CN114573495A - Preparation method of long-acting anti-aging material - Google Patents
Preparation method of long-acting anti-aging material Download PDFInfo
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 29
- MNDTVJMRXYKBPV-UHFFFAOYSA-N 4-amino-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(N)=CC(C(C)(C)C)=C1O MNDTVJMRXYKBPV-UHFFFAOYSA-N 0.000 claims abstract description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- JLOKPJOOVQELMO-UHFFFAOYSA-N 2,6-ditert-butyl-4-nitrosophenol Chemical compound CC(C)(C)C1=CC(N=O)=CC(C(C)(C)C)=C1O JLOKPJOOVQELMO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 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 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WQECNUVITHHPKC-UHFFFAOYSA-N furan-2,5-dione;propan-2-one Chemical compound CC(C)=O.O=C1OC(=O)C=C1 WQECNUVITHHPKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000007348 radical reaction Methods 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 12
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 maleimide free radical Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a preparation method of a long-acting anti-aging material, which comprises the following specific steps: s1, preparing 2, 6-di-tert-butyl-4-nitrosophenol; s2: preparing 2, 6-di-tert-butyl-4-aminophenol; s3: preparing an intermediate I; s4: preparing an intermediate II; s5: and dissolving the intermediate II in absolute methanol, adding a catalyst p-toluenesulfonic acid, refluxing and reacting for 6-8h, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl. The invention not only contains the maleic double bond of the active group which can react with the rubber macromolecule, but also can chemically react with the rubber in the vulcanization process, and is bonded in the rubber macromolecule network by the chemical bond, thus having the advantages of non-migration, non-volatilization and non-extraction; meanwhile, the phenolic hydroxyl group with the function of inhibiting rubber aging does not generate substances harmful to human bodies, and easily captures R or ROO generated in an aging reaction, thereby inhibiting a free radical reaction and achieving the purpose of preventing rubber aging.
Description
Technical Field
The invention belongs to the field of rubber additives, and relates to a preparation method of a long-acting anti-aging material.
Background
In the using process, the rubber is aged under the influence of external factors (such as ozone aging, thermal oxidation aging and the like), so that the physical and mechanical properties of the rubber are changed, the elasticity of the rubber is lost, the mechanical properties are reduced, and the service life is shortened. In order to solve the problem of rubber aging, an anti-aging material is necessary to be added into rubber so as to inhibit or delay the aging process and prolong the service life of rubber products.
The universal anti-aging material added into the rubber in a mixing mode can be extracted under the use condition of the rubber product to lose the function of protecting rubber macromolecules, and the escaped anti-aging material can pollute the environment. Therefore, the development of the anti-aging material with the advantages of non-migration, non-volatilization and extraction resistance has important significance for prolonging the service life of rubber.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a long-acting anti-aging material, wherein a maleic double bond is introduced into a hindered phenol structure, so that the anti-aging material is connected in a network of vulcanized rubber through the reaction of an active maleimide group and rubber in the vulcanization process, thereby greatly improving the migration resistance, the volatilization resistance and the extraction resistance of the anti-aging material, and further realizing the long-term maintenance of the protective performance of the anti-aging material.
The invention mainly adopts the technical scheme that:
the preparation method of the long-acting anti-aging material comprises the following steps:
s1 preparation of 2, 6-di-tert-butyl-4-nitrosophenol: under the protection of nitrogen, keeping the temperature at 15-20 ℃ under normal pressure, firstly dissolving 2, 6-di-tert-butylphenol in 95% ethanol, then sequentially adding 38% concentrated hydrochloric acid and sodium nitrite solution for reaction for 2.0-2.5h, filtering the reaction solution to obtain a filter cake, pulping the filter cake into slurry by using petroleum ether at 60-90 ℃, washing for multiple times, and drying in vacuum to obtain a bright yellow solid, namely 2, 6-di-tert-butyl-4-nitrosophenol;
s2: preparation of 2, 6-di-tert-butyl-4-aminophenol: under the protection of nitrogen, dissolving the 2, 6-di-tert-butyl-4-nitrosophenol prepared in the step S1 in 5mol/L sodium hydroxide solution at normal temperature, mixing and stirring for 20min, adding a sulfur-containing reducing agent, heating to 45-55 ℃, carrying out heat preservation reaction for 2.0-2.5h, carrying out reduced pressure distillation, washing and suction filtration to obtain 2, 6-di-tert-butyl-4-aminophenol;
s3: preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution and an acetone solution of 2, 6-di-tert-butyl-4-aminophenol, then mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 1.5 to 3 hours, then carrying out vacuum filtration, and drying to obtain an intermediate I;
s4: preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I prepared in the step S3, anhydrous sodium acetate serving as a catalyst and acetic anhydride for a period of time to form a suspension, heating to 80 ℃, carrying out heat preservation reaction for 1-1.5h, washing for many times, carrying out suction filtration and drying to obtain an intermediate II;
s5: and dissolving the intermediate II in anhydrous methanol, adding a catalyst p-toluenesulfonic acid, carrying out reflux reaction for 6-8h, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl groups, thus obtaining the target product.
Preferably, in the step S1, the reaction molar ratio of the 2, 6-di-tert-butylphenol to the sodium nitrite is 1: 1.25-1.5.
Preferably, in the step S1, the mass concentration of the sodium nitrite solution is 25% to 40%.
Preferably, in the step S1, the molar concentration of the 2, 6-di-tert-butylphenol dissolved in 95% ethanol is 1.5-2.0 mol/L.
Preferably, in the step S1, the 38% concentrated hydrochloric acid is used in an amount of 1.6 to 2.4 times the molar amount of 2, 6-di-tert-butylphenol.
Preferably, in step S2, the sulfurous reducing agent is one of sodium dithionite, sodium thiosulfate or sodium sulfite, and the amount of the sulfurous reducing agent is 2.8 to 4 times of the molar amount of 2, 6-di-tert-butyl-4-nitrosophenol.
Preferably, in the step S2, the amount of the 5mol/L sodium hydroxide solution is 1.5 to 3.0 times of the molar amount of the 2, 6-di-tert-butylphenol.
Preferably, in the step S3, the molar concentration of the acetone solution of maleic anhydride is 1.8mol/L, the molar concentration of the acetone solution of 2, 6-di-tert-butyl-4-aminophenol is 0.86mol/L, and the reaction molar ratio of the maleic anhydride and the 2, 6-di-tert-butyl-4-aminophenol is 1.01-1: 1.
Preferably, in step S4, the addition amount of the anhydrous sodium acetate is 0.25 to 0.3 times of the molar amount of the intermediate I, and the addition amount of the acetic anhydride is 2.2 to 3 times of the molar amount of the intermediate I.
Preferably, in the step S5, the molar concentration of the intermediate II dissolved in the anhydrous methanol is 0.07-0.2 mol/L.
Has the advantages that: the invention provides a preparation method of a long-acting anti-aging material, which has the following advantages:
(1) the invention not only contains the maleic double bond of the active group which can react with the rubber macromolecule, but also can chemically react with the rubber in the vulcanization process, and is bonded in the rubber macromolecule network by the chemical bond, thus having the advantages of non-migration, non-volatilization and non-extraction; a phenolic hydroxyl group which has a rubber aging-inhibiting function, does not generate substances harmful to the human body, and easily traps R or ROO generated in an aging reaction-Thereby inhibiting free radical reaction and achieving the purpose of rubber aging.
(2) The maleimide group can generate maleimide free radical under the action of the free radical initiator, and the free radical can interact with rubber to form stable maleimide heat-resistant bond, so that the heat resistance of the rubber can be improved.
Drawings
FIG. 1 is a partial schematic diagram of the synthesis of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application.
The method for preparing the long-acting anti-aging material comprises the following steps:
s1: preparation of 2, 6-di-tert-butyl-4-nitrosophenol: under the protection of nitrogen, keeping the temperature at 20 ℃ under normal pressure, firstly dissolving 2, 6-di-tert-butylphenol in 95% ethanol, wherein the molar concentration is 2.0mol/L, then sequentially adding 38% concentrated hydrochloric acid and 30% sodium nitrite solution for reaction for 2.5h, wherein the reaction molar ratio of 2, 6-di-tert-butylphenol to sodium nitrite is 1:1.25, the use amount of 38% concentrated hydrochloric acid is 2 times of the molar amount of 2, 6-di-tert-butylphenol, filtering the reaction solution to obtain a filter cake, beating the filter cake into slurry by using 80 ℃ petroleum ether for 3 times of washing, and carrying out vacuum drying to obtain bright yellow solid, namely 2, 6-di-tert-butyl-4-nitrosophenol;
s2: preparation of 2, 6-di-tert-butyl-4-aminophenol: under the protection of nitrogen, dissolving pre-prepared 2, 6-di-tert-butyl-4-nitrosophenol in 5mol/L sodium hydroxide solution with the dosage of 2 times of the molar weight of 2, 6-di-tert-butylphenol at normal temperature, mixing and stirring for 20min, adding sodium hydrosulfite with the dosage of 3 times of the molar weight of 2, 6-di-tert-butyl-4-nitrosophenol, heating to 55 ℃, reacting for 2.0-2.5h under reduced pressure, distilling, washing and filtering to obtain 2, 6-di-tert-butyl-4-aminophenol.
S3: preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution and an acetone solution of 2, 6-di-tert-butyl-4-aminophenol, then mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 1.5 to 3 hours, then carrying out vacuum filtration, and drying to obtain an intermediate I;
s4: preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I prepared in the step S3, anhydrous sodium acetate serving as a catalyst and acetic anhydride for a period of time to form a suspension, heating to 80 ℃, carrying out heat preservation reaction for 1-1.5h, washing for many times, carrying out suction filtration and drying to obtain an intermediate II;
s5: and dissolving the intermediate II in anhydrous methanol, adding a catalyst p-toluenesulfonic acid, carrying out reflux reaction for 6-8h, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl groups, thus obtaining the target product.
In examples 1 to 3, 2, 6-di-tert-butyl-4-aminophenol was prepared by the steps of S1 and S2, and then used as a raw material for subsequent reactions to prepare maleimide containing phenolic hydroxyl groups, i.e., a long-acting anti-aging material, according to the synthetic reaction principle shown in fig. 1.
Example 1
Preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution with the molar concentration of 1.8mol/L and an acetone solution of 2, 6-di-tert-butyl-4-aminophenol with the molar concentration of 0.86mol/L, wherein the reaction molar ratio of maleic anhydride to 2, 6-di-tert-butyl-4-aminophenol is 1.01:1, then mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 1.5h, then carrying out vacuum filtration, and drying to obtain an intermediate I;
preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I, anhydrous sodium acetate as a catalyst and acetic anhydride to form a suspension, heating to 80 ℃, then carrying out heat preservation reaction for 1h, washing, filtering and drying for multiple times to obtain an intermediate II, wherein the addition amount of the anhydrous sodium acetate is 0.25 times of the molar weight of the intermediate I, and the addition amount of the acetic anhydride is 2.2 times of the molar weight of the intermediate I;
dissolving the intermediate II in anhydrous methanol, adding a catalyst p-toluenesulfonic acid for reflux reaction for 6 hours, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl.
Example 2
Preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution with the molar concentration of 1.8mol/L and an acetone solution with the molar concentration of 0.86 mol/L2, 6-di-tert-butyl-4-aminophenol, wherein the reaction molar ratio of maleic anhydride to 2, 6-di-tert-butyl-4-aminophenol is 1:1, mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 2 hours, then carrying out vacuum filtration, and drying to obtain an intermediate I;
preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I, anhydrous sodium acetate serving as a catalyst and acetic anhydride for a period of time to form a suspension, heating to 80 ℃, carrying out heat preservation reaction for 1.5 hours, washing, filtering and drying for multiple times to obtain an intermediate II, wherein the addition amount of the anhydrous sodium acetate is 0.28 times of the molar weight of the intermediate I, and the addition amount of the acetic anhydride is 2.5 times of the molar weight of the intermediate I;
dissolving the intermediate II in anhydrous methanol with the molar concentration of 0.1mol/L, adding a catalyst p-toluenesulfonic acid, refluxing and reacting for 8 hours, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl.
Example 3
Preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution with the molar concentration of 1.8mol/L and an acetone solution of 2, 6-di-tert-butyl-4-aminophenol with the molar concentration of 0.86mol/L, then mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 3 hours, then carrying out vacuum filtration, and drying to obtain an intermediate I, wherein the reaction molar ratio of the maleic anhydride to the 2, 6-di-tert-butyl-4-aminophenol is 1.01: 1;
preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I prepared in the step S3, anhydrous sodium acetate serving as a catalyst and acetic anhydride to form a suspension, heating to 80 ℃, carrying out heat preservation reaction for 1.5 hours, washing, filtering and drying for multiple times to obtain an intermediate II, wherein the addition amount of the anhydrous sodium acetate is 0.3 times of the molar weight of the intermediate I, and the addition amount of the acetic anhydride is 3 times of the molar weight of the intermediate I;
dissolving the intermediate II in anhydrous methanol with the molar concentration of 0.2mol/L, adding a catalyst p-toluenesulfonic acid, refluxing and reacting for 8 hours, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl.
The samples 1, 2, 3 and the anti-aging material 4020 were respectively compounded using NBR rubber compounding formula (sulfur vulcanization system) to obtain sample 1, sample 2, sample 3 and sample 4, and a blank control sample (sample 5) without the anti-aging material was prepared and the anti-aging property and mechanical property of the sample were respectively tested, and the test results are shown in Table 1
Table 1: test results of each sample on mechanical property and aging resistance of NBR rubber
The following conclusions can be drawn from the above experimental results:
1) regarding the mechanical properties: the mechanical properties of the vulcanized rubber of the samples 1 to 3 (added with maleimide containing phenolic hydroxyl) and the sample 4 (anti-aging material 4020) are relatively close. The tensile stress was slightly lower than that of the blank (sample 5), and the tensile strength and elongation at break were higher than those of the blank.
2) Regarding the aging resistance: the oil aging resistance, the wet heat aging resistance and the hot air aging resistance of the samples 1 to 3 (to which maleimide containing a phenolic hydroxyl group is added) are all superior to those of the sample 4 (the anti-aging material 4020) and the sample 5 (the blank comparative sample). The maleimide containing phenolic hydroxyl contains maleic double bond, and can react with rubber molecules, so that molecules of the anti-aging material are bonded in a rubber macromolecular network, and are prevented from being extracted by oiling, and the mechanical property of vulcanized rubber after aging is ensured. The aging resistant material 4020 is very easily extracted by oils of ASTM3# having similar polarity. In addition, the phenolic hydroxyl group in the application does not generate substances harmful to human bodies, and easily captures R & or ROO & lt- & gt generated in the aging reaction, thereby inhibiting the free radical reaction and achieving the purpose of rubber aging.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a long-acting anti-aging material is characterized by comprising the following specific preparation processes:
s1 preparation of 2, 6-di-tert-butyl-4-nitrosophenol: under the protection of nitrogen, keeping the temperature at 15-20 ℃ under normal pressure, firstly dissolving 2, 6-di-tert-butylphenol in 95% ethanol, then sequentially adding 38% concentrated hydrochloric acid and sodium nitrite solution for reaction for 2.0-2.5h, filtering the reaction solution to obtain a filter cake, pulping the filter cake into slurry by using petroleum ether at 60-90 ℃, washing for multiple times, and drying in vacuum to obtain a bright yellow solid, namely 2, 6-di-tert-butyl-4-nitrosophenol;
s2: preparation of 2, 6-di-tert-butyl-4-aminophenol: under the protection of nitrogen, dissolving the 2, 6-di-tert-butyl-4-nitrosophenol prepared in the step S1 in 5mol/L sodium hydroxide solution at normal temperature, mixing and stirring for 20min, adding a sulfur-containing reducing agent, heating to 45-55 ℃, carrying out heat preservation reaction for 2.0-2.5h, carrying out reduced pressure distillation, washing and suction filtration to obtain 2, 6-di-tert-butyl-4-aminophenol;
s3: preparation of intermediate I: under the protection of nitrogen and at normal temperature and normal pressure, respectively preparing a maleic anhydride acetone solution and an acetone solution of 2, 6-di-tert-butyl-4-aminophenol, then mixing and stirring the maleic anhydride acetone solution and the acetone solution of 2, 6-di-tert-butyl-4-aminophenol for reaction for 1.5 to 3 hours, then carrying out vacuum filtration, and drying to obtain an intermediate I;
s4: preparation of intermediate II: under the protection of nitrogen and at normal temperature and normal pressure, mixing and stirring the intermediate I prepared in the step S3, anhydrous sodium acetate serving as a catalyst and acetic anhydride for a period of time to form a suspension, heating to 80 ℃, carrying out heat preservation reaction for 1-1.5h, washing for many times, carrying out suction filtration and drying to obtain an intermediate II;
s5: and dissolving the intermediate II in anhydrous methanol, adding a catalyst p-toluenesulfonic acid, carrying out reflux reaction for 6-8h, distilling off a methanol/methyl acetate azeotrope at normal pressure, and recrystallizing in isopropanol to obtain the maleimide containing phenolic hydroxyl, namely the target product.
2. The method for preparing a long-acting anti-aging material according to claim 1, wherein in the step S1, the reaction molar ratio of the 2, 6-di-tert-butylphenol to the sodium nitrite is 1: 1.25-1.5.
3. The method for preparing a long-acting anti-aging material according to claim 1, wherein in the step S1, the mass concentration of the sodium nitrite solution is 25% to 40%.
4. The method for preparing a long-acting anti-aging material according to claim 1, wherein in the step S1, the molar concentration of 2, 6-di-tert-butylphenol dissolved in 95% ethanol is 1.5 to 2.0 mol/L.
5. The method for preparing a long-acting anti-aging material according to claim 1, wherein in the step S1, the 38% concentrated hydrochloric acid is used in an amount of 1.6 to 2.4 times the molar amount of 2, 6-di-tert-butylphenol.
6. The method for preparing a long-acting anti-aging material according to claim 1, wherein in step S2, the sulfur-containing reducing agent is one of sodium dithionite, sodium thiosulfate or sodium sulfite, and the amount of the sulfur-containing reducing agent is 2.8 to 4 times of the molar amount of 2, 6-di-tert-butyl-4-nitrosophenol.
7. The method for preparing a long-acting anti-aging material according to claim 1, wherein in the step S2, the amount of the 5mol/L sodium hydroxide solution is 1.5 to 3.0 times of the molar amount of the 2, 6-di-tert-butylphenol.
8. The method for preparing the long-acting anti-aging material according to claim 1, wherein in the step S3, the molar concentration of the acetone solution of maleic anhydride is 1.8mol/L, the molar concentration of the acetone solution of 2, 6-di-tert-butyl-4-aminophenol is 0.86mol/L, and the reaction molar ratio of the maleic anhydride to the 2, 6-di-tert-butyl-4-aminophenol is 1.01-1: 1.
9. The method for preparing a long-acting anti-aging material according to claim 1, wherein in step S4, the anhydrous sodium acetate is added in an amount of 0.25 to 0.3 times the molar amount of intermediate I, and the acetic anhydride is added in an amount of 2.2 to 3 times the molar amount of intermediate I.
10. The method for preparing the long-acting anti-aging material according to claim 1, wherein in the step S5, the molar concentration of the intermediate II dissolved in the anhydrous methanol is 0.07-0.2 mol/L.
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