Preparation method of polyester polyol containing hindered amine light-stable group
By directly adding light stabilizer to the synthesis of polyester polyols, a polyester polyol containing hindered amine light stabilizer groups is solved, and the problem of insufficient anti-ultraviolet ability of polyurethane materials is achieved, efficient anti-ultraviolet effect and prolong product service life.
Patent Information
- Application Number
- CN202411683759.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-03-14
AI Technical Summary
Polyurethane materials have generally poor UV resistance, and their mechanical properties decline after long-term exposure to ultraviolet radiation. In existing solutions, the light stabilizer has poor compatibility with the matrix, which makes it easy to exudate and affect the service life of the product.
The light stabilizer is directly added to the synthesis of polyester polyols, so that it reacts with dibasic acid or anhydride and polyols to form a polyester polyol containing hindered amine light stabilizer groups, so that no additional light stabilizer is required.
By directly adding light stabilizer to the polyester polyol, the problem of insufficient UV resistance of polyurethane materials is solved, and the problem of short service life caused by the exudation of light stabilizer is avoided, and the anti-ultraviolet effect of polyurethane is improved.
Smart Images
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Figure BDA0005148962420000061
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polyester polyols, in particular to a method for preparing polyester polyols containing hindered amine light-stabilizing groups. Background Art
[0002] Polyurethane materials are widely used in adhesives, foams, elastomers, coatings and other fields due to their excellent strength, elasticity and wear resistance. Polyester polyols are one of the main raw materials for polyester polyurethanes and are often used in products such as PU slurry, elastomers, sole stock solution and adhesives. As a soft segment in the polyurethane structure, they provide the product with good mechanical properties such as elongation, resilience and softness.
[0003] At present, the UV resistance of polyurethane materials is generally poor. After being exposed to ultraviolet radiation for a long time, the mechanical properties are reduced on a macro scale. The current solution to the UV resistance of polyurethane is to add additives such as light stabilizers to polyurethane. However, the compatibility of additives with the matrix is relatively poor and they are easy to seep out of the matrix, thus affecting the long-term use of polyurethane products. Summary of the invention
[0004] In order to solve the above technical problems, the present invention provides a method for preparing a polyester polyol containing a hindered amine light-stabilizing group. A light stabilizer is directly added during the synthesis of the polyester polyol to form a polyester polyol containing a hindered amine light-stabilizing group. After the polyester polyol is applied to polyurethane, there is no need to add an additional light stabilizer.
[0005] The present invention provides a method for preparing a polyester polyol containing a hindered amine light-stabilizing group, which adopts the following technical scheme: A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: under the protection of an inert gas, stirring and reacting a dibasic acid or anhydride, a polyol, a light stabilizer and a catalyst at 140-220° C. for 6-8 hours to obtain the polyester polyol.
[0006] Preferably, the molar ratio of the dibasic acid or anhydride to the sum of the polyol and the light stabilizer is 2:(2.1-2.4).
[0007] Preferably, the molar ratio of the light stabilizer to the polyol is 1:9-10:0.
[0008] Preferably, the dibasic acid or anhydride is one of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride, succinic anhydride and maleic anhydride.
[0009] Preferably, the polyol is one of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, trimethylolpropane and glycerol.
[0010] Preferably, the light stabilizer is light stabilizer 201.
[0011] Preferably, the catalyst is one of p-toluenesulfonic acid, tetraisopropyl titanate and dioctyltin oxide.
[0012] Preferably, in the preparation step, the temperature is raised to 140-220° C. at a rate of 0.5-1° C. / min and stirred for reaction for 6-8 hours to obtain the polyester polyol.
[0013] In summary, the present invention has the following beneficial effects: In the preparation of polyester polyols, the present application directly adds a light stabilizer, so that the groups in the light stabilizer react with dibasic acids or acid anhydrides and polyols to directly synthesize polyester polyols containing hindered amine light stabilizing groups, so that the performance of the polyester polyols is diversified. In the production of polyurethane, the polyester polyols containing hindered amine light stabilizing groups obtained in the present application can be directly added, thereby omitting the addition of the light stabilizer, which not only makes the final polyurethane product have a good anti-ultraviolet effect, but also avoids the problem of short service life of the polyurethane product caused by the addition of additional light stabilizers. DETAILED DESCRIPTION
[0014] The present invention is further described in detail below with reference to the embodiments.
[0015] The raw materials used in this application are all commercially available.
[0016] A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: under the protection of an inert gas, stirring and reacting a dibasic acid or anhydride, a polyol, a light stabilizer and a catalyst at 140-220° C. for 6-8 hours to obtain the polyester polyol.
[0017] In a preferred embodiment, the molar ratio of the dibasic acid or anhydride to the sum of the polyol and the light stabilizer is 2:(2.1-2.4).
[0018] In a preferred embodiment, the molar ratio of the light stabilizer to the polyol is 1:9-10:0.
[0019] In a preferred embodiment, the dibasic acid or anhydride is one of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride, succinic anhydride, and maleic anhydride, and the effects that can be achieved are basically the same, so adipic acid and sebacic acid are used as examples in this application.
[0020] In a preferred embodiment, the polyol is one of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and glycerol, and the effects that can be achieved are basically the same, so ethylene glycol and 1,4-butanediol are used as examples in this application.
[0021] In a preferred embodiment, the light stabilizer is light stabilizer 201 .
[0022] In a preferred embodiment, the catalyst is one of p-toluenesulfonic acid, tetraisopropyl titanate and dioctyltin oxide.
[0023] In a preferred embodiment, in the preparation step, the temperature is raised to 140-220° C. at a rate of 0.5-1° C. / min and stirred for reaction for 6-8 hours to obtain polyester polyol.
[0024] In this application, the synthesis reaction formula of polyester polyol is as follows: Example 1 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 1.89 mol (170.3 g) of 1,4-butanediol, 2 mol (292 g) of adipic acid, 0.21 mol (42.3 g) of light stabilizer 201, and 5.5 g of p-toluenesulfonic acid as a catalyst into a three-necked flask, that is, the molar ratio of light stabilizer 201 to 1,4-butanediol is 1:9; S2, gradient heating, under the condition of a heating rate of 0.5°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 140°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 8h until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 40ppm, the hydroxyl value is 55.6, the acid value is 0.08, and the average molecular weight of the polyester polyol is 2000.
[0025] Example 2 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 1.89 mol (117.2 g) of ethylene glycol, 2 mol (404.6 g) of sebacic acid, 0.21 mol (42.3 g) of light stabilizer 201, and 5.5 g of p-toluenesulfonic acid as catalyst into a three-necked flask, that is, the molar ratio of light stabilizer 201 to ethylene glycol is 1:9. S2, gradient heating, under the condition of a heating rate of 0.5°C / min, the mixture of step S1 is heated to 120°C and then stirring is started to make the system gradually change from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 140°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 8h until no water is discharged from the system, and then the heating is stopped and stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 35ppm, the hydroxyl value is 55.4, the acid value is 0.07, and the average molecular weight of the polyester polyol is 2000.
[0026] Example 3 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 2.07 mol (186.5 g) of 1,4-butanediol, 2 mol (292 g) of adipic acid, 0.23 mol (46.3 g) of light stabilizer 201, and 5.7 g of p-toluenesulfonic acid as a catalyst into a three-necked flask, that is, the molar ratio of light stabilizer 201 to 1,4-butanediol is 1:9; S2, gradient heating, under the condition of a heating rate of 1°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 180°C at a rate of 1°C / min, and the reaction is carried out at this temperature for 8 hours until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 38ppm, the hydroxyl value is 55.5, the acid value is 0.10, and the average molecular weight of the polyester polyol is 2000.
[0027] Example 4 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 2.16 mol (194.7 g) of 1,4-butanediol, 2 mol (292 g) of adipic acid, 0.24 mol (48.3 g) of light stabilizer 201, and 5.5 g of p-toluenesulfonic acid as a catalyst into a three-necked flask, that is, the molar ratio of light stabilizer 201 to 1,4-butanediol is 1:9; S2, gradient heating, under the condition of a heating rate of 1°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 220°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 6 hours until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 41ppm, the hydroxyl value is 55.4, the acid value is 0.09, and the average molecular weight of the polyester polyol is 2000.
[0028] Example 5 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 2 mol (165.8 g) of 1,4-butanediol, 2 mol (292 g) of adipic acid, 0.46 mol (92.6 g) of light stabilizer 201, and 5.7 g of p-toluenesulfonic acid as a catalyst into a three-necked flask, that is, the total molar amount of 1,4-butanediol and light stabilizer is 2.3 mol, wherein the molar ratio of light stabilizer 201 to 1,4-butanediol is 2:8; S2, gradient heating, under the condition of a heating rate of 0.5°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 140°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 8h until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 42ppm, the hydroxyl value is 55.6, the acid value is 0.07, and the average molecular weight of the polyester polyol is 2000.
[0029] Example 6 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, 1.15 mol (103.6 g) of 1,4-butanediol, 2 mol (292 g) of adipic acid, 1.15 mol (231.5 g) of light stabilizer 201, and 6.6 g of p-toluenesulfonic acid as a catalyst were added into a three-necked flask, i.e., the total molar amount of 1,4-butanediol and light stabilizer was 2.3 mol, wherein the molar ratio of light stabilizer 201 to 1,4-butanediol was 5:5; S2, gradient heating, under the condition of a heating rate of 0.5°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 140°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 8h until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 40ppm, the hydroxyl value is 42.1, the acid value is 0.12, and the average molecular weight of the polyester polyol is 2500.
[0030] Example 7 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group comprises the following preparation steps: S1. Under nitrogen protection, add 2 mol (292 g) of adipic acid, 2.3 mol (463 g) of light stabilizer 201, and 6.6 g of p-toluenesulfonic acid as a catalyst into a three-necked flask, that is, the molar ratio of light stabilizer 201 to 1,4-butanediol is 10:0; S2, gradient heating, under the condition of a heating rate of 0.5°C / min, the mixture of step S1 is heated to 120°C and then stirred, so that the system gradually changes from a turbid state to a colorless and transparent state, and then the temperature is continued to be raised to 140°C at a rate of 0.5°C / min, and the reaction is carried out at this temperature for 8h until no water is discharged from the system, and then the heating is stopped and the stirring is continued. After the system temperature drops to 50°C, a polyester polyol is obtained. After testing, the moisture content of the polyester polyol is 38ppm, the hydroxyl value is 36.5, the acid value is 0.06, and the average molecular weight of the polyester polyol is 3000.
[0031] Example 8 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group, which is different from Example 7 in that an equal amount of catalyst tetraisopropyl titanate is used instead of p-toluenesulfonic acid, and the rest is the same as Example 7. After testing, the moisture content of the polyester polyol finally obtained is 41 ppm, the hydroxyl value is 37.2, the acid value is 0.09, and the average molecular weight of the polyester polyol is 3000.
[0032] Example 9 A method for preparing a polyester polyol containing a hindered amine light-stabilizing group, which is different from Example 7 in that an equal amount of dioctyltin oxide catalyst is used instead of p-toluenesulfonic acid, and the rest is the same as Example 7. After testing, the moisture content of the polyester polyol finally obtained is 40 ppm, the hydroxyl value is 37.8, the acid value is 0.11, and the average molecular weight of the polyester polyol is 3000.
[0033] Performance Testing The polyester polyol obtained in the above embodiment was applied to polyurethane, and the anti-ultraviolet ability of the polyurethane was tested. The test results are shown in Table 1, wherein the preparation of the polyurethane is as follows: 10 kg of the polyester polyol prepared in the above embodiment, 5 kg of polyisocyanate, 0.5 kg of chain extender, 0.02 kg of catalyst, and 0.5 kg of cross-linking agent were added into a twin-screw extruder for melt blending and then extruded to obtain the polyurethane; the control example is 10 kg of commercially available polyester polyol, 5 kg of polyisocyanate, 0.5 kg of chain extender, 0.02 kg of catalyst, 0.5 kg of cross-linking agent, and 0.4 kg of light stabilizer 201 added into a twin-screw extruder for melt blending and then extruded to obtain the polyurethane.
[0034] The aging performance test of polyurethane is as follows: According to the standard GB / T16422.2-2022, a xenon arc lamp and a daylight filter are used to simulate the radiation spectrum of sunlight. The aging cycle conditions include 102min illumination (0.51w / (m 2 ·nm), 340nm), and then 18min of light exposure (0.51w / (m 2 ·nm) with spraying, the blackboard temperature is 63±3℃, the test box temperature is 38±2℃, the relative humidity is 50±10%, and the tensile strength and elongation at break of the polyurethane are tested after 120h of aging test. The testing standard of tensile strength and elongation at break is GB / T1040.2-2022, and the test speed is 50mm / min.
[0035] Table 1 Polyurethane performance test results From the table above we can see that: After the polyester polyol obtained in the example of the present application is applied to polyurethane, compared with the polyurethane of the control example, when the light stabilizer is omitted, the polyester polyol containing hindered amine light stabilizing groups obtained in the present application can effectively improve the anti-ultraviolet ability of the polyurethane. At the same time, since the polyester polyol containing hindered amine light stabilizing groups in the present application is obtained by reacting the light stabilizer with the polyacid and the polyol, the problem of light stabilizer migration in the polyurethane will not occur, thereby effectively ensuring the long-term anti-ultraviolet effect of the polyurethane.
[0036] The embodiments of this specific implementation method are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a polyester polyol containing a hindered amine light-stabilizing group, characterized in that: The method comprises the following preparation steps: under the protection of inert gas, dibasic acid or anhydride, polyol, light stabilizer and catalyst are stirred and reacted at 140-220 DEG C for 6-8 hours to obtain polyester polyol.
2. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The molar ratio of the dibasic acid or anhydride to the total of the polyol and the light stabilizer is 2:(2.1-2.4).
3. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The molar ratio of the light stabilizer to the polyol is 1:9-10:
0.
4. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The dibasic acid or anhydride is one of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride, succinic anhydride and maleic anhydride.
5. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The polyol is one of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, trimethylolpropane and glycerol.
6. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The light stabilizer is light stabilizer 201.
7. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: The catalyst is one of p-toluenesulfonic acid, tetraisopropyl titanate and dioctyltin oxide.
8. The method for preparing a polyester polyol containing hindered amine light-stabilizing groups according to claim 1, characterized in that: In the preparation step, the temperature is raised to 140-220° C. at a rate of 0.5-1° C. / min, and the mixture is stirred for reaction for 6-8 hours to obtain polyester polyol.