CN113004331A - Synthetic method of antioxidant - Google Patents
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- CN113004331A CN113004331A CN202110252409.2A CN202110252409A CN113004331A CN 113004331 A CN113004331 A CN 113004331A CN 202110252409 A CN202110252409 A CN 202110252409A CN 113004331 A CN113004331 A CN 113004331A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 47
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 229920000642 polymer Polymers 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 150000008301 phosphite esters Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a synthetic method of an antioxidant, which comprises the steps of reacting cyanuric chloride with an intermediate 8 and an intermediate 11 in sequence through temperature control to prepare an intermediate 12, hydrolyzing the intermediate 12, grafting the hydrolyzed intermediate on nano silicon dioxide to prepare the antioxidant, grafting the antioxidant with the nano silicon dioxide to ensure that the antioxidant can be fully dispersed when being mixed with a polymer, can not migrate along with the increase of the using time, contains hindered phenol and phosphite ester structures, can provide hydrogen atoms to prevent the formation of chain free radicals, can react with the chain free radicals to achieve the purpose of inhibiting oxidation, can decompose unstable hydrogen peroxide into stable compounds to further prevent the formation of new polymerized free radicals, and achieves the purpose of terminating chain reaction.
Description
Technical Field
The invention relates to the technical field of antioxidant preparation, and particularly relates to a synthetic method of an antioxidant.
Background
The antioxidant is a plastic auxiliary agent which effectively reduces the autoxidation reaction speed of the plastic material and delays the aging and degradation of the plastic material, and has the application of the antioxidant in the polymerization, granulation, storage, processing and other stages of the plastic. Phosphite antioxidants are multifunctional auxiliary antioxidants, and are widely applied to the processing of various plastic products due to the advantages of decomposing hydroperoxides, inhibiting the autocatalysis of hydroperoxides, having good synergistic effect with main antioxidants and the like. The pentaerythritol diphosphite antioxidant is an antioxidant which takes pentaerythritol as a skeleton and trivalent phosphorus as a functional group.
The existing antioxidant has a certain antioxidant effect, but the antioxidant effect is general, and after the antioxidant agent is mixed with a polymer, a precipitation phenomenon can occur after the polymer is used for a long time.
Disclosure of Invention
The invention aims to provide a synthetic method of an antioxidant.
The technical problems to be solved by the invention are as follows:
the existing antioxidant has a certain antioxidant effect, but the antioxidant effect is general, and after the antioxidant agent is mixed with a polymer, a precipitation phenomenon can occur after the polymer is used for a long time.
The purpose of the invention can be realized by the following technical scheme:
a synthetic method of an antioxidant specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 150-200r/min and the temperature is 10-15 ℃, reacting for 1-1.5h at 40-45 deg.C to obtain intermediate 1, adding intermediate 1 and anhydrous potassium carbonate into reaction kettle, stirring and adding triethyl phosphite under the condition of the rotation speed of 200-300r/min, reacting for 2-4h at the temperature of 120-130 ℃ to obtain an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into a reaction kettle, reacting for 2-4h at the rotation speed of 150-;
the reaction process is as follows:
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 200-300r/min and the temperature of 45-55 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 20-30 ℃ for 60-70min to react for 4-5h to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting for 3-5h at the rotation speed of 150-200r/min and the temperature of 90-95 ℃ to prepare an intermediate 5;
the reaction process is as follows:
step S3: mixing the intermediate 5 with deionized water, refluxing for 10-20min at the temperature of 110-120 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150-200r/min and the temperature of 30-35 ℃, reacting for 3-5h, heating to the temperature of 70-80 ℃, refluxing for 5-8min, adding a hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 40-50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, reacting at the temperature of 25-30 ℃, reacting for 30-50min to obtain an intermediate 8;
the reaction process is as follows:
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of a rotation speed of 150-;
the reaction process is as follows:
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 10-15min at the rotation speed of 300-50 ℃ for 500r/min, introducing nitrogen to discharge air, adding triethylamine to react for 4-5h at the temperature of 40-50 ℃ to obtain an intermediate 11, dissolving cyanuric chloride in acetone, adding an intermediate 8, reacting for 3-5h at the rotation speed of 150-200r/min at the temperature of 40-50 ℃, adding the intermediate 11, reacting at the temperature of 80-90 ℃ to obtain an intermediate 12, adding nano silicon dioxide, ethanol and deionized water into the reaction kettle, performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz, adjusting the pH value to 4, adding the intermediate 12, reacting for 1-1.5h at the temperature of 100-110 ℃, and filtering to remove the filtrate to obtain the antioxidant.
The reaction process is as follows:
further, in the step S1, the dosage ratio of the aluminum trichloride, the carbon tetrachloride and the phenol is 13g, 25mL and 7.5g, the dosage ratio of the intermediate 1, the anhydrous potassium carbonate and the triethyl phosphite is 0.05mol, 0.6g and 0.15mol, the dosage molar ratio of the intermediate 2, the pentaerythritol and the triethyl phosphite is 1:2:1, and the dosage of the dimethyl tin is 0.8-1% of the mass of the intermediate 2.
Further, the dosage ratio of the tert-butyl alcohol, the paraformaldehyde and the potassium ethoxide in the step S2 is 30mL:0.05mol:0.001mol, and the dosage ratio of the 2, 6-di-tert-butylphenol and the depolymerization solution is 30mL: 0.02mol, and the using amount ratio of the intermediate 3, the intermediate 4, the toluene and the tetraphenyltin is 0.05mol, 0.1mol, 40mL and 0.8 g.
Further, the using amount ratio of the intermediate 5 and the deionized water in the step S3 is 0.5g:4mL, the using amount ratio of the intermediate 6, the ammonium acetate and the sodium borohydride is 6g:3.5g:20mL, the mass fraction of the ethanol solution is 80%, the mass fraction of the hydrochloric acid solution is 10-15%, the using amount ratio of the intermediate 7, the zinc powder, the concentrated hydrochloric acid, the ammonia water and the sodium hydroxide solution is 0.02mol:0.25mol:0.45mol:30mL:60mL, the mass fraction of the concentrated hydrochloric acid is 36%, the mass fraction of the ammonia water is 30%, and the mass fraction of the sodium hydroxide solution is 20%.
Further, the using amount ratio of the sodium nitrate, the concentrated sulfuric acid, the deionized water and the phenol in the step S4 is 8g:5mL:15mL:3g, and the using amount molar ratio of the deionized water, the iron powder, the hydrochloric acid, the intermediate 9 and the chloropropene is 4:9:0.5:4: 4.
Further, the mass ratio of the intermediate 10, the gamma-mercaptopropyltrimethoxysilane and the triethylamine in the step S5 is 10:3:1, the molar ratio of the cyanuric chloride to the intermediate 8 to the intermediate 11 is 1:2:1, and the mass ratio of the nano-silica, the ethanol, the deionized water and the intermediate 12 is 1g:0.3g:2mL:4 mL.
The invention has the beneficial effects that: the invention provides an antioxidant, which is prepared by taking phenol and carbon tetrachloride as raw materials to react to prepare an intermediate 1, further reacting the intermediate 1 with triethyl phosphite to prepare an intermediate 2, reacting the intermediate 2 with pentaerythritol and then reacting with the triethyl phosphite to prepare an intermediate 3, depolymerizing paraformaldehyde to prepare depolymerization liquid, reacting the depolymerization liquid with 2, 6-di-tert-butylphenol to prepare an intermediate 4, reacting the intermediate 3 with the intermediate 4 to prepare an intermediate 5, refluxing the intermediate 5 with deionized water to prepare an intermediate 6, carrying out one-step treatment on the intermediate 6 to prepare an intermediate 7, reacting the intermediate 7 to prepare an intermediate 8, treating phenol to prepare an intermediate 9, reducing the intermediate 9 and reacting with chloropropene to prepare an intermediate 10, the preparation method comprises the following steps of reacting an intermediate 10 with gamma-mercaptopropyl trimethoxysilane to obtain an intermediate 11, reacting cyanuric chloride with the intermediate 8 and the intermediate 11 in sequence through temperature control to obtain an intermediate 12, hydrolyzing the intermediate 12, grafting the hydrolyzed intermediate on nano silicon dioxide to obtain an antioxidant, grafting the antioxidant with the nano silicon dioxide to ensure that the antioxidant can be fully dispersed when being mixed with a polymer, and cannot migrate along with the increase of the using time, and the antioxidant contains hindered phenol and phosphite ester structures, can provide hydrogen atoms to prevent the formation of chain free radicals, can react with the chain free radicals to achieve the purpose of inhibiting oxidation, can decompose unstable hydrogen peroxide into stable compounds to further prevent the formation of new polymerization free radicals, and achieves the purpose of terminating the chain reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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
A synthetic method of an antioxidant specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 150r/min and the temperature is 10 ℃, reacting for 1h under the condition that the temperature is 40 ℃ to prepare an intermediate 1, adding the intermediate 1 and anhydrous potassium carbonate into the reaction kettle, stirring and adding triethyl phosphite under the condition that the rotating speed is 200r/min, reacting for 2h under the condition that the temperature is 120 ℃ to prepare an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into the reaction kettle, reacting for 2h under the conditions that the rotating speed is 150r/min and the temperature is 125 ℃, adding the triethyl phosphite, and continuing to react for 1h to prepare an intermediate 3;
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 200r/min and the temperature of 45 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 20 ℃ for 60min, reacting for 4h to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting for 3h at the rotation speed of 150r/min and the temperature of 90 ℃ to prepare an intermediate 5;
step S3: mixing the intermediate 5 with deionized water, refluxing for 10min at the temperature of 110 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150r/min and the temperature of 30 ℃, reacting for 3h, heating to the temperature of 70 ℃, refluxing for 5min, adding a hydrochloric acid solution, stirring for 5min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3h at the rotation speed of 200r/min and the temperature of 40 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, and reacting for 30min at the temperature of 25 ℃ to obtain an intermediate 8;
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of the rotating speed of 150r/min and the temperature of 15 ℃ to react for 3 hours to obtain an intermediate 9, adding deionized water into the reaction kettle, stirring and adding iron powder and hydrochloric acid under the conditions of the rotating speed of 200r/min and the temperature of 95 ℃, stirring for 3 minutes, adding the intermediate 9, and reacting for 2 hours to obtain an intermediate 10;
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 10min at the rotating speed of 300r/min, introducing nitrogen to discharge air, adding triethylamine to react for 4h at the temperature of 40 ℃ to prepare an intermediate 11, dissolving cyanuric chloride in acetone, adding the intermediate 8, reacting for 3 hours at the rotating speed of 150r/min and the temperature of 40 ℃, adding the intermediate 11, reacting at 80 deg.C to obtain intermediate 12, adding nanometer silicon dioxide, ethanol and deionized water into a reaction kettle, performing ultrasonic treatment for 10min at frequency of 3MHz, adjusting pH to 4, adding intermediate 12, reacting for 1h at the temperature of 100 ℃, and filtering to remove filtrate to obtain the antioxidant.
Example 2
A synthetic method of an antioxidant specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 150r/min and the temperature is 15 ℃, reacting for 1.5 hours under the condition that the temperature is 40 ℃ to prepare an intermediate 1, adding the intermediate 1 and anhydrous potassium carbonate into the reaction kettle, stirring and adding triethyl phosphite under the condition that the rotating speed is 200r/min, reacting for 2 hours under the condition that the temperature is 130 ℃ to prepare an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into the reaction kettle, reacting for 4 hours under the conditions that the rotating speed is 200r/min and the temperature is 125 ℃, adding the triethyl phosphite, and continuing to react for 1 hour to prepare an intermediate 3;
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 300r/min and the temperature of 45 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 30 ℃ for 60min, reacting for 5h to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting for 3h at the rotation speed of 150r/min and the temperature of 95 ℃ to prepare an intermediate 5;
step S3: mixing the intermediate 5 with deionized water, refluxing for 10min at 120 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 200r/min and a temperature of 30 ℃, reacting for 5h, heating to 70 ℃, refluxing for 8min, adding a hydrochloric acid solution, stirring for 5min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5h at a rotation speed of 300r/min and a temperature of 40 ℃, cooling to 0 ℃, adding ammonia water and a sodium hydroxide solution, and reacting for 50min at a temperature of 25 ℃ to obtain an intermediate 8;
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of the rotating speed of 150r/min and the temperature of 20 ℃ to react for 3 hours to obtain an intermediate 9, adding deionized water into the reaction kettle, stirring and adding iron powder and hydrochloric acid under the conditions of the rotating speed of 300r/min and the temperature of 95 ℃, stirring for 5 minutes, adding the intermediate 9, and reacting for 2 hours to obtain an intermediate 10;
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 10min at the rotating speed of 500r/min, introducing nitrogen to discharge air, adding triethylamine to react for 4h at the temperature of 50 ℃ to prepare an intermediate 11, dissolving cyanuric chloride in acetone, adding the intermediate 8, reacting for 5 hours at the rotating speed of 200r/min and the temperature of 40 ℃, adding the intermediate 11, reacting at 80 deg.C to obtain intermediate 12, adding nanometer silicon dioxide, ethanol and deionized water into a reaction kettle, performing ultrasonic treatment for 10min at frequency of 5MHz, adjusting pH to 4, adding intermediate 12, reacting for 1h at the temperature of 110 ℃, and filtering to remove filtrate to obtain the antioxidant.
Example 3
A synthetic method of an antioxidant specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 200r/min and the temperature is 10 ℃, reacting for 1h under the condition that the temperature is 45 ℃ to prepare an intermediate 1, adding the intermediate 1 and anhydrous potassium carbonate into the reaction kettle, stirring and adding triethyl phosphite under the condition that the rotating speed is 300r/min, reacting for 4h under the condition that the temperature is 120 ℃ to prepare an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into the reaction kettle, reacting for 2h under the conditions that the rotating speed is 150r/min and the temperature is 135 ℃, adding the triethyl phosphite, and continuing to react for 3h to prepare an intermediate 3;
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 200r/min and the temperature of 55 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 20 ℃ for 70min to react for 4h to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting for 5h at the rotation speed of 200r/min and the temperature of 90 ℃ to prepare an intermediate 5;
step S3: mixing the intermediate 5 with deionized water, refluxing for 20min at the temperature of 110 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150r/min and the temperature of 35 ℃, reacting for 3h, heating to the temperature of 80 ℃, refluxing for 5min, adding a hydrochloric acid solution, stirring for 10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3h at the rotation speed of 200r/min and the temperature of 50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, and reacting for 30min at the temperature of 30 ℃ to obtain an intermediate 8;
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of the rotating speed of 200r/min and the temperature of 15 ℃ to react for 5 hours to obtain an intermediate 9, adding deionized water into the reaction kettle, stirring and adding iron powder and hydrochloric acid under the conditions of the rotating speed of 200r/min and the temperature of 98 ℃, stirring for 3 minutes, adding the intermediate 9, and reacting for 3 hours to obtain an intermediate 10;
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 15min at the rotating speed of 300r/min, introducing nitrogen to discharge air, adding triethylamine to react for 5h at the temperature of 40 ℃ to obtain an intermediate 11, dissolving cyanuric chloride in acetone, adding the intermediate 8, reacting for 3 hours at the rotating speed of 150r/min and the temperature of 50 ℃, adding the intermediate 11, reacting at 90 deg.C to obtain intermediate 12, adding nanometer silicon dioxide, ethanol and deionized water into a reaction kettle, performing ultrasonic treatment for 15min at frequency of 3MHz, adjusting pH to 4, adding intermediate 12, reacting for 1.5h at the temperature of 100 ℃, filtering and removing filtrate to obtain the antioxidant.
Example 4
A synthetic method of an antioxidant specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 200r/min and the temperature is 15 ℃, reacting for 1.5 hours under the condition that the temperature is 45 ℃ to prepare an intermediate 1, adding the intermediate 1 and anhydrous potassium carbonate into the reaction kettle, stirring and adding triethyl phosphite under the condition that the rotating speed is 300r/min, reacting for 4 hours under the condition that the temperature is 130 ℃ to prepare an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into the reaction kettle, reacting for 4 hours under the conditions that the rotating speed is 200r/min and the temperature is 135 ℃, adding the triethyl phosphite, and continuing to react for 3 hours to prepare an intermediate 3;
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 300r/min and the temperature of 55 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 30 ℃ for 70min for 5h to react to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting at the rotation speed of 200r/min and the temperature of 95 ℃ for 5h to prepare an intermediate 5;
step S3: mixing the intermediate 5 with deionized water, refluxing for 20min at 120 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 200r/min and a temperature of 35 ℃, reacting for 5h, heating to 80 ℃, refluxing for 8min, adding a hydrochloric acid solution, stirring for 10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5h at a rotation speed of 300r/min and a temperature of 50 ℃, cooling to 0 ℃, adding ammonia water and a sodium hydroxide solution, and reacting for 50min at a temperature of 30 ℃ to obtain an intermediate 8;
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of the rotating speed of 200r/min and the temperature of 20 ℃ to react for 5 hours to obtain an intermediate 9, adding deionized water into the reaction kettle, stirring and adding iron powder and hydrochloric acid under the conditions of the rotating speed of 300r/min and the temperature of 98 ℃, stirring for 5 minutes, adding the intermediate 9, and reacting for 3 hours to obtain an intermediate 10;
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 15min at the rotating speed of 500r/min, introducing nitrogen to discharge air, adding triethylamine to react for 5h at the temperature of 50 ℃ to obtain an intermediate 11, dissolving cyanuric chloride in acetone, adding the intermediate 8, reacting for 5 hours at the rotating speed of 200r/min and the temperature of 50 ℃, adding the intermediate 11, reacting at 90 deg.C to obtain intermediate 12, adding nanometer silicon dioxide, ethanol and deionized water into a reaction kettle, performing ultrasonic treatment for 15min at frequency of 5MHz, adjusting pH to 4, adding intermediate 12, reacting for 1.5h at the temperature of 110 ℃, filtering and removing filtrate to obtain the antioxidant.
Comparative example
The comparative example is a common antioxidant on the market.
The antioxidants prepared in examples 1 to 4 and comparative example were subjected to a performance test, and the test results are shown in table 1 below;
adding the antioxidant prepared in the examples 1-4 and the comparative example into the preparation process of PVC plastic to prepare a PVC plate, detecting the tensile strength, the impact strength and the notch impact strength of the PVC plate, and then using a plastic plate with the wavelength of 340nm and the irradiation intensity of 0.68W/m2The temperature of the blackboard is 60 ℃, and the condensation temperature is 60 ℃; a single cycle process; illuminating for 3h, and blowing for 10 min; the cycle was repeated continuously for a total experimental time 168h; after aging, testing whether the tensile strength, the impact strength and the notch impact strength are reduced;
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Tensile strength | Is not lowered | Is not lowered | Is not lowered | Is not lowered | Is greatly reduced |
| Impact strength | Is not lowered | Is not lowered | Is not lowered | Is not lowered | Is greatly reduced |
| Notched impact strength | Is not lowered | Is not lowered | Is not lowered | Is not lowered | Is greatly reduced |
From table 1 above, it can be seen that the PVC sheets processed with the antioxidants of examples 1 to 4 did not show a decrease in tensile strength, impact strength, and notched impact strength after aging, while the PVC sheets processed with the antioxidants of comparative examples did not show a significant decrease in tensile strength, impact strength, and notched impact strength after aging, indicating that the present invention has a very good antioxidant effect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A synthetic method of an antioxidant is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding phenol under the conditions that the rotating speed is 150-200r/min and the temperature is 10-15 ℃, reacting for 1-1.5h at 40-45 deg.C to obtain intermediate 1, adding intermediate 1 and anhydrous potassium carbonate into reaction kettle, stirring and adding triethyl phosphite under the condition of the rotation speed of 200-300r/min, reacting for 2-4h at the temperature of 120-130 ℃ to obtain an intermediate 2, adding the intermediate 2, pentaerythritol and dimethyltin into a reaction kettle, reacting for 2-4h at the rotation speed of 150-;
step S2: adding tert-butyl alcohol, paraformaldehyde and potassium ethoxide into a reaction kettle, reacting at the rotation speed of 200-300r/min and the temperature of 45-55 ℃ until polyformaldehyde is completely depolymerized to prepare depolymerization liquid, adding 2, 6-di-tert-butylphenol into the reaction kettle, introducing nitrogen to remove oxygen, dropwise adding the depolymerization liquid at the temperature of 20-30 ℃ for 60-70min to react for 4-5h to prepare an intermediate 4, adding the intermediate 3, the intermediate 4, toluene and tetraphenyltin into the reaction kettle, and reacting for 3-5h at the rotation speed of 150-200r/min and the temperature of 90-95 ℃ to prepare an intermediate 5;
step S3: mixing the intermediate 5 with deionized water, refluxing for 10-20min at the temperature of 110-120 ℃ to obtain an intermediate 6, adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150-200r/min and the temperature of 30-35 ℃, reacting for 3-5h, heating to the temperature of 70-80 ℃, refluxing for 5-8min, adding a hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 40-50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, reacting at the temperature of 25-30 ℃, reacting for 30-50min to obtain an intermediate 8;
step S4: adding sodium nitrate, concentrated sulfuric acid and deionized water into a reaction kettle, stirring and adding phenol under the conditions of a rotation speed of 150-;
step S5: adding the intermediate 10, gamma-mercaptopropyltrimethoxysilane and toluene into a reaction kettle, stirring for 10-15min at the rotation speed of 300-50 ℃ for 500r/min, introducing nitrogen to discharge air, adding triethylamine to react for 4-5h at the temperature of 40-50 ℃ to obtain an intermediate 11, dissolving cyanuric chloride in acetone, adding an intermediate 8, reacting for 3-5h at the rotation speed of 150-200r/min at the temperature of 40-50 ℃, adding the intermediate 11, reacting at the temperature of 80-90 ℃ to obtain an intermediate 12, adding nano silicon dioxide, ethanol and deionized water into the reaction kettle, performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz, adjusting the pH value to 4, adding the intermediate 12, reacting for 1-1.5h at the temperature of 100-110 ℃, and filtering to remove the filtrate to obtain the antioxidant.
2. The method for synthesizing an antioxidant according to claim 1, wherein the method comprises the following steps: the dosage ratio of the aluminum trichloride, the carbon tetrachloride and the phenol in the step S1 is 13g, 25mL and 7.5g, the dosage ratio of the intermediate 1, the anhydrous potassium carbonate and the triethyl phosphite is 0.05mol, 0.6g and 0.15mol, the dosage molar ratio of the intermediate 2, the pentaerythritol and the triethyl phosphite is 1:2:1, and the dosage of the dimethyltin is 0.8-1% of the mass of the intermediate 2.
3. The method for synthesizing an antioxidant according to claim 1, wherein the method comprises the following steps: the dosage ratio of the tert-butyl alcohol, the paraformaldehyde and the potassium ethoxide in the step S2 is 30mL to 0.05mol to 0.001mol, and the dosage ratio of the 2, 6-di-tert-butylphenol and the depolymerization solution is 30mL: 0.02mol, and the using amount ratio of the intermediate 3, the intermediate 4, the toluene and the tetraphenyltin is 0.05mol, 0.1mol, 40mL and 0.8 g.
4. The method for synthesizing an antioxidant according to claim 1, wherein the method comprises the following steps: the using amount ratio of the intermediate 5 to the deionized water in the step S3 is 0.5g to 4mL, the using amount ratio of the intermediate 6, the ammonium acetate and the sodium borohydride is 6g to 3.5g to 20mL, the mass fraction of the ethanol solution is 80%, the mass fraction of the hydrochloric acid solution is 10-15%, the using amount ratio of the intermediate 7, the zinc powder, the concentrated hydrochloric acid, the ammonia water and the sodium hydroxide solution is 0.02mol to 0.25mol to 0.45mol to 30mL to 60mL, the mass fraction of the concentrated hydrochloric acid is 36%, the mass fraction of the ammonia water is 30% and the mass fraction of the sodium hydroxide solution is 20%.
5. The method for synthesizing an antioxidant according to claim 1, wherein the method comprises the following steps: the using amount ratio of the sodium nitrate, the concentrated sulfuric acid, the deionized water and the phenol in the step S4 is 8g to 5mL to 15mL to 3g, and the using amount molar ratio of the deionized water, the iron powder, the hydrochloric acid, the intermediate 9 and the chloropropene is 4 to 9 to 0.5 to 4.
6. The method for synthesizing an antioxidant according to claim 1, wherein the method comprises the following steps: the mass ratio of the intermediate 10, the gamma-mercaptopropyltrimethoxysilane and the triethylamine in the step S5 is 10:3:1, the molar ratio of the cyanuric chloride to the intermediate 8 to the intermediate 11 is 1:2:1, and the mass ratio of the nano silicon dioxide to the ethanol to the deionized water to the intermediate 12 is 1g:0.3g:2mL:4 mL.
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