Preparation method of cyanuric acid polyether polyol
By polymerizing cyanoic acid with liquid small molecule alcohol and propylene oxide in an alkaline catalytic environment, the application difficulties of cyanoic acid in the synthesis of polyether polyols is solved, and the high conversion rate and flame retardant performance are improved, and its application scope is expanded.
Patent Information
- Application Number
- CN202411875793.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-19
- Publication Date
- 2025-04-25
AI Technical Summary
In the prior art, cyanoic acid is not widely used in the synthesis of polyether polyols, and its structural speciality leads to difficulty in reaction, resulting in limited application range of cyanoic acid.
Cyanolic acid and liquid small molecule alcohol are used as starting agents to polymerize with propylene oxide under the action of an alkaline catalyst. Through low-temperature and high-temperature polymerization reaction, the complete conversion and reaction of cyanolic acid are ensured.
The high conversion rate and residue-free cyanide acid are achieved, which expands its application range and improves the flame retardant performance of the resulting polyether polyol.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polyether polyols, and particularly relates to a method for preparing cyanuric acid polyether polyol. Background Art
[0002] Cyanuric acid, also known as cyanuric acid or isocyanuric acid, is an important fine chemical. Finished cyanuric acid is a white, odorless, non-toxic crystalline solid that is slightly soluble in water and most solvents such as benzene, acetone, ether, and ethanol. Cyanuric acid mainly has two tautomer structures, the enol form and the keto form. Both structures exist in some cyanuric acid finished products. In industry, cyanuric acid and its derivatives have many important applications, involving industries such as medical pesticides, textile dyes and coatings, and mechanical and electrical manufacturing.
[0003] Polyether polyols are important raw materials for the polyurethane industry and are widely used in the fields of home appliance insulation, pipe insulation, sandwich panels, automotive interiors, coatings, etc. Polyether polyols are prepared by addition polymerization of initiators (compounds with active hydrogen groups) and epoxy compounds (ethylene oxide, propylene oxide). Currently, the most widely used initiators include sucrose, glycerol, mannitol, sorbitol, monoethanolamine, diethanolamine, etc. Due to the particularity of the structure of cyanuric acid, cyanuric acid is not a commonly used initiator for the synthesis of polyether polyols. Summary of the invention
[0004] In order to solve the above technical problems, the present invention provides a method for preparing cyanuric acid polyether polyol, which has scientific and reasonable design, safety and environmental protection, expands the application scope of cyanuric acid, has high cyanuric acid conversion rate and no residue, and the obtained polyether polyol has good flame retardant effect.
[0005] The preparation method of the cyanuric acid polyether polyol of the present invention uses cyanuric acid and liquid small molecule alcohol as initiators, and performs polymerization reaction with propylene oxide under the action of an alkaline catalyst.
[0006] Preferably, the method comprises the following steps:
[0007] (1) Low temperature polymerization: cyanuric acid, liquid small molecule alcohol and alkaline catalyst are added into the reaction kettle, stirred to make the materials uniformly mixed, heated after nitrogen replacement, controlled at 75-85°C, propylene oxide is added dropwise, and matured;
[0008] (2) High temperature polymerization: Control the temperature to 90-110°C, continue to dropwise add the remaining propylene oxide, and mature;
[0009] (3) Polyether post-treatment: Control the temperature to 100-120°C and remove the unreacted propylene oxide under vacuum.
[0010] Preferably, the liquid small molecule alcohol is one or more of glycerol, ethylene glycol, diethylene glycol or propylene glycol.
[0011] Preferably, the alkaline catalyst is one or more of 2,4,6-tris(dimethylaminomethyl)phenol, trimethylamine, triethylamine, triethanolamine, and potassium hydroxide, and more preferably 2,4,6-tris(dimethylaminomethyl)phenol.
[0012] Preferably, the amount of the alkaline catalyst added is 0.1% to 10% of the total mass of cyanuric acid, liquid small molecule alcohol and the alkaline catalyst.
[0013] Preferably, the mass ratio of cyanuric acid, liquid small molecule alcohol and the total amount of propylene oxide in step (1) and step (2) is 1:(0.1-2):(1-30).
[0014] Preferably, the mass ratio of cyanuric acid, liquid small molecule alcohol and the total amount of propylene oxide in step (1) and step (2) is 1:(0.2-1.5):(1-5).
[0015] Preferably, the mass ratio of propylene oxide in step (1) to step (2) is 1:(0.1-10).
[0016] Preferably, the mass ratio of propylene oxide in step (1) to step (2) is 1:(0.2-5).
[0017] Cyanuric acid mainly has two tautomers, alcohol and keto, and its solid mainly exists in keto form. The present invention uses an alkaline catalytic environment, cyanuric acid and a liquid small molecule alcohol compound as an initiator, firstly performs a polymerization reaction with propylene oxide under an environment of 75 to 85°C, and propylene oxide reacts with the cyanuric acid with an alcohol structure until the cyanuric acid with a keto structure is completely converted into an alcohol structure and polymerizes with propylene oxide to obtain a liquid form of cyanuric acid polyether polyol. The present invention uses cyanuric acid and a liquid small molecule alcohol as an initiator, and adopts the above process to simply synthesize cyanuric acid polyether polyol.
[0018] Compared with the prior art, the present invention has the following beneficial effects:
[0019] 1. The present invention effectively expands the application scope of cyanuric acid and has certain economic value; the cyanuric acid polyether polyol prepared by the method of the present invention can be used in the fields of polyurethane rigid foam insulation, soft foam and CASE polyether polyol.
[0020] 2. The cyanuric acid polyether polyol prepared by the present invention has a high cyanuric acid conversion rate and no residue;
[0021] 3. The cyanuric acid polyether polyol prepared by the present invention is used to prepare polyurethane rigid foam plastics, which can effectively improve the flame retardant properties of the polyurethane rigid foam. DETAILED DESCRIPTION
[0022] The technical solution of the present invention will be clearly and completely described below in conjunction with embodiments.
[0023] Unless otherwise specified, all raw materials used in the examples are commercially available.
[0024] Example 1
[0025] 103 g of cyanuric acid, 110 g of glycerol and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor, and a stamping test was performed on the polymerization reactor to ensure good sealing. The materials were mixed evenly by stirring. After nitrogen replacement, the mixture was evacuated to a minimum vacuum degree of -0.093 MPa. The temperature was controlled at 75°C, and propylene oxide was added dropwise until the amount of propylene oxide added was 300 g. The propylene oxide was stopped and the mixture was aged for 30 min. The temperature was raised to 106°C, and 80 g of propylene oxide was continued to be added dropwise. After the addition was completed, the mixture was continued to be aged for 1 h. The temperature was controlled at 100°C, and the unreacted monomers were removed by decompression to obtain cyanuric acid polyether polyol.
[0026] Example 2
[0027] 129 g of cyanuric acid, 92 g of glycerol and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor, and a stamping test was performed on the polymerization reactor to ensure good sealing. The materials were mixed evenly by stirring. After nitrogen replacement, the mixture was evacuated to a minimum vacuum degree of -0.093 MPa. The temperature was controlled at 80°C, and propylene oxide was added dropwise until the amount of propylene oxide added was 300 g. The propylene oxide was stopped and the mixture was aged for 30 min. The temperature was raised to 108°C, and 80 g of propylene oxide was continued to be added dropwise. After the addition was completed, the mixture was aged for 1 h. The temperature was controlled at 110°C, and the unreacted monomers were removed by decompression to obtain cyanuric acid polyether polyol.
[0028] Example 3
[0029] 155 g of cyanuric acid, 74 g of glycerol and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor, and a stamping test was performed on the polymerization reactor to ensure good sealing. The materials were mixed evenly by stirring. After nitrogen replacement, the mixture was evacuated to a minimum vacuum degree of -0.093 MPa. The temperature was controlled at 80°C, and propylene oxide was added dropwise until the amount of propylene oxide added was 300 g. The propylene oxide was stopped and the mixture was aged for 30 min. The temperature was raised to 110°C, and 80 g of propylene oxide was continued to be added dropwise. After the addition was completed, the mixture was continued to be aged for 1 h. The temperature was controlled at 115°C, and the unreacted monomers were removed by decompression to obtain cyanuric acid polyether polyol.
[0030] Example 4
[0031] 194 g of cyanuric acid, 46 g of glycerol and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor, and a stamping test was performed on the polymerization reactor to ensure good sealing. The materials were mixed evenly by stirring. After nitrogen replacement, the mixture was evacuated to a minimum vacuum degree of -0.093 MPa. The temperature was controlled at 85°C, and propylene oxide was added dropwise until the amount of propylene oxide added was 300 g. The propylene oxide was stopped and the mixture was aged for 30 min. The temperature was raised to 108°C, and 80 g of propylene oxide was continued to be added dropwise. After the addition was completed, the mixture was continued to be aged for 1 h. The temperature was controlled at 120°C, and the unreacted monomers were removed by decompression to obtain cyanuric acid polyether polyol.
[0032] Comparative Example 1
[0033] 129 g of cyanuric acid and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor, and a stamping test was performed on the polymerization reactor to ensure that the sealing was good. The materials were stirred to mix evenly. After nitrogen replacement, the mixture was evacuated to a minimum vacuum degree of -0.093 MPa. The temperature was controlled at 80°C, and propylene oxide was added dropwise until the amount of propylene oxide added was 300 g. The propylene oxide was stopped and the mixture was aged for 30 min. The temperature was raised to 108°C, and 80 g of propylene oxide was continued to be added dropwise. After the addition was completed, the mixture was continued to be aged for 1 h. The temperature was controlled at 110°C, and the unreacted monomers were removed under reduced pressure to obtain cyanuric acid polyether polyol.
[0034] Comparative Example 2
[0035] 129 g of cyanuric acid, 92 g of glycerol and 6 g of 2,4,6-tris(dimethylaminomethyl)phenol were added into a polymerization reactor. The polymerization reactor was punched and tested to ensure good sealing. The materials were stirred to mix evenly. After nitrogen replacement, the vacuum was evacuated to the minimum vacuum degree of -0.093 MPa. The temperature was controlled at 108°C. Propylene oxide was added dropwise until the amount of propylene oxide added was 380 g. The addition of propylene oxide was stopped. After the addition was completed, the reactor was matured for 1 h. The temperature was controlled at 110°C. The unreacted monomers were removed by decompression to obtain cyanuric acid polyether polyol.
[0036] Comparative Example 3
[0037] This comparative example 3 is polyether R4110, Shandong Yinuowei New Materials Co., Ltd.
[0038] Performance Testing
[0039] The indicators of the polyether polyols obtained in Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1.
[0040] Table 1 Index of polyether polyols obtained in Examples 1 to 4 and Comparative Examples 1 to 2
[0041]
[0042]
[0043] As can be seen from Table 1, the method of the present invention can successfully synthesize cyanuric acid polyether polyols with different hydroxyl values, and the appearance of the obtained polyether polyol is relatively transparent, proving that the cyanuric acid reaction is relatively sufficient and there is no residue. It can be seen from Examples 1 to 4 and Comparative Examples 1 and 2 that the preparation method of the present invention can effectively solve the dissolution and reaction problems of cyanuric acid, and make cyanuric acid react well with oxidized olefins, and finally prepare suitable cyanuric acid polyether polyols. Comparative Example 1 Since cyanuric acid is not compounded with liquid small molecule alcohol, cyanuric acid is difficult to participate in the reaction, and finally cyanuric acid does not participate in the reaction completely, resulting in turbid appearance of the polyether polyol; Comparative Example 2 reacts at a relatively high temperature throughout the process, and cyanuric acid decomposes at high temperature, resulting in the index completely deviating from expectations, and the high temperature causes the reaction to be too fast, which all causes the cyanuric acid to react insufficiently and fail to fully participate in the reaction process, so that a usable polyether polyol cannot be obtained.
[0044] Flame retardant performance test, by mass:
[0045] The polyether polyols of Examples 1 to 4 were used to prepare flame-retardant rigid foam composite polyethers according to the following formula: 50 parts of cyanuric acid polyether polyol, 50 parts of polyether R4110 (Shandong Yinuowei New Materials Co., Ltd.), and 30 parts of flame retardant TCPP.
[0046] Comparative Example 3: A flame retardant rigid foam composite polyether was prepared according to the following formula: 100 parts of polyether R4110 and 30 parts of flame retardant TCPP.
[0047] The flame retardant rigid foam composite polyether obtained in Examples 1 to 4 and Comparative Example 3 was mixed with isocyanate PM200 (Wanhua Chemical Group Co., Ltd.), and the material ratio was controlled to be 1:1 for foaming to prepare polyurethane rigid foam. The oxygen index test was carried out according to GB / T16581-1996. The test results are shown in Table 2.
[0048] Table 2 Flame retardant properties test table of polyurethane rigid foam of Examples 1 to 4 and Comparative Example 3
[0049]
[0050] It can be seen from the data in Table 2 that the cyanuric acid polyether polyol prepared in the present invention has a more obvious flame retardant effect than the conventional sucrose rigid foam polyether polyol R4110.
Claims
1. A method for preparing cyanuric acid polyether polyol, characterized in that: Cyanuric acid and liquid small molecule alcohol are used as initiators to carry out polymerization reaction with propylene oxide under the action of alkaline catalyst.
2. The method for preparing cyanuric acid polyether polyol according to claim 1, characterized in that: The steps include: (1) Low temperature polymerization: cyanuric acid, liquid small molecule alcohol and alkaline catalyst are added into the reaction kettle, stirred to mix the materials, replaced with nitrogen and heated to 75-85°C, propylene oxide is added dropwise and matured; (2) High temperature polymerization: Control the temperature to 90-110°C, continue to dropwise add the remaining propylene oxide, and mature; (3) Polyether post-treatment: Control the temperature to 100-120°C and remove the unreacted propylene oxide under vacuum.
3. The method for preparing cyanuric acid polyether polyol according to claim 1, characterized in that: The liquid small molecule alcohol is one or more of glycerol, ethylene glycol, diethylene glycol or propylene glycol.
4. The method for preparing cyanuric acid polyether polyol according to claim 1, characterized in that: The alkaline catalyst is one or more of 2,4,6-tris(dimethylaminomethyl)phenol, trimethylamine, triethylamine, triethanolamine and potassium hydroxide.
5. The method for preparing cyanuric acid polyether polyol according to claim 1, characterized in that: The amount of alkaline catalyst added accounts for 0.1% to 10% of the total mass of cyanuric acid, liquid small molecule alcohol and alkaline catalyst.
6. The method for preparing cyanuric acid polyether polyol according to claim 2, characterized in that: The mass ratio of cyanuric acid, liquid small molecule alcohol and the total amount of propylene oxide in step (1) and step (2) is 1:(0.1-2):(1-30).
7. The method for preparing cyanuric acid polyether polyol according to claim 2, characterized in that: The mass ratio of cyanuric acid, liquid small molecule alcohol and the total amount of propylene oxide in step (1) and step (2) is 1:(0.2-1.5):(1-5).
8. The method for preparing cyanuric acid polyether polyol according to claim 2, characterized in that: The mass ratio of propylene oxide in step (1) and step (2) is 1:(0.1-10).
9. The method for preparing cyanuric acid polyether polyol according to claim 2, characterized in that: The mass ratio of propylene oxide in step (1) and step (2) is 1:(0.2-5).