Process for the preparation of a polyether polyol and its use

Abstract

The application provides a preparation method of polyether polyol and application thereof, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: (1) polyeicosanol, cyclohexanol and boron trifluoride ether are put into a polymerization reactor, nitrogen is replaced, and the temperature is increased to 90-110 DEG C; (2) propylene oxide is continuously introduced, and the temperature in the reactor is controlled to be 90-110 DEG C; (3) after the introduction of propylene oxide, the reaction temperature in the reactor is controlled to be 90-110 DEG C; when the pressure in the reactor is reduced to-0.1 MPa, vacuum is drawn, and the temperature is reduced to room temperature, thereby obtaining hard foam polyether polyol. The polyether polyol prepared by the method does not need post-treatment and can be directly used for the production of polyurethane hard foam plastic products, and the polyurethane hard foam plastic product prepared has good dimensional stability and good heat preservation effect.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing polyether polyols and their applications. Background Technology

[0002] Rigid polyurethane foam (RPUF) is a porous polymer material formed by foaming polyurethane (PU) as a matrix using a foaming agent. It possesses properties such as lightweight, high strength, thermal insulation, waterproofing, flame retardancy, good chemical stability, and acid and alkali resistance, and is widely used in construction, cold chain logistics, transportation, and electronics. However, the thermal insulation performance and stability of existing rigid polyurethane foam products do not yet fully meet the requirements of refrigerators, freezers, cold storage facilities, and the construction industry. Summary of the Invention

[0003] This invention provides a method for preparing polyether polyols. The resulting polyether polyols can be directly used in the production of rigid polyurethane foam products without post-treatment. The resulting rigid polyurethane foam products have good dimensional stability and good thermal insulation effect.

[0004] The objective of this invention is achieved through the following technical solution: A method for preparing a polyether polyol includes the following steps: (1) Add polyeicosylglycerol, cyclohexanol and boron trifluoride ether to the polymerization reactor, purge with nitrogen, and heat to 90-110℃; (2) Continuously introduce propylene oxide and control the temperature inside the reactor to 90-110℃. (3) After introducing propylene oxide, control the reaction temperature inside the reactor to 90-110℃; when the pressure inside the reactor drops to -0.1MPa, evacuate and cool to room temperature to obtain rigid foam polyether polyol.

[0005] In this invention, the molar ratio of polyeicoglycerol to cyclohexanol is 1:0.9-1.1.

[0006] In this invention, the molar ratio of the mixture of polyeicosuccinic acid and cyclohexanol to propylene oxide is 1:1.05-1.5.

[0007] In this invention, the mass of boron trifluoride ether is 0.5-3‰ of the total mass of polyeicoglycerol, cyclohexanol and propylene oxide.

[0008] This invention also provides a method for preparing rigid polyurethane foam, comprising the following steps: (1) Preparation of component A: Mix 90-110 parts by weight of the polyether polyol described in claim 1, 4.5-5.5 parts by weight of foam stabilizer L6863, 1-2 parts by weight of pentamethyldiethylenetriamine, 1-3 parts by weight of tertiary amine catalyst and 10-30 parts by weight of cyclopentane evenly; (2) Quickly pour component B into component A, mechanically stir, pour into a mold for foaming, and obtain rigid polyurethane foam; component B is polyisocyanate PAPI; the mass ratio of component A to component B is 1:1.05-1.2.

[0009] The polyether polyol prepared by the method of this invention can be directly used in the production of rigid polyurethane foam products without post-treatment. The resulting rigid polyurethane foam products have good dimensional stability and good thermal insulation effect, fully meeting the requirements of refrigerators, freezers, cold storage and the construction industry. Detailed Implementation

[0010] The following embodiments will further illustrate the synthesis method in the invention, but the invention is not limited to the listed embodiments and should also include other known modifications within the scope of the invention claims.

[0011] The reagents used in this invention are sourced from the following sources: Polyeicosylglycerol was purchased from Shandong Binzhou Jinsheng New Material Technology Co., Ltd.

[0012] Cyclohexanol, structural formula: Purchased from Shandong Qixing Chemical Co., Ltd.

[0013] Boron trifluoride ether was purchased from Tesco Chemicals Ltd.

[0014] Polydecylglycerol, structural formula is Purchased from Shandong Binzhou Jinsheng New Material Technology Co., Ltd.

[0015] Benzyl alcohol, structural formula is Purchased from Jinan Huiteng Chemical Co., Ltd.

[0016] Cyclopentane, structural formula is Purchased from Shanghai Luyang Chemical Co., Ltd.

[0017] The three polyethers, INOVOL R6001C, INOVOL R5118G, and INOVOL R6205, were all purchased from Shandong Yinuowei New Materials Co., Ltd.

[0018] Example 1: Synthesis of polyether polyols a and b 1. Synthesizing polyether polyol a includes the following steps: (1) 714g of polyeicosylglycerol, 95g of cyclohexanol and 0.8g of boron trifluoride ether were added to a 1L polymerization reactor at room temperature. The pressure inside the reactor was reduced to -0.1MPa by evacuation. After nitrogen purging, the pressure inside the reactor was reduced to -0.1MPa again and the vacuum was closed. The temperature was then raised to 100℃.

[0019] (2) 191g of propylene oxide was continuously introduced. During the process of introducing propylene oxide, the pressure inside the reactor was controlled at 0.15MPa and the temperature inside the reactor was controlled at 100℃.

[0020] After introducing propylene oxide, the reaction temperature inside the reactor was controlled at 100℃. When the pressure inside the reactor dropped to -0.1MPa, the reaction ended, and a vacuum was applied at 100℃ for 1 hour. Finally, the product was cooled to room temperature and discharged to obtain rigid polyurethane foam polyether polyol a.

[0021] Synthetic polyether polyols b The synthesis of polyether polyol b includes the following steps: (1) 917g of polyeicosylglycerol and 0.8g of boron trifluoride ether were added to a 1L polymerization reactor at room temperature. The pressure inside the reactor was reduced to -0.1MPa by evacuation. After nitrogen purging, the pressure inside the reactor was reduced to -0.1MPa again and the vacuum was closed. The temperature was then raised to 100℃.

[0022] (2) 83g of propylene oxide was continuously introduced. During the process of introducing propylene oxide, the pressure inside the reactor was controlled at 0.15MPa and the temperature inside the reactor was controlled at 100℃.

[0023] (3) After introducing propylene oxide, the reaction temperature inside the reactor is controlled at 100℃. When the pressure inside the reactor drops to -0.1MPa, the reaction ends, and a vacuum is applied at 100℃ for 1 hour. Finally, the product is discharged at room temperature to obtain rigid foam polyether polyol b.

[0024] Example 2: Synthesis of polyether polyols c, d, and e 1. Synthesizing polyether polyol C includes the following steps: 361g of polydecylglycerol, 95g of cyclohexanol and 0.8g of boron trifluoride ether were added to a 1L polymerization reactor at room temperature. The reactor was evacuated to reduce the pressure inside to -0.1MPa. After nitrogen purging, the reactor was evacuated again to reduce the pressure inside to -0.1MPa. The vacuum was then closed. The temperature was raised to 100℃.

[0025] 544g of propylene oxide was continuously introduced. During the process of introducing propylene oxide, the pressure inside the reactor was controlled at 0.15MPa and the temperature inside the reactor was controlled at 100℃.

[0026] After introducing propylene oxide, the reaction temperature inside the reactor was controlled at 100℃. When the pressure inside the reactor dropped to -0.1MPa, the reaction ended, and a vacuum was applied at 100℃ for 1 hour. Finally, the product was cooled to room temperature and discharged to obtain rigid polyurethane foam polyether polyol C.

[0027] 2. Synthesis of polyether polyols d The synthesis of polyether polyol d includes the following steps: 713g of polyeicosylglycerol, 103g of benzyl alcohol, and 0.8g of boron trifluoride ether were added to a 1L polymerization reactor at room temperature. The reactor was evacuated to reduce the pressure inside to -0.1MPa. After nitrogen purging, the reactor was evacuated again to reduce the pressure inside to -0.1MPa, and the vacuum was closed. The temperature was then raised to 100℃.

[0028] 184g of propylene oxide was continuously introduced. During the process of introducing propylene oxide, the pressure inside the reactor was controlled at 0.15MPa and the temperature inside the reactor was controlled at 100℃.

[0029] After introducing propylene oxide, the reaction temperature inside the reactor was controlled at 100℃. When the pressure inside the reactor dropped to -0.1MPa, the reaction ended, and a vacuum was applied at 100℃ for 1 hour. Finally, the product was cooled to room temperature and discharged to obtain rigid polyurethane foam polyether polyol d.

[0030] 3. Preparation of rigid foam polyether polyol e The preparation of rigid foam polyether polyol e includes the following steps: uniformly mixing three polyethers, INOVOL R6001C, INOVOL R5118G, and INOVOL R6205, in a mass ratio of 30:20:50 to obtain rigid foam polyether polyol e.

[0031] 4. Rigid foam polyether polyol f The rigid foam polyether polyol f is polyether polyol NJ-6305C purchased from Jurong Ningwu New Material Co., Ltd.

[0032] Example 3: Preparation of Rigid Polyurethane Foam Products Rigid polyurethane foams were prepared using the rigid polyether polyol af prepared in Examples 1-2, and the performance of each rigid polyurethane foam was tested.

[0033] I. Raw materials for rigid polyurethane foam The raw materials for rigid polyurethane foam include: (1) Component A: 100 parts by weight of rigid foam polyether polyol (a, b, c, d, e or f), 5 parts by weight of foam stabilizer L6863 (purchased from Momentive Advanced Materials Group), 2 parts by weight of catalyst pentamethyldiethylenetriamine, 2 parts by weight of catalyst A33 (purchased from Air Products, brand name: Dabco33-LV) and 20 parts by weight of blowing agent cyclopentane, mixed evenly. (2) Component B: Polyisocyanate PAPI (polymethylene polyphenyl polyisocyanate, purchased from Wanhua Chemical Co., Ltd., product number: WANNATEPM-2010). The mass ratio of component A to component B is 1:1.1.

[0034] II. Preparation methods of rigid polyurethane foam At an ambient temperature of 25°C, 100 parts by weight of component A were placed in a plastic cup, and 110 parts by weight of component B were placed in another plastic cup. After quickly pouring component B into the plastic cup containing component A, the mixture was mechanically stirred (3000 r / min) for about 10 seconds. The mixture was then poured into a mold, and the milky white time, gel time, and post-curing time of the foamed material were recorded to obtain rigid polyurethane foams A, B, C, D, E, and F (the correspondence with the rigid polyether polyol in the raw material is shown in Table 2).

[0035] III. Performance Testing and Results of Rigid Foam Polyether Polyols (1) Performance testing The hydroxyl value of polyether polyols was analyzed according to GB / T12008.3-2009, the moisture content according to GB / T22313-2008, the acid value according to GB / T12008.5-2010, the pH value according to GB / T12008.2-2010, the viscosity according to GB / T12008.7-2010, and the potassium and sodium ion content according to GB / T12008.4-2009. The compatibility (i.e., solubility) of polyether polyols with cyclopentane was tested according to GB / T21845-2008.

[0036] (2) Test results The results of various performance tests are shown in Table 1.

[0037] Table 1 Performance test results of rigid foam polyether polyols

[0038] Note: In Table 1, " / " indicates that the manufacturer did not provide this parameter.

[0039] IV. Performance Testing and Results of Rigid Polyurethane Foam (1) Performance testing The dimensional stability of rigid polyurethane foam was tested according to the method of GB / T8811-2008, and the thermal insulation effect (i.e., thermal conductivity) was tested according to the method of GB / T10294-2008.

[0040] (2) Test results The results of various performance tests are shown in Table 2.

[0041] Table 2. Performance test results of rigid polyurethane foams prepared from different rigid polyether polyols.

[0042] As shown in Tables 1 and 2, the rigid polyurethane foam A prepared using polyether polyol a (prepared in Example 1) exhibits significantly higher dimensional stability and thermal insulation performance than rigid polyurethane foams prepared using other polyether polyols. Therefore, it is less prone to shrinkage or expansion deformation due to temperature changes, effectively preventing heat transfer and demonstrating significant advantages in the field of thermal insulation. It can be applied in industries such as refrigerators, freezers, cold storage, and construction. Since no post-processing is required during preparation, the yield is high, the production process is simple, and it is environmentally friendly.

Claims

1. A method for preparing a polyether polyol, characterized in that... Includes the following steps: (1) Add polyeicosylglycerol, cyclohexanol and boron trifluoride ether to the polymerization reactor, purge with nitrogen, and heat to 90-110℃; (2) Continuously introduce propylene oxide and control the temperature inside the reactor to 90-110℃; (3) After introducing propylene oxide, control the reaction temperature inside the reactor to 90-110℃; when the pressure inside the reactor drops to -0.1MPa, evacuate and cool to room temperature to obtain rigid foam polyether polyol; The molar ratio of polyeicosylglycerol to cyclohexanol is 1:0.9-1.1; the molar ratio of the mixture of polyeicosylglycerol and cyclohexanol to propylene oxide is 1:1.05-1.5; the mass of boron trifluoride ether is 0.5-3‰ of the total mass of polyeicosylglycerol, cyclohexanol and propylene oxide.

2. A method for preparing rigid polyurethane foam, characterized in that... Includes the following steps: (1) Preparation of component A: Mix 90-110 parts by weight of the polyether polyol prepared by the method described in claim 1, 4.5-5.5 parts by weight of foam stabilizer L6863, 1-2 parts by weight of pentamethyldiethylenetriamine, 1-3 parts by weight of A33 and 10-30 parts by weight of cyclopentane evenly; (2) Quickly pour component B into component A, mechanically stir, pour into a mold for foaming, and obtain rigid polyurethane foam; component B is polyisocyanate PAPI; the mass ratio of component A to component B is 1:1.05-1.2.

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