CN111689856B - Preparation method of hindered phenol antioxidant and intermediate thereof - Google Patents
Preparation method of hindered phenol antioxidant and intermediate thereof Download PDFInfo
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Abstract
The application provides a preparation method of a hindered phenol antioxidant and an intermediate thereof. The preparation method comprises the steps of carrying out Friedel-crafts reaction on a compound a and a compound b under the action of main catalyst organic sulfonic acid and/or trifluoroacetic acid and a cocatalyst to obtain a hindered phenol antioxidant intermediate shown in a formula I; wherein, the structural formulas of the compound a, the compound b and the formula I are respectively as follows:R 1 selected from H, C 1 ～C 4 Substituted or unsubstituted alkyl, R 2 Selected from C 1 ～C 4 Substituted or unsubstituted alkyl. The preparation of the hindered phenol antioxidant intermediate adopts organic sulfonic acid and/or trifluoroacetic acid to replace a hydrogen chloride gas catalyst, so that the safety of the reaction is greatly improved, the requirement on equipment is reduced, and the equipment cost is also reduced.
Description
Technical Field
The application relates to the technical field of synthesis of hindered phenol antioxidants, in particular to a preparation method of a hindered phenol antioxidant and an intermediate thereof.
Background
The hindered phenol antioxidant is an anti-aging agent for plastics, rubber and high polymer materials with wide application, and can effectively protect the plastics, rubber and high polymer materials from aging and damage caused by oxygen in the environment, thereby prolonging the service life of the materials. However, the hindered phenol antioxidant has such properties and applications, and through long-term researches by researchers, such as an antioxidant Hostanox O3, the structure of which is shown in a formula II, and the chemical name of which is ethylene glycol bis [3, 3-di (3-tert-butyl-4-hydroxyphenyl) butyric acid ], the development of the antioxidant Hostanox O3 and structural analogues thereof has been started in the ages of 60 and 70, and initially, the structural substances are mainly used in polyolefin such as low-density polyethylene, high-density polyethylene, polypropylene, polystyrene and the like, and the antioxidant Hostanox O3 and the structural analogues thereof have the antioxidant function and the ultraviolet-proof effect, so that the development and the application of the stabilizer with such structures are favored by the researchers (such as patents DE2503050, US3450746 and CN 104448573A). With the continued search for the nature of such materials, new uses thereof have been increasingly discovered, as disclosed in CN109605708A as antioxidant O3 and its structural analogues also begin to function in polyesters such as polyethylene terephthalate.
At present, two synthetic routes of an antioxidant HostanoxO3 mainly exist, namely, o-tert-butylphenol and methyl acetoacetate are taken as raw materials, mercaptan and hydrogen chloride gas are taken as catalysts, a formula I is synthesized firstly, and then the formula I and ethylene glycol are subjected to transesterification reaction to obtain a target product (formula II); secondly, methyl acetoacetate and dihydric alcohol such as ethylene glycol are subjected to transesterification reaction to obtain a compound shown in a formula III, and then the compound shown in the formula III and o-tert-butylphenol are used as raw materials, mercaptan and hydrogen chloride gas are used as catalysts to react to obtain a target product, wherein the two synthesis paths are as follows:
in the route 1, the synthesis of the formula I takes hydrogen chloride gas as a catalyst, and the second step of reaction takes dibutyl tin oxide as a catalyst, wherein the hydrogen chloride gas has strong acidity and has extremely high requirements on production equipment and pipelines, the dibutyl tin oxide is a highly toxic substance, and the two catalysts are substances which are less favorable for industrial production, so that a large safety accident can be caused by trace leakage; the synthesis of formula III in scheme 2 may be catalysed by non-organotin, but the second step of the synthesis process is also catalysed by hydrogen chloride, with the same potential risk as in scheme 1.
Disclosure of Invention
The application mainly aims to provide a preparation method of a hindered phenol antioxidant and an intermediate thereof, which aims to solve the problems of great potential safety hazard and great environmental pressure in the synthesis process of an antioxidant Hostanox O3 in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for preparing a hindered phenol antioxidant intermediate, comprising performing a friedel-crafts reaction of a compound a, a compound b, under the action of a main catalyst organic sulfonic acid and/or trifluoroacetic acid and a cocatalyst to obtain a hindered phenol antioxidant intermediate of formula I; wherein, the structural formulas of the compound a, the compound b and the formula I are respectively as follows:
R 1 selected from H, C 1 ～C 4 Substituted or unsubstituted alkyl, R 2 Selected from C 1 ～C 4 Substituted or unsubstituted alkyl.
Further, the organic sulfonic acid has R-SO 3 H structure, R represents C 1-10 A substituted or unsubstituted alkyl or aryl group, the substituent may be a fluoroalkyl group; preferably, the organic sulfonic acid is at least one selected from benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid.
Further, the molar ratio of the main catalyst to the compound b is 0.01 to 0.35:1, preferably 0.01 to 0.2:1.
Further, the cocatalyst is substituted or unsubstituted C 1 ～C 12 Further preferred cocatalysts are selected from any one or more of methyl mercaptan, ethyl mercaptan, propyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, 1-pentanethiol, 2-pentanethiol, cyclopentanethiol, hexanethiol, heptanethiol, n-octyl mercaptan, n-nonanethiol, t-nonanethiol, n-decanethiol, n-dodecyl mercaptan, t-dodecyl mercaptan; and/or the molar ratio of the cocatalyst to the main catalyst is 0.5-30:1.
Further, R is as described above 1 、R 2 Each independently selected from C 1 ～C 4 Straight or branched alkyl, C 3 ～C 4 Straight-chain or branched alkyl of (2), further preferably R 1 Is tert-butyl, R 2 Is methyl.
Further, the preparation method comprises the steps that the molar ratio of the compound a to the compound b is 3-5:1; and/or the reaction temperature of Friedel-crafts reaction is 0-30 ℃.
According to another aspect of the present application, there is provided a method for producing a hindered phenol antioxidant, the method comprising producing a hindered phenol antioxidant intermediate by the above production method; the hindered phenol antioxidant intermediate and ethylene glycol are subjected to transesterification reaction under the action of a strong base catalyst to obtain the hindered phenol antioxidant shown in the formula II,
wherein the strong base catalyst is at least one selected from lithium acetate, lithium hydroxide, lithium methoxide, lithium ethoxide or lithium amide.
Further, the molar ratio of the hindered phenol antioxidant intermediate to the strong base catalyst is 1:0.01-0.1, preferably 1:0.02-0.08.
Further, the molar ratio of the hindered phenol antioxidant intermediate to ethylene glycol is 1:0.5-1.5, preferably 1:1.
Further, the preparation method further comprises a post-treatment process of crystallizing the hindered phenol antioxidant, and preferably the solvent used in crystallization is selected from one or more of toluene, xylene and chlorobenzene.
By adopting the technical scheme of the application, the preparation process of the hindered phenol antioxidant intermediate adopts organic sulfonic acid and/or trifluoroacetic acid as a catalyst to replace a hydrogen chloride gas catalyst, so that the use of the gas catalyst and high-corrosiveness hydrogen chloride is avoided, the safety of the reaction is greatly improved, the requirement on production equipment is reduced, and the equipment cost is also reduced. The preparation method of the hindered phenol antioxidant uses strong alkaline lithium salt as a catalyst to carry out transesterification reaction between the intermediate and glycol, thereby avoiding the use of organic tin highly toxic chemicals and reducing environmental pollution. The method for preparing the hindered phenol and the intermediate thereof is a green, low-toxicity and environment-friendly process route, and is suitable for industrial production.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed by the background technology, the problem that the synthesis process of the antioxidant Hostanox O3 has great potential safety hazard and great environmental pressure exists in the prior art, and the application provides a preparation method of the hindered phenol antioxidant and the intermediate thereof for solving the problem.
In a typical embodiment of the application, there is provided a process for preparing a hindered phenolic antioxidant intermediate comprising subjecting compound a, compound b, to friedel-crafts reaction under the action of a main catalyst organic sulphonic acid and/or trifluoroacetic acid and a cocatalyst to give a hindered phenolic antioxidant intermediate of formula I; wherein, the structural formulas of the compound a, the compound b and the formula I are respectively as follows:
R 1 selected from H, C 1 ～C 4 Substituted or unsubstituted alkyl, R 2 Selected from C 1 ～C 4 Substituted or unsubstituted alkyl.
The equation for the Friedel-crafts reaction is:
the research shows that the selectivity to the catalyst is very high in the preparation process of the compound of the formula I, and the substrate hardly reacts when inorganic protonic acid is used as the catalyst, such as concentrated hydrochloric acid and concentrated sulfuric acid are used as the catalyst; organic acid is used as a catalyst, for example oxalic acid is used as a catalyst, and the substrate does not react; the substrate does not react when Lewis acid is used as a catalyst, such as boron trifluoride diethyl etherate. Through a great deal of research, the application surprisingly discovers that the catalytic effect on the preparation of the formula I is greatly improved by using organic protonic acid (preferably organic sulfonic acid) or trifluoroacetic acid as a catalyst. In addition, in the preparation process of the hindered phenol antioxidant intermediate, the organic sulfonic acid and/or trifluoroacetic acid is used as a catalyst to replace a hydrogen chloride gas catalyst, so that the use of the gas catalyst and high-corrosiveness hydrogen chloride is avoided, the safety of the reaction is greatly improved, the requirement on production equipment is reduced, and the equipment cost is also reduced.
"C" in the present application 1 ～C 4 The substituted or unsubstituted alkyl group of (a) includes a substituted or unsubstituted straight-chain or branched alkyl group, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and the like.
The term "organic sulfonic acid" in the present application means a catalyst having the general formula R-SO 3 H compounds of the formula wherein R represents C 1-10 The substituent may be a fluoroalkyl group. Examples of R groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, neopentyl, isopentyl, octyl, decyl, methyl-substituted phenyl, perfluorohexyl, perfluorooctyl, trifluoromethyl, and the like. In order to enhance the catalytic activity of the organic sulfonic acid of the present application, it is preferable that the organic sulfonic acid is at least one selected from the group consisting of benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid. In the method, the organic sulfonic acid and/or trifluoroacetic acid are used as catalysts, which is more beneficial to improving the efficiency of the Friedel-crafts reaction of the application.
In the application, the dosage of the catalyst can influence the product yield of the Friedel-crafts reaction, and in order to ensure that the Friedel-crafts reaction can fully react, the lower limit of the dosage of the main catalyst is as follows: the molar ratio of the main catalyst to the compound b is 0.01:1, and experiments show that when the molar ratio is 0.01:1, the yield of the compound of the formula I can reach more than 80% by adopting any one of the organic sulfonic acids to catalyze Friedel-crafts reaction. It was found that the upper limit of the amount of the catalyst is not particularly limited, and the reaction yield increases with the increase of the amount of the catalyst, for example, when the molar ratio of the main catalyst to the above-mentioned compound b is 0.3:1, the yield of the compound of formula I can reach 93%, and the amount of the main catalyst is continuously increased, for example, when the molar ratio of the main catalyst to the compound b is 0.35:1, the yield of the compound of formula I can reach 95%. In view of economical efficiency, it is preferable that the molar ratio of the main catalyst to the compound b is 0.01 to 0.35 in order to achieve both production cost and production efficiency: 1, more preferably 0.01 to 0.2:1. In a specific embodiment the molar ratio may be 0.15:1 or 0.1:1.
in order to incorporate the procatalyst to make it more conducive to the efficiency of the Friedel-crafts reaction, the cocatalyst is preferably a substituted or unsubstituted C 1 ～C 12 Alkyl mercaptans of (C) are preferred 8 -C 12 Further preferred cocatalysts are selected from any one or more of methyl mercaptan, ethyl mercaptan, propyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, 1-pentanethiol, 2-pentanethiol, cyclopentanethiol, hexanethiol, heptanethiol, n-octyl mercaptan, n-nonanethiol, t-nonanethiol, n-decanethiol, dodecyl mercaptan, t-dodecyl mercaptan. Substantially the same catalytic effect can be achieved with any one or more of the above cocatalysts. Preferably, the molar ratio of cocatalyst to procatalyst is from 0.5 to 30:1. For example, the molar ratio of the cocatalyst to the main catalyst is 1.5:1,3:1,5:1, 10:1, 15:1, 20:1, 25:1, 28:1, and the ratio of the cocatalyst to the main catalyst can fully play the roles of the two in the range so as to achieve the optimal catalytic activity.
In one embodiment of the application, R is 1 、R 2 Each independently selected from C 1 ～C 4 Straight or branched alkyl, C 3 ～C 4 Straight-chain or branched alkyl of (2), further preferably R 1 Is tert-butyl, R 2 Is methyl.
The friedel-crafts range of the present application is exothermic reaction, and in order to reduce side reactions during the addition, organic sulfonic acid and/or trifluoroacetic acid are added to the mixture of compound a and compound b preferably at 0 to 15 ℃, more preferably at 0 to 5 ℃ or 5 to 10 ℃; the main catalyst is preferably added dropwise to better control the reaction process.
In one embodiment of the present application, the above preparation method includes a molar ratio of the compound a to the compound b of 3 to 5:1; and/or the reaction temperature of Friedel-crafts reaction is 0-30 ℃.
The Friedel-crafts reaction of the application is carried out at a temperature of 0-30 ℃. In order to reduce the production of by-products while simultaneously compromising the overall reaction efficiency, it is preferred that the friedel-crafts reaction be carried out at a stepwise elevated reaction temperature, and in a typical embodiment, the friedel-crafts reaction is carried out at a temperature of from 0 to 15 ℃, for example, from 0 to 5 ℃ or from 5 to 10 ℃ followed by a preliminary reaction at a temperature of from 20 to 30 ℃, for example, from 20 to 25 ℃ or from 20 to 30 ℃ to obtain a hindered phenol antioxidant intermediate.
In the Friedel-crafts reaction of the present application, the molar ratio of the compound a to the compound b is preferably 3 to 5:1, more preferably 4:1, in order to facilitate the reaction. After the reaction is finished, the hindered phenol intermediate with the purity of more than 98% can be prepared by reduced pressure distillation.
In another exemplary embodiment of the present application, there is also provided a method for preparing a hindered phenol antioxidant, the method comprising: preparing a hindered phenol antioxidant intermediate by adopting the preparation method; the hindered phenol antioxidant intermediate and ethylene glycol are subjected to transesterification reaction under the action of a strong base catalyst to obtain the hindered phenol antioxidant shown in the formula II,
wherein the strong base catalyst is at least one selected from lithium acetate, lithium hydroxide, lithium methoxide, lithium ethoxide or lithium amide.
The preparation method avoids the use of a highly toxic organotin catalyst used in the prior art, thereby greatly improving the safety of the reaction, reducing the environmental pollution, reducing the requirement on production equipment and reducing the equipment cost.
In order to improve the efficiency of the transesterification reaction and to reduce the formation of impurities, the molar ratio of the hindered phenol antioxidant intermediate to the strong base catalyst is preferably 1:0.01 to 0.1, and more preferably 1:0.02 to 0.08. In particular embodiments, a molar ratio of 1:0.05 may be selected.
The waste of raw materials is reduced as much as possible on the basis of improving the reaction effect of the hindered phenol antioxidant intermediate and ethylene glycol, and the molar ratio of the hindered phenol antioxidant intermediate to ethylene glycol is preferably 1:0.5 to 1.5, and more preferably 1:1.
In one embodiment of the present application, the above preparation method further comprises a post-treatment process of crystallizing the hindered phenol antioxidant, preferably the solvent used in crystallization is selected from any one or more of toluene, xylene, chlorobenzene.
The solvent is adopted to carry out the post-treatment of crystallization on the hindered phenol antioxidant, so that the purification loss of the hindered phenol antioxidant can be reduced, and the purity of the product is ensured. The application prepares the hindered phenol antioxidant with the purity of more than 98 percent.
The starting compounds a, b and other reagents of the present application are commercially available and may be prepared according to techniques known in the art.
The following examples are illustrative of the application and are not intended to limit the scope of the application. The operations referred to in the examples, unless otherwise specified, are all conventional in the art.
EXAMPLES 1 to 6 preparation of hindered phenolic antioxidant intermediate methyl 3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate
Example 1
465.7g (3.1 mol) of o-tert-butylphenol (compound a), 90g (0.78 mol) of methyl acetoacetate (compound b) and 47g (0.23 mol) of dodecyl mercaptan were added successively to a reactor equipped with electric stirringIn a 1000mL four-neck flask with a device and a thermometer, the four-neck flask is placed in an ice-water bath at 0 ℃ under the protection of nitrogen, 14.9g (0.16 mol) of methane sulfonic acid is dripped after the four-neck flask is cooled to 5-10 ℃, the dripping time is 30min, the dripping temperature is 5-10 ℃ all the time, a mixture is obtained after dripping, the mixture is reacted for 2 hours at the temperature, the ice-water bath is removed, the temperature is naturally raised to room temperature, the reaction is continued for about 20 hours, then the reaction is stopped, water is added for washing to neutrality, reduced pressure distillation is carried out, excessive o-tert-butylphenol and dodecyl mercaptan are recovered at 120 ℃, residual o-tert-butylphenol is distilled at 160 ℃, and the residual is 3, 3-bis (3-tert-butyl-4-hydroxyphenyl) methyl butyrate, the yield is 88 percent, and the structure is as follows:the nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 ):δ7.111(s,2H),6.883(d,2H),6.509(d,2H),3.497(d,3H),3.119(s,2H),1.871(s,3H),1.310-1.871(m,18H). 13 C NMR(400MHz,CDCl 3 ):δ172.91,152.36,140.02,135.10,125.86,125.42,116.02,51.46,47.29,44.93,34.70,29.66,28.83。
example 2
The difference from example 1 was that the amount of methanesulfonic acid added dropwise was 7.4g (0.08 mol), and methyl 3, 3-bis (3-t-butyl-4-hydroxyphenyl) butyrate was finally obtained in a yield of 86%.
Example 3
The difference from example 1 was that the amount of methanesulfonic acid added dropwise was 0.7g (0.01 mol), and methyl 3, 3-bis (3-t-butyl-4-hydroxyphenyl) butyrate was finally obtained in 80% yield.
Example 4
465.7g (3.1 mol) of o-tert-butylphenol, 90g (0.78 mol) of methyl acetoacetate and 47g (0.23 mol) of dodecyl mercaptan are sequentially added into a 1000mL four-neck flask equipped with an electric stirrer and a thermometer, and the four-neck flask is placed in an ice-water bath at 0 ℃ under the protection of nitrogen and cooled to 0-5 ℃; then 7.4g (0.08 mol) of methane sulfonic acid is added dropwise for 30min, the temperature of the dropwise addition is 0-5 ℃, the reaction is carried out for 2h at the temperature after the dropwise addition, an ice water bath is removed, the temperature is naturally raised to room temperature, the reaction is continued for about 20h, the reaction is stopped, the water is added for washing to neutrality, the distillation is carried out under reduced pressure, the excessive o-tert-butylphenol and catalyst dodecyl mercaptan are recovered at 120 ℃, the residual o-tert-butylphenol is distilled at 160 ℃, and the residual is 3, 3-di (3-tert-butyl-4-hydroxyphenyl) methyl butyrate, and the yield is 88%.
Example 5
The difference from example 4 was that the main catalyst was 14.7g (0.08 mol) of p-toluenesulfonic acid, and methyl 3, 3-bis (3-t-butyl-4-hydroxyphenyl) butyrate was finally obtained in a yield of 80%.
Example 6
The difference from example 4 was that the main catalyst was 12.0g (0.08 mol) of trifluoromethanesulfonic acid, and methyl 3, 3-bis (3-t-butyl-4-hydroxyphenyl) butyrate was finally obtained in a yield of 89%.
Example 7
The difference from example 4 was that 9.12g (0.08 mol) of trifluoroacetic acid was used as the catalyst, and methyl 3, 3-bis (3-t-butyl-4-hydroxyphenyl) butyrate was finally obtained in a yield of 82%.
Example 8
The difference from example 1 is that the cocatalyst was octyl mercaptan and methyl 3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate was finally obtained in 80% yield.
Example 9 to example 13 preparation of hindered phenol antioxidant O3
Example 9
250g (0.63 mol) of methyl 3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate, 39g (0.63 mol) of ethylene glycol and 0.24g (0.006 mol) of lithium methoxide are added into a 1000mL four-necked flask equipped with an electric stirrer, a thermometer and a water separator at room temperature, heating is started under the protection of nitrogen, the temperature is kept at 160-180 ℃ for 8 hours under normal pressure, then a decompression reaction is started, the decompression reaction is carried out for 12 hours under 5-10 mmHg, and then the reaction is ended. Cooling to 130 ℃ after the reaction is finished, adding a certain amount of dimethylbenzene and a small amount of formic acid into a four-mouth bottle, refluxing for 1.0h, cooling to room temperature, carrying out suction filtration and drying to obtain ethylene glycol bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid, white solid powder, wherein the melting point is 126-130 ℃, the yield is 53%, and the nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 ):δ7.061(s,4H),6.869-6.851(m,4H),6.522(d,4H),4.790(s,4H),3.749(s,4H),3.036(s,4H),1.821(s,6H),1.374-1.347(m,36H). 13 C NMR(400MHz,CDCl 3 ) Delta 172.91,152.20,135.20,125.97,125.39,115.99,61.51,47.06,44.87,34.66,29.63,28.64, the structure of which is:
example 10
The difference from example 9 is that: the addition amount of lithium methoxide was 0.48g (0.01 mol), and finally, hindered phenol antioxidant O3 was obtained in a yield of 62%.
Example 11
The difference from example 9 is that: the addition amount of lithium methoxide was 2.4g (0.06 mol), and finally, hindered phenol antioxidant O3 was obtained in a yield of 59%.
Example 12
The difference from example 9 is that: the catalyst used was 0.29g (0.01 mol) of lithium amide, and finally, hindered phenol antioxidant O3 was obtained in a yield of 52%.
Example 13
The difference from example 9 is that: the crystallization solvent is chlorobenzene, and finally the hindered phenol antioxidant O3 is obtained with the yield of 53 percent. The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (13)
1. A process for preparing a hindered phenolic antioxidant intermediate, the process comprising:
performing Friedel-crafts reaction on a compound a and a compound b under the action of main catalyst organic sulfonic acid and/or trifluoroacetic acid and a cocatalyst to obtain a hindered phenol antioxidant intermediate shown in a formula I;
wherein the structural formulas of the compound a, the compound b and the formula I are respectively as follows:
，
R 1 is H, R 2 Is methyl;
the molar ratio of the main catalyst to the compound b is 0.01-0.35: 1, a step of;
the cocatalyst being a substituted or unsubstituted C 1 ~C 12 Alkyl mercaptans of (a);
the molar ratio of the cocatalyst to the main catalyst is 0.5-30:1.
2. The method of claim 1, wherein the organic sulfonic acid has R-SO 3 H structure, R represents C 1-10 The substituent may be a fluoroalkyl group.
3. The method according to claim 2, wherein the organic sulfonic acid is at least one selected from the group consisting of benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of the procatalyst to the compound b is 0.01 to 0.2:1.
5. A production method according to any one of claims 1 to 3, wherein the cocatalyst is selected from any one or more of methyl mercaptan, ethyl mercaptan, propyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, 1-pentyl mercaptan, 2-pentyl mercaptan, cyclopentyl mercaptan, hexyl mercaptan, heptyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, t-nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan.
6. A production method according to any one of claims 1 to 3, characterized in that the production method comprises:
the molar ratio of the compound a to the compound b is 3-5:1; and/or
The reaction temperature of the Friedel-crafts reaction is 0-30 ℃.
7. A method for preparing a hindered phenol antioxidant, the method comprising:
preparing the hindered phenol antioxidant intermediate using the preparation method of any one of claims 1 to 6;
the hindered phenol antioxidant intermediate and ethylene glycol are subjected to transesterification reaction under the action of a strong base catalyst to obtain the hindered phenol antioxidant shown in the formula II,
，
wherein the strong base catalyst is at least one selected from lithium acetate, lithium hydroxide, lithium methoxide, lithium ethoxide or lithium amide.
8. The method of claim 7, wherein the molar ratio of the hindered phenol antioxidant intermediate to the strong base catalyst is 1:0.01-0.1.
9. The method of claim 8, wherein the molar ratio of the hindered phenol antioxidant intermediate to the strong base catalyst is 1:0.02-0.08.
10. The method of claim 7, wherein the molar ratio of the hindered phenol antioxidant intermediate to the ethylene glycol is 1:0.5 to 1.5.
11. The method of claim 10, wherein the molar ratio of the hindered phenolic antioxidant intermediate to the ethylene glycol is 1:1.
12. The method of claim 7, further comprising a post-treatment step of crystallizing the hindered phenol antioxidant.
13. The method according to claim 12, wherein the solvent used in the crystallization is selected from one or more of toluene, xylene, and chlorobenzene.
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