CN113831592B - Phenolic amine antioxidant and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a phenol amine antioxidant and a preparation method and application thereof. The preparation process includes dissolving compound I and compound II in organic solvent, and adding Na 2 CO 3 Heating the aqueous solution and a Pd catalyst for reaction, cooling the reaction product to room temperature, and performing post-treatment and chromatographic separation to obtain a compound III; dissolving compound III in EtOH, then adding Pd/C catalyst and N 2 H 4 ‑H 2 O, heating for reaction, filtering and drying after the reaction, and then spin-drying to obtain a compound IV; mixing compound IV, dry toluene, pd (dba) 2 、t‑Bu 3 Mixing P and NaOBu-t, slowly adding a toluene solution of a compound V, and heating for reaction to obtain a product C; cooling the product C to room temperature, washing, standing, taking the upper organic phase, drying, performing rotary evaporation, and performing chromatographic separation to obtain a compound VI. The phenol amine antioxidant belongs to a novel composite antioxidant, has the characteristics of good oxidation resistance and small dyeing pollution, and can be widely applied to synthetic resin; and the preparation condition is mild, the raw materials are easy to obtain, and the industrial popularization is easy.
Description
Technical Field
The invention relates to an antioxidant, a preparation method and application thereof, in particular to a phenol amine antioxidant, a preparation method and application thereof.
Background
Antioxidants are a class of chemicals which, when present in only small amounts in polymer systems, retard or inhibit the progress of the polymer oxidation process, thereby preventing the aging of the polymer and extending its useful life, also known as "age resistors". There are many types of antioxidants currently on the market, and hindered phenol antioxidants and hindered amine antioxidants are the two common types.
Wherein, the hindered phenol antioxidant is mostly used for plastic products and shows synergistic effect with auxiliary antioxidants such as phosphite ester, thioether and the like. Representative examples thereof include 2, 8-di-tert-butyl-4-methylphenol, antioxidant 1010 and the like. Hindered amine is a relatively new type anti-ultraviolet/anti-aging agent, because the aging of the high polymer is caused by photo-redox reaction caused by ultraviolet light, free radicals are caused to destroy the molecular structure of the high polymer, and the degradation of the high polymer is finally caused, namely the aging process of the polymer, and the hindered amine can stop or inhibit chain initiation reaction and chain growth reaction by capturing oxygen free radicals, thereby terminating the free radical chain reaction, and achieving the purpose of preventing oxidation.
Although the hindered phenol antioxidant and the hindered amine antioxidant can play good roles of oxidation resistance and aging resistance when applied to high molecular polymers, both of the hindered phenol antioxidant and the hindered amine antioxidant have certain defects in practical application. Among them, hindered phenol antioxidants have a low molecular weight, resulting in high volatility and migration, easily coloring plastic products, and causing a decrease in oxidation resistance. Hindered amines, while less volatile and migratory, are susceptible to deterioration, which can lead to discoloration and contamination of the plastic article. Therefore, at present, hindered phenol and hindered amine antioxidants are mostly used for materials with low requirements on product color, dark and black rubber and plastic products, and the application of the hindered phenol and hindered amine antioxidants is limited to a certain extent.
The research of researchers of the subject discovers that the phenolic antioxidant and the amine antioxidant are combined in molecules, so that the antioxidant capacity of the antioxidant can be improved, the molecular weight can be improved, the problems of high volatility and migration of a single antioxidant and discoloration of plastic products caused by deterioration pollution are solved, and the application of the hindered phenolic antioxidant and the hindered amine antioxidant in synthetic resin can be expanded. Although reports of compound antioxidants formed by intramolecular compounding of hindered phenols and hindered amines appear in the existing reports, for example, patent CN102516157B discloses a synthesis method of hindered phenol/hindered amine intramolecular compound antioxidants, but the types of antioxidants are still few, and the diversified demands of the market can not be met.
Disclosure of Invention
The invention aims to provide a phenolic amine antioxidant, and a preparation method and application thereof. The phenol amine antioxidant belongs to a novel composite antioxidant, has the characteristics of good oxidation resistance and small dyeing pollution, and can be widely applied to synthetic resin; and the preparation condition is mild, the raw materials are easy to obtain, and the industrial popularization is easy.
The technical scheme of the invention is as follows: a phenolic amine antioxidant has the following chemical structural formula:
wherein Ar is 1 And Ar 2 Are aryl groups of the same or different structure.
The preparation method of the phenolic amine antioxidant comprises the following synthetic route:
wherein Ar is 1 And Ar 2 Are aryl groups of the same or different structure.
Compounds I and II include, but are not limited to, the following:
a compound I:
compound II:
the preparation method of the phenol amine antioxidant comprises the following specific steps:
(1) Dissolving compound I and compound II in organic solvent, and adding Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 Under the protection of nitrogen, heating the aqueous solution and the Pd catalyst for reaction, cooling a reaction product to room temperature, performing post-treatment, and performing chromatographic separation on the post-treatment product to obtain a compound III;
(2) Dissolving compound III in EtOH, then adding Pd/C catalyst and N 2 H 4 -H 2 O, heating for reaction, filtering after the reaction, drying a filtered substance by using anhydrous magnesium sulfate, and then spin-drying a solvent to obtain a compound IV;
(3) Mixing compound IV, dry toluene, pd (dba) 2 、t-Bu 3 Mixing P and NaOBu-t to obtain product A; wherein the mass volume ratio of the compound IV to the dry toluene is 1:5-10, compound IV, pd (dba) 2 、t-Bu 3 The molar ratio of P to NaOBu-t is 100:1:2:200 of a carrier;
(4) Mixing the compound V with dry toluene to obtain a product B;
(5) Heating the product A under the protection of nitrogen, slowly dripping the product B into the product A, and continuously reacting after finishing dripping to obtain a product C; wherein the molar ratio of compound IV to compound V is 1;
(6) And cooling the product C to room temperature, adding water for washing, standing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing the solvent by rotary evaporation, and carrying out chromatographic separation to obtain a final product, namely the compound VI.
In the preparation method of the phenol amine antioxidant, in the step (1), the molar ratio of the compound I to the compound II is 1:1; the organic solvent is toluene or dioxane; the Na is 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 The concentration of the aqueous solution of (1) is 2mol/L, wherein Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 The molar ratio of the compound I or the compound II is 2-3:1; the molar addition amount of the Pd catalyst is 3-9% of that of the compound I or the compound II; the heating temperature is 70-100 ℃, and the reaction time is 4-8h.
In the preparation method of the phenol amine antioxidant, when the organic solvent is toluene, the post-treatment is to cool the reaction product to room temperature, add water to wash, stand to take the upper organic phase, dry with anhydrous magnesium sulfate or anhydrous sodium sulfate, remove the solvent by rotary evaporation, and perform 200-300 mesh silica gel column chromatography; when the organic solvent is dioxane, the post-treatment comprises the steps of cooling the reaction product to room temperature, adding water with the volume 3-5 times that of the reaction liquid, separating out a crude product, filtering, dissolving in dichloromethane, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, and performing 200-300-mesh silica gel column chromatography; the eluent components of the chromatography are dichloromethane pure in volume ratio: petroleum ether =3:1.
in the preparation method of the phenol amine antioxidant, in the step (1), the Pd catalyst is Pd (PPh) 3 ) 4 、PdCl 2 、Pd(dppf)Cl 2 、Pd(OAc) 2 Or Pd (PPh) 3 ) 2 Cl 2 To (3) is provided.
In the preparation method of the phenolic amine antioxidant, in the step (2), 30-70g of Pd/C catalyst and 150-250ml of N are added into 1mol of the compound III 2 H 4 -H 2 O。
In the preparation method of the phenol amine antioxidant, the heating temperature in the step (2) is 55-65 ℃, and the reaction time is 1-3h.
In the preparation method of the phenol amine antioxidant, the heating temperature in the step (5) is 75-85 ℃, and the continuous reaction time is 0.5-1.5h.
In the preparation method of the phenol amine antioxidant, the chromatographic column in the step (6) is a 200-300 mesh silica gel column, and the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1.
an application of the phenolic amine antioxidant in synthetic resin.
The invention has the advantages of
1. The composite antioxidant disclosed by the invention is novel in structure, belongs to a novel composite antioxidant, has the characteristics of an amine antioxidant and a phenol antioxidant, and has the advantage of strong oxidation resistance.
2. Compared with single hindered phenol antioxidant and hindered amine antioxidant, the composite antioxidant has the advantages of larger molecular weight, smaller volatility and mobility, difficult deterioration and small dyeing pollution.
3. The synthetic raw materials of the antioxidant are common and easy to obtain, the reaction conditions are mild, and the industrial popularization is easy.
Drawings
FIG. 1 is a schematic view of the molecular structure of the antioxidant of the present invention;
FIG. 2 is a mass spectrum of Compound III;
FIG. 3 is a mass spectrum of Compound IV;
FIG. 4 is a mass spectrum of Compound VI;
FIG. 5 is a hydrogen nuclear magnetic diagram of Compound III;
FIG. 6 is a hydrogen nuclear magnetic diagram of Compound IV;
FIG. 7 is the hydrogen nuclear magnetic diagram of Compound VI.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1
The synthetic route is as follows:
the synthesis steps are as follows:
(1) Compound I (1 mol) and compound II (1 mol) are dissolved in toluene, and 2.5mol of Na are added 2 CO 3 Prepared 2mol/L aqueous solution and 0.06mol of Pd (PPh) 3 ) 4 After replacing nitrogen for three times, reacting for 6 hours at 85 ℃ under the protection of nitrogen;
(2) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate, removing a solvent by rotary evaporation, and then carrying out silica gel column chromatography by using a 200-300-mesh silica gel column, wherein the eluent comprises the following components in volume ratio of dichloromethane: petroleum ether =3:1, obtaining a compound III;
(3) Compound III (1 mol), pd/C catalyst (50 g) and N 2 H 4 -H 2 Dissolving O (hydrazine hydrate, 200 ml) in EtOH, reacting for 2h at 60 ℃, after the reaction is finished, filtering to remove the Pd/C catalyst, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a compound IV;
(4) In a two-necked flask, compound IV, dry toluene, pd (dba) 2 、t-Bu 3 P and NaOBu-t, adding the compound V and dry toluene into another constant-pressure dropping funnel, connecting a condenser pipe with one mouth of the two flasks and connecting the constant-pressure dropping funnel with one mouth of the two flasks, replacing nitrogen for three times, heating to 80 ℃ under the protection of nitrogen, opening the constant-pressure dropping funnel at the moment, dropwise and slowly dropping the toluene solution of the compound V, and continuing to react for 1h after the dropwise addition is finished;
(5) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing a solvent by rotary evaporation, and then carrying out silica gel column chromatography by using 200-300 meshes, wherein the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1 to obtain the final product compound VI.
Example 2
The synthetic route is the same as example 1, and the synthetic steps are as follows:
(1) Dissolving compound I (1 mol) and compound II (1 mol) in dioxane, and adding 2.5mol of K 2 CO 3 Prepared 2mol/L aqueous solution and 0.06mol of PdCl 2 After replacing nitrogen for three times, reacting for 6 hours at 85 ℃ under the protection of nitrogen;
(2) After the reaction is finished, cooling to room temperature, adding water with the volume 3-5 times of that of the reaction liquid, separating out a large amount of crude products, filtering, dissolving in dichloromethane, drying by using anhydrous magnesium sulfate, and performing 200-300-mesh silica gel column chromatography to obtain eluent with the components of dichloromethane in volume ratio: petroleum ether =3:1, obtaining a compound III;
(3) Compound III (1 mol), pd/C catalyst (50 g) and N 2 H 4 -H 2 Dissolving O (hydrazine hydrate, 200 ml) in EtOH, reacting for 2h at 60 ℃, after the reaction is finished, filtering to remove the Pd/C catalyst, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a compound IV;
(4) In a two-necked flask, compound IV, dry toluene, pd (dba) 2 、t-Bu 3 P and NaOBu-t, adding the compound V and dry toluene into another constant-pressure dropping funnel, connecting a condenser pipe with one mouth of the two flasks and connecting the constant-pressure dropping funnel with one mouth of the two flasks, replacing nitrogen for three times, heating to 80 ℃ under the protection of nitrogen, opening the constant-pressure dropping funnel at the moment, dropwise and slowly dropping the toluene solution of the compound V, and continuing to react for 1h after the dropwise addition is finished;
(5) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing a solvent by rotary evaporation, and then carrying out silica gel column chromatography by using 200-300 meshes, wherein the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1 to obtain the final product compound VI.
Example 3
The synthetic route is as follows:
the synthesis steps are as follows:
(1) Neutralizing the Compound I (1 mol)Compound II (1 mol) is dissolved in toluene or dioxane, and 2mol Cs are added 2 CO 3 Prepared 2mol/L aqueous solution and 0.03mol of Pd (dppf) Cl 2 After replacing nitrogen for three times, reacting for 8 hours at 70 ℃ under the protection of nitrogen;
(2) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous sodium sulfate, removing a solvent by rotary evaporation, and then carrying out silica gel column chromatography by using a 200-300-mesh silica gel column, wherein the eluent comprises the following components in volume ratio: petroleum ether =3:1, obtaining a compound III;
(3) Compound III (1 mol), pd/C catalyst (30 g) and N 2 H 4 -H 2 Dissolving O (hydrazine hydrate, 150 ml) in EtOH, reacting for 3h at 55 ℃, after the reaction is finished, filtering to remove the Pd/C catalyst, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a compound IV;
(4) In a two-necked flask, compound IV, dry toluene, pd (dba) 2 、t-Bu 3 P and NaOBu-t, adding the compound V and dry toluene into another constant-pressure dropping funnel, connecting a condenser pipe with one mouth of the two flasks and connecting the constant-pressure dropping funnel with one mouth of the two flasks, replacing nitrogen for three times, heating to 75 ℃ under the protection of nitrogen, opening the constant-pressure dropping funnel at the moment, dropwise and slowly dropping the toluene solution of the compound V, and continuing to react for 0.5 hour after the dropwise addition is finished;
(5) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing a solvent by rotary evaporation, and performing silica gel column chromatography by using a 200-300-mesh column, wherein the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1 to obtain the final product compound VI.
Example 4
The synthetic route is the same as that of example 3, and the synthetic steps are as follows:
(1) Dissolving compound I (1 mol) and compound II (1 mol) in dioxane, and adding 3mol of K 3 PO 4 Prepared 2mol/L aqueous solution and 0.09mol of Pd (PPh) 3 ) 2 Cl 2 After replacing nitrogen for three times, reacting for 4 hours at 100 ℃ under the protection of nitrogen;
(2) After the reaction is finished, cooling to room temperature, adding water with the volume 3-5 times of that of the reaction liquid, separating out a large amount of crude products, filtering, dissolving in dichloromethane, drying by anhydrous sodium sulfate, and performing 200-300-mesh silica gel column chromatography to obtain an eluent with the components of dichloromethane in volume ratio: petroleum ether =3:1, obtaining a compound III;
(3) Compound III (1 mol), pd/C catalyst (70 g) and N 2 H 4 -H 2 Dissolving O (hydrazine hydrate, 250 ml) in EtOH, reacting for 1h at 65 ℃, after the reaction is finished, filtering to remove the Pd/C catalyst, drying by anhydrous magnesium sulfate, and spin-drying the solvent to obtain a compound IV;
(4) In a two-necked flask, compound IV, dry toluene, pd (dba) 2 、t-Bu 3 P and NaOBu-t, adding the compound V and dry toluene into another constant-pressure dropping funnel, connecting a condenser pipe with one mouth of the two flasks and connecting the constant-pressure dropping funnel with one mouth of the two flasks, replacing nitrogen for three times, heating to 85 ℃ under the protection of nitrogen, opening the constant-pressure dropping funnel at the moment, dropwise and slowly dropping the toluene solution of the compound V, and continuing to react for 1.5 hours after the dropwise addition is finished;
(5) After the reaction is finished, cooling to room temperature, adding water for washing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing a solvent by rotary evaporation, and performing silica gel column chromatography by using a 200-300-mesh column, wherein the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1 to obtain the final product compound VI.
Examples of the experiments
200g of the compound VI prepared in example 1 are melt-blended with 100kg of PBAT, extruded and granulated, blown into a film and subjected to an aging test with pure PBAT film in an aging oven according to GB/T16422.1.
The results of the experiment are shown in the following table:
from the above table, it can be seen that the properties of the PBAT material after adding the antioxidant are all improved by times in several aspects of tensile strength (transverse direction), tensile strength (longitudinal direction), elongation at break (transverse direction) and elongation at break (longitudinal direction) compared with pure PBAT material, which indicates that the antioxidant of the present invention has stronger antioxidant property when applied to synthetic resin.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (8)
1. The preparation method of the phenolic amine antioxidant is characterized in that the synthetic route is as follows:
wherein Ar is 1 And Ar 2 Are aryl groups of the same or different structure.
2. The method for preparing the phenolic amine antioxidant as claimed in claim 1, which comprises the following steps:
(1) Dissolving compound I and compound II in organic solvent, and adding Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 The aqueous solution and the Pd catalyst are heated to react under the protection of nitrogen, the reaction product is cooled to room temperature and then is subjected to post-treatment, and the post-treatment product is subjected to chromatographic separation to obtain a compound III;
(2) Dissolving compound III in EtOH, then adding Pd/C catalyst and N 2 H 4 -H 2 O, heating for reaction, filtering after the reaction, drying the filtrate by anhydrous magnesium sulfate, and then spin-drying the solvent to obtain a compound IV;
(3) Mixing compound IV, dry toluene, pd (dba) 2 、t-Bu 3 Mixing P and NaOBu-t to obtain product A; wherein the mass volume ratio of the compound IV to the dry toluene is 1:5-10, compound IV, Pd(dba) 2 、t-Bu 3 The molar ratio of P to NaOBu-t is 100:1:2:200 of a carrier;
(4) Mixing the compound V and dry toluene to obtain a product B;
(5) Heating the product A under the protection of nitrogen, slowly dripping the product B into the product A, and continuously reacting after finishing dripping to obtain a product C; wherein the molar ratio of compound IV to compound V is 1;
(6) And cooling the product C to room temperature, adding water for washing, standing, taking an upper layer organic phase, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, removing the solvent by rotary evaporation, and carrying out chromatographic separation to obtain a final product, namely the compound VI.
3. The method for producing a phenolic amine antioxidant as claimed in claim 2, wherein: the molar ratio of the compound I to the compound II in the step (1) is 1:1; the organic solvent is toluene or dioxane; the Na is 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 In an aqueous solution of (2) mol/L, wherein Na is 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Or K 3 PO 4 The molar ratio of the compound I or the compound II is 2-3:1; the molar addition amount of the Pd catalyst is 3-9% of that of the compound I or the compound II; the heating temperature is 70-100 ℃, and the reaction time is 4-8h.
4. The method for producing a phenolic amine antioxidant as claimed in claim 3, wherein: when the organic solvent is toluene, the post-treatment is to cool the reaction product to room temperature, add water for washing, stand to take the upper organic phase, dry with anhydrous magnesium sulfate or anhydrous sodium sulfate, remove the solvent by rotary evaporation, and perform 200-300 mesh silica gel column chromatography; when the organic solvent is dioxane, the post-treatment comprises the steps of cooling the reaction product to room temperature, adding water with the volume 3-5 times that of the reaction liquid, separating out a crude product, filtering, dissolving in dichloromethane, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, and performing 200-300-mesh silica gel column chromatography; the eluent composition of the chromatography is dichloromethane-pure in volume ratio: petroleum ether =3:1.
5. the method for producing a phenolic amine antioxidant as claimed in claim 2, characterized in that: the Pd catalyst in the step (1) is Pd (PPh) 3 ) 4 、PdCl 2 、Pd(dppf)Cl 2 、Pd(OAc) 2 Or Pd (PPh) 3 ) 2 Cl 2 One kind of (1).
6. The method for producing a phenolic amine antioxidant as claimed in claim 2, wherein: in the step (2), 30-70g of Pd/C catalyst and 150-250ml of N are added into every 1mol of compound III 2 H 4 -H 2 O; the heating temperature is 55-65 ℃, and the reaction time is 1-3h.
7. The method for producing a phenolic amine antioxidant as claimed in claim 2, wherein: the heating temperature in the step (5) is 75-85 ℃, and the continuous reaction time is 0.5-1.5h.
8. The method for producing a phenolic amine antioxidant as claimed in claim 2, wherein: the chromatographic column for chromatographic separation in the step (6) adopts a 200-300-mesh silica gel column, and the eluent comprises the following components in volume ratio of dichloromethane: methanol =40:1.
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| CN105294543A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Method for preparing weather-proof anti-aging auxiliary agent simultaneously containing hindered phenol and hindered amine structures |
| CN105505525A (en) * | 2015-10-16 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Phenolic amine antioxidant and preparation method and application thereof |
| CN111393381A (en) * | 2020-04-08 | 2020-07-10 | 玛可索(苏州)石化有限公司 | Phenolic amine compound and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6770785B1 (en) * | 2003-03-25 | 2004-08-03 | Council Of Scientific And Industrial Research | Antiozonant cum antioxidant, process for preparation |
| CN101528668A (en) * | 2006-10-17 | 2009-09-09 | 雅宝公司 | Macromolecular amine-phenolic antioxidant compositions, process technology thereof, and uses thereof |
| CN105505525A (en) * | 2015-10-16 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Phenolic amine antioxidant and preparation method and application thereof |
| CN105294543A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Method for preparing weather-proof anti-aging auxiliary agent simultaneously containing hindered phenol and hindered amine structures |
| CN111393381A (en) * | 2020-04-08 | 2020-07-10 | 玛可索(苏州)石化有限公司 | Phenolic amine compound and preparation method and application thereof |
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