst, and the reaction product is prepared after neutralization with phosphoric acid, adsorption, dehydration and filtration, with a functionality of 4 and a hydroxyl value of 600 mgKOH / g, and the ring-opening polymerization reaction temperature is 120℃.

[0029] The polyether polyol C2 is prepared by ring-opening polymerization of propylene oxide in the presence of potassium hydroxide catalyst and using o-tolidine and triethanolamine as a complex initiator, and the reaction product is neutralized by phosphoric acid, and then is prepared by adsorption, dehydration and filtration, and has a functionality of 3.5, a hydroxyl value of 500 mgKOH / g, and a ring-opening polymerization temperature of 120 DEG C.

[0030] Example 1 The high-temperature-resistant rigid polyurethane foam material for pipeline is prepared from A component and B component in a mass ratio of 100:150, wherein the A component is composed of the following raw materials in mass fraction: Polyether polyol A1: 30 parts; Polyether polyol B1: 50 parts; Polyether polyol C1: 20 parts; PC-5: 1 part; PC-8: 3 parts; PC-41: 1.5 parts; Nano zirconium dioxide: 20 parts; Sodium polyacrylate: 6 parts; TEGOSTAB B 8407: 2 parts; Cyclopentane: 10 parts; The B component is polymethylene polyphenyl isocyanate. The preparation method of the high-temperature-resistant rigid polyurethane foam material for pipeline comprises the following steps: The polyether polyol A1, the polyether polyol B1, the polyether polyol C1, the TEGOSTAB B 8407, the PC-5, the PC-8, the PC-41, the nano zirconium dioxide, the sodium polyacrylate and the cyclopentane are sequentially mixed and stirred at room temperature for 2 hours to obtain the A component (combined polyether); when used, the A component is mixed with the polymethylene polyphenyl isocyanate according to the weight ratio, foaming and curing to obtain the high-temperature-resistant rigid polyurethane foam material for pipeline.

[0031] Example 2 The high-temperature-resistant rigid polyurethane foam material for pipeline is prepared from A component and B component in a mass ratio of 100:130, wherein the A component is composed of the following raw materials in mass fraction: Polyether polyol A2: 10 parts; Polyether polyol B2: 40 parts; Polyether polyol C2: 50 parts; PC-5: 3.3 parts; PC-8: 3.3 parts; PC-41: 3.3 parts; Nano zirconium dioxide: 5 parts; Sodium polyacrylate: 0.5 parts; TEGOSTAB B 84823: 3 copies; Isopentane: 20 parts; Component B is polymethylene polyphenyl isocyanate; The method for preparing the high-temperature resistant rigid polyurethane foam material for pipes involves sequentially mixing polyether polyol A2, polyether polyol B2, polyether polyol C2, TEGOSTAB B 84823, PC-5, PC-8, PC-41, nano-zirconia, sodium polyacrylate, and isopentane, and stirring at room temperature for 1 hour to obtain component A (combined polyether). In use, component A is mixed with polymethylene polyphenyl isocyanate in a specific weight ratio, and then foamed and cured to obtain the high-temperature resistant rigid polyurethane foam material for pipes.

[0032] Example 3 The aforementioned high-temperature resistant rigid polyurethane foam material for pipelines is made of component A and component B in a mass ratio of 100:140, wherein component A consists of the following raw materials in parts by mass: Polyether polyol A2: 50 parts; Polyether polyol B1: 20 parts; Polyether polyol C2: 30 parts; PC-5: 1 copy; PC-8: 4 copies; PC-41: 2 copies; Nano-zirconia: 15 parts; Sodium polyacrylate: 3 parts; TEGOSTAB B 8460: 2.5 servings; n-Pentane: 15 parts; Component B is polymethylene polyphenyl isocyanate; The method for preparing the high-temperature resistant rigid polyurethane foam material for pipes involves sequentially mixing polyether polyol A2, polyether polyol B1, polyether polyol C2, TEGOSTAB B 8460, PC-5, PC-8, PC-41, nano-zirconia, sodium polyacrylate, and n-pentane, and stirring at room temperature for 1.5 hours to obtain component A (combined polyether). In use, component A is mixed with polymethylene polyphenyl isocyanate at a specific weight ratio, and then foamed and cured to obtain the high-temperature resistant rigid polyurethane foam material for pipes.

[0033] Comparative Example 1 The difference from Example 1 is that nano-zirconia is not added to component A, otherwise it is the same as Example 1.

[0034] Comparative Example 2 The difference from Example 2 is that sodium polyacrylate is not added to component A, otherwise it is the same as Example 2.

[0035] Comparative Example 3 The rigid polyurethane foam material is made of component A and component B in a mass ratio of 100:140, wherein component A consists of the following raw materials in parts by mass: INOVOL R8243: 50 copies; INOVOL R6205: 20 copies; INOVOL R305: 30 servings; PC-5: 1 copy; PC-8: 4 copies; PC-41: 2 copies; Nano-zirconia: 15 parts; Sodium polyacrylate: 3 parts; TEGOSTAB B 8460: 2.5 servings; n-Pentane: 15 parts; Component B is polymethylene polyphenyl isocyanate; The preparation method of the rigid polyurethane foam material is the same as in Example 3.

[0036] Comparative Example 4 The rigid polyurethane foam material described herein differs from that in Example 1 in that it is made of component A and component B in a mass ratio of 100:100, otherwise it is the same as in Example 1.

[0037] The rigid polyurethane foam materials prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, and the test methods are as follows: Appearance of component A: After placing component A at room temperature for 7 days, observe the changes in its appearance; Compressive strength: Tested in accordance with GB / T 8813-2008; Dimensional deformation rate: Samples with dimensions of 10cm×10cm×2.5cm were placed at corresponding temperatures (150℃ or -50℃) for 48h, and the dimensional deformation rate of the samples was measured and calculated. The calculation formula is: (volume after placement - initial volume) / initial volume × 100%.

[0038] The test results are shown in Table 1.

[0039] Table 1 Performance Test Results

[0040] As shown in Table 1, the rigid polyurethane foam materials prepared in Examples 1-3 exhibit significantly improved compressive strength and dimensional stability compared to the product in Comparative Example 1 (without nano-zirconia), demonstrating a clear advantage. Comparative Example 2, lacking a dispersant, not only showed a small amount of particles and precipitation but also negatively impacted the mechanical properties of the product. The rigid polyurethane foam materials prepared in Comparative Example 3 using conventional polyether polyols and Comparative Example 4 using a non-excessive B component method showed significantly lower compressive strength and dimensional stability than the products obtained in Examples 1-3, indicating a substantial performance difference.

Claims

1. A rigid polyurethane foam material for high-temperature resistant pipes, characterized in that, It is made from component A and component B in a mass ratio of 100:(130~150), wherein component A comprises the following raw materials by mass percentage: Polyether polyol A: 7~36%; Polyether polyol B: 13~35%; Polyether polyol C: 13~37%; Catalyst: 3~8%; Additives: 3~14%; Dispersant: 0.3~4.2%; Foam stabilizer: 1.3~2.5%; Pentane foaming agent: 6~15%; Component B is polymethylene polyphenyl isocyanate; The initiator of the polyether polyol A includes sucrose, with a functionality of 6-8 and a hydroxyl value of 500-600 mgKOH / g; The initiator of the polyether polyol B includes pentaerythritol, with a functionality of 4-8 and a hydroxyl value of 500-600 mgKOH / g; The initiator of the polyether polyol C includes o-toluenediamine, with a functionality of 3-4 and a hydroxyl value of 500-600 mgKOH / g.

2. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The polyether polyol A is prepared by ring-opening polymerization of propylene oxide with sucrose as a single initiator or by a combination of sucrose and trimethylolpropane as a composite initiator under the action of potassium hydroxide catalyst.

3. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The polyether polyol B is prepared by ring-opening polymerization of propylene oxide with pentaerythritol as a single initiator or a combination of pentaerythritol and sucrose as a composite initiator under the action of potassium hydroxide catalyst.

4. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The polyether polyol C is prepared by ring-opening polymerization of propylene oxide with o-toluenediamine as a single initiator or a combination of o-toluenediamine and triethanolamine as a composite initiator under the action of potassium hydroxide catalyst.

5. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The catalyst is a mixture of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine and tris(dimethylaminopropyl)hexahydrotriazine, with a mixing mass ratio of (1-2):(1-6):(1-3).

6. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The additive is nano-zirconia with a particle size of 20-50 nm.

7. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The dispersant is sodium polyacrylate.

8. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The foam stabilizer is a polyether-modified organosilicon surfactant.

9. The rigid polyurethane foam material for high-temperature resistant pipelines according to claim 1, characterized in that, The pentane blowing agent is one or more of cyclopentane, isopentane, or n-pentane.

10. A method for preparing a rigid polyurethane foam material for high-temperature pipelines according to any one of claims 1 to 9, characterized in that, Includes the following steps: Polyether polyol A, polyether polyol B, polyether polyol C, foam stabilizer, catalyst, additives, dispersant, and pentane blowing agent are mixed sequentially and stirred at room temperature for 1-2 hours to obtain component A. When using, component A and component B are mixed in the weight ratio, foamed and cured to obtain rigid polyurethane foam material for high-temperature pipelines.

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