CN113292431A - Hindered phenol antioxidant and preparation method thereof - Google Patents
Hindered phenol antioxidant and preparation method thereof Download PDFInfo
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- CN113292431A CN113292431A CN202110615415.XA CN202110615415A CN113292431A CN 113292431 A CN113292431 A CN 113292431A CN 202110615415 A CN202110615415 A CN 202110615415A CN 113292431 A CN113292431 A CN 113292431A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 62
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 58
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 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 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical compound COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 abstract description 10
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000006698 induction Effects 0.000 description 10
- 239000002861 polymer material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a hindered phenol antioxidant and a preparation method thereof, and the hindered phenol antioxidant disclosed by the invention is prepared by addition reaction and ester exchange reaction in the presence of a catalyst; the hindered phenol antioxidant prepared by the invention not only introduces long-chain alkyl ester at the para position of benzene ring hydroxyl, but also introduces two hindered phenol functional groups, and one hindered phenol functional group is more than that of the commonly used hindered phenol antioxidant 1076 in the market, so that the molecular weight of the antioxidant is increased, the thermal stability is improved, and the corresponding antioxidant performance is also improved.
Description
Technical Field
The invention relates to the field of light stabilizers, in particular to a hindered phenol antioxidant and a preparation method thereof.
Background
With the development of industrial production, the usage amount of polymer materials is increasing, but the polymer materials are inevitably aged in the using process. In order to prevent the aging of the polymer material and prolong the service life of the polymer material, antioxidants are usually added into the polymer material, wherein hindered phenol antioxidants are a class of commonly used antioxidants. The antioxidant 1076 is a typical product of hindered phenol antioxidants, has no toxicity, no odor, high antioxidant performance, good compatibility with high polymer materials, difficult discoloration and low volatility in the processing process, and is an antioxidant widely applied in the current market.
Research shows that the antioxidant effect of the hindered phenol antioxidant has great relationship with the chemical structure of the antioxidant, and the number and the type of the substituent groups on the benzene ring of the hindered phenol antioxidant determine the antioxidant activity of the hindered phenol antioxidant. The traditional hindered phenol antioxidants are easy to migrate and volatilize in the processes of processing, storage and use due to small molecular weight, have poor extraction resistance, have poor oxidation resistance and cause environmental pollution. However, the antioxidants with excellent performance are not all due to their high molecular weight, because the high molecular weight is too high to be beneficial to the dispersion of the antioxidants in the polymer, and adversely affects the use of the material. Therefore, the molecular weight of the hindered phenol antioxidant is generally 500-1000. Further research shows that the antioxidant performance of the antioxidant is mainly related to the number of phenolic hydroxyl groups and the activity of main functional groups, and the antioxidant has stronger antioxidant performance when the main functional groups of the antioxidant are more and more active.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hindered phenol antioxidant and a preparation method thereof, and aims to solve the problems in the prior art.
The first object of the present invention is to provide a hindered phenol antioxidant.
The second purpose of the invention is to provide a preparation method of the hindered phenol antioxidant.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a hindered phenol antioxidant having a structure represented by formula (1):
the molecular formula of the antioxidant is C49H82O4。
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of hindered phenol antioxidant comprises the following synthetic process route:
the preparation method comprises the following steps:
1) carrying out addition reaction on 2, 6-di-tert-butylphenol and methyl propiolate in the presence of a catalyst 1 to obtain an intermediate compound shown as a formula (2);
2) in the presence of a catalyst 2, an intermediate compound shown in a formula (2) and stearyl alcohol are subjected to transesterification reaction to obtain a hindered phenol antioxidant shown in a formula (1).
Further, in the step 1), the mass ratio of the 2, 6-di-tert-butylphenol, methyl propiolate and the catalyst 1 is 1.6-2.4: 1: 0.05 to 2.
Further, in the step 1), the catalyst 1 is any one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.
Further, in the step 1), the reaction solvent is any one of acetonitrile, cyclohexane, petroleum ether, toluene and xylene.
Further, in the step 1), the reaction temperature of the addition reaction is 50-170 ℃. Exemplary reaction temperatures for the addition reaction include, but are not limited to, 60-65 ℃, 80-85 ℃, 130-135 ℃, and the like.
Further, in the step 1), the reaction time of the addition reaction is 2-16 hours.
Further, in step 2), the amount ratio of the intermediate compound represented by formula (2), stearyl alcohol and the substance of catalyst 2 is 1: 0.8-1.4: 0.001 to 0.05.
Further, in the step 2), the catalyst 2 is any one of tetraethyl titanate and dibutyltin oxide.
Further, in the step 2), the reaction solvent is any one of cyclohexane, petroleum ether, toluene and xylene.
Further, in the step 2), the reaction temperature of the ester exchange reaction is 90-170 ℃. Exemplary reaction temperatures for the addition reaction include, but are not limited to, 95-100 deg.C, 110-115 deg.C, 160-165 deg.C, and the like.
Further, in the step 2), the reaction time of the ester exchange reaction is 4-20 hours.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
the hindered phenol antioxidant prepared by the invention not only introduces long-chain alkyl ester at the para position of benzene ring hydroxyl, but also introduces two hindered phenol functional groups, and one hindered phenol functional group is more than that of the commonly used hindered phenol antioxidant 1076 in the market, so that the molecular weight of the antioxidant is increased, the thermal stability is improved, and the corresponding antioxidant performance is also improved.
Drawings
FIG. 1 is an infrared spectrum of a target product prepared in example 1.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A preparation method of a hindered phenol antioxidant comprises the following steps:
into a 2L four-necked round-bottomed flask, 200g of 2, 6-di-tert-butylphenol, 39g of methyl propiolate, 27g of potassium carbonate and 200g of acetonitrile were charged, nitrogen gas was replaced, the mixture was stirred while the temperature was raised to 80 ℃ to carry out a heat-insulating reaction for 16 hours, and then the reaction mixture was cooled to room temperature, and then the reaction mixture was subjected to suction filtration, washing with water and distillation under reduced pressure to obtain 229g of a white intermediate represented by formula (2). Putting the intermediate shown in the formula (2) into a 2L four-neck round-bottom flask, adding 137g of octadecanol and 400g of toluene into a reaction bottle, replacing nitrogen, starting stirring, heating to 100 ℃, adding 0.88g of tetraethyl titanate after 0.5h, carrying out heat preservation reaction for 10h, adjusting the reaction solution to be alkalescent after HPLC (high performance liquid chromatography) detection is qualified, carrying out suction filtration and washing, and carrying out reduced pressure distillation to obtain 321g of light yellow target product with the yield of 95%.
The target product prepared in the example is detected by an infrared spectrometer, and an infrared spectrum shown in figure 1 can be seen in a fingerprint area of 870cm-1Has sharp characteristic absorption peak at 739cm, which is tetra-substituted on benzene ring-1There is a sharp characteristic absorption peak indicating more than four consecutive methylene groups.
At 1470cm-1、1343cm-1Absorption peaks indicate the presence of the stretching and bending vibration vC-H of vCH3 and vCH 2.
At 1450cm-1、1425cm-1Characteristic absorption peak at (a), indicating the presence of vC ═ C of the benzene ring.
At 1771cm-1Has a strong absorption peak of vC ═ O, and the molecule has 4 oxygen atoms and is 1077cm-1There is a strong absorption peak for vC-O indicating the presence of ester groups in the molecule.
At 2800 and 3000cm-1Is in fullAnd characteristic absorption peaks of CH and benzene ring CH.
At 3610cm-1Has a stretching vibration absorption peak of phenolic hydroxyl group vOH.
The product molecule can thus be demonstrated to have the following structural formula:
example 2
A preparation method of a hindered phenol antioxidant comprises the following steps:
into a 2L four-necked round-bottomed flask, 200g of 2, 6-di-tert-butylphenol, 40g of methyl propiolate, 13.7g of potassium carbonate and 200g of toluene were charged, nitrogen gas was replaced, the mixture was heated to 95 ℃ with stirring, the temperature was maintained for 6 hours, the reaction mixture was cooled to room temperature, and then the reaction mixture was suction-filtered, washed with water and distilled under reduced pressure to obtain 236g of a white intermediate represented by formula (2). Putting the intermediate shown in the formula (2) into a 2L four-neck round-bottom flask, adding 137g of octadecanol and 800g of xylene into a reaction bottle, replacing nitrogen, starting stirring, heating to 105 ℃, adding 0.72g of dibutyltin oxide after 0.5h, keeping the temperature for reaction for 10h, detecting by HPLC to be qualified, adjusting the reaction solution to be alkalescent, performing suction filtration and washing, and performing reduced pressure distillation to obtain 343g of a pale yellow target product with the yield of 98%.
Example 3
A preparation method of a hindered phenol antioxidant comprises the following steps:
400g of 2, 6-di-tert-butylphenol, 80g of methyl propiolate, 27g of potassium carbonate and 400g of xylene were put into a 3L four-necked round-bottomed flask, nitrogen gas was replaced, the mixture was stirred while the temperature was raised to 95 ℃ to carry out a reaction for 16 hours, the temperature was lowered to room temperature, and 470g of a white intermediate represented by the formula (2) was obtained by suction-washing the reaction mixture with water and distilling the reaction mixture under reduced pressure. Putting the intermediate shown in the formula (2) into a 3L four-neck round-bottom flask, adding 300g of octadecanol and 1400g of xylene into a reaction flask, replacing nitrogen, starting stirring, heating to 100 ℃, adding 1.32g of dibutyltin oxide after 0.5h, keeping the temperature for reaction for 10h, detecting by HPLC to be qualified, adjusting the reaction solution to be alkalescent, performing suction filtration and washing, and performing reduced pressure distillation to obtain 686g of light yellow target product with the yield of 98%.
Example 4
A preparation method of a hindered phenol antioxidant comprises the following steps:
into a 2L four-necked round-bottomed flask, 200g of 2, 6-di-tert-butylphenol, 39g of methyl propiolate, 14g of potassium carbonate and 200g of acetonitrile were charged, nitrogen gas was replaced, the mixture was stirred while the temperature was raised to 80 ℃ to carry out a reaction for 16 hours while maintaining the temperature, and after the temperature was lowered to room temperature, the reaction mixture was washed with water by suction filtration and distilled under reduced pressure to obtain 228g of a white intermediate represented by formula (2). Putting the intermediate shown in the formula (2) into a 2L four-neck round-bottom flask, adding 137g of octadecanol and 200g of toluene into a reaction bottle, replacing nitrogen, starting stirring, heating to 100 ℃, adding 0.48g of dibutyltin oxide after 0.5h, carrying out heat preservation reaction for 10h, detecting by HPLC to be qualified, adjusting the reaction solution to be alkalescent, carrying out suction filtration and washing, recrystallizing to obtain 276g of light yellow target product, and obtaining the yield of 81%. Test example:
the oxidation induction time of the high polymer material can directly reflect the aging degree of the material, and a Differential Scanning Calorimeter (DSC) is generally used for testing, wherein the longer the oxidation induction time is, the higher the oxidation induction temperature is, and the better the oxidation resistance of the antioxidant is. The antioxidant 1076, the hindered phenol antioxidant prepared according to the present invention, and high density polyethylene were made into a sheet, and the antioxidant properties of the antioxidant 1076 and the hindered phenol antioxidant prepared according to the present invention were evaluated.
Sample preparation: sample 1 accurately weighed 1kg of high density polyethylene powder, and then added with 4g of calcium stearate and 1.2g of antioxidant 1076 according to a conventional mixing method. The resulting mixture was thoroughly mixed in a SHR-500A type high-speed mixer at room temperature, and the mixed powder was placed in a ZJL-200 type torque rheometer and a single-screw extruder (conditions were set such as a screw length-diameter ratio L: D: 25:1, a screw diameter Φ 20mm, a screw compression ratio 2.5:1, and a screw extrusion temperature 220. + -.5 ℃) to extrude, draw and pelletize the mixture using a ZJL-200 type torque rheometer (conditions were set such that the rated torque was 300Nm, the rotation speed was 100rpm, the temperature was 220. + -.5 ℃ and the reduction ratio was 15: 1). Pressing the powder particles into tablets of 10 x 1mm at 200 +/-2 ℃ for later use.
Sample preparation: sample 2 accurately weighed 1kg of high density polyethylene powder, and then added with 4g of calcium stearate and 1.2g of the hindered phenol antioxidant prepared by the invention according to a conventional mixing method. The resulting mixture was thoroughly mixed in a SHR-500A type high-speed mixer at room temperature, and the mixed powder was placed in a ZJL-200 type torque rheometer and a single-screw extruder (conditions were set such as a screw length-diameter ratio L: D: 25:1, a screw diameter Φ 20mm, a screw compression ratio 2.5:1, and a screw extrusion temperature 220. + -.5 ℃) to extrude, draw and pelletize the mixture using a ZJL-200 type torque rheometer (conditions were set such that the rated torque was 300Nm, the rotation speed was 100rpm, the temperature was 220. + -.5 ℃ and the reduction ratio was 15: 1). Pressing the powder particles into tablets of 10 x 1mm at 200 +/-2 ℃ for later use.
Cutting the pressed sample 1 and sample 2 into 2 x 2cm sheets, placing the sheets into an autoclave filled with deionized water, screwing the autoclave, filling the pressure in the autoclave to 2Mpa by using oxygen, heating the autoclave to 95 ℃, carrying out an aging test for 120h, sampling within a certain time (20h, 40h, 80h and 120h), and drying and keeping the samples at room temperature for 36h for later use. The oxidation induction time was measured using a Differential Scanning Calorimeter (DSC).
The test results were as follows:
the oxidation induction time decreased, indicating a deterioration in thermal stability. As can be seen from the table, with the extension of the aging time, when the antioxidant is not added, the oxidation induction time of the aging temperature at 95 ℃ is 9min when the aging time is 120h, and the oxidation induction time of the high-density polyethylene sample to which the antioxidant 1076 is added and the antioxidant of the invention are added is 33min and 45min respectively when the aging temperature at 95 ℃ is 120h, which shows that the antioxidant 1076 and the hindered phenol antioxidant prepared by the invention both have better oxidation resistance, and the thermal-oxygen stability of the hindered phenol antioxidant prepared by the invention is better than that of the antioxidant 1076. It can be seen from the table that the oxidation induction time of the polymer material is continuously decreased in the whole aging process, and it is supposed that the content of the antioxidant is continuously consumed, and further, the chain of the polymer material is broken to generate carbonyl and alkoxy radicals, so that the molecular weight is decreased, the stability of the polymer material is deteriorated, and the oxidation induction time is decreased. According to the structure analysis, the molecular weight of the hindered phenol antioxidant prepared by the invention is higher than that of the antioxidant 1076, and because one more hindered phenol functional group is added, the oxidation induction time is high, and the oxidation resistance is good.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. A hindered phenol antioxidant characterized by having a structure represented by the formula (1):
2. a method for preparing the hindered phenol antioxidant of claim 1, wherein the synthetic process route is as follows:
3. the method of preparing a hindered phenol antioxidant of claim 2, comprising the steps of:
1) carrying out addition reaction on 2, 6-di-tert-butylphenol and methyl propiolate in the presence of a catalyst 1 to obtain an intermediate compound shown as a formula (2);
2) in the presence of a catalyst 2, an intermediate compound shown in a formula (2) and stearyl alcohol are subjected to transesterification reaction to obtain a hindered phenol antioxidant shown in a formula (1).
4. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the mass ratio of the 2, 6-di-tert-butylphenol, methyl propiolate to the catalyst 1 is 1.6-2.4: 1: 0.05 to 2.
5. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the catalyst 1 is any one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.
6. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the reaction temperature of the addition reaction is 50-170 ℃; the reaction time is 2-16 hours.
7. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in step 2), the mass ratio of the intermediate compound represented by formula (2), stearyl alcohol and the catalyst 2 is 1: 0.8-1.4: 0.001 to 0.05.
8. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 2), the catalyst 2 is any one of tetraethyl titanate and dibutyltin oxide.
9. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 2), the reaction temperature of the ester exchange reaction is 90-170 ℃; the reaction time of the ester exchange reaction is 4 to 20 hours.
10. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the reaction solvent is any one of acetonitrile, cyclohexane, petroleum ether, toluene and xylene; in the step 2), the reaction solvent is any one of cyclohexane, petroleum ether, toluene and xylene.
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