High-temperature resistant hot-pressed polyurethane sheet insole composite material and its preparation method

Abstract

The present invention belongs to the technical field of polyurethane elastomers, and particularly relates to a high temperature resistant hot pressing polyurethane sheet insole composite material and a preparation method thereof. The composite material is composed of component A and component B, wherein component A is physically mixed with polyester ether polyol, polyether polymer polyol, chain extender, crosslinking agent, foam leveling agent, catalyst and foaming agent, and component B is isocyanate modified by polyester ether polyol. Components A and B are mixed in a certain proportion to prepare a high temperature resistant hot pressing polyurethane sheet product. The polyurethane sheet insole prepared by the present invention has good mechanical properties and high temperature resistant hot pressing performance, and can use a higher hot pressing temperature, shorten the hot pressing time, shorten the production cycle, and reduce the probability of insole fracturing, thereby improving production efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a high-temperature resistant hot-pressed polyurethane sheet shoe insole composite material and a preparation method thereof. Background Art

[0002] Polyurethane materials have the advantages of superior physical and mechanical properties, high load-bearing performance and a wide hardness range. They have become one of the mainstream materials in the shoe material market and are currently widely used in the production of insoles. There are currently two main types of polyurethane insoles. One is molded cloth insoles. The production process is that a low-pressure pouring machine directly injects the mixed material into a mold with a surface cloth, forming it in one piece, and cutting it to the required size according to requirements after maturation. The process is simple and quick to operate, but molded cloth insoles have the disadvantages of high product density, poor air permeability, a single experience, and easy mildew and odor. The other is a sheet insole. The production process is that a low-pressure pouring machine directly injects the mixed material into a thicker mold. After molding, the sole is taken out for maturation, cut in the middle, and half is combined with the surface cloth and other material layers (material layers that optimize the touch, such as polyurethane slow rebound layers, etc.) by high-temperature hot pressing in a vulcanizer, and finally cut to the required size according to requirements.

[0003] The advantages of sheet insoles are low product density, good porosity, and the ability to press other material layers to optimize the user experience. The disadvantage is that the operation process is complicated, high-temperature hot pressing is required, and the overall production cycle is long. When hot pressing sheet soles, if the hot pressing temperature is low, the hot pressing time needs to be extended, and the production cycle is long; if the hot pressing temperature is high, the insole is easy to crack, resulting in a high defective rate. At present, the hot pressing temperature of sheet insoles on the market is generally 180-200℃, and the hot pressing time is 70-90s. The overall hot pressing temperature is low and the hot pressing time is long. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a composite material of a high-temperature resistant hot-pressed polyurethane sheet insole, by introducing ester bonds into polyether polyols so that the prepared insole has the good flexibility and elasticity of polyether products while also having better mechanical properties, thereby maintaining comfort while extending the service life of the insole.

[0005] Another object of the present invention is to provide a method for preparing a high-temperature resistant hot-pressed polyurethane sheet insole assembly. The prepared sheet insole has excellent mechanical properties and significant high-temperature hot-pressing resistance. A higher hot-pressing temperature can be used to shorten the hot-pressing time while reducing the probability of insole fracturing and improving production efficiency.

[0006] The technical solution adopted by the present invention is:

[0007] The composite material of the high temperature resistant hot pressed polyurethane sheet insole is characterized by being composed of component A and component B, wherein:

[0008] Component A is composed of the following raw materials in weight percentage, wherein the total mass of polyester ether polyol and polyether polymer polyol is 100%, and the remaining raw materials are calculated as a percentage of the total mass of polyester ether polyol and polyether polymer polyol:

[0009]

[0010] Component B consists of the following raw materials in weight percentage plus storage stabilizer:

[0011] Polyester ether polyol 10-30%;

[0012] Isocyanate 70-90%.

[0013] The polyester ether polyol adopts low molecular weight polyether polyol with functionality of 2 and 3 as a mixed initiator, is compounded with phthalic anhydride, and then polymerized with propylene oxide by catalysis of double metal cyanide complex catalyst DMC, and then polymerized with ethylene oxide by catalysis of alkali metal catalyst KOH to obtain low saturation high activity polyester ether polyol; the polyether ester polyol has a number average molecular weight of 6000-9000 and a functionality of 2.5-2.9.

[0014] The molecular weight of the low molecular weight polyether polyol with functionality 2 and 3 is 300-1000, and the ratio is 1:(1-10); the amount of phthalic anhydride is 5-15wt% of the polyester ether polyol; and the amount of ethylene oxide is 15-25wt% of the polyester ether polyol.

[0015] The preparation method of the polyester ether polyol comprises the following steps: adding a low molecular weight polyether polyol with a functionality of 2 and 3, phthalic anhydride and a double metal cyanide complex catalyst DMC accounting for 0.02-0.06 wt% of the polyester ether polyol into a pressure-resistant reactor, performing nitrogen replacement, evacuating to -0.090--0.093 MPa, heating to 130-135° C., adding propylene oxide in an amount of 10-15 wt% of the low molecular weight polyether polyol, and when the catalyst is successfully induced and activated, controlling the temperature in the reactor to 135-145° C., continuously adding the remaining propylene oxide, and maintaining the internal pressure at 0.5-1 after the addition is completed. .5h, remove unreacted monomers and small molecule by-products under vacuum conditions of -0.090 to -0.093MPa for 0.5 to 1h, add 0.10 to 0.15wt% of the alkali metal catalyst KOH of the polyester ether polyol, dehydrate at 100 to 115°C under vacuum conditions of -0.090 to -0.093MPa for 1 to 2h, continuously add ethylene oxide, and continue the internal pressure reaction for 0.5 to 1.5h after the addition is completed, remove unreacted monomers and small molecule by-products under vacuum conditions of -0.090 to -0.093MPa for 0.5 to 1h, then cool down and carry out neutralization, adsorption, drying and filtration in sequence to obtain polyester ether polyol.

[0016] The polyether polymer polyol is one or both of styrene and acrylonitrile. The polyether polymer polyol is used as a monomer to graft copolymerize a polyether polyol with a functionality of 2.9 to 3.1 and a number average molecular weight of 2000 to 5000 to obtain a polyether polymer polyol with a solid content of 20 to 45%.

[0017] The chain extender is one or two of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propylene glycol, dipropylene glycol or 1,6-hexanediol.

[0018] The cross-linking agent is one or two of diethanolamine, triethanolamine, glycerol and trimethylolpropane.

[0019] The foam leveling agent is a polysiloxane-olefin oxide block copolymer; the catalyst is a tertiary amine catalyst; and the foaming agent is water.

[0020] The isocyanate is one or two of pure MDI, carbodiimide-modified MDI, MDI-50 or polymeric MDI; in the preparation process of component B, a storage stabilizer is generally required to be added, and the storage stabilizer is one or two of phosphoric acid or benzoyl chloride, and the dosage is 40ppm.

[0021] The method for preparing the high temperature resistant hot pressed polyurethane sheet insole composite material comprises the following steps:

[0022] (1) Preparation of component A:

[0023] Put polyester ether polyol, polyether polymer polyol, chain extender, crosslinking agent, foaming agent, catalyst and blowing agent into a reaction kettle at room temperature, control the material temperature at 40-50°C, and stir for 1-2 hours to obtain component A;

[0024] (2) Preparation of component B:

[0025] Put the polyester ether polyol based on the formula into a reaction kettle at room temperature, stir and heat to 90-110° C., dehydrate and degas for 2-3 hours under vacuum conditions, then cool to 50° C., add the measured storage stabilizer and isocyanate, and react at 70-80° C. for 2-3 hours to obtain component B;

[0026] (3) Preparation of sheet insoles:

[0027] Preparation: Inject component A and component B into the material tank of a low-pressure casting machine respectively, control the material temperature of component A and component B at 22-25°C, adjust the discharge speed of component A and component B, make the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B be 1:(0.9-1.1), mix component A and component B at a speed of 4000-6000 r / min, inject into a sheet mold at 40-60°C, open the mold after 3-5 minutes, and obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0028] Polyether insoles are generally divided into cloth insoles and sheet insoles. The process of sheet insoles is simple, but they are relatively closed-cell and have a single category. Sheet insoles have low density and good open-cell properties, and can be pressed with other material layers to enrich the user experience. However, the operation process is complicated, high-temperature hot pressing is required, and the overall production cycle is relatively long. When the sheet sole is hot-pressed, if the hot-pressing temperature is low, the hot-pressing time needs to be extended, and the production cycle is long; if the hot-pressing temperature is high, the insole is easily cracked, resulting in a high defective rate. The present invention introduces partial ester bonds into the polyether polyol by adding phthalic anhydride during the production process of the polyether polyol. The ester bond performance is better than the ether bond mechanical property, so that the prepared insole has good flexibility and elasticity of polyether products, as well as better mechanical properties and high temperature resistance, and the service life of the insole is extended while maintaining comfort. Phthalic anhydride is added during the production of polyether polyols, and benzene rings are introduced into the polyether structure at the same time as ester bonds. The benzene ring is a rigid group with strong high temperature resistance, so that the prepared insoles have excellent high temperature resistance. When the insoles are subjected to high-temperature hot pressing, they can withstand higher temperatures while shortening the hot pressing time. At the same time, the probability of insole fracturing is also reduced, thereby improving production efficiency and reducing production costs.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) Polyester ether polyols with special molecular design are used, and ester bonds are introduced into the polyether polyols, so that the prepared insoles have good flexibility and elasticity of polyether products and better mechanical properties, maintaining comfort while extending the service life of the insoles.

[0031] (2) The introduction of the ester bond and the benzene ring at the same time make the prepared insole have excellent high temperature resistance. When the insole is subjected to high temperature hot pressing, it can withstand higher temperatures while shortening the hot pressing time. At the same time, it also reduces the probability of insole cracking, thereby improving production efficiency and reducing production costs. DETAILED DESCRIPTION

[0032] The present invention is further described below with reference to the embodiments, but they do not limit the implementation of the present invention.

[0033] Raw materials used in the embodiments and comparative examples:

[0034] INOV0LF330N is a commercial product of Shandong Yinuowei New Materials Co., Ltd.;

[0035] 10LD83EK is a commercial product of Shandong Bluestar Dongda Chemical Co., Ltd.;

[0036] CHP-H45 is a commercial product from Changhua Chemical Technology Co., Ltd.;

[0037] POP36 / 28 is a commercial product of Shandong Bluestar Dongda Chemical Co., Ltd.;

[0038] DC2525 is a commercial product of Air Products & Chemicals Inc., USA;

[0039] Isocyanate CDMDI-100L is a commercial product of Wanhua Chemical Group Co., Ltd.;

[0040] INOVOL C204 2-functionality, 400 molecular weight polyether polyol, commercially available from Shandong INOVOL New Materials Co., Ltd.;

[0041] INOVOL C307 3-functionality, 700 molecular weight polyether polyol is a commercial product of Shandong INOVOL New Materials Co., Ltd.

[0042] Example 1

[0043] 182g INOVOL C204, 319g INOVOL C307, 409g phthalic anhydride and 1.64g DMC were added to the pressure reactor for nitrogen replacement. The pressure was evacuated to -0.093MPa, the temperature was raised to 133°C, and 50g propylene oxide was added to initiate the reaction. When the pressure in the reactor dropped significantly and the temperature rose sharply, the catalyst was successfully induced and activated. The temperature in the reactor was controlled at 135°C, and the remaining 5586g propylene oxide was added continuously. After the addition was completed, the internal pressure was maintained for 1h. Unreacted monomers and small molecular by-products were removed under a vacuum condition of -0.090MPa for 1h, and 5.4g KOH, dehydrate at 115°C for 1h under -0.090MPa vacuum conditions, continuously add 1636g ethylene oxide, continue internal pressure reaction for 1h after the addition is completed, remove unreacted monomers and small molecular by-products under -0.092MPa vacuum conditions for 1h, cool to 80°C, add 286g water and 41g phosphoric acid for neutralization, then add 8.2g magnesium silicate for adsorption in sequence, and then dry and filter to obtain the target polyester ether polyol a1. The product has a functionality of 2.5 and a number average molecular weight of 9000.

[0044] Example 2

[0045] 98g INOVOL C204, 402g INOVOL C307, 655g phthalic anhydride and 2.62g DMC were added to the pressure reactor for nitrogen replacement. The reactor was evacuated to -0.092MPa, the temperature was raised to 135°C, and 65g propylene oxide was added to initiate the reaction. When the pressure in the reactor dropped significantly and the temperature rose sharply, the catalyst was successfully activated. The temperature in the reactor was controlled at 140°C, and the remaining 4156g propylene oxide was added continuously. After the addition was completed, the internal pressure was maintained for 1h. Unreacted monomers and small molecular by-products were removed under a vacuum condition of -0.093MPa for 0.5h. 8.2g KOH, dehydrated at 105°C for 2h under -0.093MPa vacuum conditions, continuously added 1180g ethylene oxide, continued internal pressure reaction for 1.5h after the addition was completed, removed unreacted monomers and small molecular by-products under -0.093MPa vacuum conditions for 0.5h, cooled to 80°C, added 229g water and 33g phosphoric acid for neutralization, then added 6.6g magnesium silicate for adsorption in sequence, and then dried and filtered to obtain the target polyester ether polyol a2. The product has a functionality of 2.7 and a number average molecular weight of 8000.

[0046] Example 3

[0047] 30g INOVOL C204, 472g INOVOL C307, 787g phthalic anhydride and 3.15g DMC were added to the pressure reactor for nitrogen replacement. The reactor was evacuated to -0.090MPa, the temperature was raised to 137°C, and 60g propylene oxide was added to initiate the reaction. When the pressure in the reactor dropped significantly and the temperature rose sharply, the catalyst was successfully activated. The temperature in the reactor was controlled at 145°C, and the remaining 2745g propylene oxide was added continuously. After the addition was completed, the internal pressure was maintained for 1.5h. Unreacted monomers and small molecular by-products were removed under a vacuum condition of -0.091MPa for 1h, and 7.9g KOH, dehydrate at 110°C for 1.5h under -0.091MPa vacuum conditions, continuously add 1155g ethylene oxide, continue internal pressure reaction for 1h after the addition is completed, remove unreacted monomers and small molecular by-products under -0.091MPa vacuum conditions for 1h, cool to 80°C, add 184g water and 26g phosphoric acid for neutralization, then add 5.2g magnesium silicate for adsorption in sequence, and then dry and filter to obtain the target polyester ether polyol a3. The product has a functionality of 2.9 and a number average molecular weight of 7000.

[0048] Example 4

[0049] Preparation of component A: 85 kg of polyester ether polyol a1, 35 kg of polyether polymer polyol CHP-H45, 4 kg of chain extender ethylene glycol, 0.5 kg of crosslinking agent diethanolamine, 1 kg of crosslinking agent triethanolamine, 0.5 kg of foam leveling agent DC2525, 0.9 kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2 kg of water were put into a reactor and stirred at 40°C for 2 hours to obtain component A;

[0050] Preparation of component B: 20 ​​kg of measured polyester ether polyol a1 was put into a reactor at room temperature, heated to 95°C with stirring, dehydrated and degassed under vacuum conditions for 3 hours, then cooled to 50°C, 4 g of storage stabilizer phosphoric acid and 50 kg of pure 4,4-diphenylmethane diisocyanate and 30 kg of carbodiimide-modified isocyanate were added, and reacted at 80°C for 2 hours to obtain component B.

[0051] Preparation of sheet insoles: inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B to 25°C, adjust the discharge speeds of components A and B so that the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B is 1:1, mix components A and B at a speed of 5000r / min, inject them into a 40°C sheet mold, and open the mold after 5 minutes to obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0052] Example 5

[0053] Preparation of component A: put 75kg of polyester ether polyol a2, 25kg of polyether polymer polyol POP36 / 28, 1kg of chain extender ethylene glycol, 1.5kg of chain extender 1,4-butanediol, 1kg of crosslinker diethanolamine, 0.5kg of foam leveler DC2525, 1kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2kg of water into a reactor, stir at 45°C for 1.5 hours to obtain component A;

[0054] Preparation of component B: 25 kg of measured polyester ether polyol a2 is put into a reactor at room temperature, stirred and heated to 100°C, dehydrated and degassed under vacuum conditions for 2.5 hours, then cooled to 50°C, 4 g of storage stabilizer phosphoric acid and 40 kg of pure 4,4-diphenylmethane diisocyanate and 35 kg of carbodiimide-modified isocyanate are added, and reacted at 70°C for 3 hours to obtain component B.

[0055] Preparation of sheet insoles: Inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B at 23°C, adjust the discharge speeds of components A and B, make the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B to be 1:0.95, mix components A and B at a speed of 5000 r / min, inject them into a 50°C sheet mold, open the mold after 4 minutes, and obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0056] Example 6

[0057] Preparation of component A: 85 kg of polyester ether polyol a3, 15 kg of polyether polymer polyol CHP-H45, 3 kg of chain extender 1,4-butanediol, 1 kg of cross-linking agent diethanolamine, 0.5 kg of foam leveling agent DC2525, 1.1 kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2 kg of water were put into a reactor and stirred at 50°C for 1 hour to obtain component A;

[0058] Preparation of component B: 30 kg of measured polyester ether polyol a3 was put into a reactor at room temperature, heated to 110°C with stirring, dehydrated and degassed under vacuum for 2 hours, then cooled to 50°C, 4 g of phosphoric acid as a storage stabilizer, 40 kg of pure 4,4-diphenylmethane diisocyanate, and 30 kg of carbodiimide-modified isocyanate were added, and reacted at 75°C for 2.5 hours to obtain component B.

[0059] Preparation of sheet insoles: Inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B at 24°C, adjust the discharge speeds of components A and B so that the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B is 1:1.1, mix components A and B at a speed of 6000 r / min, inject them into a 60°C sheet mold, and open the mold after 3 minutes to obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0060] Comparative Example 1

[0061] Preparation of component A: 75 kg of polyether polyol INOVOLF330N, 25 kg of polyether polymer polyol POP36 / 28, 3.5 kg of chain extender ethylene glycol, 1.5 kg of cross-linking agent triethanolamine, 0.5 kg of foam leveling agent DC2525, 1 kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2 kg of water were put into a reactor and stirred at 45°C for 2 hours to obtain component A;

[0062] Preparation of component B: put 20 kg of measured polyether polyol INOVOLF330N into a reactor at room temperature, stir and heat to 100°C, dehydrate and degas under vacuum conditions for 2.5 hours, then cool to 50°C, add 4 g of storage stabilizer phosphoric acid and 45 kg of pure 4,4-diphenylmethane diisocyanate and 35 kg of carbodiimide-modified isocyanate, and react at 75°C for 2.5 hours to obtain component B.

[0063] Preparation of sheet insoles: Inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B to 25°C, adjust the discharge speeds of components A and B so that the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B is 1:1, mix components A and B at a speed of 5000r / min, inject them into a 45°C sheet mold, and open the mold after 5 minutes to obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0064] Comparative Example 2

[0065] Preparation of component A: 70 kg of polyether polyol INOVOLF330N, polyether polymer polyol CHP-H45, 2.5 kg of ethylene glycol, 1 kg of diethanolamine, 0.5 kg of DC2525, 0.8 kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2 kg of water were added into a reaction kettle and stirred at 50°C for 1 hour to obtain component A;

[0066] Preparation of component B: put 20 kg of measured polyether polyol 10LD83EK into a reactor at room temperature, stir and heat to 105°C, dehydrate and degas under vacuum conditions for 2 hours, then cool to 50°C, add 4 g of storage stabilizer phosphoric acid and 50 kg of pure 4,4-diphenylmethane diisocyanate and 30 kg of carbodiimide-modified isocyanate, and react at 70°C for 3 hours to obtain component B.

[0067] Preparation of sheet insoles: Inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B at 23°C, adjust the discharge speeds of components A and B so that the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B is 1:1.05, mix components A and B at a speed of 5000r / min, inject them into a 50°C sheet mold, and open the mold after 4 minutes to obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0068] Comparative Example 3

[0069] Preparation of component A: 80 kg of polyether polyol 10LD83EK, 20 kg of polyether polymer polyol POP36 / 28, 4 kg of chain extender 1,4-butanediol, 1 kg of cross-linking agent triethanolamine, 0.5 kg of foam leveling agent DC2525, 1.1 kg of triethylenediamine glycol solution with a catalyst mass fraction of 33%, and 2 kg of water were put into a reactor and stirred at 40°C for 2 hours to obtain component A;

[0070] Preparation of component B: put 25 kg of measured polyether polyol 10LD83EK into a reactor at room temperature, stir and heat to 95°C, dehydrate and degas under vacuum conditions for 3 hours, then cool to 50°C, add 4 g of storage stabilizer phosphoric acid and 45 kg of pure 4,4-diphenylmethane diisocyanate and 30 kg of carbodiimide-modified isocyanate, and react at 80°C for 2 hours to obtain component B.

[0071] Preparation of sheet insoles: Inject components A and B into the material tank of a low-pressure casting machine respectively, control the material temperature of components A and B at 24°C, adjust the discharge speeds of components A and B so that the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B is 1:0.9, mix components A and B at a speed of 6000 r / min, inject them into a 60°C sheet mold, and open the mold after 3.5 minutes to obtain a high-temperature resistant hot-pressed polyurethane sheet.

[0072] The high temperature resistant hot-pressed polyurethane sheets obtained in Examples 4-6 and Comparative Examples 1-2 were subjected to performance tests, and the performance tests were performed on 10 mm thick samples. The product density was tested with reference to GB / T 6343-2009, the hardness was tested with reference to GB / T3903.4-2017, the tensile strength and elongation were tested with reference to GB / T 528-2009, and the product density was tested with reference to GB / T6343-2009.

[0073] The performance test results of the polyurethane sheet insoles of Examples 4 to 6 and Comparative Examples 1 to 3 are shown in Table 3.

[0074] Table 3 Performance test results of polyurethane sheet insoles of Examples 4 to 6 and Comparative Examples 1 to 3

[0075]

[0076] It can be seen from Table 3 that the sheet insole prepared from the high-temperature resistant hot-pressed polyurethane sheet insole combination material prepared by the present invention has excellent mechanical properties, significant high-temperature hot-pressing resistance, and can use a higher hot-pressing temperature to shorten the hot-pressing time while reducing the probability of insole fracturing and improving production efficiency.

Claims

1. A composite material of a high temperature resistant hot pressed polyurethane sheet insole, characterized in that: It consists of component A and component B, wherein: Component A is composed of the following raw materials in percentage by weight, wherein the total mass of polyester ether polyol and polyether polymer polyol is 100%, and the remaining raw materials are calculated as a percentage of the total mass of polyester ether polyol and polyether polymer polyol: Polyester ether polyol 60~90%; Polyether polymer polyol 10~40%; Chain extender 0~5%; Cross-linking agent 0~5%; Foam leveling agent 0.1~1%; Catalyst 0.5~2%; Foaming agent 1~3%; Component B is composed of the following raw materials in weight percentage: Polyester ether polyol 10~30%; Isocyanate 70~90%; The polyester ether polyol adopts low molecular weight polyether polyol with functionality of 2 and 3 as a mixed initiator, is compounded with phthalic anhydride, and then polymerized with propylene oxide by catalysis of double metal cyanide complex catalyst DMC, and then polymerized with ethylene oxide by catalysis of alkali metal catalyst KOH to obtain low saturation high activity polyester ether polyol; the polyester ether polyol has a number average molecular weight of 6000-9000 and a functionality of 2.5-2.

9.

2. The high temperature resistant hot pressing polyurethane sheet insole composite material according to claim 1, characterized in that: The molecular weight of the low molecular weight polyether polyol with functionality of 2 and 3 is 300-1000, and the ratio is 1:(1-10); the amount of phthalic anhydride is 5-15wt% of the polyester ether polyol; and the amount of ethylene oxide is 15-25wt% of the polyester ether polyol.

3. The composite material of the high temperature resistant hot pressing polyurethane sheet insole according to claim 1, characterized in that: The preparation method of the polyester ether polyol comprises the following steps: adding a low molecular weight polyether polyol with a functionality of 2 and 3, phthalic anhydride and a double metal cyanide complex catalyst DMC accounting for 0.02-0.06 wt% of the polyester ether polyol into a reactor, performing nitrogen replacement, evacuating to -0.090-0.093 MPa, heating to 130-135° C., adding propylene oxide in an amount of 10-15 wt% of the low molecular weight polyether polyol, and when the catalyst is successfully induced and activated, controlling the temperature in the reactor to 135-145° C., continuously adding the remaining propylene oxide, and maintaining the internal pressure at 0.5-1. 5h, remove unreacted monomers and small molecule by-products under vacuum conditions of -0.090~-0.093MPa for 0.5~1h, add 0.10~0.15wt% of the alkali metal catalyst KOH of polyester ether polyol, dehydrate at 100~115℃ under vacuum conditions of -0.090~-0.093MPa for 1~2h, continuously add ethylene oxide, and continue the internal pressure reaction for 0.5~1.5h after the addition is completed, remove unreacted monomers and small molecule by-products under vacuum conditions of -0.090~-0.093MPa for 0.5~1h, then cool down and carry out neutralization, adsorption, drying and filtration in sequence to obtain polyester ether polyol.

4. The combination material of the high temperature resistant hot pressed polyurethane sheet insole according to claim 1, characterized in that: The polyether polymer polyol is one or both of styrene and acrylonitrile as monomers, and the polyether polymer polyol with a functionality of 2.9-3.1 and a number average molecular weight of 2000-5000 is graft copolymerized to obtain a polyether polymer polyol with a solid content of 20-45%.

5. The combination material of the high temperature resistant hot pressing polyurethane sheet insole according to claim 1, characterized in that: The chain extender is one or two of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propylene glycol, dipropylene glycol or 1,6-hexanediol.

6. The combination material of the high temperature resistant hot pressing polyurethane sheet insole according to claim 1, characterized in that: The cross-linking agent is one or two of diethanolamine, triethanolamine, glycerol and trimethylolpropane.

7. The combination material of the high temperature resistant hot pressing polyurethane sheet insole according to claim 1, characterized in that: The foam leveling agent is a polysiloxane-olefin oxide block copolymer; the catalyst is a tertiary amine catalyst; and the foaming agent is water.

8. The combination material of the high temperature resistant hot pressing polyurethane sheet insole according to claim 1, characterized in that: The isocyanate is one or two of pure MDI, carbodiimide-modified MDI, MDI-50 or polymerized MDI.

9. A method for preparing the high temperature resistant hot pressed polyurethane sheet insole assembly according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Preparation of component A: Put polyester ether polyol, polyether polymer polyol, chain extender, crosslinking agent, foaming agent, catalyst and foaming agent into a reaction kettle at room temperature, control the material temperature at 40-50°C, and stir for 1-2 hours to obtain component A; (2) Preparation of component B: Put the polyester ether polyol based on the formula into a reactor at room temperature, stir and heat to 90-110°C, dehydrate and degas for 2-3 hours under vacuum conditions, then cool to 40-60°C, add the measured storage stabilizer and isocyanate, and react at 70-80°C for 2-3 hours to obtain component B; (3) Preparation of sheet insoles: Preparation: Inject component A and component B into the material tank of a low-pressure casting machine respectively, control the material temperature of component A and component B at 22~25℃, adjust the discharge speed of component A and component B, make the ratio of the molar number of active hydrogen in component A to the molar number of isocyanate groups in component B to be 1:(0.9~1.1), mix component A and component B at a speed of 4000~6000r / min, inject into a sheet mold at 40~60℃, open the mold after 3~5min, and obtain a high temperature resistant hot-pressed polyurethane sheet.

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