Resin catalyst, preparation method and application thereof, and method for preparing aliphatic dibasic acid diester
By using a resin catalyst composed of cationic resin, alkylbenzene sulfonate and phosphorus pentoxide, the problem of poor heat resistance and stability of strong acidic cationic exchange resin catalyst is solved, the product generation rate of the esterification reaction is improved and the cost is reduced.
Patent Information
- Application Number
- CN202410492137.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-23
- Publication Date
- 2025-10-24
AI Technical Summary
Existing strongly acidic cation exchange resin catalysts have poor heat stability in esterification reactions, which affects the catalytic activity and leads to low esterification reaction yields.
A resin catalyst containing cationic resin, alkylbenzene sulfonate and phosphorus pentoxide is used to improve the catalytic activity through interaction and promote the esterification reaction to proceed to the right.
The production rate of esterification reaction products is improved, the reaction time is shortened, and the production cost is reduced.
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Figure BDA0004805737860000101 
Figure BDA0004805737860000111
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of high polymer chemical industry, in particular, to a resin catalyst, a preparation method and application thereof. In addition, the present application also relates to a method for preparing aliphatic dibasic acid diester. BACKGROUND
[0002] Esterification reaction is a kind of organic chemical reaction, which is the reaction of alcohol with carboxylic acid or inorganic acid containing oxygen to generate ester and water. Esterification reaction can be divided into three types: carboxylic acid and alcohol reaction, inorganic acid containing oxygen and alcohol reaction, and strong inorganic acid and alcohol reaction. The esterification reaction of carboxylic acid and alcohol is reversible, and the reaction is generally very slow, so a catalyst is usually used.
[0003] Sulfuric acid is a commonly used catalyst in esterification reaction, but it has strong corrosion and relatively long reaction time for esterification reaction. Strong acid cation exchange resin catalyst overcomes the strong corrosion problem of homogeneous acid catalysis, and has the advantage of easy separation from the product, and is widely used in various manufacturing fields such as petroleum chemical industry, fine chemical industry and pharmaceutical industry. However, strong acid cation exchange resin catalyst generally has the technical problem of poor heat stability, and esterification reaction is generally carried out under heating conditions, which will affect the catalytic activity of strong acid cation exchange resin catalyst, and further affect the esterification reaction, thereby reducing the yield of esterification reaction. SUMMARY
[0004] The purpose of the present application is to overcome the technical problem that the activation activity of strong acid cation exchange resin catalyst needs to be improved in the prior art, and to provide a resin catalyst, a preparation method and application thereof. The resin catalyst has good catalytic activity in esterification reaction, and can effectively improve the generation rate of esterification reaction product when applied to esterification reaction.
[0005] In addition, the present application also provides a method for preparing aliphatic dibasic acid diester.
[0006] In order to achieve the above purpose, the first aspect of the present application provides a resin catalyst, which contains cationic resin, alkyl benzene sulfonate and phosphorus pentoxide.
[0007] The second aspect of the present application provides a preparation method of resin catalyst, which comprises: contacting cationic resin, alkyl benzene sulfonate and phosphorus pentoxide.
[0008] The third aspect of the present application provides the application of the above-mentioned resin catalyst or the resin catalyst prepared by the above-mentioned preparation method in esterification reaction.
[0009] The fourth aspect of the present application provides a method for preparing aliphatic dibasic acid diester, which comprises the following steps:
[0010] The aliphatic dibasic acid, the alcohol and the resin catalyst are contacted under esterification reaction conditions;
[0011] The alcohol is a C1-C6 monohydric alcohol; the resin catalyst is the resin catalyst of the first aspect or the resin catalyst prepared by the preparation method of the second aspect.
[0012] The resin catalyst provided by the application has high catalytic activity due to the interaction between the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide, promotes the esterification reaction to proceed to the right, and can effectively improve the generation rate of the esterification reaction product when applied to the esterification reaction. DETAILED DESCRIPTION
[0013] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The exact numerical values of the endpoints of the ranges and the separate points are not to be construed as being precise values by themselves, but are understood to be used in a generic sense to describe the approximate values. The endpoints of the ranges of values and the separate values can be combined with one another to form one or more new ranges of values whether explicitly stated or not.
[0014] As described above, the first aspect of the application provides a resin catalyst containing a cationic resin, an alkyl benzene sulfonate and phosphorus pentoxide.
[0015] The various components in the resin catalyst can be detected by elemental analysis, infrared, mass spectrometry, nuclear magnetic resonance, etc. The components can also be separated by their solubility before detection, and then measured separately.
[0016] The resin catalyst provided by the application can significantly improve its catalytic activity through the interaction between the components during the catalytic process. In particular, when applied to esterification reaction, it can promote the esterification reaction to proceed to the right, and effectively improve the generation rate of the esterification reaction product.
[0017] Preferably, the mass ratio of the cationic resin, the alkyl benzene sulfonate and phosphorus pentoxide is 1-4:1.5-5:1. Research has found that controlling the mass ratio of the components under the above conditions can further improve the catalytic activity of the catalyst, and in turn can further improve the generation rate of the esterification reaction product. In order to further improve the catalytic activity of the resin catalyst, it is further preferred that the mass ratio of the cationic resin, the alkyl benzene sulfonate and phosphorus pentoxide is 1.5-3:2-4:1.
[0018] According to the present application, the content of each component can be obtained by detecting the content of a special element in each component, and then converting the content of the special element into the content of the detected substance.
[0019] According to the present application, the cationic resin can be a weakly acidic cationic resin (such as a carboxyl cationic resin) or a strongly acidic cationic resin (such as a sulfonic acid group cationic resin), and is preferably a strongly acidic cationic resin, which can further improve the catalytic activity of the resin catalyst. In order to further improve the catalytic activity of the resin catalyst, it is further preferred that the cationic resin is a sulfonic acid group cationic resin. The sulfonic acid group cationic resin is a cationic resin treated by sulfonation.
[0020] Preferably, the sulfonic acid group cationic resin is a sulfonated polystyrene cationic resin. It has been found through experiments that the resin catalyst containing the sulfonated polystyrene cationic resin has higher catalytic activity.
[0021] Preferably, the alkyl benzene sulfonate is sodium C8-C30 alkyl benzene sulfonate and / or potassium C8-C30 alkyl benzene sulfonate. Specifically, it can be octyl benzene sulfonate, nonyl benzene sulfonate, decyl benzene sulfonate, dodecyl benzene sulfonate, tridecyl benzene sulfonate, hexadecyl benzene sulfonate, and tetracosyl benzene sulfonate, etc. The resin catalyst containing the above alkyl benzene sulfonate has higher catalytic activity. In order to further improve the catalytic activity of the catalyst, it is further preferred that the alkyl benzene sulfonate is sodium C10-C25 alkyl benzene sulfonate and / or potassium C10-C25 alkyl benzene sulfonate. More preferably, the alkyl benzene sulfonate is sodium dodecyl benzene sulfonate and / or potassium dodecyl benzene sulfonate. The resin catalyst containing sodium dodecyl benzene sulfonate and / or potassium dodecyl benzene sulfonate has higher catalytic activity.
[0022] The second aspect of the present application provides a preparation method of a resin catalyst, which comprises: contacting a cationic resin, an alkyl benzene sulfonate, and phosphorus pentoxide.
[0023] According to the present application, the cationic resin can be prepared or obtained by commercial purchase. The alkyl benzene sulfonate and phosphorus pentoxide are both obtained by commercial purchase.
[0024] According to the present application, preferably, the cationic resin can be contacted with the alkyl benzene sulfonate and phosphorus pentoxide in a molten state, which can further improve the reaction efficiency.
[0025] The inventors have found that the catalyst prepared by the above preparation method has a shell-core structure, with the outer shell being a phosphorus pentoxide layer and the inner core being a mixture of the cationic resin and the alkyl benzene sulfonate.
[0026] The resin catalyst prepared by the preparation method has high catalytic activity by the interaction between the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide in structure and chemical properties, and can promote the esterification reaction to the right and effectively improve the yield of the esterification reaction product when applied to the esterification reaction.
[0027] Preferably, the mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1-4:1.5-5:1. It is found that controlling the mass ratio of the raw materials within the above range can further improve the catalytic activity of the prepared catalyst, and further improve the yield of the esterification reaction product. In order to further improve the catalytic activity of the prepared resin catalyst, more preferably, the mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1.5-3:2-4:1.
[0028] According to the present application, the cationic resin can be a weakly acidic cationic resin (such as a carboxyl cationic resin) or a strongly acidic cationic resin (such as a sulfonic acid group cationic resin), preferably a strongly acidic cationic resin, which can further improve the catalytic activity of the resin catalyst. In order to further improve the catalytic activity of the resin catalyst, more preferably, the cationic resin is a sulfonic acid group cationic resin. The sulfonic acid group cationic resin is a sulfonated cationic resin.
[0029] Preferably, the sulfonic acid group cationic resin is a sulfonated polystyrene cationic resin. It is found that the resin catalyst prepared by using the sulfonated polystyrene cationic resin has higher catalytic activity.
[0030] Preferably, the alkyl benzene sulfonate is C8-C30 alkyl benzene sulfonate sodium and / or C8-C30 alkyl benzene sulfonate potassium. Specifically, it can be octyl benzene sulfonate, nonyl benzene sulfonate, cetyl benzene sulfonate, dodecyl benzene sulfonate, tridecyl benzene sulfonate, hexadecyl benzene sulfonate, tetracosyl benzene sulfonate, etc. The resin catalyst prepared by using the above alkyl benzene sulfonate has higher catalytic activity. In order to further improve the catalytic activity of the catalyst, more preferably, the alkyl benzene sulfonate is C10-C25 alkyl benzene sulfonate sodium and / or C10-C25 alkyl benzene sulfonate potassium. More preferably, the alkyl benzene sulfonate is dodecyl benzene sulfonate sodium and / or dodecyl benzene sulfonate potassium. The resin catalyst prepared by using dodecyl benzene sulfonate sodium and / or dodecyl benzene sulfonate potassium has higher catalytic activity.
[0031] Preferably, the contacting reaction is carried out under conditions of a temperature of 120-160℃, specifically 120℃, 130℃, 140℃, 150℃, 160℃, or any value between these values; and a time of 20-40min, specifically 20min, 25min, 30min, 35min, 40min, or any value between these values. The catalyst prepared under the above reaction conditions has higher catalytic activity.
[0032] The third aspect of the present application provides a use of the resin catalyst provided by the first aspect or prepared by the preparation method provided by the second aspect in an esterification reaction.
[0033] The catalyst provided by the first aspect and the catalyst prepared by the preparation method provided by the second aspect have higher catalytic activity and better application in esterification reactions. In particular, in the esterification reaction of aliphatic diacids and aliphatic monohydric alcohols, the aliphatic diacid diester has a higher generation rate. Preferably, the aliphatic monohydric alcohol is a C1-C6 monohydric alcohol, and the aliphatic diacid is a C4-C10 cyclic diacid.
[0034] The fourth aspect of the present application provides a method for preparing an aliphatic diacid diester, comprising: contacting an aliphatic diacid, an alcohol, and a resin catalyst under esterification reaction conditions;
[0035] Preferably, the method comprises: (1) contacting the aliphatic diacid, part of the alcohol, and part of the resin catalyst under primary esterification reaction conditions to obtain a mixture; and (2) contacting the mixture, the remaining alcohol, and the remaining resin catalyst under secondary esterification reaction conditions.
[0036] According to the present application, the aliphatic diacid can be a chain aliphatic diacid and / or a cyclic aliphatic diacid, specifically a C2-C12 aliphatic diacid, such as succinic acid, adipic acid, pimelic acid, sebacic acid, cyclohexane dicarboxylic acid, cyclopentane dicarboxylic acid, etc. Preferably, it is a C4-C10 cyclic diacid, further preferably a C6-C8 cyclic diacid, and more preferably 1,4-cyclohexane dicarboxylic acid. The alcohol is preferably a C1-C4 alcohol, and further preferably methanol.
[0037] The inventors found during research that, by using this method, the aliphatic diacid diester has a higher generation rate, does not corrode the reaction equipment, has a relatively short reaction time, and can greatly save production costs.
[0038] Preferably, the method comprises: (1) contacting the aliphatic diacid, part of the alcohol, and part of the resin catalyst under primary esterification reaction conditions to obtain a mixture; and (2) contacting the mixture, the remaining alcohol, and the remaining resin catalyst under secondary esterification reaction conditions.
[0039] The above method can make the catalyst and the reaction raw material fully mixed, and further improve the generation rate of the reaction product.
[0040] Preferably, the primary esterification reaction conditions at least meet: temperature of 50-60℃, rotation speed of 100-400r / min, and time of 3-6h; and the secondary esterification reaction conditions at least meet: temperature of 100-140℃. Under the above conditions, the aliphatic dibasic acid and the methanol have good reaction effect.
[0041] Preferably, in step (1), the mass ratio of the aliphatic dibasic acid and the resin catalyst is 100:2-4; and in step (2), the mass ratio of the mixture and the resin catalyst is 100:2-5. The method can catalyze more raw materials and reduce the reaction time as far as possible while ensuring the cost.
[0042] Preferably, in step (1), the molar ratio of the aliphatic dibasic acid and the alcohol is 1:4-6; and in step (2), the addition amount of the alcohol is 6-10mol relative to 1mol of the aliphatic dibasic acid. Under the above conditions, the conversion rate of the aliphatic dibasic acid can be further improved.
[0043] According to a particularly preferred embodiment of the present application, the preparation method of the resin catalyst comprises:
[0044] mixing the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide with a mass ratio of 1-4:1.5-5:1, and then reacting for 20-40min at a temperature of 120-160℃;
[0045] The cationic resin is sulfonated polystyrene cationic resin, and the alkyl benzene sulfonate is sodium dodecyl benzene sulfonate and / or potassium dodecyl benzene sulfonate.
[0046] The resin catalyst prepared by the above method has high catalytic activity because the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide can interact with each other in structure and chemical properties, and can effectively improve the generation rate of the esterification reaction product when applied to the esterification reaction.
[0047] The present application will be described in detail through the following examples.
[0048] In the following examples, the sulfonated polystyrene cationic resin is DuPont AmberLite HPR1300 H strong acid cationic resin, the sulfonated phenolic cationic resin is Rohm & Haas AmberLite HPR650H strong acid cation exchange resin, and the remaining raw materials and reagents used are conventional commercial products unless otherwise specified.
[0049] Example 1
[0050] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0051] Example 2
[0052] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0053] Example 3
[0054] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0055] Example 4
[0056] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0057] Example 5
[0058] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0059] Example 6
[0060] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cation resin and mixed uniformly, and then the mixture was put into a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol 3 times and freeze-dried to obtain a resin catalyst.
[0061] Example 7
[0062] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cationic resin and mixed uniformly to obtain a resin catalyst.
[0063] Example 8
[0064] The resin catalyst was prepared according to the method described in Example 1, except that the sulfonated polystyrene cationic resin was replaced with a sulfonated phenol formaldehyde cationic resin.
[0065] Example 9
[0066] The resin catalyst was prepared according to the method described in Example 1, except that sodium dodecylbenzenesulfonate was replaced with sodium 4-octylbenzenesulfonate.
[0067] Example 10
[0068] Sodium dodecylbenzenesulfonate 2.5 g and phosphorus pentoxide 1 g were added to 2 g of sulfonated polystyrene cationic resin and mixed uniformly to obtain a resin catalyst.
[0069] Comparative Example 1
[0070] The resin catalyst was prepared according to the method described in Example 1, except that sodium dodecylbenzenesulfonate was replaced with sodium benzenesulfonate.
[0071] Comparative Example 2
[0072] Sodium dodecylbenzenesulfonate 2.5 g was added to 2 g of sulfonated polystyrene cationic resin and mixed uniformly, and then the mixture was placed in a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol for 3 times and freeze-dried to obtain a resin catalyst.
[0073] Comparative Example 3
[0074] Phosphorus pentoxide 1 g was added to 2 g of sulfonated polystyrene cationic resin and mixed uniformly, and then the mixture was placed in a reactor, the reaction temperature was set to 140°C, and reacted at this temperature for 30 min, washed with ethanol for 3 times and freeze-dried to obtain a resin catalyst.
[0075] Test Example 1
[0076] (1) 172 g of 1,4-cyclohexanedicarboxylic acid, 80 g of methanol and 6.88 g of the resin catalyst were reacted at a temperature of 55°C and a rotation speed of 200 r / min for 4 h to obtain a mixture.
[0077] (2) 180 g of the mixture, 96 g of methanol and 7 g of the resin catalyst were reacted at a temperature of 110°C until the water production reached 80% of the theoretical value;
[0078] wherein the resin catalyst is the resin catalyst in the examples or the comparative examples, or a sulfonated polystyrene cation resin.
[0079] Table 1
[0080]
[0081]
[0082] As can be seen from the data in Table 1, the yield of the esterification product in the examples is higher than that in the comparative examples, indicating that the resin catalyst prepared in the examples has higher catalytic activity.
[0083] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.
Claims
1. A resin catalyst characterized by, The resin catalyst contains a cationic resin, an alkyl benzene sulfonate and phosphorus pentoxide.
2. The catalyst according to claim 1, characterized in that, The mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1-4:1.5-5:
1. Preferably, the mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1.5-3:2-4:
1.
3. Catalyst according to claim 1 or 2, characterized in that The cationic resin is a sulfonic acid group cationic resin, preferably a sulfonated polystyrene cationic resin. Preferably, the alkyl benzene sulfonate is C8-C30 alkyl benzene sulfonate sodium and / or C8-C30 alkyl benzene sulfonate potassium, further preferably C10-C25 alkyl benzene sulfonate sodium and / or C10-C25 alkyl benzene sulfonate potassium, and more preferably dodecyl benzene sulfonate sodium and / or dodecyl benzene sulfonate potassium.
4. A method for producing a resin catalyst, characterized by, The method comprises: The cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide are subjected to a contact reaction.
5. The preparation method according to claim 4, characterized in that The mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1-4:1.5-5:
1. Preferably, the mass ratio of the cationic resin, the alkyl benzene sulfonate and the phosphorus pentoxide is 1.5-3:2-4:
1.
6. The production method according to claim 4 or 5, characterized by, The cationic resin is a sulfonic acid group cationic resin, preferably a sulfonated polystyrene cationic resin. Preferably, the alkyl benzene sulfonate is C8-C30 alkyl benzene sulfonate sodium and / or C8-C30 alkyl benzene sulfonate potassium, further preferably C10-C25 alkyl benzene sulfonate sodium and / or C10-C25 alkyl benzene sulfonate potassium, and more preferably dodecyl benzene sulfonate sodium and / or dodecyl benzene sulfonate potassium. Preferably, the contact reaction at least meets the following conditions: temperature is 120-160℃, and time is 20-40min.
7. Application of the resin catalyst of any one of claims 1-3 or the resin catalyst prepared by the preparation method of any one of claims 4-6 in an esterification reaction. Preferably, the esterification reaction is the esterification reaction of aliphatic dibasic acid and aliphatic monohydric alcohol.
8. A method of preparing aliphatic dibasic acid diesters, characterized by, The method comprises the following steps: Under esterification reaction conditions, aliphatic dibasic acid, alcohol and resin catalyst are subjected to a contact reaction. The alcohol is C1-C6 monohydric alcohol; and the resin catalyst is the resin catalyst of any one of claims 1-3 or the resin catalyst prepared by the preparation method of any one of claims 4-6.
9. The method of claim 8, wherein, The method comprises: (1) under primary esterification reaction conditions, aliphatic dibasic acid, part of alcohol and part of resin catalyst are subjected to a contact reaction to obtain a mixture; (2) under secondary esterification reaction conditions, the mixture, the remaining alcohol and the remaining resin catalyst are subjected to a contact reaction; Preferably, the primary esterification reaction conditions at least meet the following conditions: temperature is 50-60℃, rotation speed is 100-400r / min, and time is 3-6h. The secondary esterification reaction conditions at least meet the following conditions: temperature is 100-140℃.
10. The method according to claim 8 or 9, characterized in that, The aliphatic dibasic acid is C4-C10 cyclic dibasic acid, preferably C6-C8 cyclic dibasic acid, and further preferably 1,4-cyclohexane dicarboxylic acid; The alcohol is C1-C4 alcohol, preferably methanol. Preferably, in step (1), the mass ratio of the aliphatic dibasic acid and the resin catalyst is 100:2-4; in step (2), the mass ratio of the mixture and the resin catalyst is 100:2-5; Preferably, in step (1), the molar ratio of the aliphatic dibasic acid and the alcohol is 1:4-6; in step (2), the addition amount of the alcohol is 6-10 mol relative to 1 mol of the aliphatic dibasic acid.