Dicofol flame retardant polyether polyol and preparation method and application thereof
By using trichlorocarcinol and polyol in polyether polyol polymerization under the action of composite catalyst, the problem of poor compatibility of traditional flame retardants is solved, and polyether polyol with long-lasting flame retardant properties and high mechanical strength is achieved, which significantly improves the The flame retardant grade and application fields of the material.
Patent Information
- Application Number
- CN202411154152.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-22
- Publication Date
- 2024-12-13
- Estimated Expiration
- 2044-08-22
AI Technical Summary
The flame retardant of traditional flame retardant polyether polyols has poor compatibility with polyether polyols and is unstable in flame retardant effect, which limits its application.
Trichlorocarcinol is used as a mixture starting agent and polyol polymerized with alkylene oxide under the action of a composite catalyst to prepare a flame-retardant polyether polyol. By optimizing reaction conditions and catalyst compounding, the reaction activity and production efficiency are improved.
It has achieved a polyether polyol with long-lasting flame retardant properties and high mechanical strength, which significantly improved the flame retardant grade of the material, extended the flame retardant life, and expanded the application field of polyether polyols.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polyether polyol preparation, and particularly relates to dicofol flame-retardant polyether polyol and a preparation method and application thereof. Background Art
[0002] With the development of science and technology and the progress of society, flame retardant materials are being used more and more widely in various fields. In the field of polyurethane foam, the improvement of flame retardant properties is of great significance to ensure its safe use.
[0003] China's invention patent application publication number CN114456345A proposes a flame retardant polyether polyol, comprising the following ingredients: 20-35% amine compound, 20-35% aldehyde compound, 10-20% polyether component, 1.2-4.6% catalyst, 0.4-0.8% solution regulator, 4-9% propylene oxide and 2-4.6% flame retardant. Polyether polyol with flame retardant properties can be prepared, so that the articles prepared using the polyether polyol have flame retardancy.
[0004] Traditional flame-retardant polyether polyols mainly achieve flame-retardant effects by adding flame retardants. However, this method often has problems such as poor compatibility between flame retardants and polyether polyols and unstable flame retardant effects, which restricts the application of flame-retardant polyether polyols. Summary of the invention
[0005] In order to solve the above technical problems, the present invention provides a dicofol flame retardant polyether polyol with good flame retardant performance and activity and high mechanical strength. The present invention also provides a preparation method thereof and application in rigid polyurethane foam.
[0006] The dicofol flame retardant polyether polyol of the present invention is obtained by polymerizing dicofol and polyol as mixed initiators with alkylene oxide under the action of a composite catalyst;
[0007] The polyol is one or more of sucrose, solid sorbitol, 1,4-butanediol, triethanolamine, diethylene glycol, glycerol, hexylene glycol, and propylene glycol.
[0008] The structure of dicofol is as follows:
[0009] .
[0010] Preferably, the mass percentage of dicofol in the mixed initiator is 20.23% to 49.6%.
[0011] Preferably, the composite catalyst is a mixture of catalyst A and catalyst B; catalyst A is one or both of KOH and sodium oxide; catalyst B is one or more of dimethylamine, N,N-dimethylbenzylamine, and dimethylcyclohexylamine. Catalyst B has high catalytic activity in the early stage of the reaction, but its catalytic activity decreases in the later stage of the reaction, and even loses its catalytic activity as the reaction time increases. Therefore, the present invention uses two catalysts to compound to improve the catalytic activity of the entire reaction process, thereby shortening the production cycle.
[0012] Preferably, the mass ratio of catalyst A to catalyst B is (0.33~0.8):1.
[0013] Preferably, the added amount of the composite catalyst is 0.61% to 0.89% of the total mass of the mixed initiator and the alkylene oxide.
[0014] Preferably, the alkylene oxide is one or both of propylene oxide and ethylene oxide.
[0015] Preferably, the mass ratio of alkylene oxide to mixed initiator is (0.69-1.45):1.
[0016] The method for preparing the dicofol flame-retardant polyether polyol of the present invention comprises the following steps:
[0017] (1) Adding dicofol, polyol and composite catalyst into a reaction kettle, adding alkylene oxide dropwise at a temperature of 85-90°C and a vacuum degree of -0.08--0.1 MPa to carry out polyether chain extension, and continuing the internal pressure reaction for 1.5-2 hours after the feeding is completed to obtain a dicofol flame-retardant polyether polyol intermediate;
[0018] (2) The intermediate of dicofol flame retardant polyether polyol is heated to 105-110°C, and alkylene oxide is added dropwise for end-capping synthesis. After the feeding is completed, the internal pressure reaction is continued for 2-3 hours to obtain a crude polymer of dicofol flame retardant polyether polyol, and the residual small molecules are removed by nitrogen bubbling to obtain dicofol flame retardant polyether polyol.
[0019] Preferably, in step (1), the amount of alkylene oxide added is 28.00% to 36.28% of the total mass of alkylene oxide in steps (1) and (2).
[0020] Preferably, in step (2), during nitrogen bubbling, the reactor is filled with nitrogen and pressurized to 0.2-0.25 MPa, and the dicofol flame-retardant polyether polyol crude polymer is cooled to 90-95°C.
[0021] The present invention firstly allows the mixed initiator and the alkylene oxide to undergo polymerization reaction at a relatively low temperature, and then raises the temperature to a relatively high temperature for reaction. This is because small molecule alcohols have high activity under high temperature conditions, and reacting under low temperature conditions first helps dicofol and alkylene oxide to fully react, thereby avoiding dicofol residue.
[0022] Specifically, the preparation method of the dicofol flame retardant polyether comprises the following steps:
[0023] (1) Add dicofol, polyol and composite catalyst into a reactor, pressurize to 0.25 MPa for 20 min, raise the temperature to 85-90° C. under vacuum negative pressure atmosphere, evacuate to -0.08-0.1 MPa, dropwise add alkylene oxide for polyether chain extension, continue internal pressure reaction for 1.5-2 h after the feeding is completed, and obtain dicofol flame retardant polyether polyol intermediate;
[0024] (2) The intermediate of dicofol flame retardant polyether polyol is heated to 105-110°C, and alkylene oxide is added dropwise for end-capping synthesis. After the feeding is completed, the internal pressure reaction is continued for 2-3 hours to obtain a crude polymer of dicofol flame retardant polyether polyol. The crude polymer of dicofol flame retardant polyether polyol is pressurized to 0.2-0.25 MPa with nitrogen filling and the pressure is no longer reduced. The crude polymer of dicofol flame retardant polyether polyol is cooled to 90-95°C and nitrogen is bubbled to remove residual small molecules. After bubbling for 1.5-2 hours, the temperature is cooled to 75-85°C and the material is discharged to obtain dicofol flame retardant polyether polyol.
[0025] The application of the dicofol flame-retardant polyether polyol of the present invention is used for preparing rigid polyurethane foam.
[0026] Compared with the prior art, the present invention has the following beneficial effects:
[0027] 1. Since the molecular structure of dicofol in the present invention contains chlorine and a double benzene ring structure, when used as a reactive flame retardant, the synthesized polyether polyol has a long-lasting flame retardant performance, which not only solves the problem that the flame retardant effect of traditional additive flame retardants is not long-lasting, but also expands the application field of polyether polyols; when the content of dicofol is lower than 20.23%, it is impossible to achieve better flame retardant performance; when the content of dicofol is too high (more than 49.59%), since dicofol is a solid with a high melting point, it will lead to the inability to stir during production, resulting in the inability to produce normally;
[0028] 2. The dicofol flame-retardant polyether of the present invention has better mechanical strength, activity and flame retardant properties than other polyether polyols when used for polyurethane synthesis by introducing chlorine element and double benzene ring structure in dicofol.
[0029] 3. The dicofol flame-retardant polyether polyol used in the present invention can significantly improve the flame retardancy of the material and reduce the possibility of fire. At the same time, as a reactive flame retardant, the structure is more stable, so that the prepared material has a longer flame retardant life;
[0030] 4. The present invention achieves efficient synthesis and performance improvement of polyether by optimizing the preparation method and controlling the reaction conditions, which not only enriches the types and application fields of flame retardant polyether polyols, but also provides strong technical support for the development of related industries. DETAILED DESCRIPTION
[0031] The technical solution of the present invention will be clearly and completely described below in conjunction with embodiments.
[0032] Unless otherwise specified, all raw materials used in the examples are commercially available.
[0033] Example 1
[0034] The dicofol flame retardant polyether polyol is prepared according to the following steps:
[0035] (1) Add 495g of dicofol, 323g of sucrose, 121g of triethanolamine, 25g of diethylene glycol, 34g of propylene glycol, 6g of KOH, and 8g of dimethylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum negative pressure atmosphere, evacuate to -0.09MPa, add 250g of ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 2h after the feeding is completed to obtain a dicofol flame retardant polyether polyol intermediate;
[0036] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 110°C, and 439 g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 2 h. The reactor was pressurized to 0.25 MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 90°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 2 h, the temperature was lowered to 85°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0037] Example 2
[0038] The dicofol flame retardant polyether polyol is prepared according to the following steps:
[0039] (1) Add 370g of dicofol, 302g of sucrose, 87g of triethanolamine, 20g of diethylene glycol, 42g of hexanediol, 4g of KOH, and 5g of N,N-dimethylbenzylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum negative pressure atmosphere, evacuate to -0.08MPa, add 182g of ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 2h after the feeding is completed to obtain a dicofol flame retardant polyether polyol intermediate;
[0040] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 110°C, and 468g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 3h. The reactor was pressurized to 0.25MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 95°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 1.5h, the temperature was lowered to 80°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0041] Example 3
[0042] The dicofol flame retardant polyether polyol is prepared according to the following steps:
[0043] (1) Add 345g of dicofol, 295g of sucrose, 55g of triethanolamine, 62g of glycerol, 3g of sodium oxide, 5g of N,N-dimethylbenzylamine, and 4g of dimethylcyclohexylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 85°C under vacuum atmosphere, evacuate to -0.09MPa, add 212g of ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 1.5h after the feeding is completed to obtain a dicofol flame retardant polyether polyol intermediate;
[0044] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 105°C, and 462 g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 2.5 h. The reactor was pressurized to 0.25 MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 95°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 1.5 h, the temperature was lowered to 80°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0045] Example 4
[0046] The dicofol flame retardant polyether polyol is prepared according to the following steps:
[0047] (1) Add 110g of dicofol, 220g of sucrose, 14g of solid sorbitol, 165g of triethanolamine, 23g of 1,4-butanediol, 4g of KOH, 3g of N,N-dimethylbenzylamine, and 4g of dimethylcyclohexylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum atmosphere, evacuate to -0.09MPa, add 228g of ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 2h after the feeding is completed to obtain a dicofol flame retardant polyether polyol intermediate;
[0048] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 110°C, and 510 g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 2 h. The reactor was pressurized to 0.2 MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 75°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 2 h, the temperature was lowered to 80°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0049] Comparative Example 1
[0050] The polyether polyols were prepared as follows:
[0051] (1) Add 495g of dicofol, 323g of sucrose, 121g of triethanolamine, 25g of diethylene glycol, 34g of propylene glycol, and 8g of dimethylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum negative pressure atmosphere, evacuate to -0.09MPa, add 250g of ethylene oxide dropwise for polyether chain extension, continue the internal pressure reaction for 2h after the feeding is completed, and obtain a dicofol flame retardant polyether polyol intermediate;
[0052] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 110°C, and 439 g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 2 h. The reactor was pressurized to 0.25 MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 90°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 2 h, the temperature was lowered to 85°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0053] Comparative Example 2
[0054] The polyether polyols were prepared as follows:
[0055] (1) Add 370g of dicofol, 302g of sucrose, 87g of triethanolamine, 20g of diethylene glycol, 42g of hexanediol, 4g of KOH, and 5g of N,N-dimethylbenzylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 110°C under vacuum, evacuate to -0.08MPa, add 182g of ethylene oxide dropwise for polyether chain extension, continue the internal pressure reaction for 2h after the feeding is completed, and obtain a dicofol flame retardant polyether polyol intermediate;
[0056] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 110°C, and 468g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 3h. The reactor was pressurized to 0.25MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was lowered to 95°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 1.5h, the temperature was lowered to 80°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0057] Comparative Example 3
[0058] The polyether polyols were prepared as follows:
[0059] (1) Add 370g of dicofol, 302g of sucrose, 87g of triethanolamine, 20g of diethylene glycol, 42g of hexanediol, 4g of KOH, and 5g of N,N-dimethylbenzylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum negative pressure atmosphere, evacuate to -0.08MPa, add 182g of ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 2h after the feeding is completed to obtain a dicofol flame retardant polyether polyol intermediate;
[0060] (2) The intermediate of dicofol flame retardant polyether polyol was heated to 90°C, and 468g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 3h. The reactor was pressurized to 0.25MPa with nitrogen and the pressure in the reactor was no longer reduced. Nitrogen bubbling was performed to remove residual small molecular substances in the product. After bubbling for 1.5h, the temperature was lowered to 80°C and the material was discharged to obtain dicofol flame retardant polyether polyol.
[0061] Comparative Example 4
[0062] The polyether polyol is prepared according to the following steps:
[0063] (1) Add 140g sucrose, 14g solid sorbitol, 165g triethanolamine, 23g 1,4-butanediol, 4g KOH, 3g N,N-dimethylbenzylamine, and 4g dimethylcyclohexylamine into a reactor, pressurize to 0.25MPa for leak test for 20min, raise the temperature to 90°C under vacuum, evacuate to -0.09MPa, add 228g ethylene oxide dropwise for polyether chain extension, and continue the internal pressure reaction for 2h after the feeding is completed to obtain a polyether polyol intermediate;
[0064] (2) The polyether polyol intermediate was heated to 110°C, and 510 g of propylene oxide was continuously added dropwise for end-capping synthesis. After the feeding was completed, the temperature was kept high and the internal pressure reaction was continued for 2 h. The reactor was pressurized to 0.2 MPa with nitrogen and the pressure in the reactor did not decrease any more. The temperature was then reduced to 75°C and nitrogen was bubbled to remove residual small molecules in the product. After bubbling for 2 h, the temperature was reduced to 80°C and the material was discharged to obtain polyether polyol.
[0065] Performance Testing
[0066] The performance indicators of the polyether polyols obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1 below.
[0067] Table 1 Performance indexes of polyether polyols in Examples 1 to 4 and Comparative Examples 1 to 4
[0068]
[0069] The polyether polyols prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were formulated according to the raw material composition in Table 2 to obtain material A, wherein the catalyst was MAYCAT PC8 produced by Jiangsu Meside Chemical Co., Ltd., the flame retardant was tri(2-chloroethyl) phosphate (TCEP), and the physical foaming agent was cyclopentane; material B was PM200 produced by Wanhua Chemical Group Co., Ltd.
[0070] Material A and material B were prepared according to an NCO index of 1.03, mixed evenly and foamed to obtain a polyurethane foam sample.
[0071] Table 2 Ingredients of polyurethane foams of Examples 1 to 4 and Comparative Examples 1 to 4
[0072]
[0073] The obtained polyurethane foam samples were subjected to performance tests, wherein the strength was tested in accordance with the standard GB / T8813-2020, the oxygen index was tested in accordance with the standard GB / T2918-1988, and the activity refers to the time taken from the beginning of stirring of the mixture of material A and material B to the beginning of hair drawing. The shorter the time, the higher the activity. The test results are shown in Table 3.
[0074] Table 3 Polyurethane foam test table of Examples 1 to 4 and Comparative Examples 1 to 4
[0075]
[0076] From Table 1, it can be seen from the comparison between Comparative Example 2 and Example 2 that when the temperature of step (1) and step (2) are both high, the polyether head obtained in Comparative Example 2 is not completely reacted. This is because the temperature of step (1) is too high, which will lead to a large difference between the reaction activity of the solid head and the reaction activity of the liquid head, such as residual sugar and trichlorodicofol, which will lead to a decrease in the functionality and hydroxyl value of the finished polyether. In addition, in Comparative Example 3, when the reaction temperature of step (1) and step (2) with alkylene oxide is 90°C, the cycle of preparing the finished polyether will be longer, and the reaction activity will be lower at this temperature. At the same time, the low activity at low temperature will also lead to a high content of small molecules in the formed polyether, resulting in a decrease in viscosity. Comparing Comparative Example 1 with Example 1, Comparative Example 1 does not use a composite catalyst but a single catalyst B, and the catalytic activity is reduced in the later stage, and the strength, activity and flame retardant properties of the prepared polyurethane foam are all reduced.
[0077] From the comparison between Comparative Example 4 and Example 4 in Table 3, it can be seen that the oxygen index of the polyurethane foam prepared by the polyether polyol obtained without using dicofol as the initiator is significantly lower than the oxygen index of the polyurethane foam prepared by the reaction with dicofol. This shows that dicofol can effectively improve the flame retardant properties. At the same time, it can also be seen that compared with Comparative Example 4, the polyurethane foam prepared by the polyether prepared by dicofol in Example 4 has a higher compression strength.
[0078] The flame retardant performance, strength and activity of the rigid polyurethane foam prepared by the dicofol flame retardant polyether polyol of the present invention are significantly improved.
Claims
1. A dicofol flame retardant polyether polyol, characterized in that: The dicofol and polyol are used as mixed initiators, and polymerized with alkylene oxide under the action of a composite catalyst to obtain the product. The polyol is one or more of sucrose, solid sorbitol, 1,4-butanediol, triethanolamine, diethylene glycol, glycerol, hexylene glycol, and propylene glycol; The mass percentage of dicofol in the mixed initiator is 20.23%~49.6%; The composite catalyst is a mixture of catalyst A and catalyst B; catalyst A is one or two of KOH and sodium oxide; catalyst B is one or more of dimethylamine, N,N-dimethylbenzylamine, and dimethylcyclohexylamine; The mass ratio of catalyst A to catalyst B is (0.33~0.8):1; The method for preparing the dicofol flame-retardant polyether polyol comprises the following steps: (1) Adding dicofol, polyol and composite catalyst into a reaction kettle, adding alkylene oxide dropwise at a temperature of 85-90°C and a vacuum degree of -0.08--0.1 MPa to carry out polyether chain extension, and continuing the internal pressure reaction for 1.5-2 hours after the feeding is completed to obtain a dicofol flame-retardant polyether polyol intermediate; (2) The intermediate of dicofol flame retardant polyether polyol is heated to 105-110°C, and alkylene oxide is added dropwise for end-capping synthesis. After the feeding is completed, the internal pressure reaction is continued for 2-3 hours to obtain a crude polymer of dicofol flame retardant polyether polyol, and the residual small molecules are removed by nitrogen bubbling to obtain dicofol flame retardant polyether polyol.
2. The dicofol flame retardant polyether polyol according to claim 1, characterized in that: The addition amount of the composite catalyst is 0.61% to 0.89% of the total mass of the mixed initiator and the alkylene oxide.
3. The dicofol flame retardant polyether polyol according to claim 1, characterized in that: The alkylene oxide is one or both of propylene oxide and ethylene oxide.
4. The dicofol flame retardant polyether polyol according to claim 1, characterized in that: The mass ratio of alkylene oxide to mixed initiator is (0.69~1.45):
1.
5. The dicofol flame retardant polyether polyol according to claim 1, characterized in that: In step (1), the amount of alkylene oxide added is 28.00% to 36.28% of the total mass of alkylene oxide in steps (1) and (2).
6. Use of the dicofol flame retardant polyether polyol according to any one of claims 1 to 5, characterized in that: Used to prepare rigid polyurethane foam.