CN114195659B - Polyphenol type antioxidant and preparation method and application thereof - Google Patents

Polyphenol type antioxidant and preparation method and application thereof Download PDF

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CN114195659B
CN114195659B CN202111466542.4A CN202111466542A CN114195659B CN 114195659 B CN114195659 B CN 114195659B CN 202111466542 A CN202111466542 A CN 202111466542A CN 114195659 B CN114195659 B CN 114195659B
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antioxidant
compound
butyl
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preparation
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CN114195659A (en
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陈炜
杨东升
周彦博
杜荻
高勇年
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Beijin Tiangang Auxiliary Co ltd
Tiangang New Material Langfang Co ltd
Tianji Chemical Additive Cangzhou Ltd
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Beijin Tiangang Auxiliary Co ltd
Tiangang New Material Langfang Co ltd
Tianji Chemical Additive Cangzhou Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/14—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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

Abstract

The application discloses a polyphenol type antioxidant and a preparation method and application thereof. The antioxidant molecule designed by the application not only contains a hindered phenol functional group serving as a main antioxidant, but also contains an alcohol amine skeleton unit with metal ion bonding capability, so that the antioxidant molecule has a synergistic antioxidant effect in the processing and using processes of the polymer, and the antioxidant capability of the antioxidant molecule per unit mass is improved. The antioxidant solves the problem that the antioxidant effect of a single-function antioxidant on a high polymer material is poor, and improves the antioxidant capacity of the antioxidant molecule per unit mass. The preparation method has the advantages of low energy consumption, low raw material cost, simple and convenient operation, easy recovery of materials, recoverable solvent and high product yield and purity.

Description

Polyphenol type antioxidant and preparation method and application thereof
Technical Field
The application belongs to the field of chemical auxiliary agent antioxidant synthesis, and particularly relates to a polyphenol type antioxidant and a preparation method and application thereof.
Background
With the rapid development of the polymerization industry, various novel functional plastics have been developed. These plastics are mainly processed from high molecular weight polymers. The high molecular polymer is easy to be influenced by light, heat, electric field, rays, metal ions, chemical agents and the like in the processes of polymerization, granulation, storage, processing, molding and long-term use, so that the mechanical properties of the polymer are lost, and changes such as discoloration, cracking, loss of glossiness and the like occur, and the phenomenon is called aging or thermo-oxidative aging.
In 1946, bolland and Gee proposed for the first time that oxidation of organic lipid chains is a radical reaction process. Since many years, chemists have conducted extensive mechanistic studies on the oxidation of organic materials to determine the concomitant production of by-products (e.g., acids, alcohols, aldehydes, ketones, or higher molecular weight organic chains) during these complex oxidation processes, which ultimately lead to degradation phenomena such as discoloration, cracking, loss of functionality of the organic materials, and the like. If the alkyl peroxy radicals generated during oxidation are effectively scavenged, the rate of by-product generation is reduced. Therefore, the antioxidant is added in the production process, and the oxidation and decomposition of the material can be prevented, so that the processing stability and the long-term use stability of the high polymer are improved.
The hindered phenol antioxidant is the most applied antioxidant in the field of high polymer materials, and has the advantages of good antioxidant effect, high thermal stability, no pollution to products, no coloration, good compatibility and the like. The monophenol type hindered phenol antioxidant has lower relative molecular mass, higher volatility and migration loss, and lower antioxidation efficiency, and can only be used in high-molecular polymers with low performance requirements. The polyphenol type hindered phenol antioxidant is generally synthesized by a monophenol type hindered phenol structure and other chemical raw materials with specific structures, has larger relative molecular mass, good extraction resistance, high thermal stability and good lasting effect, and is widely applied. Researchers prepare the intramolecular composite antioxidant containing phosphorus, nitrogen, silicon, sulfur and heterocyclic structures by changing the skeleton structure of the polyphenol type hindered phenol reaction intermediate. The intramolecular composite antioxidant has excellent molecular designability. However, the development of novel polyphenol antioxidants is very difficult, and the problems of compatibility, dispersibility, migration resistance, volatilization resistance, extraction resistance and the like of the antioxidants in polymer materials need to be considered. In addition, during the processing of high molecular polymers, trace amounts of transition metal ions catalyze the acceleration of the oxidation process of the lipid chains. Therefore, the development of a novel antioxidant which has the advantages of large molecular weight, volatilization resistance, high thermal stability, high content of effective functional groups in unit mass, lasting antioxidant effect, no pollution to products, no coloring, good compatibility and capability of inhibiting the catalysis of metal ions has become a problem to be solved urgently.
In order to solve the problems, the inventor develops a novel double-effect polyphenol type antioxidant which structurally has two functional groups of polyphenol type hindered phenol and alcohol amine. The antioxidant not only has the free radical inhibition capability of a polyphenol type hindered phenol structure, but also has the poisoning capability of alcohol amine on transition metal ions, and can play a role in synergistic antioxidation.
Disclosure of Invention
In order to meet the requirements of the market on higher and higher safety, health and environmental protection of the antioxidant, the application designs and develops a novel star-shaped multifunctional polyphenol antioxidant with high temperature resistance and good antioxidant effect, and provides a method for preparing the polyphenol antioxidant, which has the advantages of low energy consumption, easy recovery of materials, simple and convenient operation and high product yield and purity.
The application provides a compound, which has the structure shown in the general formula I:
wherein R is 1 And R is 3 Independently selected from: alkyl, alkoxy, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, carboxyl, ester, amide, amino, halogen, nitro, cyano, oxycarbonylA radical, an aminocarbonyl group;
R 2 selected from: hydrogen, alkyl, aryl, cycloalkyl.
Further, R 1 And R is 3 Independently selected from C 1-18 An alkyl group.
Further, R 1 Is C 1-18 An alkyl group.
Further, R 3 Is C 1-18 An alkyl group.
Further, R 1 And R is 3 At least one of (or both) is a C3-C8 branched alkyl group such as isopropyl, t-butyl, t-amyl, t-hexyl, t-octyl. In one embodiment of the application, R 1 Is H or methyl, R 3 Branched alkyl of C3-C8; in another embodiment of the present application, R 1 And R is 3 A branched alkyl group independently selected from C3-C8; for example R 1 And R is 3 Are all tert-butyl groups.
Further, R 2 Selected from C 1-18 Alkyl radicals, e.g. C 1-6 An alkyl group;
further, R 2 Selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl;
in one embodiment of the application, R 2 Is methyl.
In another embodiment of the present application, R 2 Is hydrogen.
Further, the above compound may have the following structure:
in an embodiment of the present application, the above compound has the following structure:
the application also provides a preparation method of the compound, which comprises the following specific steps:
step a):
will beAnd an acyl halogenating reagent to give ∈>
Step b):
and then will beReacting to obtain a compound shown in a general formula I;
wherein X is halogen (e.g., F, cl, br, I), especially Cl.
Further, step a) comprises: will beDispersing in organic solvent, heating, dripping acyl halogenating reagent, and reacting to completion.
Further, the above-mentioned acid halogenating agent may be an acid chlorination agent, for example, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, solid phosgene, phosphorus tribromide, or the like, particularly thionyl chloride.
Further, the above organic solvent may be, for example, benzene, toluene, xylene, acetone, cyclohexanone, methylene chloride, particularly xylene.
Further, the method comprises the steps of,the molar ratio to the acyl halide reagent is 1:2 to 2:1 (e.g., 1:2, 1:1.5, 1:1.1, 1:1, 1.1:1, 1.5:1, 2:1).
Further, the heating in step a) is to 55-65 ℃ (e.g. 56, 58, 60, 62, 64 ℃), in particular 60 ℃.
Further, the reaction temperature in step a) is 40-80 ℃ (e.g. 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃), in particular 50-70 ℃.
Further, the reaction time in step a) is from 1 to 10h (e.g. 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10 h), in particular from 3 to 5h.
In one embodiment of the application, the step a) includes: dispersing a compound shown in a formula III (such as 3, 5-di-tert-butyl-4-hydroxybenzoic acid) in an organic solvent (such as dimethylbenzene), heating to 55-65 ℃, dropwise adding an acyl halogenating agent (such as thionyl chloride), and preserving the temperature at 50-70 ℃ for 3-5h.
Still further, step a) further comprises passing the acid tail gas into an alkaline liquor.
Further, the lye is selected from the group consisting of: triethylamine aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution.
Still further in one embodiment of the application, the lye is 5% aqueous sodium hydroxide.
Further, step b) comprises: adding a base to the reaction system of step a) and then dropwise addingThe reaction gives the compounds of the formula I.
Further, step b) further comprises: cooling the reaction system to room temperature, adding an aqueous solution of alkali, stirring at room temperature (10-60 minutes), separating the solution, washing the organic phase with water, separating the solution, and evaporating the organic phase solvent under reduced pressure to obtain a target product (namely the compound shown in the general formula I).
Further, the base in step b) is selected from: potassium carbonate, sodium bicarbonate, pyridine, triethylamine.
Still further, the base in step b) is triethylamine.
Further, in the step b), the feeding amount of the reactant is as in the step a)The molar amount of (2) is referred to.
Further, in the step b), the base is mixed withThe molar ratio of (1:1) to (5:1) (e.g., 1:1, 1.2:1, 1.5:1, 2:1, 3:1, 4:1, 5:1).
Further, in the step b), theAnd->The molar ratio of (1) to (2) is 1:10-1:1 (e.g., 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1).
Further, in the step b), theSelected from: triethanolamine and triisopropanolamine.
Further, in the step b), the reaction temperature is 50 to 120 ℃ (e.g., 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃).
Further, in the step b), the reaction time is 2 to 12 hours (e.g., 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours).
Further, in the step b), the aqueous solution of the base is 5% aqueous solution of sodium hydroxide.
Further, in the step b), the reduced pressure distillation temperature is 20-50 ℃ and the vacuum degree is-0.1 to-0.05 MPa.
In one embodiment of the application, step b) comprises: adding a base to the reaction system of step a) and then dropwise addingHeating to 50-120deg.C, stirring for 2-12 hr, cooling to room temperature, adding appropriate amount of alkali aqueous solution, stirring at room temperature (10-60 min) (removing unreacted compound of formula IV), separating, washing the organic phase with water (removing unreacted compound of formula V, unreacted salt of compound of formula V and alkali, and unreacted salt of compound of formula III and alkali), separatingAnd (3) evaporating the organic phase solvent under reduced pressure, and drying to obtain a target product (a compound shown in a general formula I).
The application also provides the compound and the application of the preparation method thereof in antioxidants.
Specifically, the antioxidant can be used for the antioxidation in the polymerization, granulation, storage, processing, forming and using processes of the high polymer material.
The application also provides an application of the compound and a preparation method thereof in antioxidation of high polymer materials.
Specifically, the polymer material is plastic, such as Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), polyamide (PA), polytetrafluoroethylene (PTFE), and the like.
The application has the advantages and positive effects as follows:
the novel star-shaped multifunctional polyphenol antioxidant with high temperature resistance, metal bonding capability and excellent antioxidant effect is provided, the problem that a single-function antioxidant has poor antioxidant effect on a high polymer material is solved, and the antioxidant capability of the antioxidant molecule per unit mass is improved; and the preparation process has the advantages of low energy consumption, low raw material cost, simple and convenient operation, easily-recovered materials, recoverable solvent and high product yield and purity.
The polyphenol antioxidant molecule prepared by the application not only contains hindered phenol functional groups serving as main antioxidants, but also contains alcohol amine skeleton units with metal ion bonding capability, and can play a role in synergistic antioxidation in the processing and using processes of the high polymer material.
Detailed Description
Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application relates.
The term "alkyl" refers to a hydrocarbon chain radical that is straight or branched and contains no unsaturation, and is attached to the rest of the molecule by a single bond. Typical alkyl groups contain 1 to 18 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18) carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, isohexyl, and the like. If the alkyl group is substituted with cycloalkyl, it is correspondingly "cycloalkylalkyl", such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, and the like. If the alkyl group is substituted with an aryl group, it is correspondingly "aralkyl" such as benzyl, benzhydryl or phenethyl. If an alkyl group is substituted with a heterocyclic group, then it is correspondingly "heterocyclylalkyl".
The term "cycloalkyl" refers to an alicyclic hydrocarbon such as having 1 to 4 monocyclic and/or condensed rings, having 3 to 18 carbon atoms, preferably 3 to 10 (e.g., 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, or the like.
The term "aryl" refers to a monocyclic or polycyclic radical, including polycyclic radicals containing from 1 to 3 monocyclic or fused rings and from 6 to 18 (e.g., 6, 8, 10, 12, 14, 16, 18) carbon ring atoms, and aryl of from 6 to 12 carbon ring atoms, such as phenyl, naphthyl, biphenyl, indenyl, and the like.
The term "heterocyclyl" includes heteroaromatic and heteroalicyclic groups containing 1 to 3 monocyclic and/or fused rings and 3 to about 18 ring atoms, which may be selected from N, O or S atoms.
The term "halogen" refers to bromine, chlorine, iodine, or fluorine.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Example 1: preparation of 1,1' -nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) tris-2-propanol ester
(a) Preparation of 3, 5-di-tert-butyl-4-hydroxybenzoyl chloride
20.0g (80 mmol) of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 100mL of xylene solvent are sequentially put into a 250mL three-necked flask, uniformly stirred to be well dispersed, slowly heated to 60 ℃, 6.4mL (88 mmol) of thionyl chloride is slowly added dropwise into the reaction system, the reaction system is kept at 50-70 ℃ for 3-5h, and TLC monitoring reaction is complete to obtain pale yellow clear acyl chloride xylene solution. The acidic tail gas was introduced into 200ml of 5% aqueous sodium hydroxide solution during the reaction.
(b) Preparation of 1,1' -nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) tris-2-propanol ester
13.3mL (96 mmol) of triethylamine, 4.58g (24 mmol) of triisopropanolamine solid powder, heating the reaction system to 110 ℃, keeping the temperature and stirring for 10 hours, naturally cooling to room temperature, adding 150mL of 5% sodium hydroxide aqueous solution into the three-necked flask, stirring at room temperature for 30 minutes, and removing unreacted 3, 5-di-tert-butyl-4-hydroxybenzoyl chloride; separating out the aqueous phase, adding 100mL of water into the oil phase, stirring for 10min, and removing redundant ammonium salt, triisopropanolamine and 3, 5-di-tert-butyl-4-hydroxy sodium benzoate from the oil phase; finally, the oil phase was separated, and the organic phase xylene solvent was distilled off under reduced pressure to give the objective antioxidant (white solid, 15.1g, yield 71%).
Nuclear magnetism and mass spectrum characterization of 1,1',1 "-nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) tris-2-propanol ester: white solid; 1 H NMR(400MHz,CDCl 3 )δ1.19(m,9H),1.43(s,54H),2.69(m,6H),4.96(m,3H),5.65(s,3H),7.88(s,6H).HRMS(ESI-TOF)calcd for C 54 H 82 NO 9 + ([M+H] + )888.5984,found 888.5989.
example 2: preparation of 2,2' -nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) triethanolamine ester
(a) Preparation of 3, 5-di-tert-butyl-4-hydroxybenzoyl chloride
20.0g (80 mmol) of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 100mL of xylene solvent are sequentially put into a 250mL three-necked flask, uniformly stirred to be well dispersed, slowly heated to 60 ℃, 6.4mL (88 mmol) of thionyl chloride is slowly added dropwise into the reaction system, the reaction system is kept at 50-70 ℃ for 3-5h, and TLC monitoring reaction is complete to obtain pale yellow clear acyl chloride xylene solution. The acidic tail gas was introduced into 200ml of 5% aqueous sodium hydroxide solution during the reaction.
(b) Preparation of 2,2' -nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) triethanolamine ester
13.3mL (96 mmol) of triethylamine is added into the three-port bottle, 3.2mL (24 mmol) of triethanolamine is then added dropwise, the reaction system is heated to 100 ℃, the reaction system is naturally cooled to room temperature after being stirred for 8 hours under heat preservation, 150mL of 5% sodium hydroxide aqueous solution is then added into the three-port bottle, the reaction system is stirred for 30 minutes at room temperature, and unreacted 3, 5-di-tert-butyl-4-hydroxybenzoyl chloride is removed; separating out the water phase, adding 100mL of water into the oil phase, stirring for 10min, and removing redundant ammonium salt, triethanolamine and 3, 5-di-tert-butyl-4-hydroxy sodium benzoate in the oil phase; finally, the oil phase was separated, and the organic phase xylene solvent was distilled off under reduced pressure to give the objective antioxidant (white solid, 15.8g, yield 78%).
Nuclear magnetic and mass spectrometry characterization of 2,2',2 "-nitrilotris (3, 5-di-tert-butyl-4-hydroxybenzoic acid) triethanolate: white solid; 1 HNMR(400MHz,CDCl 3 )δ1.42(s,54H),2.82(t,J＝7.5Hz,6H),4.12(t,J＝7.8Hz,6H),5.65(s,3H),7.89(s,6H).HRMS(ESI-TOF)calcd for C 51 H 75 NNaO 9 + ([M+Na] + )868.5334,found868.5337.
example 3
Oxidation induction period test: the test is carried out on a DSC 200PC thermal analysis device, oxygen and nitrogen are connected, a gas switching device is opened to respectively adjust the flow rates of the two gases so that the flow rates reach (50+/-5) ml/min, and then the flow rates are switched into nitrogen. An open aluminum dish containing (15.+ -. 0.5) mg of the sample was placed on the sample holder of the thermal analyzer, the temperature was raised to (200.+ -. 0.1) ℃ at a rate of 20 ℃/min, and the temperature was made constant, and the thermal profile was started to be recorded. After keeping the temperature for 5min, the oxygen is switched rapidly. The test was terminated when the oxidation exotherm reached a maximum recorded on the thermal curve. The composition information of the samples is shown in Table 1, and the test results are shown in tables 2 and 3.
Table 1 sample composition:
numbering device Resin composition Antioxidant Content of Light stabilizers Content of
1 PE powder IrganoxB215 0.2％
2 PE powder Example 1 product 0.2％
3 PE powder Example 2 product 0.2％
4 PP powder IrganoxB225 0.2％
5 PP powder Example 1 product 0.2％
6 PP powder Example 2 product 0.2％
Table 2 oxidation induction period of PE sample
Table 3 oxidation induction period of PP sample
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 (10)

1. A compound having the structure of formula i:
；
wherein R is 1 And R is 3 Independently selected from: a branched alkyl group of 3 to 8 carbon atoms;
R 2 selected from: hydrogen, C 1-6 An alkyl group.
2. The compound of claim 1, wherein R 1 And R is 3 At least one of the components is isopropyl, tertiary butyl, tertiary amyl, tertiary hexyl and tertiary octyl.
3. The compound of claim 2, wherein R 1 And R is 3 Are all tert-butyl groups.
4. The compound of claim 1, wherein R 2 Selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl.
5. The compound of claim 1, wherein the compound has the structure:
or (b)
。
6. A process for the preparation of a compound as claimed in any one of claims 1 to 5 comprising the steps of:
step a):
will be(III) and an acyl halogenating reagent to give +.>（Ⅳ）；
Step b):
will beAnd->(V) reacting to obtain a compound of formula I;
wherein X is halogen.
7. The method of claim 6, wherein step a) comprises: dispersing a compound shown in a formula III in an organic solvent, heating to 55-65 ℃, dropwise adding an acyl halogenating reagent, and preserving heat for 3-5h at 50-70 ℃.
8. The method of claim 6, wherein step b) comprises: adding a base to the reaction system of step a) and then dropwise addingHeating to 50-120 ℃, preserving heat, stirring for 2-12h, cooling to room temperature, adding a proper amount of alkali aqueous solution, stirring at room temperature, separating liquid, washing an organic phase, separating liquid, evaporating an organic phase solvent under reduced pressure, and drying to obtain a target product.
9. Use of a compound according to any one of claims 1 to 5 or a method of preparation according to claims 6 to 8 for the antioxidation of polymeric materials.
10. The compound of claim 9, wherein the polymeric material is a plastic.
CN202111466542.4A 2021-11-30 2021-11-30 Polyphenol type antioxidant and preparation method and application thereof Active CN114195659B (en)

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