CN113214540A - Composite antioxidant and preparation process thereof - Google Patents
Composite antioxidant and preparation process thereof Download PDFInfo
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- CN113214540A CN113214540A CN202110515517.4A CN202110515517A CN113214540A CN 113214540 A CN113214540 A CN 113214540A CN 202110515517 A CN202110515517 A CN 202110515517A CN 113214540 A CN113214540 A CN 113214540A
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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 118
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 162
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 88
- 239000011259 mixed solution Substances 0.000 claims description 83
- 238000003756 stirring Methods 0.000 claims description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 28
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 24
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 24
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 claims description 22
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 21
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 18
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a composite antioxidant and a production process thereof, wherein the composite antioxidant comprises the following raw materials in parts by weight: 1-10 parts of a first antioxidant, 1-5 parts of a second antioxidant, 5-10 parts of KH590, 0.1-0.3 part of triethylamine, 25-30 parts of nano silicon dioxide, 50-100 parts of a 30% ethanol aqueous solution with volume fraction and 20-30 parts of toluene; adding a second antioxidant and KH590 into a three-neck flask filled with toluene, adding triethylamine through magnetic stirring, and carrying out reflux reaction for 2 hours at the temperature to obtain an intermediate 1; adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing, homogenizing for 10min, adjusting the pH =4, then adding the intermediate 1 and the first antioxidant, continuing dispersing for 10min to prepare a mixture, reacting the mixture for 4h, cooling, performing suction filtration and vacuum drying after the reaction is finished to prepare the composite antioxidant, and the composite antioxidant has excellent antioxidant performance.
Description
Technical Field
The invention belongs to the technical field of fine chemical products, and particularly relates to a composite antioxidant and a preparation process 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"; the composite antioxidant is compounded by two or more of main antioxidant and auxiliary antioxidant, can show positive synergistic effect, has the characteristics of high oxidation resistance, small addition amount, convenient use and the like, and is the latest development trend of the current antioxidant technology. The composite antioxidant obtained by adopting different formulas shows excellent oxidation resistance and application prospect in practical application.
Chinese patent CN108239301B discloses an emulsion type composite antioxidant and a preparation method thereof. The method comprises the following steps: mixing and melting a first antioxidant, a second antioxidant and solvent oil to obtain a melt; mixing the melt with an emulsifier to obtain a first mixture; shearing the first mixture at a first shearing speed to obtain a pre-sheared object; mixing the pre-shear with desalted water to obtain a second mixture; shearing the second mixture at a second shearing speed to obtain the emulsion type composite antioxidant; wherein the first shear rate is higher than the second shear rate. The emulsion type composite antioxidant prepared by the preparation method provided by the invention has small emulsion particle size which can approach the particle size of a latex body, and meanwhile, the dispersion degree is lower, so that the stability of a product is obviously improved.
Disclosure of Invention
The invention provides a composite antioxidant and a preparation process thereof.
The purpose of the invention can be realized by the following technical scheme:
the composite antioxidant comprises the following raw materials in parts by weight: 1-10 parts of a first antioxidant, 1-5 parts of a second antioxidant, 5-10 parts of KH590, 0.1-0.3 part of triethylamine, 25-30 parts of nano silicon dioxide, 50-100 parts of a 30% ethanol aqueous solution with volume fraction and 20-30 parts of toluene;
the compound antioxidant is prepared by the following method:
adding a second antioxidant and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65-80 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 500r/min for 400 plus one year, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to prepare a mixture, transferring the mixture into a three-neck flask, heating to 60-75 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, filtering, and drying in vacuum after the reaction is finished to prepare the composite antioxidant.
In the first step, an antioxidant GM is mixed with KH590 in toluene, the KH590 and the antioxidant GM undergo a mercapto-alkene addition reaction to generate an intermediate 1, the intermediate 1 has alkoxy and phenolic hydroxyl, then the intermediate 1 and the nano-silica are mixed in an ethanol aqueous solution, the alkoxy on the intermediate 1 can react with the hydroxyl on the surface of the nano-silica, and then the intermediate 1 is loaded on the silica and mixed with a first antioxidant to exert an antioxidant effect.
Further, the second antioxidant is antioxidant GM.
Further, the first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60-100r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after complete dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, performing rotary evaporation at 40-45 ℃ to remove the tetrahydrofuran, adding ice methanol to shake, performing layering and liquid separation to obtain a crude product, dissolving the crude product in the tetrahydrofuran, performing methanol precipitation, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45-60 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3-5.
Step S1 is to dissolve hydroxyl-terminated polybutadiene into tetrahydrofuran, wherein molecular chain of the hydroxyl-terminated polybutadiene contains a large number of unsaturated carbon-carbon double bonds, the hydroxyl-terminated polybutadiene is mixed with 2-mercaptoethanol, azobisisobutyronitrile is added as an initiator, the hydroxyl-terminated polybutadiene reacts with the 2-mercaptoethanol to introduce hydroxyl groups and thioether groups, so that the hydroxyl groups and the thioether groups can be introduced, the antioxidant performance is endowed, and then the intermediate 2 is prepared by refining, step S2 is to mix the intermediate 2 with isophorone diisocyanate, the intermediate 2 reacts with the isophorone diisocyanate to generate an adduct containing isocyanate, the adduct is mixed with 2,2 '-thiobis (4-methyl-6-tert-butylphenol), and the adduct reacts with one phenolic hydroxyl group on the 2, 2' -thiobis (4-methyl-6-tert-butylphenol) to prepare a first antioxidant The agent is isophorone diisocyanate as a bridging agent, the first antioxidant contains thioether, carbamate and hindered phenol, and the thioether, the carbamate and the hindered phenol can mutually exert synergistic antioxidation.
Further, the mixed solution A is prepared by adding 2-mercaptoethanol and azobisisobutyronitrile into tetrahydrofuran and mixing, wherein the dosage ratio of the 2-mercaptoethanol, the azobisisobutyronitrile and the tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and a catalyst into toluene and mixing, the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the catalyst is 1% of the weight of the isophorone diisocyanate; the mixed solution E is formed by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and a catalyst into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the catalyst is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
Further, the catalyst is dibutyltin dilaurate.
A preparation process of a compound antioxidant comprises the following steps:
adding a second antioxidant and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65-80 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 500r/min for 400 plus one year, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to prepare a mixture, transferring the mixture into a three-neck flask, heating to 60-75 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, filtering, and drying in vacuum after the reaction is finished to prepare the composite antioxidant.
The invention has the beneficial effects that:
(1) the composite antioxidant is prepared from raw materials such as a first antioxidant, a second antioxidant and the like, in the preparation process, in the first step, an antioxidant GM is mixed with KH590 in toluene, the KH590 and the antioxidant GM undergo a mercapto-alkene addition reaction to generate an intermediate 1, the intermediate 1 has alkoxy and phenolic hydroxyl, then the intermediate 1 and nano-silica are mixed in an ethanol aqueous solution, the alkoxy on the intermediate 1 can react with the hydroxyl on the surface of the nano-silica, and the intermediate 1 is loaded on the silica and mixed with the first antioxidant to exert an antioxidant effect.
(2) The first antioxidant is prepared by dissolving hydroxyl-terminated polybutadiene in tetrahydrofuran in a step S1, wherein a molecular chain of the hydroxyl-terminated polybutadiene contains a large amount of unsaturated carbon-carbon double bonds, mixing the hydroxyl-terminated polybutadiene with 2-mercaptoethanol, adding azobisisobutyronitrile as an initiator, reacting the hydroxyl-terminated polybutadiene with 2-mercaptoethanol to introduce hydroxyl groups and thioether groups to endow the hydroxyl-terminated polybutadiene with oxidation resistance, refining to obtain an intermediate 2, mixing the intermediate 2 with isophorone diisocyanate in a step S2, reacting the intermediate 2 with isophorone diisocyanate to generate an adduct containing isocyanate, and mixing the adduct with 2, 2' -thiobis (4-methyl-6-tert-butylphenol), the first antioxidant is prepared by reacting the adduct with one phenolic hydroxyl group on 2, 2' -thiobis (4-methyl-6-tert-butylphenol), isophorone diisocyanate is used as a bridging agent, the first antioxidant contains thioether, carbamate and hindered phenol, and the thioether, the carbamate and the hindered phenol can exert synergistic antioxidant effect with each other.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The composite antioxidant comprises the following raw materials in parts by weight: 1 part of a first antioxidant, 1 part of an antioxidant GM, 5 parts of KH590, 0.1 part of triethylamine, 25 parts of nano silicon dioxide, 50 parts of ethanol aqueous solution with the volume fraction of 30 percent and 20 parts of toluene;
the compound antioxidant is prepared by the following method:
firstly, adding an antioxidant GM and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 400r/min, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to obtain a mixture, transferring the mixture into a three-neck flask, heating to 60 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration after the reaction is finished, and performing vacuum drying to obtain the composite antioxidant.
The first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, then dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after completely dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, rotationally evaporating at 40 ℃ to remove the tetrahydrofuran, adding methanol for shaking, demixing, separating to obtain a crude product, dissolving the crude product with tetrahydrofuran, precipitating with methanol, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3.
The mixed solution A is prepared by adding 2-mercaptoethanol and azobisisobutyronitrile into tetrahydrofuran and mixing, wherein the dosage ratio of the 2-mercaptoethanol, the azobisisobutyronitrile and the tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and dibutyltin dilaurate into toluene and mixing, wherein the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the dibutyltin dilaurate is 1% of the weight of the isophorone diisocyanate; the mixed solution E is prepared by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and dibutyltin dilaurate into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the dibutyltin dilaurate is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
Example 2
The composite antioxidant comprises the following raw materials in parts by weight: 5 parts of a first antioxidant, 3 parts of an antioxidant GM, 6 parts of KH590, 0.2 part of triethylamine, 26 parts of nano silicon dioxide, 60 parts of an ethanol aqueous solution with the volume fraction of 30% and 22 parts of toluene;
the compound antioxidant is prepared by the following method:
firstly, adding an antioxidant GM and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 400r/min, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to obtain a mixture, transferring the mixture into a three-neck flask, heating to 60 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration after the reaction is finished, and performing vacuum drying to obtain the composite antioxidant.
The first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, then dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after completely dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, rotationally evaporating at 40 ℃ to remove the tetrahydrofuran, adding methanol for shaking, demixing, separating to obtain a crude product, dissolving the crude product with tetrahydrofuran, precipitating with methanol, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3.
The mixed solution A is prepared by adding 2-mercaptoethanol and azobisisobutyronitrile into tetrahydrofuran and mixing, wherein the dosage ratio of the 2-mercaptoethanol, the azobisisobutyronitrile and the tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and dibutyltin dilaurate into toluene and mixing, wherein the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the dibutyltin dilaurate is 1% of the weight of the isophorone diisocyanate; the mixed solution E is prepared by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and dibutyltin dilaurate into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the dibutyltin dilaurate is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
Example 3
The composite antioxidant comprises the following raw materials in parts by weight: 8 parts of a first antioxidant, 4 parts of an antioxidant GM, 8 parts of KH590, 0.3 part of triethylamine, 28 parts of nano-silica, 80 parts of an ethanol aqueous solution with a volume fraction of 30% and 28 parts of toluene;
the compound antioxidant is prepared by the following method:
firstly, adding an antioxidant GM and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 400r/min, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to obtain a mixture, transferring the mixture into a three-neck flask, heating to 60 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration after the reaction is finished, and performing vacuum drying to obtain the composite antioxidant.
The first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, then dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after completely dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, rotationally evaporating at 40 ℃ to remove the tetrahydrofuran, adding methanol for shaking, demixing, separating to obtain a crude product, dissolving the crude product with tetrahydrofuran, precipitating with methanol, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3.
The mixed solution A is prepared by adding 2-mercaptoethanol and azobisisobutyronitrile into tetrahydrofuran and mixing, wherein the dosage ratio of the 2-mercaptoethanol, the azobisisobutyronitrile and the tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and dibutyltin dilaurate into toluene and mixing, wherein the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the dibutyltin dilaurate is 1% of the weight of the isophorone diisocyanate; the mixed solution E is prepared by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and dibutyltin dilaurate into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the dibutyltin dilaurate is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
Example 4
The composite antioxidant comprises the following raw materials in parts by weight: 10 parts of a first antioxidant, 5 parts of an antioxidant GM, 10 parts of KH590, 0.3 part of triethylamine, 30 parts of nano silicon dioxide, 100 parts of an ethanol aqueous solution with the volume fraction of 30 percent and 20-30 parts of toluene;
the compound antioxidant is prepared by the following method:
firstly, adding an antioxidant GM and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
and secondly, adding nano silicon dioxide into an ethanol aqueous solution with the volume fraction of 30%, ultrasonically dispersing for 10min, homogenizing for 10min at the rotating speed of 400r/min, dropwise adding dilute hydrochloric acid with the mass fraction of 10% to adjust the pH until the pH is 4, then adding the intermediate 1 and the first antioxidant, continuously dispersing for 10min to obtain a mixture, transferring the mixture into a three-neck flask, heating to 60 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration after the reaction is finished, and performing vacuum drying to obtain the composite antioxidant.
The first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, then dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after completely dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, rotationally evaporating at 40 ℃ to remove the tetrahydrofuran, adding methanol for shaking, demixing, separating to obtain a crude product, dissolving the crude product with tetrahydrofuran, precipitating with methanol, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3.
The mixed solution A is prepared by adding 2-mercaptoethanol and azobisisobutyronitrile into tetrahydrofuran and mixing, wherein the dosage ratio of the 2-mercaptoethanol, the azobisisobutyronitrile and the tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and dibutyltin dilaurate into toluene and mixing, wherein the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the dibutyltin dilaurate is 1% of the weight of the isophorone diisocyanate; the mixed solution E is prepared by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and dibutyltin dilaurate into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the dibutyltin dilaurate is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
Comparative example 1
This comparative example compares to example 1 without the addition of the first antioxidant.
Comparative example 2
This comparative example compares to example 1 without the addition of a second antioxidant.
Comparative example 3
This comparative example is an antioxidant for natural rubber in the market.
Weighing 50.0gNR latex, adding into a beaker, and sequentially and quantitatively adding 0.2-0.4g of the composite antioxidant of the embodiments 1-4 of the invention; 0.2-0.4g of composite antioxidant in comparative examples 1-3, and heating to 60 ℃ at a proper stirring speed for later use;
1. period of oxidative induction
Using DSC200PC type differential scanning calorimetry analyzer, placing NR grafting powder sample with mass of (15.0 + -0.5) mg in an aluminum dish, introducing nitrogen at the rate of (50 + -5) mL/min, controlling the heating rate to 20 deg.C/min, and heating to 160 deg.C. Keeping the temperature for 3min, replacing nitrogen with oxygen, keeping the temperature at 160 ℃ until the maximum heat release signal appears, and recording the time as an oxidation induction period min.
2. Hot air aging test
The NR grafted powder is filled in an aluminum dish, the thickness of the NR grafted powder is about 5mm, the NR grafted powder is placed in an LR016A type thermal oxidation aging box to be subjected to a hot air aging test, the temperature of the aging test is set to be 180 ℃, ventilation conditions are set, the appearance color change condition of the powder is observed regularly, the time min is recorded when the powder is changed into dark brown, the coking time is set, and the longer the coking time is, the longer the sample shows that the anti-oxidation performance is good.
It can be seen from the above table that the oxidation induction period is 96-98min for examples 1-4 and 80-88min for comparative examples 1-3; the coking times of examples 1-4 were 396-398min, and those of comparative examples 1-3 were 325-358 min; therefore, the composite antioxidant prepared by the invention has excellent antioxidant performance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. The composite antioxidant is characterized by comprising the following raw materials in parts by weight: 1-10 parts of a first antioxidant, 1-5 parts of a second antioxidant, 5-10 parts of KH590, 0.1-0.3 part of triethylamine, 25-30 parts of nano silicon dioxide, 50-100 parts of a 30% ethanol aqueous solution with volume fraction and 20-30 parts of toluene;
the compound antioxidant is prepared by the following method:
adding a second antioxidant and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65-80 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
secondly, adding nano silicon dioxide into 30% ethanol water solution by volume fraction, performing ultrasonic dispersion for 10min, homogenizing for 10min at the rotating speed of 500r/min of 400 plus materials, dropwise adding 10% diluted hydrochloric acid by mass fraction to adjust the pH until the pH is =4, then adding the intermediate 1 and the first antioxidant, continuing dispersing for 10min to prepare a mixture, transferring the mixture into a three-neck flask, heating to 60-75 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration and vacuum drying after the reaction is finished, and preparing the composite antioxidant.
2. The complex antioxidant as claimed in claim 1, wherein the second antioxidant is antioxidant GM.
3. The compound antioxidant as claimed in claim 1, wherein the first antioxidant is prepared by the following method:
step S1, adding hydroxyl-terminated polybutadiene and tetrahydrofuran into a three-neck flask, magnetically stirring for 30min at a speed of 60-100r/min, dropwise adding the mixed solution A after stirring, controlling the dropwise adding time to be 5min, magnetically stirring and reacting for 2h, dropwise adding the mixed solution B, controlling the dropwise adding time to be 5min, stopping heating and stirring after complete dropwise adding, reacting for 30min to obtain a reaction product, transferring the reaction product into a single-neck flask, performing rotary evaporation at 40-45 ℃ to remove the tetrahydrofuran, adding ice methanol to shake, performing layering and liquid separation to obtain a crude product, dissolving the crude product in the tetrahydrofuran, performing methanol precipitation, repeating for 3 times to obtain an intermediate 2, and controlling the dosage ratio of the hydroxyl-terminated polybutadiene, the mixed solution A, the mixed solution B and the tetrahydrofuran to be 10 g: 10 mL: 3 mL: 5mL;
step S2, adding the intermediate 2 into a three-neck flask filled with toluene, magnetically stirring for 15min to obtain a mixed solution C, slowly dropwise adding the mixed solution C into the mixed solution D, stirring at a constant speed, reacting for 2h to obtain an adduct, tracking by measuring the content of isocyanate groups in the reaction process, adding the mixed solution E into the adduct, heating in a water bath at 45-60 ℃ for reacting, monitoring by infrared until the isocyanate groups disappear, stopping the reaction, performing rotary evaporation, removing the toluene, refining in the same step S1 to obtain a first antioxidant, and controlling the volume ratio of the intermediate 2, the mixed solution D and the mixed solution E to be 1: 3-5.
4. The compound antioxidant as claimed in claim 3, wherein the mixture A is prepared by mixing 2-mercaptoethanol and azobisisobutyronitrile with tetrahydrofuran, and the dosage ratio of 2-mercaptoethanol, azobisisobutyronitrile and tetrahydrofuran is 1 g: 0.05 g: 10 mL; the mixed solution B is formed by mixing 2, 6-di-tert-butyl-4-methylphenol and tetrahydrofuran according to the dosage ratio of 0.1g to 3 mL; the mixed solution D is formed by adding isophorone diisocyanate and a catalyst into toluene and mixing, the using amount ratio of the isophorone diisocyanate to the toluene is 3.5 g: 10g, and the using amount of the catalyst is 1% of the weight of the isophorone diisocyanate; the mixed solution E is formed by adding 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) and a catalyst into toluene and mixing, wherein the weight ratio of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol) to the toluene is 1: 5, and the dosage of the catalyst is 1% of the weight of the 2,2 ' -thiobis (4-methyl-6-tert-butylphenol).
5. The complex antioxidant as claimed in claim 4, wherein the catalyst is dibutyltin dilaurate.
6. The preparation process of the compound antioxidant as claimed in claim 1, comprising the steps of:
adding a second antioxidant and KH590 into a three-neck flask filled with toluene, introducing nitrogen to discharge air, heating to 65-80 ℃, magnetically stirring for 30min, adding triethylamine, and carrying out reflux reaction for 2h at the temperature to obtain an intermediate 1;
secondly, adding nano silicon dioxide into 30% ethanol water solution by volume fraction, performing ultrasonic dispersion for 10min, homogenizing for 10min at the rotating speed of 500r/min of 400 plus materials, dropwise adding 10% diluted hydrochloric acid by mass fraction to adjust the pH until the pH is =4, then adding the intermediate 1 and the first antioxidant, continuing dispersing for 10min to prepare a mixture, transferring the mixture into a three-neck flask, heating to 60-75 ℃, introducing nitrogen to discharge air, reacting for 4h at the temperature, cooling, performing suction filtration and vacuum drying after the reaction is finished, and preparing the composite antioxidant.
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