CN115109002A - Method for preparing anti-aging agent from catechol - Google Patents
Method for preparing anti-aging agent from catechol Download PDFInfo
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- CN115109002A CN115109002A CN202210916102.2A CN202210916102A CN115109002A CN 115109002 A CN115109002 A CN 115109002A CN 202210916102 A CN202210916102 A CN 202210916102A CN 115109002 A CN115109002 A CN 115109002A
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- Prior art keywords
- phenylenediamine
- catalyst
- catechol
- reaction
- alkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing an anti-aging agent from catechol, which comprises the steps of adding catechol and o-phenylenediamine or alkyl o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, adding a catalyst, reacting at the temperature of 200-300 ℃, stopping the reaction after theoretical amount of water is obtained, decompressing and recovering o-phenylenediamine or alkyl o-phenylenediamine after the reaction is finished, and washing or filtering to remove the catalyst; and (3) carrying out vacuum distillation on the mixture from which the catalyst is removed, and distilling off low-boiling-point impurities influencing the melting point to obtain the final antioxidant product. The invention has the obvious advantages that pyrocatechol is used for replacing hydroquinone with higher price, thereby not only reducing the production cost, but also taking the advantages of the anti-aging agents 3100 and 4020 into account, avoiding the generation of quinone by ozonization reaction and reducing the dosage in practical use; the invention has high conversion rate of raw materials, high content of effective components and long anti-aging effect, and is particularly suitable for industrial production.
Description
Technical Field
The invention relates to the field of preparation of an anti-aging agent, and particularly relates to a method for preparing the anti-aging agent from catechol.
Background
Hydrocarbon polymer materials such as rubber and plastic are subject to oxidative deterioration by oxygen, heat, light (particularly ultraviolet rays), metal ions, or dynamic fatigue. In addition, ozone aging occurs by the action of ozone, and the aging process of rubber is a radical chain reaction which not only breaks the molecular chain of rubber (softening of rubber) but also causes chain crosslinking (hardening of rubber). Therefore, the anti-aging agents are classified into radical inhibitors and peroxide decomposers according to the mechanism of action. The rubber anti-aging agents produced at home and abroad at present can be generally classified into amines, phenols, phosphites, heterocycles and other types. The commonly used anti-aging agent such as 4010NA is a universal excellent anti-aging agent, has excellent protection performance on ozone and flex cracking, is suitable for natural rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber and latex, and the anti-aging agent 3100 is a typical post-effect p-phenylenediamine rubber anti-aging agent, and can effectively make up the defects that the anti-aging agents 4020 and 4010NA have good early anti-aging effect and slightly poor later stage. From the chemical structure, the series of products are derivatives of p-phenylenediamine. They generally have good oxidative degradation and barrier properties, as well as ozone resistance and excellent protection against bending fractures.
The anti-aging agents have the defects of large usage amount, high toxicity and pollution and the like. According to the report of journal of science, quinone generated by the reaction of p-phenylenediamine antioxidants and ozone in natural environment is the substance with the highest toxicity in tires, so that the development of an environment-friendly antioxidant is urgently needed, the quinone generated by ozone aging is prevented, and the harm of tire rubber residues to the environment and human health is reduced; therefore, the method for preparing the anti-aging agent by using the catechol is provided.
Disclosure of Invention
The invention aims to provide a method for preparing an anti-aging agent from catechol aiming at the defects of the prior art so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing an anti-aging agent from catechol, wherein the anti-aging agent has a structure shown in a formula (I):
in the formula R 1 、R 2 、R 3 、R 4 Respectively is straight-chain alkyl with 1-8 carbon atoms and isomers or hydrogen thereof;
the specific method of reaction and separation is as follows:
s1: adding pyrocatechol and o-phenylenediamine or alkyl o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, adding a catalyst, reacting at the temperature of 200-300 ℃, and stopping the reaction after theoretical water is obtained, wherein the pyrocatechol: o-phenylenediamine or alkyl-o-phenylenediamine: the molar ratio of the catalyst is 1: (1.0-2.0): (0.01-0.10), after the reaction is finished, recovering o-phenylenediamine or alkyl o-phenylenediamine under reduced pressure, washing with water or filtering to remove the catalyst;
s2: and (3) carrying out vacuum distillation on the mixture from which the catalyst is removed, and distilling off low-boiling-point impurities influencing the melting point to obtain the final antioxidant product.
In a preferable technical scheme of the invention, R1, R2, R3 and R4 in the S1 are respectively one or more mixtures of straight-chain alkyl with 1-8 carbon atoms and isomers thereof or hydrogen, and are preferably o-phenylenediamine and methyl-o-phenylenediamine.
As a preferred embodiment of the present invention, in the S1 reaction, catechol: o-phenylenediamine or alkyl-o-phenylenediamine: the molar ratio of the catalyst is preferably 1: (1.1-1.5): (0.01-0.05).
In a preferred embodiment of the present invention, the catalyst in S1 is a lewis acid, and includes any one of AlCl3, ZnCl2, FeCl3, benzenesulfonic acid and salts thereof, and trifluoromethanesulfonic acid and salts thereof.
As a preferred technical scheme of the invention, the catalyst in S1 is preferably FeCl 3.
The invention has the beneficial effects that:
(1) the invention has the obvious advantages that pyrocatechol is used for replacing hydroquinone with higher price, thereby not only reducing the production cost, but also having the advantages of the anti-aging agents 3100 and 4020, avoiding the generation of quinone by ozonization reaction and reducing the dosage in actual use;
(2) the invention has high conversion rate of raw materials, high content of effective components and long anti-aging effect, and is particularly suitable for industrial production.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more clearly understand the advantages and features of the present invention, and to clearly define the scope of the present invention.
Example 1:
(1) adding 110g of catechol and 129.6g of o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, and adding 2.7g of catalyst ZnCl 2 The reaction is carried out at 240 ℃ until the theoretical amount of water is obtained and stopped, wherein the molar ratio of catechol: o-phenylenediamine: ZnCl 2 1: 1.2: 0.02, after the reaction is finished, decompressing and recovering o-phenylenediamine, and filtering to remove the catalyst while the reaction is hot;
(2) and carrying out vacuum distillation on the mixture from which the catalyst phosphorus is removed, and evaporating hydroxyl aniline-containing impurities affecting the melting point to obtain a final anti-aging agent product with the effective component content of 96.7%.
Example 2:
(1) adding 110g of catechol and 158.6g of o-methyl o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, and adding 1.6g of catalyst FeCl 3 And the reaction is carried out at 250 ℃ until a theoretical amount of water is obtained, and the reaction is stopped, wherein the molar ratio of catechol: o-methyl o-phenylenediamine: FeCl 3 1: 1.3: 0.01, after the reaction is finished, decompressing and recovering the o-methyl o-phenylenediamine, and filtering to remove the catalyst when the reaction is hot;
(2) and carrying out vacuum distillation on the mixture from which the catalyst is removed, and evaporating hydroxyl aniline impurities affecting the melting point to obtain a final anti-aging agent product with the effective component content of 97.0%.
Example 3:
(1) adding 110g of catechol, 64.8g of o-phenylenediamine and 73.2g of p-methyl o-phenylenediamine into a reactor at normal pressure, introducing nitrogen, heating to 100 ℃, and adding 8.1g of catalyst FeCl 3 And the reaction is carried out at 260 ℃ until a theoretical amount of water is obtained, and the reaction is stopped, wherein the molar ratio of catechol: o-phenylenediamine: p-methyl o-phenylenediamine: FeCl 3 1: 0.6: 0.6: 0.05, after the reaction is finished, decompressing and recovering o-phenylenediamine and p-methyl o-phenylenediamine, and filtering to remove the catalyst when the reaction is hot;
(2) and carrying out vacuum distillation on the mixture from which the catalyst is removed, and evaporating hydroxyl aniline impurities affecting the melting point to obtain a final anti-aging agent product with the effective component content of 96.8%.
Example 4:
(1) adding 110g of catechol and 118.8g of o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, and adding 4.9g of catalyst FeCl 3 And the reaction is carried out at 230 ℃ until a theoretical amount of water is obtained, and the reaction is stopped, wherein the molar ratio of catechol: o-phenylenediamine: FeCl 3 1: 1.1: 0.03, after the reaction is finished, decompressing and recovering o-phenylenediamine, and washing with hot water to remove the catalyst to obtain monohydroxy amine;
(2) and carrying out vacuum distillation on the mixture from which the catalyst is removed, and evaporating hydroxyl aniline impurities affecting the melting point to obtain a final anti-aging agent product with the effective component content of 96.5%.
The samples obtained in the above examples 1 to 4 are respectively coded as # 1 to # 4, the anti-aging agent 3100 is coded as # 5, the mixing and vulcanization are carried out by adopting the conventional mixing method and formula, and the performance test is carried out on the obtained corresponding rubber compound, and the results are shown in tables 1 to 5.
1, formula and process;
1.1, a formula;
table 1 formula table
1.2, a rubber mixing process;
mixing by adopting a two-stage mixing process.
(1) Banburying (temperature: 80 ℃; rotation speed: 80 rpm)
The rubber, the small material, the carbon black and the asphalt-like substance are cleaned for 3.5min for 2min to remove the rubber (the temperature is 150 ℃).
(2) Open mill
One segment of matrigel → sulfur, promoter → Bo Tong 6 times, and the lower piece.
2. The performance of the rubber compound;
2.1, mixing performance of rubber materials;
TABLE 2 elastomeric compounds test results
2.2, the performance of the rubber compound;
TABLE 3 elastomeric compounds test results
3. The performance of vulcanized rubber;
TABLE 4 vulcanizate Properties
4. The thermal oxidation aging performance of vulcanized rubber;
TABLE 5 thermo-oxidative aging Properties of vulcanizates (100 ℃ C. 24h)
The aging factor is (tensile strength × elongation at break) after aging/(tensile strength × elongation at break) before aging;
as can be seen from the table, the anti-aging agent provided by the invention can achieve the same or better physical properties as the prior anti-aging agent 3100.
Aging the vulcanized rubber compounds of FL-1, FL-2, FL-3 and FL-4, extracting, and detecting the extractive solution by liquid chromatography-tandem mass spectrometry without detecting quinone compounds; aging the vulcanized rubber compound of the comparative rubber compound FL-5, extracting, and detecting the extract to detect the quinone compound; therefore, the environment-friendly anti-aging agent provided by the invention does not generate a high-toxicity quinone conversion product in rubber residues, and is an environment-friendly rubber anti-aging agent.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. A method for preparing an anti-aging agent from catechol is characterized by comprising the following steps: the anti-aging agent has a structure shown in a formula (I):
in the formula R 1 、R 2 、R 3 、R 4 Respectively is straight-chain alkyl with 1-8 carbon atoms and isomers or hydrogen thereof;
the specific method of reaction and separation is as follows:
s1: adding pyrocatechol and o-phenylenediamine or alkyl o-phenylenediamine into a reactor under normal pressure, introducing nitrogen, heating to 100 ℃, adding a catalyst, reacting at the temperature of 200-300 ℃, and stopping the reaction after theoretical water is obtained, wherein the pyrocatechol: o-phenylenediamine or alkyl-o-phenylenediamine: the molar ratio of the catalyst is 1: (1.0-2.0): (0.01-0.10), after the reaction is finished, recovering o-phenylenediamine or alkyl o-phenylenediamine under reduced pressure, washing with water or filtering to remove the catalyst;
s2: and (3) carrying out vacuum distillation on the mixture from which the catalyst is removed, and distilling off low-boiling-point impurities influencing the melting point to obtain the final antioxidant product.
2. The method for preparing the anti-aging agent from the catechol as described in claim 1, wherein the method comprises the following steps: r1, R2, R3 and R4 in the S1 are respectively straight-chain alkyl with 1-8 carbon atoms and isomers thereof or one or more mixtures of hydrogen, and are preferably o-phenylenediamine and methyl-o-phenylenediamine.
3. The method for preparing the antioxidant from the catechol according to claim 1, wherein: catechol in the S1 reaction: o-phenylenediamine or alkyl-o-phenylenediamine: the molar ratio of the catalyst is preferably 1: (1.1-1.5): (0.01-0.05).
4. The method for preparing the antioxidant from the catechol according to claim 1, wherein: the catalyst in the S1 is Lewis acid and comprises any one of AlCl3, ZnCl2, FeCl3, benzenesulfonic acid and salts thereof, and trifluoromethanesulfonic acid and salts thereof.
5. The method for preparing the anti-aging agent from the catechol as described in claim 1, wherein the method comprises the following steps: the catalyst in S1 is preferably FeCl 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210916102.2A CN115109002A (en) | 2022-08-01 | 2022-08-01 | Method for preparing anti-aging agent from catechol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210916102.2A CN115109002A (en) | 2022-08-01 | 2022-08-01 | Method for preparing anti-aging agent from catechol |
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| Publication Number | Publication Date |
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| CN115109002A true CN115109002A (en) | 2022-09-27 |
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| CN202210916102.2A Pending CN115109002A (en) | 2022-08-01 | 2022-08-01 | Method for preparing anti-aging agent from catechol |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242602B1 (en) * | 1999-03-29 | 2001-06-05 | Gentex Corporation | One pot synthesis of 5,10-dihydrophenazine compounds and 5,10-substituted dihydrophenazines |
| WO2009083532A2 (en) * | 2007-12-28 | 2009-07-09 | Universite De La Mediterranee Aix-Marseille Ii | Novel method for the preparation of derivatives of dihydrotetraazapentacenes, products such as obtained, and uses thereof |
| CN103304496A (en) * | 2012-03-08 | 2013-09-18 | 南京工业大学 | Method for synthesizing phenazine-1-carboxylic acid |
| KR20200089172A (en) * | 2019-01-16 | 2020-07-24 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
-
2022
- 2022-08-01 CN CN202210916102.2A patent/CN115109002A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242602B1 (en) * | 1999-03-29 | 2001-06-05 | Gentex Corporation | One pot synthesis of 5,10-dihydrophenazine compounds and 5,10-substituted dihydrophenazines |
| WO2009083532A2 (en) * | 2007-12-28 | 2009-07-09 | Universite De La Mediterranee Aix-Marseille Ii | Novel method for the preparation of derivatives of dihydrotetraazapentacenes, products such as obtained, and uses thereof |
| CN103304496A (en) * | 2012-03-08 | 2013-09-18 | 南京工业大学 | Method for synthesizing phenazine-1-carboxylic acid |
| KR20200089172A (en) * | 2019-01-16 | 2020-07-24 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARKUS MIKULLA等: "Synthesis and properties of polyaramides and poly(amide-imide)s containing 5, 10-dihydrophenazine units", 《MACROMOL. CHEM. PHYS.》, vol. 199, pages 795 - 805, XP000774624, DOI: 10.1002/macp.1998.021990514 * |
| MORLEY, J. S.: "Chemotherapy of filariasis. II. Monoacyl derivatives of 5, 10-dihydro- and trans-1, 2, 3, 4, 5, 10, 11, 12-octahydrophenazine.", 《JOURNAL OF THE CHEMICAL SOCIETY》, pages 4008 - 4014 * |
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