CN112341372A - Reactive non-extraction anti-aging agent and preparation method thereof - Google Patents
Reactive non-extraction anti-aging agent and preparation method thereof Download PDFInfo
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- CN112341372A CN112341372A CN202011252289.8A CN202011252289A CN112341372A CN 112341372 A CN112341372 A CN 112341372A CN 202011252289 A CN202011252289 A CN 202011252289A CN 112341372 A CN112341372 A CN 112341372A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000605 extraction Methods 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
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- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
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- 239000002253 acid Substances 0.000 claims description 22
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- 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 claims description 7
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- 238000000034 method Methods 0.000 claims description 6
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 claims description 5
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- 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 claims 2
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
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- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 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
- C07D207/46—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
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of rubber products, and particularly relates to a rubber and a reactive non-extraction anti-aging agent for anti-aging of the rubber and products thereof, and a preparation method and application 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 anti-aging agent product provided by the invention is light yellow, has no coloring pollution, can be used in rubber products with deep color and light color, and has wide application range. The comparison of the application effect of the anti-aging agent 4020 with the conventional anti-aging agent shows that the film using the anti-aging agent is far superior to the existing product in the index performances such as tensile strength, elongation at break and the like, and shows better application prospect. On the other hand, the synthesis and preparation method of the antioxidant product is relatively simple, mild in reaction conditions, easy to separate, and suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of rubber products, and particularly relates to a rubber and a reactive non-extraction anti-aging agent for anti-aging of the rubber and products thereof, and a preparation method and application thereof.
Background
In the daily use process of polymer products such as rubber, plastic and the like, the breakage of a polymer chain can be caused under the influence of factors such as external light, heat, oxygen, water and the like, and free radical fragments generated by the breakage of the chain can further induce the generation of free radical chain type reaction, so that the composition and the structure of the rubber are further damaged, and finally, the mechanical property of the polymer products is reduced, and aging phenomena such as discoloration, stickiness, hardening, cracks and the like are caused. Therefore, to overcome the aging process, an appropriate amount of an anti-aging agent capable of eliminating free radicals is usually added in the preparation process of high polymer products such as rubber, plastics and the like so as to inhibit the aging process of the rubber and prolong the service life of the rubber.
In the prior art, the most widely used macromolecule anti-aging agents are hindered amine anti-aging agents and hindered phenol anti-aging agents. Hindered amine antioxidants have outstanding anti-aging effects, for example, para-phenylenediamine antioxidants are widely used in tire production for their optimal protective properties, but amine antioxidants are dark in color and have color pollution, and thus cannot be used for white and light-colored rubber products. In addition, part of the amine anti-aging agents have the defects of low melting point, easy volatilization and easy diffusion and migration from the interior of the polymer to the surface, and finally, the anti-aging effect is reduced and the long-term effect is lacked. The phenol anti-aging agent has the characteristics of no color change, no pollution and no blooming, so the phenol anti-aging agent is a pollution-free anti-aging agent, but has the problems of small molar mass, strong volatility and the like of part of the phenol anti-aging agent. In summary, although amine antioxidants and phenol antioxidants have advantages, the common disadvantage of the two antioxidants is that both have certain volatility, and therefore, the antioxidants are inevitably extracted during the use of high molecular products such as rubber, and the antioxidants escape and pollute the environment.
In the existing research, the development and research of the reactive antioxidant is a research hotspot, one of the main research and development ideas of the antioxidant is to introduce functional groups with polymerization function, such as double bonds and the like, into the antioxidant so that the antioxidant 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-term protection and aging.
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 are combined, for example, a new anti-aging agent which simultaneously contains hindered phenol and hindered amine free radical elimination functional units and has the characteristic of reactivity can be developed, and 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 the reactive antioxidant without extraction, thereby laying a certain technical foundation for improving the anti-aging performance of related rubber products.
The technical solution adopted in the present application is detailed as follows.
A reactive non-extraction anti-aging agent is prepared by a dehydration condensation reaction of a naphthol derivative (and/or a phenol derivative) and maleic anhydride and/or a derivative thereof, and specifically comprises the following preparation steps:
(I) preparing materials
Raw material A: the naphthol derivatives and/or the phenol derivatives are, for example: 3-hydroxy-2-naphthoyl hydrazide containing naphthol group, 5-hydroxy-2-naphthoyl hydrazide, 6-hydroxy-2-naphthoyl hydrazide, o-hydroxybenzoyl hydrazide containing phenol group, p-hydroxybenzoyl hydrazide, m-hydroxybenzoyl hydrazide and the like;
raw material B: maleic anhydride (maleic anhydride) and/or maleic anhydride derivatives, wherein the maleic anhydride derivatives are derivatives containing maleic anhydride structural units, and specific examples are as follows: methyl maleic anhydride (citraconic anhydride), 2-methylenedibutanoic anhydride (itaconic anhydride), dimethylmaleic anhydride, and the like;
solvent C: chloroform or ethyl acetate;
catalyst D: p-toluenesulfonic acid;
solvent E: toluene, cyclohexane or ethanol;
(II) preparation of intermediate acid
Using a solvent C (chloroform or ethyl acetate) as a solvent, and reacting the raw materials A and B to generate an intermediate acid F; specific material usage and operation:
adding 20g of the raw material A into 50-500 mL of the solvent C, stirring at room temperature for 0.5-5 h to ensure full dissolution, then dropwise adding a dissolving solution of the raw material B (the raw material B is dissolved by the solvent C in advance), stirring at room temperature (the room temperature is 0-25 ℃), reacting for 1-15 h, performing suction filtration, washing with absolute ethyl alcohol for three times, and performing vacuum drying to obtain a white solid, namely the intermediate acid F;
in terms of mole ratio, raw material a: raw material B = 1: (0.5 to 5);
(III) dehydration closed-loop generation of target product
Taking a catalyst D (p-toluenesulfonic acid) as a catalyst and a solvent E (toluene, cyclohexane or ethanol) as a solvent, and carrying out dehydration ring-closing reaction on the intermediate acid F prepared in the step (II) to finally prepare a target product; specific material usage and operation:
and (3) adding 50-300 ml of solvent E and 0.05-5 g of catalyst D (p-toluenesulfonic acid) into 5-20 g of intermediate acid F prepared in the step (II), carrying out reflux reaction at 75-140 ℃ for 1-12 h, cooling to room temperature after the reaction is finished, dropwise adding a proper amount of distilled water until the solution turns turbid, standing for 1-24 h to separate out crystals, carrying out suction filtration, washing with distilled water to obtain a crude product, further carrying out vacuum drying, and then recrystallizing with ethanol for purification to obtain a light yellow solid, namely the purified target product (the antioxidant is not extracted in reactivity).
The prepared reactive non-extraction anti-aging agent is applied to 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 the specific molecular structure, the anti-aging agent provided by the invention has the following characteristics in structure:
(1) the molecule of the anti-aging agent contains naphthol or phenol groups, and the o (or m, p) position of phenolic hydroxyl is modified with a substituent group 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 in a molecule, and active hydrogen exists on a hydrazide bond, so the anti-aging agent also has the characteristics of a hindered amine anti-aging agent;
(3) because the anti-aging agent contains the hindered phenol and hindered amine bifunctional groups, the capture mechanism of the bifunctional free radicals can capture carbon free radicals in rubber products, controls the generation of peroxy radicals and hydroperoxide, and equivalently adds an anti-aging line;
(4) the maleic anhydride skeleton in the anti-aging agent contains double bonds, and the double bonds enable the anti-aging agent to be capable of chemically reacting with rubber macromolecules in the vulcanization process, so that the anti-aging agent is bonded in a rubber macromolecule network through chemical bonds, and the anti-aging agent has the characteristics of non-migration, non-volatilization and no extraction, and finally achieves the purpose of prolonging the service life of rubber.
Generally, the anti-aging agent product provided by the invention is light yellow, has no coloring pollution, can be used in rubber products with dark colors and light colors, and has wide application range. The comparison of the application effect of the anti-aging agent 4020 with the conventional anti-aging agent shows that the film using the anti-aging agent is far superior to the existing product in the index performances such as tensile strength, elongation at break and the like, and shows better application prospect. On the other hand, the synthesis and preparation method of the antioxidant product is relatively simple, mild in reaction conditions, easy to separate, and suitable for industrial large-scale production. On the other hand, in the preparation process, the purity requirement of related reaction raw materials is low, related reaction reagents are easy to recycle, no environmental pollution is caused, and the method shows good industrial application prospects.
Drawings
FIG. 1 is a mass spectrum of an antioxidant prepared in example 1;
FIG. 2 is a mass spectrum of an antioxidant prepared in example 2;
FIG. 3 is a mass spectrum of an antioxidant prepared in example 3;
FIG. 4 is a nuclear magnetic resonance spectrum of the antioxidant prepared in example 2;
FIG. 5 is a graph showing the change in tensile strength of NR vulcanizate with different antioxidants (1.5: 100 ratio addition);
FIG. 6 is a graph showing the change of elongation at break of NR vulcanized rubber of different antioxidants (added in a ratio of 1.5: 100);
FIG. 7 is a graph showing the change in tensile strength of NR vulcanizate with different antioxidants (1: 100 ratio addition);
FIG. 8 is a graph showing the change of elongation at break of NR vulcanizate with different antioxidants (1: 100 ratio addition);
FIG. 9 shows vulcanized rubber (left: NR vulcanized rubber, right: NR vulcanized rubber after addition of the antioxidant of test example 2);
FIG. 10 shows the ultraviolet absorption spectrum of an antioxidant (left: example 1, right: example 2).
Detailed Description
The technical solution of the present application is further explained below with reference to examples.
Example 1
The reactive non-extractable antioxidant provided in the example is specifically prepared by the following steps.
(I) preparing materials
Raw material A: is 3-hydroxy-2-naphthoyl hydrazine containing naphthol group,
raw material B: maleic anhydride (maleic anhydride);
solvent C: ethyl acetate;
catalyst D: p-toluenesulfonic acid;
solvent E: toluene;
(II) preparation of intermediate acid
Using a solvent C (ethyl acetate) as a solvent, and reacting the raw material A and the raw material B to generate an intermediate acid F; specific material usage and operation:
adding 5g of raw material A into 45mL of solvent C, stirring at room temperature to form a suspension, then dropwise adding a dissolving solution of raw material B (2.94 g of maleic anhydride dissolved by 5mL of ethyl acetate in advance), reacting for 10 hours at room temperature under stirring after dropwise adding is finished within 1 hour, after the reaction is finished, enabling the solution to be in a white paste shape, performing suction filtration, washing a filter cake with absolute ethyl alcohol for three times, and performing vacuum drying to obtain a white solid, namely intermediate acid F;
raw material a (3-hydroxy-2-naphthoyl hydrazine): raw material B (maleic anhydride) = 1: 1.2;
(III) dehydration closed-loop generation of target product
Taking the catalyst D (toluenesulfonic acid) as a catalyst and the solvent E (toluene) as a solvent, and carrying out dehydration ring-closing reaction on the intermediate acid F prepared in the step (II) to finally prepare a target product; specific material usage and operation:
and (3) taking 5g of the intermediate acid F prepared in the step (II) in a three-neck flask with a reflux device, adding 100ml of a solvent E and 0.5g of a catalyst D (p-toluenesulfonic acid), gradually heating, carrying out reflux reaction at 115 ℃ for 10h, cooling to room temperature after the reaction is finished, dropwise adding 5-20 ml of distilled water until the solution becomes turbid, standing for 24h to separate out 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 recrystallizing with ethanol for purification to obtain a light yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The ethyl acetate and the toluene in the reaction process can be recycled by simple distillation.
The ESI-MS (positive) mass spectrum of the target product is shown in FIG. 1, and mass spectrometry shows that [ M + H ] at M/z =283]+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 peak of the excimer ion of (a) at M/z =336.9 is [ M + MeOH + K%]+The peak of the excimer ion of (1). The mass spectrometry was completely consistent with the theoretical calculated molecular weight of 282 for the target product M.
The final calculation and determination result showed that the yield was 87%, and the melting point of the product was: 213.3-216.1 ℃, and the specific product has the following structural formula:
example 2
The procedure of the present example for the preparation of reactive non-extractable anti-aging agent was the same as in example 1, and only a part of the operating parameters were adjusted as follows:
in the step (I):
raw material A: is 3-hydroxy-2-naphthoyl hydrazine containing naphthol group,
raw material B: citraconic anhydride;
solvent C: chloroform;
catalyst D: p-toluenesulfonic acid;
solvent E: cyclohexane;
in the step (II):
adding 20g of raw material A into 150mL of solvent C (chloroform), stirring at room temperature to form a suspension, then dropwise adding a dissolving solution of raw material B (24.9 g of citraconic anhydride is dissolved by 20mL of chloroform in advance), reacting for 5 hours at room temperature under stirring after dropwise adding is finished within 1 hour, after the reaction is finished, enabling the solution to be a white suspension, 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 hydrazine): raw material B (citraconic anhydride) = 1: 2.3;
in the step (III):
and (3) adding 300ml of solvent E and 2.0g of catalyst D (p-toluenesulfonic acid) into 20g of intermediate acid F prepared in the step (II), gradually heating, carrying out reflux reaction at 85 ℃ for 10h, cooling to room temperature after the reaction is finished, dropwise adding 20-60 ml of distilled water until the solution becomes turbid, standing for 24h to separate out a large amount of crystals, carrying out suction filtration, washing the filter cake with distilled water for three times to obtain a crude product, further carrying out vacuum drying, and then recrystallizing with ethanol for purification to obtain a light yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The ESI-MS (negative) mass spectrum of the target product is shown in FIG. 2, and mass spectrometry shows that,M-H at M/z =294.8+And (4) a negative ion peak, mass spectrometry and theoretical calculation of the molecular weight 296 of the target product M are completely consistent.
The nuclear magnetic resonance spectrum is shown in figure 4. Specifically, the method comprises the following steps: 1H NMR (400 MHz, DMSO-d 6) < delta > 2.200-2.205 (m, 3H, -CH3), 6.548-6.552 (s, 1H, hydrogen on the double bond of the anhydride), 7.250-7.299 (s, 1H, hydrogen on the carbon at position 7 of the naphthalene ring), 7.320-7.358 (m, 1H, hydrogen on the carbon at position 6 of the naphthalene ring), 7.494-7.530(m, 1H, hydrogen on the carbon at position 8 of the naphthalene ring), 7.666-7.687(m, 1H, hydrogen on the carbon at position 5 of the naphthalene ring), 7.738-7.758(m, 1H, hydrogen on the carbon at position 1 of the naphthalene ring), 8.186(s, 1H, hydrogen on the carbon at position 4 of the naphthalene ring), 8.343(s, 1H, -NH-), 10.048(s, 1H, -OH).
The final calculation and measurement result show that the yield is 91%, and the melting point of the product is as follows: 193-195 ℃, and the specific product has the following structural formula:
example 3
The procedure of the present example for the preparation of reactive non-extractable anti-aging agent was the same as in example 1, and only a part of the operating parameters were adjusted as follows:
in the step (I):
raw material A: is o-hydroxybenzoyl hydrazine containing a phenol group,
raw material B: citraconic anhydride;
solvent C: ethyl acetate;
catalyst D: p-toluenesulfonic acid;
solvent E: ethanol;
in the step (II):
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 dissolving solution of the raw material B (5.53 g of citraconic anhydride is dissolved by 20mL of ethyl acetate in advance), reacting for 3 hours at room temperature under stirring after dropwise adding is finished within 1 hour, wherein after the reaction is finished, the solution is a white suspension, performing suction filtration, washing a filter cake for three times by using ethyl acetate, and performing vacuum drying to obtain a white solid, namely intermediate acid F;
raw material a (o-hydroxybenzoyl hydrazine), in terms of molar ratios: raw material B (citraconic anhydride) = 1: 1.5;
in the step (III):
and (3) adding 80ml of solvent E and 0.5g of catalyst D (p-toluenesulfonic acid) into 5g of intermediate acid F prepared in the step (II), gradually heating, carrying out reflux reaction at 80 ℃ for 5 hours, evaporating 50ml of solvent, supplementing 50ml of absolute ethanol, continuously reacting for 3 hours, cooling to room temperature after the reaction is finished, dropwise adding 10-30 ml of distilled water until the solution becomes turbid, standing for 24 hours to separate out a large amount of crystals, carrying out suction filtration, washing the filter cake with distilled water for three times to obtain a crude product, further carrying out vacuum drying, and then recrystallizing with ethanol for purification to obtain a light yellow solid, namely the purified target product (the anti-aging agent is not extracted in reactivity).
The ESI-MS (positive) mass spectrum of the target product is shown in FIG. 3, and mass spectrometry shows that [ 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 of the excimer ion peak of (a) is completely consistent with the theoretically calculated molecular weight 246 of the target product M.
The final calculation and measurement result show that the yield is 85%, and the melting point of the product is as follows: 75.5-76.2 ℃, and the specific product has the following structural formula:
experimental example 1
The inventors further performed an anti-aging test on natural rubber using the anti-aging agents prepared in examples 1 and 2, and the detailed experimental procedures are summarized as follows.
Experiment design:
according to the mass ratio m (anti-aging agent): m (natural latex) = 1.5: weighing the anti-aging agent according to the proportion of 100, adding the anti-aging agent into the natural latex, coating the uniformly mixed latex on a template, and vulcanizing for 2.5 hours at the temperature of 80 ℃;
the width of the formed rubber sheet is 6mm, the thickness is 1.10 +/-0.10 mm, the rubber sheet is subjected to experiment in a thermal oxidation aging box, aging is carried out for 24 hours, 48 hours and 72 hours at the temperature of 60 ℃, and the tensile strength and the elongation at break after aging are tested.
The anti-aging agents prepared in the examples 1 and 2 (corresponding to the test example 1 and the test example 2 respectively) are respectively selected, and meanwhile, 4020 anti-aging agent in the prior art is used as a reference, and in the specific preparation process, SiO is added into each experimental group in the same proportion2And modifiers such as a coupling agent Si69, an accelerator CZ, an accelerator D, stearic acid, zinc oxide and the like. The specific dosage ratios are shown in the following table:
raw material dosage ratio for anti-aging experiment
The results of measuring the specific tensile strength and elongation at break are shown in fig. 5 and 6. The comparison shows that the tensile strength and the elongation at break of the NR vulcanized rubber added with the anti-aging agent are both greater than those of the NR vulcanized rubber without the anti-aging agent and also greater than those of the NR vulcanized rubber added with the 4020 anti-aging agent before aging. With the prolonging of aging time, the tensile property of the vulcanized rubber is reduced, but after the NR vulcanized rubber added with the anti-aging agent is aged for 72 hours, the tensile strength and the elongation at break of the NR vulcanized rubber are still greater than those of the aged 72 hours. The improvement effect of the example 2 on the relevant indexes is more obvious, and after aging for 72 hours, the elongation at break of the rubber sheet adopting the example 2 still reaches 2 times of that of the NR vulcanized rubber.
Experimental example 2
The anti-aging tests of natural rubber (corresponding to test example 3 and test example 4 respectively) were further performed using the anti-aging agents prepared in examples 2 and 3, and the specific experimental design was as in test example 1, except that the amount of the anti-aging agent added was changed 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 results of measuring the specific tensile strength and elongation at break are shown in fig. 7 and 8. The comparison shows that although the addition amount of the anti-aging agent synthesized in the example 2 is reduced, the related indexes of the NR vulcanized rubber added with the anti-aging agent are still improved obviously. The NR vulcanizate with the addition of the antioxidant synthesized in example 3 still has better tensile strength and elongation at break than the NR vulcanizate with the addition of 4020 antioxidant, but is inferior to the antioxidant synthesized in example 2.
The anti-aging agent provided by the application is light yellow, no coloring pollution is caused after the natural rubber is added and vulcanized, and the comparison shows that the color of the vulcanized rubber is not obviously changed when the anti-aging agent prepared in example 2 is added and the NR vulcanized rubber is aged for 72 hours in fig. 9. Further, the ultraviolet absorption spectrum of the anti-aging agent prepared in example 1 or 2 was measured (using acetonitrile as a solvent and measuring on an ultraviolet spectrometer), and the results are shown in fig. 10. It can be seen that the prepared anti-aging agent has strong three absorption peaks of 303nm, 348nm and 376nm in the range of 250nm to 400nm, and has strong absorption on ultraviolet light, which lays a foundation for the exertion of the anti-aging performance.
Claims (8)
1. The reactive non-extraction anti-aging agent is characterized by being prepared from a naphthol derivative and/or a phenol derivative and maleic anhydride and/or a derivative thereof through a dehydration condensation reaction, and specifically prepared through the following steps:
(I) preparing materials
Raw material A: naphthol derivatives and/or phenol derivatives; wherein the naphthol derivative is specifically: 3-hydroxy-2-naphthoyl hydrazine, 5-hydroxy-2-naphthoyl hydrazine and 6-hydroxy-2-naphthoyl hydrazine containing naphthol groups, wherein the phenol derivatives are specifically as follows: o-hydroxybenzoyl hydrazine, p-hydroxybenzoyl hydrazine, m-hydroxybenzoyl hydrazine containing a phenol group;
raw material B: maleic anhydride and/or maleic anhydride derivatives, wherein the maleic anhydride derivatives are derivatives containing maleic anhydride structural units, and specifically comprise: methyl maleic anhydride, 2-methylenedibutanoic anhydride, dimethylmaleic anhydride;
solvent C: chloroform and/or ethyl acetate;
catalyst D: p-toluenesulfonic acid;
solvent E: toluene and/or cyclohexane and/or ethanol;
(II) preparation of intermediate acid
Taking the solvent C as a solvent, and reacting the raw material A and the raw material B to generate an intermediate acid F;
(III) dehydration closed-loop generation of target product
And (3) taking the catalyst D as a catalyst and the solvent E as a solvent, and carrying out dehydration ring-closing reaction on the intermediate acid F prepared in the step (II) to finally prepare the target product.
2. The reactive non-leaching antioxidant according to claim 1, wherein in step (two), the specific amounts of materials and operations are as follows:
adding 20g of the raw material A into 50-500 mL of the solvent C, fully dissolving, adding the raw material B dissolved by the solvent C in advance, and reacting for 1-15 h at room temperature;
in terms of mole ratio, raw material a: raw material B = 1: 0.5 to 5.
3. The reactive non-extractable anti-aging agent according to claim 2, wherein in the step (three), the specific amounts of the materials and operations are as follows:
and (3) 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.
4. The reactive non-leaching antioxidant according to claim 3, wherein, in step (one),
raw material A: is 3-hydroxy-2-naphthoyl hydrazine containing naphthol group;
raw material B: citraconic anhydride;
solvent C: chloroform;
catalyst D: p-toluenesulfonic acid;
solvent E: cyclohexane;
in the step (II):
adding 20g of raw material A into 150mL of solvent C, and reacting for 5h under stirring at room temperature;
in terms of mole ratio, raw material a: raw material B = 1: 2.3;
in the step (III):
and (3) adding 300ml of solvent E and 2.0g of catalyst D into 20g of the intermediate acid F prepared in the step (II), carrying out reflux reaction at 85 ℃ for 10h, cooling to room temperature after the reaction is finished, adding distilled water until the solution becomes turbid, standing for 24h to separate out a large amount of crystals, carrying out suction filtration, washing a filter cake with distilled water, further carrying out vacuum drying, and then carrying out recrystallization with ethanol for purification.
5. The method for producing a reactive non-extractable anti-aging agent according to claim 1, which comprises the following production steps:
(I) preparing materials
Raw material A: naphthol derivatives and/or phenol derivatives; wherein the naphthol derivative is specifically: 3-hydroxy-2-naphthoyl hydrazine, 5-hydroxy-2-naphthoyl hydrazine and 6-hydroxy-2-naphthoyl hydrazine containing naphthol groups, wherein the phenol derivatives are specifically as follows: o-hydroxybenzoyl hydrazine, p-hydroxybenzoyl hydrazine, m-hydroxybenzoyl hydrazine containing a phenol group;
raw material B: maleic anhydride and/or maleic anhydride derivatives, wherein the maleic anhydride derivatives are derivatives containing maleic anhydride structural units, and specifically comprise: methyl maleic anhydride, 2-methylenedibutanoic anhydride, dimethylmaleic anhydride;
solvent C: chloroform and/or ethyl acetate;
catalyst D: p-toluenesulfonic acid;
solvent E: toluene and/or cyclohexane and/or ethanol;
(II) preparation of intermediate acid
Taking the solvent C as a solvent, and reacting the raw material A and the raw material B to generate an intermediate acid F;
(III) dehydration closed-loop generation of target product
And (3) taking the catalyst D as a catalyst and the solvent E as a solvent, and carrying out dehydration ring-closing reaction on the intermediate acid F prepared in the step (II) to finally prepare the target product.
6. The method for preparing the reactive non-extraction anti-aging agent according to claim 5, wherein in the step (III), after the dehydration ring-closure reaction is finished, the reaction product is cooled to room temperature, distilled water is added until the solution becomes turbid, the reaction product is kept stand for 1-24 hours to precipitate crystals, the crystals are subjected to suction filtration, the crude product is obtained after being washed with distilled water, and the crude product is further purified by ethanol recrystallization after being dried in vacuum.
7. Use of the reactive non-extractable antioxidant according to any one of claims 1 to 4 in the production of rubber products, characterized in that it is used as an anti-aging antioxidant.
8. Use of a reactive non-extracting antioxidant according to claim 7 in the production of rubber articles, characterized by the use in NR natural rubber.
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