CN115093583B - Treatment method for improving storage time of n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate - Google Patents
Treatment method for improving storage time of n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate Download PDFInfo
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- CN115093583B CN115093583B CN202210738627.1A CN202210738627A CN115093583B CN 115093583 B CN115093583 B CN 115093583B CN 202210738627 A CN202210738627 A CN 202210738627A CN 115093583 B CN115093583 B CN 115093583B
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 37
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 28
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 58
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 26
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 4
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 23
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 15
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The application belongs to the field of antioxidants, and particularly relates to a treatment method for prolonging the storage time of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol, which comprises the steps of mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol with polyvinyl alcohol to prepare an aggregate; and coating cyclodextrin on the surface of the agglomerate. The application can reduce the contact between the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and the outside, reduce volatilization, and has the function of prolonging the storage time of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester.
Description
Technical Field
The application belongs to the field of antioxidants, and particularly relates to a treatment method for prolonging storage time of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester.
Background
Phenolic antioxidants generally achieve their antioxidant effect by autoxidation. The molecular weight of the antioxidant is increased, the volatilization is reduced, and the antioxidation efficiency is improved, so that the method is an important research direction of phenolic antioxidants. Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, namely antioxidant 1076, belongs to hindered phenol antioxidants. The molecular weight of the antioxidant 1076 is relatively small, the melting point is 50-55 ℃, and compared with other phenolic antioxidants, the antioxidant 1076 is more volatile and is unfavorable for long-term storage, the storage time of the commercially available antioxidant 1076 is generally 12 months, the actual time is far less than 12 months due to the limitation of storage conditions in practical application, and the time is too short in industrial application.
Disclosure of Invention
The application mainly provides a treatment method for reducing volatilization of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester and prolonging storage time of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester. The technical scheme is as follows:
a treatment method for improving storage time of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl ester comprises the following steps: mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and polyvinyl alcohol to prepare an aggregate; and coating cyclodextrin on the surface of the agglomerate.
Further, the weight ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester to the polyvinyl alcohol is 1 (0.01-0.05); the weight ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester to the cyclodextrin is 1 (0.005-0.05).
Further, the method comprises the following steps:
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester into water at normal temperature, stirring uniformly, adding polyvinyl alcohol, slowly stirring, heating to 70-95 ℃, keeping the temperature, drying, and cooling to normal temperature to obtain agglomerates;
(2) Dissolving cyclodextrin in water to prepare a solution, placing the agglomerate obtained in the step (1) in the solution, heating, stirring for 5-10 min at 80-120 r/min, cooling, and drying to obtain a finished product.
Further, the weight ratio of the n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate to the water in the step (1) is 1 (5-20); the weight ratio of the cyclodextrin to the water in the step (2) is 1 (100-150).
Further, the speed of the slow stirring in the step (1) is 30-200 r/min.
Further, the temperature reached by the temperature rise in the step (2) is 40-60 ℃.
Further, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester is pretreated before being mixed with polyvinyl alcohol to prepare an aggregate, and the pretreatment step comprises the following steps: putting beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester into ethanol water solution, stirring uniformly, heating to 50-60 ℃ and keeping for 3-8 h.
Further, the weight ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester to the ethanol aqueous solution is 1 (2-5).
Further, the ethanol content of the ethanol aqueous solution is 40-70%.
Further, the temperature rising speed is 1-10 ℃/min.
When the antioxidant 1076 is needed, the product of the application is placed in hot water with the temperature of 70-80 ℃ and fully stirred, and then the precipitate is taken and dried.
By adopting the scheme, the method has the following advantages:
1. according to the application, the antioxidant 1076 is pretreated to reduce volatilization, then the characteristic that the antioxidant 1076 is insoluble in water is utilized, and water-soluble polyvinyl alcohol and cyclodextrin are sequentially used to respectively help the antioxidant 1076 to agglomerate and coat, so that volatilization of the antioxidant 1076 is reduced in all directions from multiple angles, and the storage time of the antioxidant 1076 is prolonged.
2. The polyvinyl alcohol of the application needs to be dissolved in hot water, and the cyclodextrin does not need to be dissolved, so that the polyvinyl alcohol can not be mutually influenced in the preparation process, and the method has simple steps and strong operability.
3. According to the application, the particles of the antioxidant 1076 are captured and aggregated by using the polyvinyl alcohol, so that the particles of the antioxidant 1076 are aggregated, the contact area with the outside is reduced, and the volatilization is reduced.
4. According to the application, cyclodextrin is used for coating, volatilization of the antioxidant 1076 is reduced, and in the coating process, the amphipathy of the cyclodextrin is utilized to promote the dispersion of the agglomerates in water, so that the dispersion degree is larger, and the coating is more complete and uniform.
5. The application carries out pretreatment before the polyvinyl alcohol is mixed to prepare the agglomerate, and uses the solubility characteristic of the antioxidant 1076 to lead the agglomerate to be produced, thereby reducing the surface area and volatilization.
6. The method only carries out treatment through the change of the solubility, does not change the raw material property of the antioxidant 1076, has few operation steps, single raw material, only water in solvent, less influence on the property of the antioxidant 1076 due to the fact that the solvent is water, low production cost, easy industrial production, simple operation during multiplexing and high feasibility.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 2
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 1 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 3
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 10 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 4
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at the weight ratio of 1:10 at normal temperature, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at the rotating speed of 30r/min, heating to 80 ℃, preserving heat, drying, and cooling to the normal temperature to obtain the agglomerates.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 5
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 200r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 6
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 3 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 7
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 8 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 8
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.01 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 9
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.05 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.02 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example 10
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate which is 0.005 times of that before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling and drying to obtain the finished product.
Example 10
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into 50% ethanol water solution according to the weight ratio of 1:3, uniformly stirring, heating to 50-60 ℃ at the speed of 5 ℃/min, and keeping for 5 hours to obtain the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester.
(2) Placing the pretreated beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate obtained in the step (1) into water at normal temperature in a weight ratio of 1:10, uniformly stirring, adding 0.03 times of polyvinyl alcohol of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-stearyl propionate before the pretreatment in the step (1), slowly stirring at a rotating speed of 100r/min, heating to 80 ℃, preserving heat, drying, and cooling to normal temperature to obtain an aggregate.
(3) Taking cyclodextrin which is 0.05 times of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester before pretreatment in the step (1), dissolving the cyclodextrin in water according to the weight ratio of 1:100 to prepare a solution, placing the agglomerate obtained in the step (2) into the solution, heating to 50 ℃, stirring for 5-10 min at 100r/min, cooling, and drying to obtain a finished product.
Example sample preparation and testing:
the examples were prepared using commercially available basf antioxidant 1076. 10g of the finished products of examples 1 to 11 were placed in hot water at 70℃respectively, and after sufficient stirring, the precipitate was taken, dried and weighed to obtain a pre-measurement comparative sample.
10g of the finished products of examples 1 to 11 were dried in a drying oven at 100℃for 48 hours, then in hot water at 70℃and after sufficient stirring, the precipitate was dried and weighed to obtain samples, and the difference between the pre-measurement comparison sample and the sample of each example was taken. Each sample takes the arithmetic mean of the results of two parallel tests as the calculation result.
Results of the volatility test:
according to the table above, the test drying time of each example of the application is 48 hours which is far longer than 2 hours in industry standard, but each example is still lower than 0.1%, even examples 1, 7, 9 and 11 are 0.02%, which shows that the volatilization amount of the antioxidant 1076 treated by the treatment method of the application is obviously reduced, and the storage time is obviously prolonged. Examples 2 and 3 show that the heating rate during pretreatment has an influence on the volatilization amount, the heating rate is low, the crystallization agglomeration effect of the antioxidant 1076 is poor, and the antioxidant 1076 may not be fully agglomerated and is stirred. When the polyvinyl alcohol of examples 4 and 5 caused the antioxidant 1076 to agglomerate, the slower the stirring speed was, the more uneven the agglomeration was likely to be caused, the faster the stirring speed was likely to cause difficulty in the agglomeration thereof, and the volatilization was increased. Too long or too short pretreatment times in examples 6 and 7 adversely affect the agglomeration, and the amounts of polyvinyl alcohol and cyclodextrin in examples 8 and 11 are both small, and their volatilities are significantly increased, but the increase in the amounts of polyvinyl alcohol and cyclodextrin ensures the effect of prolonging the storage time of the antioxidant 1076, but the improvement is not significant.
It will be apparent to those skilled in the art from this disclosure that various other changes and modifications can be made which are within the scope of the application as defined in the appended claims.
Claims (6)
1. A treatment method for increasing the storage time of n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, which is characterized by comprising the following steps: mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and polyvinyl alcohol to prepare an aggregate; coating cyclodextrin on the surface of the agglomerate; the method specifically comprises the following steps:
(1) Placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into water at normal temperature, stirring uniformly, adding polyvinyl alcohol, slowly stirring, heating to 70-95 ℃, keeping the temperature, drying, and cooling to normal temperature to obtain an aggregate;
(2) Dissolving cyclodextrin in water to prepare a solution, placing the agglomerate obtained in the step (1) in the solution, heating, stirring for 5-10 min at 80-120 r/min, cooling, and drying to obtain a finished product;
the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester is pretreated before being mixed with polyvinyl alcohol to prepare an aggregate, and the pretreatment steps comprise: placing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol ester into an ethanol water solution, uniformly stirring, heating to 50-60 ℃ at the speed of 1-10 ℃/min, and keeping for 3-8 hours;
the weight ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester to the polyvinyl alcohol is 1 (0.01-0.05); the weight ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester to the cyclodextrin is 1 (0.005-0.05).
2. The method for increasing storage time of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate according to claim 1, wherein the weight ratio of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate to water in step (1) is 1 (5-20); the weight ratio of the cyclodextrin to the water in the step (2) is 1 (100-150).
3. The method for increasing storage time of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate according to claim 1, wherein the slow stirring speed in step (1) is 30 to 200r/min.
4. The method for increasing storage time of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate according to claim 1, wherein the temperature reached in step (2) is 40 to 60 ℃.
5. The method for improving the shelf life of n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate according to claim 1, wherein the weight ratio of n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate to the aqueous ethanol solution is 1 (2-5).
6. The method for increasing storage time of n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate according to claim 1, wherein the ethanol content of the ethanol aqueous solution is 40-70%.
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|---|---|---|---|---|
| FR2665169A1 (en) * | 1990-07-30 | 1992-01-31 | Rhone Poulenc Chimie | Cyclodextrin inclusion compounds containing phenolic antioxidants and their use in polymers |
| JPH11349940A (en) * | 1998-06-11 | 1999-12-21 | Yoshitomi Fine Chemical Kk | Antioxidant dispersion |
| WO2012124219A1 (en) * | 2011-03-14 | 2012-09-20 | 住友精化株式会社 | Polyrotaxane composition |
| CN107296278A (en) * | 2017-07-10 | 2017-10-27 | 北京素维生物科技有限公司 | A kind of function nutrition hardening agent composition and preparation method thereof |
| CN112472692A (en) * | 2020-11-13 | 2021-03-12 | 沧州硕金生物科技有限公司 | Mitochondrially targeted antioxidant compositions and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2665169A1 (en) * | 1990-07-30 | 1992-01-31 | Rhone Poulenc Chimie | Cyclodextrin inclusion compounds containing phenolic antioxidants and their use in polymers |
| JPH11349940A (en) * | 1998-06-11 | 1999-12-21 | Yoshitomi Fine Chemical Kk | Antioxidant dispersion |
| WO2012124219A1 (en) * | 2011-03-14 | 2012-09-20 | 住友精化株式会社 | Polyrotaxane composition |
| CN107296278A (en) * | 2017-07-10 | 2017-10-27 | 北京素维生物科技有限公司 | A kind of function nutrition hardening agent composition and preparation method thereof |
| CN112472692A (en) * | 2020-11-13 | 2021-03-12 | 沧州硕金生物科技有限公司 | Mitochondrially targeted antioxidant compositions and uses thereof |
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