CN112341372B - Reactive anti-aging agent without extraction and preparation method thereof - Google Patents
Reactive anti-aging agent without extraction and preparation method thereof Download PDFInfo
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- CN112341372B CN112341372B CN202011252289.8A CN202011252289A CN112341372B CN 112341372 B CN112341372 B CN 112341372B CN 202011252289 A CN202011252289 A CN 202011252289A CN 112341372 B CN112341372 B CN 112341372B
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- 229920001971 elastomer Polymers 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009257 reactivity Effects 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 6
- ORAWSPLOJLYSOQ-UHFFFAOYSA-N 3-hydroxynaphthalene-1-carbohydrazide Chemical compound C1=CC=C2C(C(=O)NN)=CC(O)=CC2=C1 ORAWSPLOJLYSOQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 23
- 230000003078 antioxidant effect Effects 0.000 abstract description 9
- 238000004040 coloring Methods 0.000 abstract description 4
- 150000004780 naphthols Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 238000013341 scale-up Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000004636 vulcanized rubber Substances 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003254 radicals Chemical group 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 amine free radical Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OACGSLLKFCMXSX-UHFFFAOYSA-N 3-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC(O)=C1 OACGSLLKFCMXSX-UHFFFAOYSA-N 0.000 description 1
- FDNAQCWUERCJBK-UHFFFAOYSA-N 3-hydroxynaphthalene-2-carbohydrazide Chemical compound C1=CC=C2C=C(O)C(C(=O)NN)=CC2=C1 FDNAQCWUERCJBK-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZMZGIVVRBMFZSG-UHFFFAOYSA-N 4-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=C(O)C=C1 ZMZGIVVRBMFZSG-UHFFFAOYSA-N 0.000 description 1
- SDYWVFWTKNGYJW-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carbohydrazide Chemical compound C1=C(O)C=CC2=CC(C(=O)NN)=CC=C21 SDYWVFWTKNGYJW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/50—Nitrogen atoms
-
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application belongs to the technical field of rubber products, and particularly relates to a rubber and an anti-aging agent with anti-aging reactivity for the rubber product, and a preparation method thereof. The anti-aging agent is prepared from naphthol derivatives and/or phenol derivatives and maleic anhydride and/or derivatives thereof through dehydration condensation reaction. The antioxidant product provided by the application is light yellow, has no coloring pollution, can be used for dark and light rubber products, and has a wide application range. Compared with the conventional anti-aging agent 4020, the film applying the anti-aging agent disclosed by the application is far better than the existing product in the aspects of index performances such as tensile strength, elongation at break and the like, and has a better application prospect. On the other hand, the synthesis and preparation method of the anti-aging agent product provided by the application is relatively simple, the reaction condition is mild, the product is easy to separate, and the anti-aging agent is suitable for industrial scale-up production.
Description
Technical Field
The application belongs to the technical field of rubber products, and particularly relates to a rubber and an anti-aging agent with anti-aging reactivity for the rubber product, and a preparation method thereof.
Background
In the daily use process of high polymer products such as rubber, plastics and the like, the high polymer chains are broken due to the influence of external light, heat, oxygen, water and the like, and free radical fragments generated by the chain breakage further induce the generation of free radical chain reaction, further damage to the composition and the structure of the rubber, finally the mechanical properties of the high polymer products are reduced, and ageing phenomena such as discoloration, stickiness, hardness change, cracks and the like occur. Therefore, in order to overcome the aging process, an appropriate amount of anti-aging agent capable of eliminating free radicals is generally added in the preparation process of high polymer products such as rubber, plastic and the like, so that the aging process of the rubber is inhibited, and the service life of the rubber is prolonged.
In the prior art, the most widely used macromolecular anti-aging agents are hindered amine anti-aging agents and hindered phenol anti-aging agents. Hindered amine type antioxidants have remarkable anti-aging effects, for example, p-phenylenediamine type antioxidants are widely used in tire production with their best protective properties, but amine type antioxidants are darker in color and have coloring contamination properties, and thus cannot be used for white and light-colored rubber products. In addition, some amine antioxidants have the defects of low melting point, easy volatilization and easy diffusion and migration from the inside of the polymer to the surface, and finally the anti-aging effect is reduced and the long-acting property is lacking. The phenolic antioxidant has the characteristics of no color change, no pollution and no frosting, so the phenolic antioxidant is pollution-free, but partial phenolic antioxidant has small molar mass, and has the problems of strong volatility and the like. In summary, although amine antioxidants and phenol antioxidants have advantages, one common disadvantage of both antioxidants is that they have certain volatility, which results in unavoidable extraction during use of high molecular products such as rubber, and thus causes problems of escape of the antioxidants and environmental pollution.
In the existing research, the development and research of the reactive anti-aging agent is a research hotspot, and one of main development ideas of the anti-aging agent is to introduce functional groups with polymerization functions such as double bonds and the like into the anti-aging agent, so that the anti-aging agent can be directly combined on a rubber molecular network in the mixing and high-temperature vulcanization processes of rubber, thereby having the advantages of no migration, no volatilization and no extraction, and further having the characteristics of pollution prevention and long-acting protection and aging.
Combines the development trend of the existing reactive anti-aging agent and the respective advantages of the amine anti-aging agent and the phenol anti-aging agent, if a new anti-aging agent which contains hindered phenol and hindered amine free radical elimination functional units and has the characteristic of reactivity can be developed, the anti-aging agent has very important application value for improving the anti-aging performance of rubber and products thereof.
Disclosure of Invention
The application aims to provide a method for improving the anti-aging performance of a related rubber product by not extracting an anti-aging agent from the reactivity.
The technical scheme adopted by the application is detailed as follows.
The reactive non-extraction anti-aging agent is prepared from naphthol derivatives (and/or phenol derivatives) and maleic anhydride and/or derivatives thereof through dehydration condensation reaction, and specifically comprises the following preparation steps:
firstly, preparing materials
Raw material A: the naphthol derivative and/or phenol derivative specifically include, for example: 3-hydroxy-2-naphthoyl hydrazine, 5-hydroxy-2-naphthoyl hydrazine, 6-hydroxy-2-naphthoyl hydrazine, o-hydroxybenzoyl hydrazine, p-hydroxybenzoyl hydrazine, m-hydroxybenzoyl hydrazine, etc. containing a naphthol group;
raw material B: maleic anhydride (maleic anhydride) and/or maleic anhydride derivatives, which are derivatives containing maleic anhydride structural units, specifically exemplified by: methyl maleic anhydride (citraconic anhydride), 2-methylenedibutyl anhydride (itaconic anhydride), dimethyl maleic anhydride, and the like;
solvent C: chloroform or ethyl acetate;
catalyst D: p-toluene sulfonic acid;
solvent E: toluene, cyclohexane or ethanol;
(II) preparation of intermediate acid
Using a solvent C (chloroform or ethyl acetate) as a solvent to enable the raw materials A and B to react to generate intermediate acid F; the specific material consumption and operation are as follows:
adding 20g of raw material A into 50-500 mL of solvent C, stirring at room temperature for 0.5-5 h to ensure sufficient dissolution, then dripping a solution of raw material B (the raw material B is dissolved in the solvent C in advance), stirring at room temperature (the room temperature range is 0-25 ℃), reacting for 1-15 h, filtering, washing with absolute ethyl alcohol for three times, and vacuum drying to obtain a white solid which is intermediate acid F;
raw material A: raw material b=1: (0.5-5);
(III) dehydrating and closing ring to generate target product
Taking a catalyst D (p-toluenesulfonic acid) as a catalyst, and taking a solvent E (toluene, cyclohexane or ethanol) as a solvent to carry out dehydration ring-closure reaction on the intermediate acid F prepared in the step (II), and finally preparing and generating a target product; the specific material consumption and operation are as follows:
taking 5-20 g of the intermediate acid F prepared in the step (II), adding 50-300 ml of a solvent E and 0.05-5 g of a catalyst D (p-toluenesulfonic acid), carrying out reflux reaction for 1-12 h at 75-140 ℃, cooling to room temperature after the reaction is finished, dropwise adding a proper amount of distilled water until the solution becomes turbid, standing for 1-24 h to precipitate crystals, carrying out suction filtration, washing with distilled water to obtain a crude product, carrying out vacuum drying, and then carrying out ethanol recrystallization for purification to obtain a light yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The prepared anti-aging agent with reactivity is applied in the preparation process of rubber products and is used as an anti-aging agent, and the anti-aging agent has a strong absorption peak between 250nm and 400nm and has strong ultraviolet absorption capacity.
Regarding a specific molecular structure, the anti-aging agent provided by the application has the following structural characteristics:
(1) The molecule of the anti-aging agent contains naphthol or phenol groups, and the adjacent (or intermediate or para) position of the phenolic hydroxyl group is modified with substituent groups with larger flexibility, so that the anti-aging agent has the functional characteristics of hindered phenol anti-aging agents;
(2) The anti-aging agent also contains a hydrazide unit, and active hydrogen exists on a hydrazide bond, so the anti-aging agent also has the characteristic of hindered amine anti-aging agents;
(3) Because the antioxidant contains the difunctional groups of hindered phenol and hindered amine, the capturing mechanism of the difunctional groups of free radicals can capture carbon free radicals in rubber products, and the generation of peroxy free radicals and hydroperoxides is controlled, which is equivalent to adding an anti-aging and anti-aging line;
(4) The maleic anhydride skeleton in the anti-aging agent contains double bonds, so that the anti-aging agent can chemically react with rubber macromolecules in the vulcanization process, and further is bonded in a rubber macromolecule network through compound bonds, thereby having the characteristics of non-migration, non-volatilization and non-extraction, and finally achieving the purpose of prolonging the service life of rubber.
Generally, the antioxidant product provided by the application is light yellow, has no coloring pollution, can be used in dark and light rubber products, and has a wide application range. Compared with the conventional anti-aging agent 4020, the film applying the anti-aging agent disclosed by the application is far better than the existing product in the aspects of index performances such as tensile strength, elongation at break and the like, and has a better application prospect. On the other hand, the synthesis and preparation method of the anti-aging agent product provided by the application is relatively simple, the reaction condition is mild, the product is easy to separate, and the anti-aging agent is suitable for industrial scale-up production. On the other hand, in the preparation process, the purity requirement of the relevant reaction raw materials is low, the relevant reaction reagents are easy to recycle, the environment pollution is avoided, and the method has good industrialized application prospect.
Drawings
FIG. 1 is a mass spectrum of an anti-aging agent prepared in example 1;
FIG. 2 is a mass spectrum of the anti-aging agent prepared in example 2;
FIG. 3 is a mass spectrum of the anti-aging agent prepared in example 3;
FIG. 4 is a nuclear magnetic resonance spectrum of the anti-aging agent prepared in example 2;
FIG. 5 is a plot of tensile strength change of NR vulcanizates with different antioxidants (1.5:100 addition);
FIG. 6 is a plot of the elongation at break of NR vulcanizates of different antioxidants (1.5:100 ratio addition);
FIG. 7 is a plot of tensile strength change of NR vulcanizates with different antioxidants (1:100 ratio addition);
FIG. 8 is a plot of elongation at break change for NR vulcanizates with different antioxidants (1:100 ratio addition);
FIG. 9 is a vulcanized aged rubber (left: NR vulcanized rubber, right: NR vulcanized rubber after the addition of the anti-aging agent of test example 2);
FIG. 10 ultraviolet absorption spectrum of antioxidant (left: example 1, right: example 2).
Detailed Description
The technical scheme of the application is further explained below by combining examples.
Example 1
The reactivity provided in this example was obtained without extracting the anti-aging agent, specifically by the following steps.
Firstly, preparing materials
Raw material A: is 3-hydroxy-2-naphthoyl hydrazide containing naphthol group,
raw material B: maleic anhydride (maleic anhydride);
solvent C: ethyl acetate;
catalyst D: p-toluene sulfonic acid;
solvent E: toluene;
(II) preparation of intermediate acid
Taking a solvent C (ethyl acetate) as a solvent, and enabling a raw material A and a raw material B to react to generate intermediate acid F; the specific material consumption and operation are as follows:
adding 5g of raw material A into 45mL of solvent C, stirring at room temperature to form a suspension, then dropwise adding a solution of raw material B (5 mL of ethyl acetate is used for dissolving 2.94 g maleic anhydride in advance), reacting for 10h under stirring at room temperature after the dropwise adding is completed within 1 hour, filtering the solution after the reaction is completed, washing a filter cake with absolute ethyl alcohol for three times, and vacuum drying to obtain a white solid which is intermediate acid F;
raw material A (3-hydroxy-2-naphthoyl hydrazide) by mole ratio: raw material B (maleic anhydride) =1: 1.2;
(III) dehydrating and closing ring to generate target product
Taking a catalyst D (toluene sulfonic acid) as a catalyst, and taking a solvent E (toluene) as a solvent to carry out dehydration ring-closure reaction on the intermediate acid F prepared in the step (II), and finally preparing and generating a target product; the specific material consumption and operation are as follows:
in a three-neck flask with a reflux device, taking 5g of intermediate acid F prepared in the step (II), adding 100ml of solvent E and 0.5g of catalyst D (p-toluenesulfonic acid), heating gradually, carrying out reflux reaction at 115 ℃ for 10 hours, cooling to room temperature after the reaction is finished, dropwise adding 5-20 ml of distilled water until the solution becomes turbid, standing for 24 hours to precipitate a large amount of crystals, carrying out suction filtration, washing a filter cake with distilled water for three times to obtain a crude product, further carrying out vacuum drying, and then carrying out recrystallization with ethanol for purification to obtain a light yellow solid, namely a purified target product (the reaction does not extract an anti-aging agent).
Ethyl acetate and toluene in the reaction process can be recycled through simple distillation.
As shown in FIG. 1, the ESI-MS (positive) mass spectrum of the target product shows that the position of M/z=283 is [ M+H ]] + Is [ M+Na ] at M/z= 304.9] + Ion peak, at M/z= 320.9, [ m+k ]] + Is [ M+MeOH+Na ] at M/z=336.9] + The excimer ion peak of (2) is [ M+MeOH+K ] at M/z=336.9] + Is an excimer ion peak of (a). Mass spectrometry was in complete agreement with the theoretical calculated molecular weight 282 of the target product M.
Final calculations and measurements showed 87% yield, melting point of the product: 213.3-216.1 ℃, and the specific product has the following structural formula:
。
example 2
The preparation process of the reactive non-extraction antioxidant provided in this example is the same as that of example 1, and only some of the operating parameters are adjusted as follows:
in the step (one):
raw material A: is 3-hydroxy-2-naphthoyl hydrazide containing naphthol group,
raw material B: citraconic anhydride;
solvent C: chloroform;
catalyst D: p-toluene sulfonic acid;
solvent E: cyclohexane;
in the step (two):
adding 20g of raw material A into 150mL of solvent C (chloroform), stirring at room temperature to form a suspension, then dropwise adding a solution of raw material B (24.9 g of citraconic anhydride is dissolved by 20mL of chloroform in advance), reacting for 5h under stirring at room temperature after the dropwise addition is completed within 1 hour, obtaining a white suspension after the reaction is completed, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol for three times, and carrying out vacuum drying to obtain a white solid, namely intermediate acid F;
raw material A (3-hydroxy-2-naphthoyl hydrazide) by mole ratio: raw material B (citraconic anhydride) =1: 2.3;
in the step (III):
taking 20g of intermediate acid F prepared in the step (II), adding 300ml of solvent E and 2.0g of catalyst D (p-toluenesulfonic acid), heating gradually, refluxing at 85 ℃ for reaction for 10 hours, cooling to room temperature after the reaction is finished, dripping 20-60 ml of distilled water until the solution becomes turbid, standing for 24 hours to precipitate a large amount of crystals, filtering, washing a filter cake with distilled water for three times to obtain a crude product, further vacuum drying, and purifying by ethanol recrystallization to obtain a light yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The ESI-MS (negative) spectrum of the target product is shown in FIG. 2, and mass spectrometry shows that M-H is found at M/z=294.8 + The negative ion peak, mass spectrum analysis is completely consistent with the theoretical calculated molecular weight 296 of the target product M.
The nuclear magnetic resonance spectrum is shown in figure 4. Specifically: 1H NMR (400 MHz, DMSO-d 6): delta 2.200-2.205 (m, 3H, -CH 3), 6.548-6.552 (s, 1H, hydrogen on anhydride double bond), 7.250-7.299 (s, 1H, hydrogen on carbon at position 7 of naphthalene ring), 7.320-7.358 (m, 1H, hydrogen on carbon at position 6 of naphthalene ring), 7.494-7.530 (m, 1H, hydrogen on carbon at position 8 of naphthalene ring), 7.666-7.687 (m, 1H, hydrogen on carbon at position 5 of naphthalene ring), 7.738-7.758 (m, 1H, hydrogen on carbon at position 1 of naphthalene ring), 8.186 (s, 1H, hydrogen on carbon at position 4 of naphthalene ring), 8.343 (s, 1H, -NH-), 10.048 (s, 1H, -OH).
Final calculations and measurements showed 91% yield, melting point of the product: the specific structural formula of the product is as follows:
。
example 3
The preparation process of the reactive non-extraction antioxidant provided in this example is the same as that of example 1, and only some of the operating parameters are adjusted as follows:
in the step (one):
raw material A: is o-hydroxybenzohydrazide containing phenol group,
raw material B: citraconic anhydride;
solvent C: ethyl acetate;
catalyst D: p-toluene sulfonic acid;
solvent E: ethanol;
in the step (two):
adding 5g of raw material A into 100mL of ethyl acetate C (chloroform), stirring at room temperature to form a suspension, then dropwise adding a solution of raw material B (5.53 g of citraconic anhydride is dissolved by 20mL of ethyl acetate in advance), reacting for 3h under stirring at room temperature after the completion of the dropwise addition within 1 hour, filtering the solution to form a white suspension after the completion of the reaction, washing a filter cake with ethyl acetate for three times, and drying in vacuum to obtain a white solid which is intermediate acid F;
raw material a (o-hydroxybenzohydrazide) in molar ratio: raw material B (citraconic anhydride) =1: 1.5;
in the step (III):
taking 5g of intermediate acid F prepared in the step (II), adding 80ml of solvent E and 0.5g of catalyst D (p-toluenesulfonic acid), gradually heating, refluxing at 80 ℃ for reaction for 5h, distilling off about 50ml of solvent, supplementing 50ml of absolute ethyl alcohol, continuing to react for 3h, cooling to room temperature after the reaction is finished, dropwise adding 10-30 ml of distilled water until the solution becomes turbid, standing for 24h to precipitate a large amount of crystals, filtering, washing a filter cake with distilled water for three times to obtain a crude product, further vacuum drying, and recrystallizing with ethanol for purification to obtain a pale yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The ESI-MS (positive) spectrum of the target product is shown in FIG. 3, and mass spectrometry shows that the target product is [ M+Na ] at M/z=269.0] + Is [ M+K ] at M/z=285.0] + Is [ M+MeOH+Na ] at M/z=301.0] + The mass spectrometry analysis is completely consistent with the theoretical calculated molecular weight 246 of the target product M.
Final calculations and measurements showed 85% yield, melting point of the product: the specific structural formula of the product is as follows at 75.5-76.2 ℃:
。
experimental example 1
Using the anti-aging agents prepared in examples 1 and 2, the inventors further conducted an anti-aging test of natural rubber, and the detailed experimental procedure was outlined below.
Experiment design:
according to the mass ratio m (anti-aging agent): m (natural latex) =1.5: 100 proportion, weighing an anti-aging agent, adding the anti-aging agent into natural latex, coating the latex which is uniformly mixed on a template, and vulcanizing for 2.5 hours at 80 ℃;
the molded film had a width of 6mm and a thickness of 1.10.+ -. 0.10 mm, and was subjected to an experiment in a thermo-oxidative aging oven, and aged at 60℃for 24, 48 and 72h, respectively, to test the tensile strength and elongation at break after aging.
The anti-aging agents prepared in example 1 and example 2 (corresponding to test example 1 and test example 2 respectively) are selected respectively, meanwhile 4020 anti-aging agents in the prior art are adopted as a control, and in the specific preparation process, siO with the same proportion is added into each experimental group 2 The catalyst comprises a coupling agent Si69, an accelerator CZ, an accelerator D, stearic acid, zinc oxide and other improvers. The specific dosage ratios are shown in the following table:
raw material consumption ratio for anti-aging experiment
The specific tensile strength and elongation at break measurement results are shown in fig. 5 and 6. As can be seen by comparison, the NR vulcanized rubber added with the anti-aging agent is larger than the NR vulcanized rubber without the anti-aging agent in both tensile strength and elongation at break before aging and is also larger than the NR vulcanized rubber added with the 4020 anti-aging agent. The tensile property of the vulcanized rubber is reduced along with the aging time, but after the NR vulcanized rubber added with the anti-aging agent is aged for 72 hours, the tensile strength and the stretch-breaking elongation of the NR vulcanized rubber are still larger than those of the NR vulcanized rubber aged for 72 hours. Wherein the improvement effect of the example 2 on the related index is more remarkable, and the elongation at break of the rubber sheet adopting the example 2 still reaches 2 times of that of NR vulcanized rubber after aging for 72 hours.
Experimental example 2
Using the antioxidants prepared in examples 2 and 3, further an anti-aging test of natural rubber (corresponding to test example 3 and test example 4, respectively) was performed, and the specific experimental design was as in experiment example 1, changing only the addition amount of the antioxidant to: according to the mass ratio m (anti-aging agent): m (natural latex) =1: 100 ratio. Other experimental conditions were exactly the same as in experimental example 1.
The specific tensile strength and elongation at break measurement results are shown in fig. 7 and 8. The comparison shows that although the addition amount of the anti-aging agent synthesized in the embodiment 2 is reduced, the related index of the NR vulcanized rubber added with the anti-aging agent is still improved obviously. The NR vulcanized rubber added with the anti-aging agent synthesized in example 3 still has better tensile strength and elongation at break than the NR vulcanized rubber added with the 4020 anti-aging agent, but is not as good as the anti-aging agent synthesized in example 2.
The antioxidant provided by the application is light yellow, no coloring pollution is caused after the natural rubber is added for vulcanization, and FIG. 9 shows that the NR vulcanized rubber prepared by adding the antioxidant prepared in the example 2 is aged for 72 hours, and the color of the vulcanized rubber is not changed obviously. Further, the ultraviolet absorption spectra of the antioxidants prepared in example 1 and example 2 were measured (using acetonitrile as a solvent and measured on an ultraviolet spectrometer), and the results are shown in fig. 10. It can be seen that the prepared anti-aging agent has three strong absorption peaks between 250nm and 400nm, namely 303nm, 348nm and 376nm respectively, and has strong absorption to ultraviolet light, which lays a foundation for the anti-aging performance of the anti-aging agent.
Claims (5)
1. A reactive non-extraction anti-aging agent, wherein the anti-aging agent is selected from the group consisting of:
anti-aging agent 1:；
anti-aging agent 2:；
anti-aging agent 3:。
2. the method for preparing the reactive non-extraction anti-aging agent according to claim 1, which is characterized by comprising the following preparation steps:
firstly, preparing materials
When the anti-aging agent 1 is prepared, 3-hydroxy-2-naphthoyl hydrazide containing naphthol groups is taken as a raw material A, maleic anhydride is taken as a raw material B, ethyl acetate is taken as a solvent C, p-toluenesulfonic acid is taken as a catalyst D, and toluene is taken as a solvent E;
when the anti-aging agent 2 is prepared, 3-hydroxy-2-naphthoyl hydrazide containing naphthol groups is taken as a raw material A, 2-methyl maleic anhydride is taken as a raw material B, chloroform is taken as a solvent C, p-toluenesulfonic acid is taken as a catalyst D, and cyclohexane is taken as a solvent E;
when the anti-aging agent 3 is prepared, the o-hydroxybenzohydrazide containing a phenol group is taken as a raw material A, 2-methyl maleic anhydride is taken as a raw material B, ethyl acetate is taken as a solvent C, p-toluenesulfonic acid is taken as a catalyst D, and ethanol is taken as a solvent E;
(II) preparation of intermediate acid
Taking the solvent C as a solvent to enable the raw materials A and B to react to generate intermediate acid F; the specific material consumption and operation are as follows:
adding 20g of raw material A into 50-500 mL of solvent C, fully dissolving, adding raw material B dissolved in the solvent C in advance, and reacting for 1-15 h at room temperature;
raw material A: raw material b=1: 0.5-5;
(III) dehydrating and closing ring to generate target product
Taking the catalyst D as a catalyst and the solvent E as a solvent, and carrying out dehydration ring-closure reaction on the intermediate acid F prepared in the step (II) to finally prepare and generate a target product; the specific material consumption and operation are as follows:
and (2) taking 5-20 g of the intermediate acid F prepared in the step (II), adding 50-300 ml of the solvent E and 0.05-5 g of the catalyst D, and carrying out reflux reaction at 75-140 ℃ for 1-12 h.
3. The method for producing an anti-aging agent having no extraction of reactivity according to claim 2, wherein in step (three), after the completion of the dehydration ring-closure reaction, cooling to room temperature, adding distilled water until the solution becomes turbid, standing for 1 to 24 hours to precipitate crystals, suction-filtering, washing with distilled water to obtain a crude product, further vacuum-drying, and then recrystallizing with ethanol for purification.
4. The use of a reactive non-extractable anti-aging agent according to claim 1 in the preparation of rubber articles, characterized in that it is used as an anti-aging agent.
5. The use according to claim 4 for NR natural rubber.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068356A (en) * | 1990-02-20 | 1991-11-26 | Atochem North America, Inc. | Hindered phenolic n-(amido)imides |
| CN102775341A (en) * | 2011-05-12 | 2012-11-14 | 咸阳三精科工贸有限公司 | Composition of N-4(anilinophenyl)maleimide and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068356A (en) * | 1990-02-20 | 1991-11-26 | Atochem North America, Inc. | Hindered phenolic n-(amido)imides |
| CN102775341A (en) * | 2011-05-12 | 2012-11-14 | 咸阳三精科工贸有限公司 | Composition of N-4(anilinophenyl)maleimide and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "A Rational Design, Synthesis, Biological Evaluation and Structure-Activity Relationship Study of Novel Inhibitors against Cyanobacterial Fructose-1,6-bisphosphate Aldolase";Xinya Han等;《J. Chem. Inf. Model.》;第56卷;第73-81页 * |
| 刘庆俭编著.《有机化学（下册）》.同济大学出版社,2018,第202页. * |
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